JP2010216228A - Method of fireproof coating of steel frame - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dry method of fireproof coating of a steel frame good in workability, and capable of imparting sufficient fireproof performance with the coating thickness smaller than the conventional thickness. <P>SOLUTION: The method of fireproof coating of the steel frame is to coat a steel frame base material with an endothermic mold product. The endothermic mold product: (1) contains an organic resin component and a metal hydrate; of which (2) the organic resin component contains a nonaqueous thermosetting resin, (3) the metal hydrate has a water content of 6 wt.% or more and a dehydration or decomposition temperature of 50-200°C, (4) the weight ratio of the organic resin component and the metal hydrate is 5:95 to 90:10, and (5) the density is 0.8-4 g/cm<SP>3</SP>. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a steel fireproof coating method.

  When a structure such as a building or a civil engineering structure is exposed to a high temperature due to a fire, there is a problem that the mechanical strength of the base material (steel frame, concrete, etc.) of the structure is rapidly reduced. On the other hand, there is known a fireproof coating method in which a fireproof coating material is applied to a base material, and the temperature rise of the base material during a fire is delayed to suppress a decrease in mechanical strength of the base material.

  Examples of the fireproof coating method include, for example, 1) inorganic fibrous materials such as rock wool and glass fibers, 2) lightweight aggregates such as pearlite and vermiculite, and 3) inorganic powder containing crystal water. There is known a wet refractory coating method in which a body or the like is appropriately mixed and kneaded with water to thicken a paste or slurry mixed composition on the surface of the substrate (Patent Documents 1, 2, etc.).

  However, in the conventional wet fireproof coating method, depending on the type of material used, for example, a considerable coating thickness of about 20 to 40 mm is required in order to obtain 1 hour fireproof performance for columns, beams, etc. of steel reinforced concrete structures. Is required. Therefore, since a large amount of coating material is required at the time of construction, it is very disadvantageous in terms of handling and cost. In addition, the construction part greatly protrudes from the surface of the base material for thickening, and gives a feeling of pressure on the appearance. Furthermore, there is a possibility that peeling or detachment of the coating film may occur after construction.

  A fireproof coating method using a dry material is also known instead of the wet fireproof coating method. This is a method of coating a base material with a dry molding (for example, a dry sheet) prepared in advance. Examples of the dry sheet include an inorganic fiber mixed mat, rock wool, fireproof board, and the like (Patent Document 3, etc.). However, even in the method of coating such a dry material, conventionally, in order to obtain sufficient fire resistance, it is necessary to increase the coating thickness.

JP 58-96662 A Japanese Patent Laid-Open No. 10-147993 Japanese Patent Laid-Open No. 6-136853

  An object of the present invention is to provide a steel fireproof coating method that is a dry steel fireproof coating method, has good workability, and can provide sufficient fireproof performance with a smaller coating thickness than conventional ones. .

  As a result of intensive studies, the present inventors have found that the above object can be achieved by a method of coating a steel base with an endothermic molded body having a specific component, and have completed the present invention.

That is, the present invention relates to the following steel fireproof coating method.
1. It is a steel fireproof coating method for coating a steel base material with an endothermic molded body,
The endothermic molded body is
(1) including an organic resin component and a metal hydrate,
(2) The organic resin component contains a non-aqueous thermosetting resin,
(3) The metal hydrate has a water content of 6% by weight or more and a dehydration or decomposition temperature of 50 to 200 ° C.
(4) The weight ratio of the organic resin component to the metal hydrate is 5:95 to 90:10,
(5) The density is 0.8-4 g / cm ³ .
A steel fireproof coating method characterized by that.
2. The steel frame fireproof coating method according to Item 1, wherein the endothermic molded body is in the form of a sheet and / or a board.
3. The steel fireproof coating method according to Item 2, wherein a reinforcing layer is laminated on one side of the endothermic molded body on the side covering the steel base material.
4). Item 4. The steel fireproof coating method according to Item 2 or 3, wherein a heat reflecting layer is laminated on one side of the endothermic molded body on the side opposite to the side covering the steel substrate.
5). Item 5. The steel fireproof coating method according to any one of Items 1 to 4, wherein a part or all of the surface of the steel base is covered with the endothermic molded body directly or indirectly through an air layer.
6). The steel fireproof coating method according to any one of Items 1 to 5, wherein the steel base is at least one selected from the group consisting of H-type, I-type, square-type, and round-type.

The steel fireproof coating method of the present invention is a method of coating an endothermic molded body on a steel base material,
The endothermic molded body is
(1) including an organic resin component and a metal hydrate,
(2) The organic resin component contains a non-aqueous thermosetting resin,
(3) The metal hydrate has a water content of 6% by weight or more and a dehydration or decomposition temperature of 50 to 200 ° C.
(4) The weight ratio of the organic resin component to the metal hydrate is 5:95 to 90:10,
(5) The density is 0.8-4 g / cm ³ .
It is characterized by that. The endothermic molded body used in the above construction method is used in a mode in which a steel base is directly or indirectly coated, for example, in the form of a sheet or board. This heat-absorbing molded body is excellent in the steel base material because the crystal water of the metal hydrate is dehydrated when exposed to combustion heat in the event of a fire, and the temperature rise of the steel base material to be coated is suppressed by the latent heat of vaporization. Provides fire resistance.

It is a figure which shows the variation of the fireproof coating aspect with respect to a square-shaped steel frame base material and a round-shaped steel frame base material. It is a figure which shows the variation of the fireproof coating aspect with respect to an H-type steel frame base material. It is a figure which shows the variation of the fireproof coating aspect with respect to the pillar (A square-shaped steel base material, a round-shaped steel base material, and an H-type steel base material) provided close to the wall panel. It is a figure which shows the variation of the fireproof coating aspect with respect to the support base material (H-type steel base material) provided in the beam provided on the ceiling or the floor board. It is a figure which shows the steel frame base material used with the fireproof coating construction method of Examples 1-6. In Examples 1-2, the square steel substrate shown in FIG. 5A was used, and in Examples 3-6, the H-type steel substrate shown in FIG. 5-2 was used.

a: Steel base material (steel steel)
b: endothermic molded body c: butt portion d: overlapping portion e: fireproof caulking agent f: washer g: fixing pin

  Hereinafter, the present invention will be described in detail.

The steel fireproof coating method of the present invention is a method of coating an endothermic molded body on a steel base material,
The endothermic molded body is
(1) including an organic resin component and a metal hydrate,
(2) The organic resin component contains a non-aqueous thermosetting resin,
(3) The metal hydrate has a water content of 6% by weight or more and a dehydration or decomposition temperature of 50 to 200 ° C.
(4) The weight ratio of the organic resin component to the metal hydrate is 5:95 to 90:10,
(5) The density is 0.8 to 4 g / cm ³ .

  The said endothermic molded object is used in the aspect which coat | covers a steel-frame base material directly or indirectly in the form of a sheet form or board form, for example. In particular, by including specific organic resin components and metal hydrates, the crystal water of metal hydrates dehydrates when exposed to combustion heat in the event of a fire, and the temperature of the steel base material to be coated increases due to latent heat of evaporation. And imparts excellent fire resistance to the steel base.

  The said endothermic molded object is obtained by shape | molding an endothermic composition in a desired form. That is, it is obtained by preparing an endothermic composition that satisfies the above requirements (1) to (4) and molding it into a desired form (for example, a sheet shape or a board shape) so as to satisfy the above requirement (5). It is done.

Hereinafter, an endothermic composition, an endothermic molded body, and a steel fireproof coating method using the endothermic molded body will be described.
(Endothermic composition and endothermic molded article)
The endothermic composition used in the present invention is:
(1) including an organic resin component and a metal hydrate,
(2) The organic resin component contains a non-aqueous thermosetting resin,
(3) The metal hydrate has a water content of 6% by weight or more and a dehydration or decomposition temperature of 50 to 200 ° C.
(4) The weight ratio of the organic resin component to the metal hydrate is 5:95 to 90:10.
It is characterized by that.

  In the present specification, the organic resin component refers to a component obtained by adding a plasticizer or a catalyst to the organic resin alone or as necessary. In the present invention, by containing a non-aqueous thermosetting resin as the organic resin, an endothermic composition and an endothermic molded body (also simply referred to as “molded body” in the present specification) having excellent fire resistance and the like are obtained. .

  The content of the non-aqueous thermosetting resin is preferably 20 to 100% by weight and more preferably 40 to 80% by weight in the organic resin component.

  As said non-aqueous thermosetting resin, the non-aqueous thermosetting resin employ | adopted as a binder in field | areas, such as a well-known plastic product, a sheet | seat, and a coating material, is used. The non-aqueous thermosetting resin means a thermosetting resin that does not dissolve or disperse in water, and examples thereof include one or more of urethane resin, epoxy resin, silicone resin, alkyd resin, melamine resin, and the like.

  The non-aqueous thermosetting resin may be liquid at the time of kneading to prepare the endothermic composition, and is preferably liquid at normal temperature (5-35 ° C.). In this case, mixing and kneading with the metal hydrate is possible at room temperature (5-35 ° C.), the metal hydrate is uniformly dispersed in the endothermic composition, and the metal hydrate is an organic resin component. Can be covered. Therefore, it is possible to improve the fire resistance (heat absorption) and water resistance of the endothermic composition and the endothermic molded article.

  Among the above, urethane resin and epoxy resin are preferable as the non-aqueous thermosetting resin, and urethane resin is preferable when the endothermic molded body needs flexibility. Also, adducts or modified resins of these resins can be used.

  Examples of the urethane resin include those obtained by combining polyols such as polyether polyol, polyester polyol, acrylic polyol and isocyanates.

  Polyether polyols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, glucose, sorbitol, sucrose, and other polyhydric alcohols such as propylene oxide, ethylene oxide, and butylene. Examples thereof include polyols obtained by adding one or more of oxide, styrene oxide and the like, and polyoxytetramethylene polyol obtained by adding tetrahydrofuran to the polyhydric alcohol by ring-opening polymerization.

  Examples of polyester polyols include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, glycerin, trimethylolpropane and other low molecular polyols, and glutaric acid, adipic acid, and pimeline. Condensation polymers with one or more of acid, peric acid, sebacic acid, terephthalic acid, isophthalic acid, dimer acid, hydrogenated dimer acid or other low molecular dicarboxylic acid or oligomeric acid; and propiolactone, caprolactone And polyols which are ring-opening polymers of cyclic esters such as valerolactone. An epoxy-modified polyol obtained by modifying a polyol with an epoxy compound containing a plurality of epoxy groups can also be used.

  Among the polyols, polyester polyols are preferable, and polyester polyols having two or more functional groups having active hydrogen atoms are preferable. Furthermore, polyester polyols having 3 or more functional groups having active hydrogen atoms are preferred. When there are three or more functional groups having an active hydrogen atom, bubbles are less likely to occur during mixing and kneading with metal hydrates and during molding, so they can be easily kneaded and have a high and uniform thickness. A molded object can be manufactured stably. For this reason, the outstanding water resistance can be exhibited.

  In addition, a hydroxyl group is mentioned as a functional group which has an active hydrogen atom. Moreover, as molecular weight of polyester polyol, Preferably it is 500-10000, More preferably, it is 1000-5000.

  As isocyanates that can be used in combination with the above polyols, 4,4-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (TDI), 1,3-xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI) ), Polymethylene polyphenyl polyisocyanate (polymeric MDI), 1,5-naphthalene diisocyanate (NDI), and the like. Further, the above-mentioned isocyanates modified with water or lower monovalent or polyhydric alcohols; terminal isocyanate group-containing urethane prepolymers obtained by reacting isocyanates with polyols; terminal isocyanate group-containing urethane prepolymers with water or lower 1 Those modified with a hydric or polyhydric alcohol; and a terminal isocyanate group-containing urethane prepolymer and isocyanates, or a mixture of two or more of them can be used.

  Among the above isocyanates, hexamethylene diisocyanate (HMDI) is particularly preferable. In this case, bubbles are not easily generated during mixing and kneading with the metal hydrate and during molding, and since the rollability is excellent, a molded body having a high strength and a uniform thickness can be stably produced. Moreover, the softness | flexibility of a molded object and the flexibility are also excellent.

  When using a urethane resin, a curing catalyst can be used in combination. The curing catalyst is a substance that accelerates curing by reaction of isocyanate groups. Examples of the curing catalyst include amine-based catalysts, organometallic catalysts, and inorganic catalysts. Examples of the amine catalyst include ethylenediamine, triethylenediamine, triethylamine, ethanolamine, diethanolamine, hexamethylenediamine, and the like. Moreover, the derivative | guide_body of these amines and the mixture with a solvent are also mentioned. More specifically, examples of the organometallic catalyst include dibutyltin dilaurate, dibutyltin diacetate, and potassium acetate. Examples of the inorganic catalyst include tin chloride.

  As the epoxy resin, epi-bis type bisphenol A type epoxy resin obtained by condensation reaction of bisphenol A and epichlorohydrin, etc .; bisphenol F type epoxy resin; bisphenol AD type epoxy resin are generally used. Other examples include phenol novolac type epoxy resins, bisphenol A novolak type epoxy resins, cresol novolac type epoxy resins, diaminodiphenylmethane type epoxy resins, and the like.

  In addition, as a special one, epoxy resins such as β-methyl epichloro type, glycidyl ether type, glycidyl ester type, polyglycol ether type, glycol ether type, and urethane-modified epoxy resin can also be used. In addition, n-butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, cresyl glycidyl ether, glycidyl methacrylate, vinylcyclohexene monoepoxide, diglycidyl ether, etc. may be used as a diluent. it can. The molecular weight of the epoxy resin is preferably 100 to 2000, more preferably 200 to 1000.

  The epoxy resin can be used in combination with a curing agent. Curing agents include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine (dipropylenetriamine), bis (hexamethylene) triamine, 1,3,6-trisaminomethylhexane, polymethylenediamine, Aliphatic amines such as trimethylhexamethylenediamine, polyetherdiamine, dimethylaminopropylamine, diethylaminopropylamine, aminoethylethanolamine; mensendiamine, isophoradiamine, bis (4-amino-3-methylcyclohexyl) methane, Alicyclic polyamines such as N-aminoethylpiperazine and metaxylylenediamine; metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, benzyldi Aromatic amines such as tilamine and dimethylaminomethylbenzene; polyamine epoxy resin adduct, polyamine-ethylene oxide adduct, polyamine-propylene oxide adduct, cyanoethylated polyamine, ketimine, aromatic acid anhydride, cycloaliphatic acid anhydride, aliphatic Examples thereof include acid anhydrides, halogenated acid anhydrides; polyamide resins formed by condensation of dimer acid and polyamine.

  Examples of the plasticizer include phthalic acid esters such as dioctyl phthalate, dibutyl phthalate, and butyl benzyl phthalate; aliphatic carboxylic acid esters such as dioctyl adipate, diisodecyl succinate, dibutyl sebacate, and butyl oleate. Alcohol esters such as pentaerythritol ester; phosphate esters such as trioctyl phosphate and tricresyl phosphate; paraffin, chlorinated paraffin and the like. These plasticizers can be used alone or in combination of two or more.

  By including the plasticizer in the organic resin component, the viscosity of the organic resin component can be optimized. For this reason, kneading with the metal hydrate becomes easy. Furthermore, bubbles are less likely to be mixed and generated during mixing / kneading and molding, and the water resistance of the molded body can be improved.

  The addition amount of the plasticizer is usually 300 parts by weight or less, preferably 5 parts by weight to 300 parts by weight, and more preferably 10 parts by weight to 150 parts by weight with respect to 100 parts by weight of the organic resin. When it exceeds 300 parts by weight, the tackiness of the surface of the molded body is high and the strength tends to decrease.

As the metal hydrate, one having a water content of 6% by weight or more and a dehydration or decomposition temperature of 50 to 200 ° C. is used. The metal hydrate used in the present invention is an inorganic compound hydrate represented by the general formula MX.nH ₂ O or the like.

Such a compound MX · nH ₂ O is a compound in which M contains at least one metal cation and X consists of one or more anions. The water content of these metal hydrates is preferably 10 to 70% by weight, more preferably 30 to 50% by weight. The water content can be determined by differential thermal analysis (TG-DTA). When the water content is less than 6% by weight, the endothermic property necessary for a fire or the like cannot be exhibited. Further, when the water content exceeds 70% by weight, durability and water resistance may be lowered.

  The metal hydrate used in the present invention may have a dehydration or decomposition temperature of the metal hydrate of 50 to 200 ° C, but preferably 80 to 150 ° C. When the dehydration temperature or decomposition temperature is less than 50 ° C., there is a risk of dehydration at room temperature, and when it exceeds 200 ° C., the endothermic property at the initial stage of a fire cannot be exhibited. The dehydration or decomposition temperature is a temperature specified in “Chemical Handbook Basic Edition, Revision 5” (Edited by Chemical Society of Japan).

  In the present invention, in particular, when the water content of the metal hydrate is 30 to 50% by weight and the dehydration or decomposition temperature is 80 to 150 ° C., the substrate in the vicinity of 100 ° C. due to the endothermic action of the metal hydrate during a fire. The temperature rise can be effectively suppressed.

  Examples of the metal hydrate include, for example, ammonium aluminum sulfate 12 hydrate, sodium aluminum sulfate 12 hydrate, aluminum sulfate 27 hydrate, aluminum sulfate 18 hydrate, aluminum sulfate 16 hydrate, aluminum sulfate 10 water. Japanese hydrate, Aluminum sulfate hexahydrate, Potassium aluminum sulfate 12 hydrate, Iron sulfate 7 hydrate, Iron sulfate 9 hydrate, Potassium sulfate 12 hydrate, Magnesium sulfate 7 hydrate, Sodium sulfate 10 Sulfates such as hydrate, nickel sulfate hexahydrate, zinc sulfate heptahydrate, beryllium sulfate tetrahydrate, zirconium sulfate tetrahydrate; zinc sulfite dihydrate, sodium sulfite heptahydrate, etc. Sulfite of aluminum phosphate dihydrate, cobalt phosphate octahydrate, magnesium phosphate octahydrate, magnesium ammonium phosphate 6 water , Magnesium hydrogen phosphate trihydrate, magnesium hydrogen phosphate heptahydrate, zinc phosphate tetrahydrate, zinc dihydrogen phosphate dihydrate, etc .; aluminum nitrate nonahydrate, Zinc nitrate hexahydrate, calcium nitrate tetrahydrate, cobalt nitrate hexahydrate, bismuth nitrate pentahydrate, zirconium nitrate pentahydrate, cerium nitrate hexahydrate, iron nitrate hexahydrate, nitric acid Nitrate such as iron 9 hydrate, nickel nitrate hexahydrate, magnesium nitrate hexahydrate; acetate such as zinc acetate dihydrate, cobalt acetate tetrahydrate; cobalt chloride hexahydrate, iron chloride Chloride salts such as tetrahydrate, borax (sodium tetraborate pentahydrate, sodium tetraborate decahydrate), disodium octaborate tetrahydrate, zinc borate 3.5 hydrate Metal hydrate salts such as borates. These can be used alone or in combination of two or more.

  Among the metal hydrates, sulfates are preferable, and aluminum sulfate hydrates are particularly preferable. Although the detailed mechanism of action is not clear, in the case of aluminum sulfate hydrate, aluminum sulfate forms hollow particles simultaneously with the dehydration or decomposition reaction, and at higher temperatures, the particles fuse together to form a heat insulating layer. It is presumed that a temperature rise at a high temperature can be suppressed.

  By mixing and using sulfate and borate, the water resistance of the molded product can be further improved. In addition, the boric acid compound dissolves simultaneously with dehydration or decomposition reaction during combustion, and the combustion residue solidifies into a glassy shape, thereby suppressing the occurrence of cracking and dropping off of the molded body. The mixing ratio (weight ratio) of sulfate and borate is preferably 99: 1 to 30:70.

  When the metal hydrate satisfies the above conditions, for example, when the substrate is exposed to combustion heat during a fire, the metal hydrate in the endothermic composition is dehydrated, and the endothermic action causes the temperature of the substrate. The rise is suppressed.

  The mixing ratio of the organic resin component and the metal hydrate is 5:95 to 90:10 by weight. Among these, 10: 90-60: 40 is preferable, 15: 85-50: 50 is more preferable, 15: 85-40: 60 is more preferable, and 15: 85-35: 65 is the most preferable. If the organic resin component is less than 10:90 by weight, sufficient durability and water resistance may not be obtained. When there are more organic resin components than 60:40 by weight ratio, fireproof performance may become inadequate.

  In addition to these components, fiber materials, color pigments, dispersants, flame retardants, water repellents, fillers, aggregates, and the like can be appropriately blended as necessary. These can be used alone or in combination of two or more.

  Examples of the fiber material include inorganic fibers such as rock wool, glass fiber, aluminum fiber, stainless steel fiber, silica-alumina fiber, and carbon fiber; and organic fibers such as pulp fiber, polypropylene fiber, vinyl fiber, and aramid fiber. By blending the fiber material, the molded body can be reinforced and the flexibility can be improved.

  As the color pigment, a general paint pigment (organic pigment / inorganic pigment) can be used. In particular, inorganic pigments such as titanium dioxide, silicon carbide, alumina, bengara, yellow iron oxide, titanium yellow, chrome green, ultramarine blue, and cobalt blue are preferable. Furthermore, in order to further improve the fire resistance, expansive graphite, unexpanded vermiculite and the like may be blended.

  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 prevents or suppresses the burning of the binder. In the present invention, as the flame retardant, the same flame retardant used in known fire-resistant paints and / or sheets can be used.

  Examples of the flame retardant include tricresyl phosphate, diphenyl cresyl phosphate, diphenyl octyl phosphate, tri (β-chloroethyl) phosphate, tributyl phosphate, tri (dichloropropyl) phosphate, triphenyl phosphate, triphenyl Organic phosphorus such as (dibromopropyl) phosphate, chlorophosphonate, bromophosphonate, diethyl-N, N-bis (2-hydroxyethyl) aminomethyl phosphate, di (polyoxyethylene) hydroxymethyl phosphonate Compounds: Chlorinated polyphenyl, chlorinated polyethylene, diphenyl chloride, triphenyl chloride, pentachloride fatty acid ester, perchloropentacyclodecane, chlorinated naphthalene, tetrachlorophthalic anhydride, etc. Elemental compounds; antimony compounds such as antimony trioxide and antimony pentachloride; phosphorus compounds such as phosphorus trichloride, phosphorus pentachloride, ammonium phosphate and ammonium polyphosphate; and other inorganic compounds such as zinc borate and sodium borate It is done. These can be used alone or in combination of two or more.

  As the dispersant, anionic, cationic, nonionic, and high molecular types can be used, and those having an acid value of 0 to 400 mgKOH / g and an amine value of 0 to 200 mgKOH / g are particularly preferable. In particular, in the present invention, those having an acid value of 0 to 100 mgKOH / g and an amine value of 0 to 100 mgKOH / g are preferable, and those having an acid value of 20 to 60 mgKOH / g and an amine value of 20 to 60 mgKOH / g are more preferable. Preferably, those having an acid value of 30 to 50 mg KOH / g and an amine value of 30 to 50 mg KOH / g are most preferable (more preferably equivalent).

  Although the action mechanism of the dispersant is not clear, the viscosity at the time of mixing and kneading the organic resin component and the metal hydrate is optimized, and the dispersibility is excellent. For this reason, a metal hydrate is uniformly disperse | distributed and the composition and molded object which are excellent in a softness | flexibility and flexibility can be manufactured.

  Specific examples of the dispersant include a salt of a long-chain polyaminoamide and an acid polymer, a polycarboxylate of a polyaminoamide, a salt of a long-chain polyaminoamide and a polar acid ester, a copolymer having an acidic group, and a hydroxyl group-containing carboxylic acid ester , Alkylolaminoamide, acrylic copolymer with affinity for pigment, unsaturated polycarboxylic acid polyaminoamide, alkylammonium salt of acidic polymer, phosphate ester salt of copolymer with affinity for pigment, pigment Affinity block copolymer, alkylammonium salt of block copolymer containing acid group, modified acrylic block copolymer, acrylic copolymer having affinity for pigment, unsaturated polycarboxylic acid polymer Saturated polycarboxylic acid polymer and polysiloxane, unsaturated polycarboxylic acid polymer, high content Alkyl ammonium salt of the copolymer, high molecular copolymers with pigment affinic groups, unsaturated acidic polycarboxylic acid polyester and a polysiloxane, and the like. The above components can be used alone or in combination of two or more.

  Examples of the water repellent include wax-based water repellents such as paraffin wax, polyethylene wax, and acrylic / ethylene copolymer wax; silicone-based water repellents such as silicone resin, polydimethylsiloxane, and alkylalkoxysilane; and perfluoroalkyl. Examples thereof include fluorine-based water repellents such as carboxylate, perfluoroalkyl phosphate ester, and perfluoroalkyltrimethylammonium salt.

  In the present invention, it is particularly preferable to use a silicone-based water repellent containing an alkylalkoxy compound having an alkyl group having 3 to 12 carbon atoms (hereinafter also simply referred to as “alkylalkoxysilane compound”).

  Such an alkylalkoxysilane compound is a compound in which an alkyl group and an alkoxyl group are bonded to a silicon atom. For example, a compound represented by the following formula (1) and / or a condensate thereof can be used.

R ¹ —Si (OR ² ) ₃ (1)
Examples of the compound represented by the above formula (1) include propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, hexyltrimethoxysilane, and hexyl. Triethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, nonyltrimethoxysilane, nonyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, undecyltrimethoxysilane, Examples include undecyltriethoxysilane, dodecyltrimethoxysilane, and dodecyltriethoxysilane.

  As the alkylalkoxysilane compound, those having 3 to 12 (preferably 5 to 8) carbon atoms in the alkyl group are used. The alkyl group may be partially substituted with halogen or the like. If the carbon number of the alkyl group is within the above range, excellent performance in water resistance can be exhibited.

  Examples of the alkoxyl group in the alkylalkoxysilane compound include those having 1 to 8 carbon atoms (preferably 1 to 4, more preferably 1 to 2), and a methoxy group having 1 carbon atom is particularly suitable. When the number of carbon atoms of the alkoxyl group is in the above range, advantageous effects in performance such as water resistance can be obtained.

  The water repellent is preferably 0.2 to 10 parts by weight, more preferably 0.3 to 5 parts by weight with respect to 100 parts by weight of the organic resin component. If the amount is less than 0.2 parts by weight, it is difficult to obtain a water repellent effect, and if it exceeds 10 parts by weight, the curing of the organic resin may be hindered.

  Examples of the filler include talc, calcium carbonate, sodium carbonate, aluminum oxide, zinc oxide, silica, clay, clay, shirasu, quartz sand, quartzite powder, quartz powder, alumina, zinc borate, barium sulfate, mica glass powder, etc. Is mentioned.

  The aggregate may be natural or artificial, and may be colored. As the aggregate, for example, when using lightweight aggregates such as perlite, expanded shale, expanded vermiculite, pumice, shirasu balloon, glass balloon, hollow resin beads, ALC pulverized product, aluminosilicate foam, the heat resistance of the molded body, Flexibility can be improved.

  The endothermic composition of the present invention can be obtained by using the organic resin component and the metal hydrate as essential components and kneading them with additives as necessary. Moreover, the endothermic molded object of this invention is obtained by shape | molding the said endothermic composition.

  Although the temperature at the time of kneading | mixing and shaping | molding at the time of preparing an endothermic composition can be set suitably, it may be normal temperature normally. However, when heating, the temperature is lower than the dehydration temperature of the metal hydrate. In the present invention, a solvent can be added as needed during kneading. In this case, a non-aqueous solvent is preferable and water is not used.

  In order to produce an endothermic molded article, for example, a method in which an endothermic composition is poured into a mold and demolded after drying; a method in which the endothermic composition is applied to release paper by a coating machine and then wound up; A method in which an endothermic composition is formed into a pellet and then processed into a sheet or board by an extrusion molding machine; the endothermic composition kneaded by a Banbury mixer, a mixing roll, or the like is rolled with a calendar composed of a plurality of hot rolls to form a sheet Or a method of processing into a board shape.

  The thickness when the endothermic molded body is used in the form of a sheet or board may be appropriately set depending on fire resistance, application site, etc., but is usually about 1 to 20 mm, preferably 2 to 10 mm. If it is less than 1 mm, sufficient fire resistance may not be obtained. If it exceeds 20 mm, there may be a case where sufficient fire resistance equivalent to the thickness cannot be obtained. However, it is not necessarily limited to such thickness depending on fire resistance, application site, and the like.

The endothermic molded article of the present invention is in a state where the metal hydrate is uniformly and densely dispersed in the organic resin component. For this reason, the dehydration reaction of the metal hydrate at the time of a fire progresses slowly, and the effect which suppresses the steel material temperature rise near 100 degreeC is high. In the present invention, the density of the molded body is set to 0.8 to 4 g / cm ³ , preferably 1 to 2.4 g / cm ³ , more preferably 1.2 to 2 g / cm ³ . By setting to such a density, high endothermic performance (fire resistance performance, etc.) can be obtained.

When the density of the molded body is less than 0.8 g / cm ^{3, the} metal hydrate contained in the molded body is dehydrated and vaporized during a fire due to voids leading to the inside or outside of the molded body. Occurs instantaneously and it becomes difficult to obtain the endothermic effect obtained by the latent heat of vaporization of water, and thus there is a risk that the temperature rise suppression of the substrate cannot be sufficiently satisfied. In addition, since the foam-shaped molded body limits the content of the metal hydrate due to the voids, it is necessary to increase the thickness of the molded body in order to obtain sufficient endothermic performance. Furthermore, since water easily penetrates into the voids, it is inferior in water resistance. When water comes in contact with it, dissolution of metal hydrates, outflow, or other water-soluble metal salts coexist, new metal salts. May be generated, and the endothermic performance may be significantly reduced.

When the density of the molded body is larger than 4 g / cm ^3, the weight of the molded body is large, so that there is a possibility of dropping off when the molded body is bonded to a vertical surface such as a column or the lower surface of a beam.

  The density is a value obtained by dividing the weight of the molded body by its volume.

In the present invention, the heat-absorbing molded body may be, for example, a woven fabric, a nonwoven fabric, a glass nonwoven fabric, a ceramic paper, a synthetic paper, a non-combustible paper, a glass cloth, a reinforcing layer such as a mesh, an aluminum foil, an aluminum foil or a synthetic resin. A heat reflecting layer such as a laminated sheet, an aluminum foil / kraft paper laminated sheet, an aluminum foil / glass woven cloth laminated sheet, an aluminum foil / mesh laminated sheet, an aluminum plate, a color steel plate, a stainless steel plate or the like can be laminated. As the laminated form, for the purpose of suppressing the temperature rise due to the endothermic action of metal hydrate, the surface in contact with the steel substrate such as the beam and pillar of the building is the “back surface of the molded body” and the opposite side is the “surface of the molded body” Then,
1. 1. Laminate a reinforcing layer on the back of the molded body. 2. Laminate a plurality of reinforcing layers on the back of the molded body and inside the molded body. 3. Laminate a heat reflecting layer on the surface of the molded body. Above 1. Or 2. And 3. Are appropriately combined and laminated. In the present invention, in particular, the above 4. The laminated form is preferable.

  By laminating a reinforcing layer such as a glass nonwoven fabric or glass mesh on the back of the molded body, when the molded body is affixed to the substrate via an adhesive, the adhesion with the substrate is improved and the molded body is displaced. Can prevent falling, improving fire resistance in the event of a fire. Furthermore, by laminating heat reflecting layers such as aluminum foil, aluminum cloth, aluminum foil / glass nonwoven fabric laminated sheet, aluminum foil / mesh laminated sheet, aluminum foil / synthetic resin laminated sheet, etc. on the surface of the molded body, The dehydration rate of the Japanese product can be controlled, and an increase in the substrate temperature can be suppressed.

  When manufacturing said laminated body, it can laminate | stack simultaneously, for example, when manufacturing an endothermic molded object, or can be laminated | stacked using an adhesive agent, a metal stopper, etc. after a molded object manufacture.

The endothermic molded body of the present invention can be used as a covering material for steel base materials such as building columns and beams, and can effectively suppress a temperature rise near 100 ° C. As long as the effect of the present invention is not hindered, the substrate can be coated directly or indirectly using an adhesive such as an organic resin.
(Steel frame fireproof coating method)
In the steel fireproof coating method of the present invention, a fireproof coating is formed on a steel base material by coating the steel substrate with the heat-absorbing molded body.

  As an aspect which coat | covers a steel frame base material with an endothermic molded object, the aspect which coat | covers directly (it closely_contact | adheres) to a steel frame base material, and the aspect indirectly covered through an air layer are mentioned, for example. When fireproof coating is performed via the air layer, an air heat insulating layer is formed, and the fireproof performance can be improved more than when fireproof coating is performed directly. Further, two or more (multiple layers) endothermic molded bodies can be laminated.

  Hereinafter, the covering mode will be specifically described with reference to the drawings.

  FIG. 1 shows a mode in which a square steel base (FIG. 1-1) and a round steel base (FIG. 1-2) are fire-resistant coated. FIG. 1-1 and FIG. 1-2 both show a mode in which a fireproof coating is applied directly (in close contact). 1-3 to 1-11 show variations of the refractory coating. Here, a square steel base material is taken as an example, but the construction can be similarly applied to a round steel base material.

  In FIG. 1-3, a sheet-like endothermic molded body is wrapped around a square steel substrate to cover it. The end portions of the endothermic molded body are abutted, and in order to reinforce the fire resistance of the abutting portion, for example, the abutting portion is covered with an aluminum tape or the like. Note that an adhesive may be applied to the surface of the steel base and / or the endothermic molded body when the heat-absorbing molded body is directly coated on the steel base. The same applies to the following embodiments.

  In Fig. 1-4, a sheet-like endothermic molded body is wrapped around a square steel substrate to cover it. The end portion of the endothermic molded body is an overlapping portion. The overlapping portion is preferably fixed with an adhesive or a double-sided tape. Only the end portions of the endothermic molded body may be overlapped as shown in FIG. 1-4, or the overlap width may be increased as shown in FIG. Thus, fire resistance can be improved more by enlarging the overlap width.

  In FIG. 1-6, a sheet-like endothermic molded body is wrapped around a square steel substrate to cover it. The ends of the endothermic molded body are not in contact with each other and the joints are exposed, and a fireproof caulking agent is filled so as to cover the joints. FIGS. 1-10 and 1-11 show a case where a plurality of endothermic molded bodies are used, and each of the joints is filled with a refractory coking agent. The kind of refractory caulking agent is not limited, and a commercially available product can be used.

  In FIG. 1-7, a sheet-like endothermic molded body is wound around a square steel base material to cover it. The end portions of the endothermic molded body are overlapped portions and are fixed by metal stoppers such as washers (screws), tuckers, and fixing pins.

  In FIG. 1-8, a sheet-like endothermic molded body is wrapped around a square steel base material and covered, and a part is covered via an air layer. The end of the endothermic molded body is fixed by a metal stopper.

  In Fig. 1-9, a sheet-like endothermic molded body is wrapped around a rectangular steel base material to cover it. The end portions of the endothermic molded body are abutted, and the endothermic molded body is further covered on the outer periphery so as to cover the abutted portion. By winding the endothermic molded body a plurality of times so as to cover the inner butted portion, the fire resistance can be further improved.

  FIG. 2 shows an aspect in which a fireproof coating is applied to the H-type steel base material. Fig. 2-1 shows a mode of direct fireproof coating, and Fig. 2-2 shows a mode of fireproof coating indirectly through an air layer. When fireproof coating is performed via an air layer as shown in FIG. 2-2, an air heat insulating layer is formed, and the fireproof performance can be improved more than when fireproof coating is performed directly.

  FIGS. 2-3 to 2-10 show variations of the fireproof coating. The description of the method for fixing the end of the endothermic molded body is the same as in the case of FIG.

  In addition, when fireproof coating is performed through an air layer as shown in FIGS. 2-2 to 2-10, the endothermic heat of the present invention is applied to the web portion or the flange portion of the H-type steel base that is not in direct contact with the endothermic molded body. Or a conventional fireproof coating material can be applied or pasted. Thereby, fireproof performance can be improved more. In particular, when these are applied to the web portion of the H-type steel base material, the fire resistance can be effectively improved.

  FIG. 3 shows a variation (top view) of a fireproof coating of a pillar (square, round, H type) provided near the center of the wall panel or near the end (corner portion) of the wall panel. In any aspect, the steel base material is accommodated and covered in the space surrounded by the wall panel and the endothermic molded body. At this time, two or more layers (multiple layers) of the endothermic molded body can be laminated. The end of the endothermic molded body is fixed to the wall panel by a metal stopper or welding. Moreover, you may apply | coat an adhesive agent to the part which coat | covers the steel-frame base material directly, or the laminated part of an endothermic molded object.

  In addition, when performing fireproof coating via an air layer as shown in FIGS. Or a conventional fireproof coating material can be applied or pasted. Thereby, fireproof performance can be improved more. Thereby, fireproof performance can be improved more.

FIG. 4 shows a variation of the fireproof coating of the beam (H type) provided on the ceiling or the support base (H type) provided on the floor board. In any aspect, the steel base material is accommodated and covered in a space surrounded by the ceiling, wall panel or floor board and the endothermic molded body. At this time, two or more layers (multiple layers) of the endothermic molded body can be laminated. The end of the endothermic molded body is fixed to a ceiling, a wall panel, or a floor board by a metal stopper or welding. Moreover, you may apply | coat an adhesive agent to the part which coat | covers the steel-frame base material directly, or the laminated part of an endothermic molded object. In addition, when performing fireproof coating through an air layer as shown in FIGS. 4-2 and 4-4, the heat absorption of the present invention is applied to the web portion or flange portion of the H-type steel base that is not in direct contact with the heat absorption molded body. Or a conventional fireproof coating material can be applied or pasted. Furthermore, an endothermic material (an endothermic pack) or the like can be attached to the lower flange portion. Thereby, fireproof performance can be improved more.
In addition, when a plurality of molded bodies are bonded and covered in the longitudinal direction of the steel base material, the molded bodies can be abutted, overlapped, or jointed. In this case, it is preferable that the ends of the molded bodies are fixed with a tape, an adhesive, a fireproof caulking agent, a metal stopper, or the like. Moreover, each molded object may be fixed previously, and may be fixed after steel-base-material coating | covering.

  Furthermore, when a heat-absorbing molded body is coated on a steel frame base material, heat insulation and fire resistance can be improved by laminating a heat insulation layer and a flame retardant layer.

  Examples of the heat insulating layer include a heat insulating layer (A) made of an organic resin foam material, a heat insulating layer (A) formed from a composition containing a lightweight aggregate, and the like.

  Examples of the heat insulation layer (a) made of an organic resin foam include urethane foam, phenol foam, and styrene foam. A method for forming these foam materials is not particularly limited, and a known apparatus can be used. For example, low-pressure or high-pressure foaming machine for injection foaming, low-pressure or high-pressure foaming machine for slab foaming, low-pressure or high-pressure foaming machine for continuous line, spraying, used when manufacturing small mixers, ordinary urethane foam, etc. A spray foaming machine or the like for construction can be used.

  The heat insulating layer (A) made of a composition containing a lightweight aggregate can be formed by a composition containing a binder and a lightweight aggregate. Examples of the lightweight aggregate include inorganic lightweight bones such as pulverized particles of the organic resin foamed material (a), organic mass aggregates such as organic resin balloons, expanded perlite, expanded shale, expanded vermiculite, pumice, and shirasu balloons. Materials. In the present invention, pearlite, vermiculite and the like are particularly preferable. Further, the binder is not particularly limited. For example, acrylic resin, acrylic styrene resin, vinyl acetate resin, polyester resin, phenol resin, petroleum resin, vinyl chloride resin, epoxy resin, urethane resin, alkyd resin, melamine resin, Examples thereof include organic binders such as propylene rubber, chloroprene rubber, butyl rubber, and isobutylene rubber. A binder can be used individually or in combination of 2 or more types. Furthermore, as a form of these resins, those dissolved in a solvent or dispersed as an emulsion can be used. It is also possible to use an inorganic binder such as cement, gypsum, water glass, or silicone resin.

  The composition containing the lightweight aggregate is preferably 400 to 5000 parts by weight (preferably 1000 to 2000 parts by weight) with respect to 100 parts by weight of the binder (solid content). By being in such a range, an excellent heat insulating effect can be exhibited. It does not specifically limit as a formation method, Coating equipment, such as a spray, a roller, and a brush, can be used.

The thickness of the heat insulating layers (a) and (b) is usually about 1 to 10 mm (preferably about 2 to 5 mm). Moreover, it is preferable to laminate | stack the heat insulation layer of said (a), (b) on the back surface (steel-frame base material side) of an endothermic molded object, As a lamination | stacking method of a heat insulation layer, although it does not specifically limit,
-A method of laminating an endothermic molded body after forming a heat insulation layer on a steel base material,
-A method of laminating a heat-insulating layer when manufacturing an endothermic molded body in advance and coating it on a steel base material,
Etc.

  As a flame retardant layer, for example, a flame retardant layer (c) made of a composition containing a flame retardant, a flame retardant layer (d) made of a composition containing water glass, a flame retardant layer made of a flame retardant sheet ( E).

  The flame retardant layer (c) can be formed by a composition containing a binder and a flame retardant. As the flame retardant, in addition to the flame retardant that can be blended in the endothermic composition of the present invention, melamine and its derivatives, dicyandiamide and its derivatives, azodicarbonamide, urea, thiourea, chlorinated paraffin, etc. may be used. it can. Moreover, the binder can use the thing similar to the said heat insulation layer (I). It is preferable that the said flame retardant is 100-800 weight part normally with respect to 100 weight part of binders (solid content). By being in such a range, an excellent flame retardant effect can be exhibited. In addition to the above, a foaming agent, a carbonizing agent, a filler and the like can be added to the flame retardant layer (c) for the purpose of imparting fire resistance.

The flame retardant layer (d) made of a composition containing water glass can be formed of a composition containing water glass or the like. The water glass is a powder or an aqueous solution of an alkali silicate represented by the general formula Na ₂ O.nSiO ₂ (n = 2 to 4) (including K ₂ O and / or Li ₂ O in some cases) It is classified into No. 1 to No. 4 depending on the difference in the content ratio of SiO ₂ and Na ₂ O. Although any of them can be used in the present invention, No. 3, No. 4, etc. with relatively little alkali component are particularly advantageous in terms of water resistance. Moreover, you may use the binder similar to said (A) as needed.

  It does not specifically limit as a formation method of said (c) (d), Coating equipment, such as a spray, a roller, and a brush, can be used.

  The flame retardant layer (e) made of a flame retardant sheet is a sheet impregnated with the composition (c) and / or (d). Examples of the sheet include organic fiber, paper containing inorganic fiber, cloth, sheet of woven fabric or non-woven fabric, or non-combustible paper.

The thickness of the flame retardant layer such as (c), (d) and (e) is usually preferably about 0.1 to 0.5 mm. Moreover, the flame retardant layers such as the above (c), (d) and (e) can be laminated on either the front surface or the back surface (steel base material side) of the endothermic molded body. Further, when two or more layers of endothermic molded bodies are laminated, they can be laminated between the layers of the molded bodies. However, when the endothermic molded body has a heat reflecting layer, it is desirable that the heat reflecting layer is located on the outermost layer (exposed surface).
The method for forming the flame retardant layer is not particularly limited,
-A method of laminating an endothermic molded body on a steel base and then laminating a flame retardant layer,
-A method of laminating an endothermic molded body after forming a flame retardant layer on a steel substrate,
-A method of laminating a flame retardant layer when manufacturing an endothermic molded body in advance and coating it on a steel base material,
Etc. When a plurality of endothermic molded bodies are laminated, the above method may be repeated.
In addition to the above heat-insulating layer or flame-retardant layer, in the present invention, if necessary, an overcoat layer can be laminated on the outermost surface of the fire-resistant coating obtained by coating the steel frame base material with an endothermic molded body by the above-described method. The top coat layer can be formed by applying a known water-based or solvent-type paint, or laminating a decorative member. The topcoat layer can be formed by applying a paint such as an acrylic resin, urethane resin, acrylic silicon resin, or fluororesin. These coatings may be performed by a known coating method, and a coating instrument such as a spray, a roller, or a brush can be used.

The method for forming the overcoat layer is not particularly limited,
-A method of forming an endothermic molded body on a steel base and then laminating an overcoat layer,
・ A method of laminating a top coat layer on the outermost surface and coating it on a steel substrate etc. when manufacturing an endothermic molded body in advance

The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples.
(Production and performance evaluation of sheet-like endothermic molded bodies 1-19)
A sheet-like endothermic molded body (hereinafter referred to as “molded body”) used for the fireproof coating method was produced.

In the production of the molded body, the following raw materials were used.
Polyol A: trifunctional polyester polyol (molecular weight: 4600, hydroxyl value: 36)
Polyol B: Bifunctional polyester polyol (molecular weight: 1000, hydroxyl value: 110)
Epoxy resin: bisphenol A type (molecular weight: 400, epoxy equivalent: 190)
Dispersant: acid-base compound (acid value / amine value = 40/40)
-Urethane resin curing catalyst: Dibutyltin dilaurate-Modified aliphatic amine: Isophoradiamine-Isocyanate A: Polymeric MDI (NCO%: 30.1%)
Isocyanate B: hexamethylene diisocyanate (HMDI) (NCO%: 20.5%)
・ Water repellent: Silicone water repellent
Molded body 1
Polyol A: 12.0 parts by weight, paraffin (plasticizer): 8.0 parts by weight, aluminum sulfate 18 hydrate having a water content of about 48% by weight (decomposition temperature: 86.5 ° C.): 80 parts by weight, dispersant : 3.2 parts by weight, isocyanate A: 1.02 parts by weight, urethane resin curing catalyst: 0.1 parts by weight were mixed at room temperature (25 ° C.) to obtain a kneaded product. The kneaded product was filled into a mold (300 mm × 300 mm), cured and cured at 25 ° C. for 7 days, and then demolded to obtain a flexible sheet-like molded body 1. The molded body 1 had a thickness of 2.5 mm and a density of 1.50 g / cm ³ .

Molded body 2
Polyol A: 9.0 parts by weight, Polyol B: 3.0 parts by weight, Paraffin (plasticizer): 8.0 parts by weight, Water content of about 48% by weight Aluminum sulfate 18 hydrate (Decomposition temperature: 86.5) ° C): 80 parts by weight, dispersant: 3.2 parts by weight, isocyanate A: 1.58 parts by weight, urethane resin curing catalyst: 0.1 parts by weight are mixed at room temperature (25 ° C) to obtain a kneaded product. It was. The kneaded product was filled into a mold (300 mm × 300 mm), cured and cured at 25 ° C. for 7 days, and then demolded to obtain a flexible sheet-like molded body 2. The molded body 2 had a thickness of 2.5 mm and a density of 1.50 g / cm ³ .

Molded body 3
Polyol B: 12.0 parts by weight, paraffin (plasticizer): 8.0 parts by weight, aluminum sulfate 18 hydrate having a water content of about 48% by weight (decomposition temperature: 86.5 ° C.): 80 parts by weight, dispersant : 3.2 parts by weight, isocyanate A: 3.3 parts by weight, urethane resin curing catalyst 0.1: parts by weight were mixed at room temperature (25 ° C.) to obtain a kneaded product. The kneaded product was filled into a mold (300 mm × 300 mm), cured and cured at 25 ° C. for 7 days, and then demolded to obtain a flexible sheet-like molded body 3. The molded body 3 had a thickness of 2.5 mm and a density of 1.45 g / cm ³ .

Molded body 4
Polyol A: 20.0 parts by weight, paraffin (plasticizer): 13.0 parts by weight, aluminum sulfate 18 hydrate having a water content of about 48% by weight (decomposition temperature: 86.5 ° C.): 67 parts by weight, dispersant : 2.4 parts by weight, isocyanate A: 1.79 parts by weight, urethane resin curing catalyst: 0.1 parts by weight were mixed at room temperature (25 ° C.) to obtain a kneaded product. The kneaded product was filled in a mold (300 mm × 300 mm), cured and cured at 25 ° C. for 7 days, and then demolded to obtain a flexible sheet-like molded body 4. The molded body 4 had a thickness of 2.5 mm and a density of 1.40 g / cm ³ .

Molded body 5
Epoxy resin: 10.0 parts by weight, paraffin (plasticizer): 8.0 parts by weight, aluminum sulfate 18 hydrate having a water content of about 48% by weight (decomposition temperature: 86.5 ° C.): 80 parts by weight, dispersant : 3.2 parts by weight, modified aliphatic amine (epoxy resin curing agent): 3.01 parts by weight were mixed at room temperature (25 ° C.) to obtain a kneaded product. The kneaded product was filled into a mold (300 mm × 300 mm), cured and cured at 25 ° C. for 7 days, and then demolded to obtain a hard sheet-like molded body 5. The molded body 5 had a thickness of 2.5 mm and a density of 1.51 g / cm ³ .

Molded body 6
Polyol A: 24.0 parts by weight, paraffin (plasticizer): 16.0 parts by weight, aluminum sulfate 18 hydrate having a water content of about 48% by weight (decomposition temperature: 86.5 ° C.): 60 parts by weight, dispersant : 2.4 parts by weight, isocyanate A: 2.15 parts by weight, urethane resin curing catalyst: 0.1 parts by weight were mixed at room temperature (25 ° C.) to obtain a kneaded product. The kneaded product was filled in a mold (300 mm × 300 mm), cured and cured at 25 ° C. for 7 days, and then demolded to obtain a flexible sheet-like molded body 6. The molded body 6 had a thickness of 2.5 mm and a density of 1.36 g / cm ³ .

Molded body 7
Polyol A: 36.0 parts by weight, paraffin (plasticizer): 24.0 parts by weight, aluminum sulfate 18 hydrate having a water content of about 48% by weight (decomposition temperature: 86.5 ° C.): 40 parts by weight, dispersant : 1.6 parts by weight, isocyanate A: 3.23 parts by weight, urethane resin curing catalyst: 0.1 parts by weight were mixed at room temperature (25 ° C.) to obtain a kneaded product. The kneaded product was filled into a mold (300 mm × 300 mm), cured and cured at 25 ° C. for 7 days, and then demolded to obtain a flexible sheet-like molded body 7. The molded body 7 had a thickness of 2.5 mm and a density of 1.22 g / cm ³ .

Molded body 8
Polyol A: 12.0 parts by weight, paraffin (plasticizer): 8.0 parts by weight, aluminum sulfate 18 hydrate having a water content of about 48% by weight (decomposition temperature: 86.5 ° C.): 80 parts by weight, dispersant 3.2 parts by weight, water: 5.0 parts by weight, isocyanate A: 1.07 parts by weight, urethane resin curing catalyst: 0.1 parts by weight were mixed at room temperature (25 ° C.) to obtain a kneaded product. The kneaded product was filled in a mold (300 mm × 300 mm), cured and cured at 25 ° C. for 7 days, and then demolded to obtain a foam-like molded body 8. The density of the molded body 8 was 0.04 g / cm ³ . This molded body 8 was cut out to a thickness of 2.5 mm.

Molded body 9
Aluminum sulfate 18 hydrate having a water content of about 48% by weight (decomposition temperature: 86.5 ° C.): 80 parts by weight, dispersant: 3.2 parts by weight, water: 50 parts by weight, isocyanate A: 100 parts by weight, urethane Resin curing catalyst: 0.1 part by weight was mixed at room temperature (25 ° C.) to obtain a kneaded product. The kneaded product was filled in a mold (300 mm × 300 mm), cured and cured at 25 ° C. for 7 days, and then demolded to obtain a foam-shaped molded body 9. The density of the molded body 9 was 0.01 g / cm ³ . This molded body 9 was cut out to a thickness of 2.5 mm.

Molded body 10
Polyol A: 12.0 parts by weight, paraffin (plasticizer): 8.0 parts by weight, water content: about 48% by weight Aluminum hydroxide (decomposition temperature: 300 ° C.): 80 parts by weight, dispersing agent: 3.2 parts by weight , Isocyanate A: 1.07 parts by weight, urethane resin curing catalyst: 0.1 parts by weight were mixed at room temperature (25 ° C.) to obtain a kneaded product. The kneaded product was filled into a mold (300 mm × 300 mm), cured and cured at 25 ° C. for 7 days, and then demolded to obtain a flexible sheet-like molded body 10. The molded body 10 had a thickness of 2.5 mm and a density of 2.06 g / cm ³ .

Molded body 11
Styrene acrylic resin (thermoplastic resin): 0.8 parts by weight, ethylene acrylic resin (thermoplastic resin): 3.2 parts by weight, paraffin (plasticizer): 16 parts by weight, aluminum sulfate having a water content of about 48% by weight 18 hydrate (decomposition temperature: 86.5 ° C.): 80 parts by weight were mixed in advance and kneaded with a pressure kneader to prepare a sheet kneaded product. The kneaded product was rolled into a sheet so that the sheet thickness was 2.5 mm with a rolling roller. In this case, a kneading temperature of 85 ° C. was necessary. The molded body 11 had a thickness of 2.5 mm and a density of 1.52 g / cm ³ .

Molded body 12
Styrene acrylic resin (thermoplastic resin): 3.6 parts by weight, ethylene acrylic resin (thermoplastic resin): 14.4 parts by weight, paraffin (plasticizer): 2.0 parts by weight, water content of about 48% by weight Aluminum sulfate 18 hydrate (decomposition temperature: 86.5 ° C.): 80 parts by weight were mixed in advance and kneaded with a pressure kneader to prepare a sheet kneaded product. In this case, a kneading temperature of 150 ° C. was necessary, and the water in the aluminum sulfate 18 hydrate was dehydrated all at once, so that kneading was impossible.

Molded body 13
A glass nonwoven fabric (thickness 0.22 mm, mass 25 g / m ² ) is preliminarily placed in the mold, filled with the same kneaded material for molding as the molding 1, and the same glass nonwoven fabric as above is laminated thereon. Cured and cured at 25 ° C. for 7 days, and then demolded to obtain a sheet-like molded body 13. The molded body 13 had a thickness of 2.5 mm and a density of 1.52 g / cm ³ .

Molded body 14
A glass non-woven fabric (thickness 0.22 mm, mass 25 g / m ² ) is preliminarily placed in the mold, filled with the same kneaded material for molding as the molding 1, and further an aluminum foil / mesh laminated sheet (thickness 0.15 mm) , Mass 230 g / m ² ), cured at 25 ° C. for 2 hours, cured and cured for 7 days, and then demolded to obtain a sheet-like molded body 14. The molded body 14 had a thickness of 2.5 mm and a density of 1.53 g / cm ³ .

Molded body 15
Polyol A: 15.8 parts by weight, paraffin (plasticizer): 12.0 parts by weight, aluminum sulfate 18 hydrate having a water content of about 48% by weight (decomposition temperature: 86.5 ° C.): 70 parts by weight, dispersant : 2.8 parts by weight, isocyanate B: 2.2 parts by weight, urethane resin curing catalyst: 0.1 parts by weight were mixed at room temperature (25 ° C.) to obtain a kneaded product. The kneaded product was filled into a mold (300 mm × 300 mm), cured and cured at 25 ° C. for 7 days, and then demolded to obtain a flexible sheet-like molded body 15. The molded body 15 had a thickness of 2.5 mm and a density of 1.51 g / cm ³ .

Molded body 16
Polyol A: 15.8 parts by weight, paraffin (plasticizer): 12.0 parts by weight, aluminum sulfate 18 hydrate having a water content of about 48% by weight (decomposition temperature: 86.5 ° C.): 70 parts by weight, dispersant : 2.3 parts by weight, water repellent: 0.5 parts by weight, isocyanate B: 2.2 parts by weight, urethane resin curing catalyst: 0.1 parts by weight are mixed at room temperature (25 ° C.) to prepare a kneaded product. Obtained. The kneaded product was filled in a mold (300 mm × 300 mm), cured and cured at 25 ° C. for 7 days, and then demolded to obtain a flexible sheet-like molded body 16. The molded body 16 had a thickness of 2.5 mm and a density of 1.50 g / cm ³ .

Molded body 17
Polyol A: 15.8 parts by weight, paraffin (plasticizer): 12.0 parts by weight, aluminum sulfate 18 hydrate having a water content of about 48% by weight (decomposition temperature: 86.5 ° C.): 70 parts by weight, dispersant : 2.0 parts by weight, water repellent: 0.8 parts by weight, isocyanate B: 2.2 parts by weight, urethane resin curing catalyst: 0.1 parts by weight are mixed at room temperature (25 ° C.) to prepare a kneaded product. Obtained. The kneaded product was filled in a mold (300 mm × 300 mm), cured and cured at 25 ° C. for 7 days, and then demolded to obtain a flexible sheet-like molded body 17. The molded body 17 had a thickness of 2.5 mm and a density of 1.50 g / cm ³ .

Molded body 18
Polyol A: 15.8 parts by weight, paraffin (plasticizer): 12.0 parts by weight, aluminum sulfate 18 hydrate having a water content of about 48% by weight (decomposition temperature: 86.5 ° C.): 35 parts by weight, borax (Sodium tetraborate pentahydrate, dehydration temperature: 150 ° C.): 35 parts by weight, dispersant 2.8 parts by weight, isocyanate B: 2.2 parts by weight, urethane resin curing catalyst: 0.1 parts by weight The mixture was mixed at the bottom (25 ° C.) to obtain a kneaded product. The kneaded product was filled into a mold (300 mm × 300 mm), cured and cured at 25 ° C. for 7 days, and then demolded to obtain a flexible sheet-like molded body 18. The molded body 18 had a thickness of 2.5 mm and a density of 1.47 g / cm ³ .

Molded body 19
A glass nonwoven fabric (thickness 0.22 mm, mass 25 g / m ² ) is preliminarily placed in the mold, filled with the same kneaded material for molding as the molding 15, and an aluminum foil / mesh laminated sheet (thickness 0.15 mm) , Mass 230 g / m ² ), and cured and cured at 25 ° C. for 2 hours and at room temperature for 7 days, and then demolded to obtain a sheet-like molded body 19. The thickness of the molded body 19 was 2.5 mm, and the density was 1.49 g / cm ³ .

About the molded objects 1-19, the strength test, the water resistance tests A and B, and the fire resistance performance test were implemented. Each test method and evaluation criteria were as follows.
(Strength test)
Using a push-pull scale (manufactured by Imada Manufacturing Co., Ltd.) to which a disk-shaped shaft having a diameter of 10 mm was attached, the compression strength was measured by pushing from above the molded body with a stroke length of 2.0 mm.
(Water resistance test A)
The molded body was cut into 75 × 75 mm, immersed in water at room temperature for 24 hours, and the appearance before and after immersion was visually evaluated. Evaluation was performed in 10 stages as 10: no abnormality to 1: shape collapse.
(Water resistance test B)
The molded body was cut into 75 × 75 mm, immersed in water at room temperature for 72 hours, and the appearance before and after immersion was visually evaluated. Evaluation was performed in 10 stages as 10: no abnormality to 1: shape collapse.
(Fire resistance test)
The molded body was attached to a steel plate (150 mm × 150 mm × 6 mm) using an organic adhesive to obtain a test body. Using the test body, a heating test for 60 minutes was performed according to the standard heating curve of ISO834, and the temperature of the steel material back surface after 60 minutes was measured with a thermocouple. Evaluation was performed in five stages.
A: less than 500 ° C. B: 500 ° C. or more, less than 550 ° C. C: 550 ° C. or more, less than 600 ° C. D: 600 ° C. or more, less than 650 ° C. E: 650 ° C. or more And 1-2.

  In the molded bodies 1 to 6, the fire resistance performance test was generally good. Moreover, in the molded object 1, 2, 4, 6, it was a favorable result also regarding intensity | strength and water resistance. In the molded bodies 7 and 10, the strength and water resistance of the molded bodies were good results.

  On the other hand, in the molded bodies 8 and 9, the molded body was in the form of foam, resulting in inferior strength, water resistance, and fire resistance. The molded bodies 11 and 12 tried to produce a molded body using a thermoplastic resin. However, in the molded body 11, an excessive amount of plasticizer is required for kneading at a temperature lower than the decomposition temperature of aluminum sulfate 18 hydrate. Thus, the produced molded body was inferior in water resistance and fire resistance. Further, the molded body 12 required a kneading temperature of 150 ° C., and the water in the aluminum sulfate 18 hydrate was dehydrated all at once, so that kneading was impossible.

  Moreover, in the laminated body of the molded objects 13 and 14, it was a favorable result in all intensity | strength, water resistance, and fire resistance performance compared with the molded objects 1-12.

In the molded objects 15-19, it was a favorable result regarding a fireproof performance test and intensity | strength. Moreover, it was a result excellent in flexibility and moldability. Further, the molded bodies 16, 17, 18, and 19 were excellent in water resistance.
(Example of fireproof coating method)
A fireproof coating method was performed on the steel frame steel material (steel base material) shown in FIG. In the following examples, the molded body 19 is referred to as “sheet 1”.

Example 1
Adhesive is applied to the non-woven fabric side of sheet 1 and square steel frame (□ 300 x 300 x 9 mm, length 1200 mm: Fig. 5-1), and three sheets 1 are wrapped around the square steel frame and butt (The covering mode is the same as in FIG. 1-3). Aluminum tape was affixed to the butt portion. The obtained coated specimen was designated as specimen 1.

Example 2
Adhesive is applied to the non-woven fabric side of sheet 1 and square steel frame (□ 300 x 300 x 9 mm, length 1200 mm: Fig. 5-1), and three sheets 1 are wrapped around the square steel frame and butt (The covering mode is the same as in FIG. 1-3). Next, a urethane resin solution was applied to the outer surface of the sheet 1, and the sheet 1 was wound and abutted and pasted so that the butted portion was hidden (the covering mode was in accordance with FIG. 1-9). The obtained coated specimen was designated as specimen 2.

Example 3
An H-type steel frame material (H400 × 200 × 8 × 13 mm, length 1200 mm: FIG. 5-2) was installed on the floor plate (ALC plate). According to FIG. 4-2, the sheet 1 was wound so that the nonwoven fabric side of the sheet 1 was the H-type steel material side, and the three sheets 1 were abutted and bonded. The sheet 1 was fixed to the ALC plate with a fixing pin, and an adhesive was applied to the lower flange portion. In addition, aluminum tape was affixed to the butted parts. The obtained coated specimen was designated as specimen 3.
(Evaluation of test bodies 1 to 3)
The test bodies 1 to 3 all had good workability. Moreover, the coating film thickness was very thin compared with the conventional rock wool coating, and it was excellent in aesthetics.

  About the test bodies 1-3, the heating test for 60 minutes was done according to the standard heating curve of ISO834, and the steel-material surface temperature of 60 minutes after was measured with the thermocouple.

  In addition, the thermocouple was installed in the ▲ part in the cross sections A to C in FIGS. 5A and 5B.

  As a result of the heating test, all of the test bodies 1 to 3 had an average of 550 ° C. or less, and the fire resistance was good.

Example 4
An H-type steel frame material (H400 × 200 × 8 × 13 mm, length 1200 mm: FIG. 5-2) was installed on the floor plate (ALC plate). According to FIG. 4B, the sheet 1 was wound so that the nonwoven fabric side was the H-type steel material side, and the end portions of the three sheets 1 were overlapped and pasted so that the overlapping portion was 40 mm. The sheet 1 was fixed to the ALC plate with a fixing pin, and an adhesive was applied to the lower flange portion. Subsequently, the flame retardant composition 1 described later was applied to the surface of the sheet 1 and dried (dry film thickness: 0.2 mm). Thereafter, the sheet 1 was further wound so that the non-woven fabric side of the separately prepared sheet 1 became the flame retardant layer side, and the end portions of the three sheets 1 were overlapped and pasted so that the overlapping portion was 40 mm. . The sheet 1 was fixed to the ALC plate with a fixing pin. The obtained coated specimen was designated as specimen 4.
(Composition for flame retardant layer)
・ Composition for flame retardant layer 1: Mix 100 parts by weight of acrylic resin (non-volatile content: 50%, solvent: xylene) and 400 parts by weight of chlorinated paraffin, add xylene and stir well so that each component becomes uniform The composition 1 for a flame retardant layer was obtained.
-Flame retardant layer composition 2: Mix 100 parts by weight of acrylic resin (non-volatile content: 50%, solvent: xylene) and 400 parts by weight of melamine, add xylene, and stir enough to make each component uniform. The composition 2 for fuel layers was obtained.
Flame retardant layer composition 3: acrylic resin (nonvolatile content: 50%, solvent: xylene) 100 parts by weight, melamine 24 parts by weight, dipentaerythritol 16 parts by weight, ammonium polyphosphate 80 parts by weight, titanium oxide 14 parts by weight And xylene was added, and the mixture was sufficiently stirred so that each component was uniform to obtain a composition 3 for a flame retardant layer.

Example 5
A coated test specimen was prepared in the same manner as in Example 4 except that the flame retardant layer composition 2 was used in place of the flame retardant layer composition 1, and a test specimen 5 was obtained.

Example 6
A coated test specimen was prepared in the same manner as in Example 4 except that the flame retardant layer composition 3 was used in place of the flame retardant layer composition 1, and a test specimen 6 was obtained.
(Evaluation of specimens 4 to 6)
About the test bodies 4-6, the heating test for 60 minutes was performed according to the standard heating curve of ISO834, and the steel-material surface temperature of 60 minutes after was measured with the thermocouple.

  In addition, the thermocouple was installed in the ▲ part in the cross sections A to C in FIGS. 5A and 5B.

  As a result of the heating test, all of the test bodies 4 to 6 had an average of 450 ° C. or less, and the fire resistance was good.

Claims (6)

It is a steel fireproof coating method for coating a steel base material with an endothermic molded body,
The endothermic molded body is
(1) including an organic resin component and a metal hydrate,
(2) The organic resin component contains a non-aqueous thermosetting resin,
(3) The metal hydrate has a water content of 6% by weight or more and a dehydration or decomposition temperature of 50 to 200 ° C.
(4) The weight ratio of the organic resin component to the metal hydrate is 5:95 to 90:10,
(5) The density is 0.8-4 g / cm ³ .
A steel fireproof coating method characterized by that.   The steel frame fireproof coating method according to claim 1, wherein the endothermic molded body has a sheet shape and / or a board shape.   The steel frame fireproof coating method according to claim 2, wherein a reinforcing layer is laminated on one side of the endothermic molded body on the side covering the steel base material.   The steel fireproof coating method according to claim 2 or 3, wherein a heat reflecting layer is laminated on one side of the endothermic molded body on the side opposite to the side covering the steel base material.   The steel fireproof coating method according to any one of claims 1 to 4, wherein a part or all of the surface of the steel base is coated with the endothermic molded body directly or indirectly through an air layer.   The steel frame fireproof coating method according to any one of claims 1 to 5, wherein the steel base material is at least one selected from the group consisting of H type, I type, square type, and round type.

Images