JP5478263B2 - Endothermic composition, endothermic molded article using the same, and method for producing the same - Google Patents

Description

  The present invention relates to an endothermic composition, an endothermic molded body using the same, and a method for producing the same.

  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 physical strength of the base material (steel frame or the like) of the structure is rapidly reduced. In contrast, a fire-resistant coating material obtained by mixing and curing an inorganic binder and metal sulfate; a fire-resistant coating material obtained by dissolving metal sulfate in water and slurried is applied to the substrate, and recrystallization of the metal salt is performed. A cured fire-resistant coating material; a fire-resistant coating material obtained by reacting an aqueous solution containing isocyanates and inorganic compounds is known.

  Such a fireproof coating material improves the fire resistance of the base material, which is the object to be coated, and forms an effective heat insulating layer in the event of a fire. And the fall of physical strength is suppressed by delaying the temperature rise of the base material at the time of fire using the latent heat of vaporization of crystal water.

Patent Document 1 describes a fireproof coating composition comprising inorganic fibers and an inorganic binder as main components and mixed with aluminum sulfate hydrate and water. Patent Document 2 describes a composition in which aluminum sulfate hydrate, acrylic fiber, thickener, powder resin and water are mixed. Patent Document 3 describes a fireproof coating material composed of an inorganic compound, water, and isocyanates.
JP 58-96662 A JP 2006-143875 A Japanese Patent Application Laid-Open No. 08-266997

  The fireproof coating material needs to meet the problems such as durability to prevent surface breakage, peeling, peeling off, etc., and shortening of the coating curing time.

  However, the conventional fireproof coating material does not provide a molded body having a uniform strength to the inside in the drying process, and the metal sulfate exposed on the surface of the molded body is easily dissolved in water. It is inferior to. Further, when a metal sulfate is dissolved in water and used as a binder, the base material may be corroded during painting and curing because it shows strong acidity. On the other hand, when a metal sulfate containing crystallization water is used as a fireproof coating, it is once dissolved in water and recrystallized, so that the amount of crystallization water may change and there may be variations in fireproof performance.

  The present invention has been made in view of the above points, and is excellent in durability and water resistance, has sufficient strength in the event of a fire, and increases the temperature of the substrate by utilizing the endothermic action accompanying dehydration. It aims at providing the endothermic molded object which can be suppressed effectively. Moreover, the endothermic composition suitable for shape | molding this endothermic molded object and the manufacturing method of an endothermic molded object using the same are provided.

  As a result of intensive studies, the present inventor has found that the above object can be achieved when an endothermic composition having a specific component is used, and has completed the present invention.

That is, the present invention relates to the following endothermic composition, an endothermic molded article using the same, and a method for producing the same.
1. An endothermic composition comprising an organic resin component and a metal hydrate,
(1) The organic resin component contains a urethane resin obtained by combining polyester polyols having three or more functional groups having active hydrogen atoms and isocyanates ,
(2) The metal hydrate has a water content of 6% by weight or more and a dehydration or decomposition temperature of 50 to 200 ° C.
(3) The weight ratio of the organic resin component to the metal hydrate is 5:95 to 90:10.
An endothermic composition characterized by the above.
2. (1) The endothermic composition according to Item 1, wherein the organic resin component contains a plasticizer.
3. (1) The endothermic composition according to Item 1 or 2, wherein the organic resin component contains a urethane resin curing catalyst.
4 . The endothermic molded object obtained by shape | molding the endothermic composition in any one of said claim | item 1-3 so that a density may be 0.8-4 g / cm < ³ >.
5 . The manufacturing method of the endothermic molded object which shape | molds the endothermic composition in any one of said claim | item 1 -3 so that a density may be 0.8-4 g / cm < ³ >.

The endothermic composition of the present invention includes an organic resin component and a metal hydrate,
(1) The organic resin component contains a non-aqueous thermosetting resin,
(2) The metal hydrate has a water content of 6% by weight or more and a dehydration or decomposition temperature of 50 to 200 ° C.
(3) Since the weight ratio of the organic resin component to the metal hydrate is 5:95 to 90:10, the durability, water resistance, and fire resistance are excellent. An endothermic molded body obtained by molding such an endothermic composition so as to have a density of 0.8 to 4 g / cm ³ is particularly useful as a fireproof coating material, and is exposed to combustion heat during a fire. In this case, the crystal water of the metal hydrate is dehydrated and the temperature rise of the base material (steel frame or the like) to be coated is suppressed by the latent heat of vaporization. Such an endothermic molded body is used, for example, by directly or indirectly coating a substrate in the form of a sheet or board.

  Hereinafter, the present invention will be described in detail.

The endothermic composition of the present invention (also referred to simply as “composition” herein) comprises an organic resin component and a metal hydrate,
(1) The organic resin component contains a non-aqueous thermosetting resin,
(2) The metal hydrate has a water content of 6% by weight or more and a dehydration or decomposition temperature of 50 to 200 ° C.
(3) The weight ratio of the organic resin component to the metal hydrate is 5:95 to 90:10.

  In the present specification, the organic resin component is an organic resin alone or a component obtained by adding a plasticizer to an organic resin 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, the metal hydrate can be mixed and kneaded at room temperature (5-35 ° C.), the metal hydrate is uniformly dispersed in the endothermic composition, and the metal hydrate is covered with the resin component. be able to. 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. Further, derivatives of these amines and mixtures with solvents are also included. 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, cyclic aliphatic acid anhydride, aliphatic acid Examples thereof include 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, it is preferably 10:90 to 60:40. In particular, when used as a fireproof coating material, the weight ratio is 10:90 to 60:40, preferably 15:85 to 50:50, more preferably 15:85 to 40:60, and most preferably 15:85 to 35. : 65. 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 and an amine value of 0 to 200 are particularly preferable. In particular, in the present invention, those having an acid value of 0 to 100 and an amine value of 0 to 100 are preferred, those having an acid value of 20 to 60 and amine values of 20 to 60 are more preferred, and acid values of 30 to 50. The amine value is most preferably 30 to 50 (more preferably the equivalent amount).

  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 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, it is below the dehydration or decomposition 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 the endothermic composition is poured into a mold and demolded after drying, a method in which the endothermic composition is applied to a release paper by a coating machine and then wound up, A method in which the endothermic composition is formed into a pellet and then processed into a sheet by an extrusion molding machine, and the endothermic composition kneaded by a Banbury mixer, a mixing roll, or the like is rolled into a sheet by processing with a calendar made of a plurality of hot rolls. It is possible to adopt a method to

  The thickness when the endothermic molded body is used as a fireproof coating material may be appropriately set depending on the fireproof performance, the application site, and the like, 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, the water resistance is inferior. When water comes into contact with the metal hydrate, the metal hydrate dissolves or flows out. 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, if necessary, for example, woven fabric, nonwoven fabric, glass nonwoven fabric, ceramic paper, synthetic paper, glass cloth, mesh and other reinforcing layers, aluminum foil, aluminum foil / synthetic resin laminated sheet, A heat reflecting layer such as an aluminum foil / kraft paper laminate sheet, an aluminum foil / glass woven fabric laminate sheet, an aluminum foil / mesh laminate sheet, an aluminum plate, a color steel plate, or a stainless steel plate can be laminated. The laminated form includes base materials such as building beams, pillars, walls, ceilings, floors, electric wires and cables, and pipes and cases that contain them for the purpose of suppressing temperature rise due to the endothermic action of metal hydrate , Simply referred to as “base material”), the surface in contact with the “molded body back surface” and the opposite side as the “molded body surface”
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 a heat reflective layer such as aluminum foil, aluminum foil / glass nonwoven fabric laminated sheet, aluminum foil / mesh laminated sheet, aluminum foil / synthetic resin laminated sheet, etc. The dehydration rate can be controlled and an increase in the substrate temperature can be suppressed. Moreover, heat insulation can also be improved by laminating | stacking heat insulation layers, such as a urethane foam.

  In the case of forming the above laminate, for example, it can be laminated simultaneously when the endothermic molded body is processed, or can be laminated using an adhesive after the molded body is processed.

  In the present invention, an overcoat layer can be laminated on the surface of the endothermic molded body or the heat reflection layer as necessary. The top coat layer can be formed by applying a known water-based or solvent-type paint, or laminating a decorative member. The top coat layer can be formed by applying a paint such as an acrylic resin, a urethane resin, an acrylic silicon resin, or a fluororesin. These coatings may be performed by a known coating method, and a coating tool such as a spray, a roller, or a brush can be used.

  The endothermic molded article of the present invention can be used as a covering material for various base materials such as fireproof, heat insulating and flameproofing materials such as pillars, walls and ceilings of buildings, and around 100 ° C. The temperature rise at can be effectively suppressed. 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.

  Hereinafter, the present invention will be described in more detail with reference to test examples. However, the present invention is not limited to the following test examples.

(Test Example 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 .

  Moreover, the following evaluation was implemented about the produced molded object 1. FIG.

(Strength test)
Using a push-pull scale (manufactured by Imada Manufacturing Co., Ltd.) to which a disc-shaped shaft having a diameter of 10 mm was attached, the compression strength was measured by pressing the molded body 1 from above with a stroke length of 2.0 mm. The results are shown in Table 1.

(Water resistance test A)
The molded body 1 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. The results are shown in Table 1.

(Water resistance test B)
The molded body 1 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. The results are shown in Table 1.

(Fire resistance test)
A molded body 1 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 on the back surface of the steel material 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, or untestable

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)
・ 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

(Test Example 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 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 2. The molded body 2 had a thickness of 2.5 mm and a density of 1.50 g / cm ³ .

  About the produced molded object 2, the same evaluation as the molded object 1 was implemented.

(Test Example 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 .

  About the produced molded object 3, the same evaluation as the molded object 1 was implemented.

(Test Example 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 .

  About the produced molded object 4, the same evaluation as the molded object 1 was implemented.

(Test Example 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 .

  About the produced molded object 5, the same evaluation as the molded object 1 was implemented.

(Test Example 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 .

  About the produced molded object 6, the same evaluation as the molded object 1 was implemented.

(Test Example 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 .

  About the produced molded object 7, the same evaluation as the molded object 1 was implemented.

(Test Example 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, and the same evaluation as that of the molded body 1 was performed.

(Test Example 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, and the same evaluation as that of the molded body 1 was performed.

(Test Example 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 .

  About the produced molded object 10, evaluation similar to the molded object 1 was implemented.

(Test Example 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 .

  About the produced molded object 11, the same evaluation as the molded object 1 was implemented.

(Test Example 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.

  Subsequently, the laminated body of the molded object which has endothermic property was evaluated.

(Test Example 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 in Test Example 1, and further laminated with the same glass nonwoven fabric as above. And 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 .

  About the produced molded object 13, the same evaluation as the molded object 1 was implemented.

(Test Example 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 product for molding as in Test Example 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, 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 .

  About the produced molded object 14, the same evaluation as the molded object 1 was implemented.

(Test Example 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 .

  About the produced molded object 15, the same evaluation as the molded object 1 was implemented.

(Test Example 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 .

  About the produced molded object 16, the same evaluation as the molded object 1 was implemented.

(Test Example 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 .

  About the produced molded object 17, the same evaluation as the molded object 1 was implemented.

(Test Example 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 .

  About the produced molded object 18, the same evaluation as the molded object 1 was implemented.

(Test Example 19)
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 product for a molded product as in Test Example 15, and further 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 produced molded object 19, the same evaluation as the molded object 1 was implemented.

  The results of Test Examples 1 to 19 are shown in Table 1.

  In Test Examples 1 to 6, the fire resistance performance test was generally good. In Test Examples 1, 2, 4, and 6, good results were obtained with respect to strength and water resistance. In Test Examples 7 and 10, the strength and water resistance of the molded bodies were good results.

  On the other hand, in Test Examples 8 and 9, the molded body was in the form of foam, resulting in inferior strength, water resistance, and fire resistance. In Test Examples 11 and 12, attempts were made to produce a molded body using a thermoplastic resin, but in Test Example 11, an excessive amount of plasticizer was required by kneading at a temperature lower than the decomposition temperature of aluminum sulfate 18 hydrate. The produced molded body was inferior in water resistance and fire resistance. In Test Example 12, 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.

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

  In Test Examples 15 to 19, good results were obtained with respect to the fire resistance performance test and strength. Moreover, it was a result excellent in flexibility and moldability. Further, Test Examples 16, 17, 18, and 19 were results excellent in water resistance.

Claims (5)

An endothermic composition comprising an organic resin component and a metal hydrate,
(1) The organic resin component contains a urethane resin obtained by combining polyester polyols having three or more functional groups having active hydrogen atoms and isocyanates ,
(2) The metal hydrate has a water content of 6% by weight or more and a dehydration or decomposition temperature of 50 to 200 ° C.
(3) The weight ratio of the organic resin component to the metal hydrate is 5:95 to 90:10.
An endothermic composition characterized by the above. (1) The endothermic composition according to claim 1, wherein the organic resin component contains a plasticizer. (1) The endothermic composition according to claim 1 or 2, wherein the organic resin component contains a urethane resin curing catalyst. The endothermic molded object obtained by shape | molding the endothermic composition in any one of Claims 1-3 so that a density may be 0.8-4 g / cm < ³ >. The manufacturing method of the endothermic molded object which shape | molds the endothermic composition in any one of Claims 1-3 so that a density may be 0.8-4 g / cm < ³ >.