Panel provided with noncombustible facings on both surfaces

Abstract

To provide a panel provided with noncombustible facings on both surfaces that achieves superior fire resistance and thermal insulation.SOLUTION: A panel 10 provided with noncombustible facings on both surfaces comprises a core material 11 formed from a urethane resin composition containing a polyol compound, a polyisocyanate compound, a catalyst, a foaming agent, and mica.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a panel with double-sided non-combustible facings, the core of which is polyurethane foam. [Background technology]

[0002] Fire-resistant panels are sometimes installed in partitions in buildings to improve fire resistance. For example, a fire-resistant panel has been proposed that includes a fibrous mat made by compression molding rock wool fibers and metal plates bonded and integrated to both sides of the fibrous mat (see, for example, Patent Document 1).

[0003] In conventional fire-resistant panels made from rock wool fiber, the insulating properties of the rock wool fiber are low, so in places where insulating properties are required, it is necessary to ensure insulating properties by adding polyurethane foam, which has excellent insulating properties, after the fire-resistant panel is installed.In addition, fire-resistant panels made from rock wool fiber are difficult to handle during construction because the rock wool fiber is heavy. Therefore, the use of polyurethane foam or the like as a core material for fire-resistant panels has been considered in order to improve heat insulating performance and ease of handling (see, for example, Patent Document 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 6-123141 [Patent Document 2] Patent Publication No. 2021-088923 Summary of the Invention [Problem to be solved by the invention]

[0005] However, fire-resistant panels with polyurethane foam cores do not leave any residue in the event of a fire and do not achieve the desired level of fire resistance, so further improvements in fire resistance are required.

[0006] Therefore, an object of the present invention is to provide a panel with non-combustible facings on both sides that has excellent fire resistance and heat insulation properties. [Means for solving the problem]

[0007] As a result of extensive research, the inventors have found that the above-mentioned problems can be solved by blending mica into a urethane resin composition for forming a core material, and have completed the present invention as described below. That is, the present invention provides the following [1] to [5]. [1] A panel with double-sided non-combustible face materials, comprising a pair of opposing face materials and a core material disposed between the face materials, the core material being a foam formed from a urethane resin composition containing a polyol compound, a polyisocyanate compound, a catalyst, a foaming agent, and mica. [2] The panel with double-sided non-combustible surface material according to [1] above, wherein the mica is scaly. [3] A panel with double-sided non-combustible surface material according to [1] or [2] above, wherein the catalyst comprises a trimerization catalyst, and the trimerization catalyst comprises at least one selected from the group consisting of nitrogen-containing aromatic compounds, alkali metal carboxylic acid salts, tertiary ammonium salts, and quaternary ammonium salts. [4] The density of the core material is 60 to 180 kg / m 3 The panel with double-sided noncombustible surface materials according to any one of [1] to [3] above, wherein: [5] A panel with double-sided non-combustible face materials according to any one of [1] to [4] above, wherein the thermal conductivity of the core material is 0.035 W / (m·K) or less. [Effects of the Invention]

[0008] According to the present invention, a panel with non-combustible face materials on both sides, which has excellent fire resistance and heat insulation properties, can be provided. [Brief explanation of the drawings]

[0009] [Figure 1]1 is a cross-sectional view of a panel with non-combustible face materials on both sides according to one embodiment of the present invention. [Figure 2] FIG. 1 is a schematic diagram showing a method for evaluating fire resistance. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, the present invention will be described with reference to embodiments. The panel with double-sided non-flammable facings of the present invention has a core material, and the core material is made of a foam (polyurethane foam) formed from a urethane resin composition. The urethane resin composition used in the present invention contains a polyol compound, a polyisocyanate compound, a catalyst, a blowing agent, and mica. Each component constituting the urethane resin composition will be described in detail below.

[0011] [Polyol compounds] The polyol compound is not particularly limited, and examples thereof include polyether polyol, polyester polyol, polylactone polyol, polycarbonate polyol, and polymer polyol. The polyol compound preferably contains at least one selected from polyester polyol and polyether polyol, and preferably contains polyester polyol from the viewpoint of improving the flame retardancy and fire resistance of the polyurethane foam. Furthermore, from the viewpoint of improving the flame retardancy and fire resistance, a halogen-containing polyol or a phosphorus-containing polyol may be used. From the viewpoint of improving flame retardancy and fire resistance, the content of polyester polyol is preferably 20 parts by mass or more, more preferably 50 parts by mass or more, even more preferably 80 parts by mass or more, and particularly preferably 100 parts by mass, per 100 parts by mass of the polyol compound.

[0012] The average hydroxyl value of the polyol compound is not particularly limited, but is preferably from 100 to 700 mgKOH / g, more preferably from 150 to 500 mgKOH / g, and even more preferably from 180 to 400 mgKOH / g. When one type of polyol compound is used, the average hydroxyl value is the hydroxyl value of that one type of polyol compound, and when two or more types of polyol compounds are used, the average hydroxyl value is the average value of the hydroxyl groups according to the blending ratio of the two or more types of polyol compounds. For example, when two types of polyol compounds, polyol compound (d1) and polyol compound (d2), are used as the polyol compounds, the average hydroxyl value is expressed by the following formula, where X1 is the hydroxyl value of polyol compound (d1), m1 is the blending ratio, and X2 is the hydroxyl value of polyol compound (d2), m2 is the blending ratio. Note that the blending ratio is based on mass. Average hydroxyl value (mgKOH / g)=X1×(m1 / (m1+m2))+X2×(m2 / (m1+m2)) The hydroxyl value is a value measured in accordance with JIS K1557-1:2007.

[0013] The polyester polyol may be either an aromatic ring-containing polyester polyol or an aliphatic polyester polyol, but from the viewpoint of the flame retardancy and fire resistance of the resulting polyurethane foam, it is preferable to use an aromatic ring-containing polyester polyol. From the viewpoint of improving the flame retardancy of the polyurethane foam, the urethane resin composition of the present invention preferably contains 50 to 100 parts by mass, more preferably 70 to 100 parts by mass, and even more preferably 85 to 100 parts by mass of the aromatic ring-containing polyester polyol per 100 parts by mass of the polyol compound. The polyester polyol having an aromatic ring is preferably a condensate of an aromatic dicarboxylic acid such as o-phthalic acid (phthalic acid), m-phthalic acid (isophthalic acid), p-phthalic acid (terephthalic acid), or naphthalenedicarboxylic acid with a glycol. In particular, from the viewpoint of improving the flame retardancy and fire resistance of the polyurethane foam, the polyester polyol preferably contains a phthalic acid-based polyester polyol, which is a condensate of phthalic acid and a glycol, and more preferably contains a p-phthalic acid-based polyester polyol, which is a condensate of p-phthalic acid and a glycol. The glycol is not particularly limited, but it is preferable to use low molecular weight aliphatic glycols known as constituent components of polyester polyols, such as ethylene glycol, propylene glycol, and diethylene glycol.

[0014] Examples of polyether polyols include polyoxyalkylene polyols obtained by ring-opening addition polymerization of alkylene oxide with an initiator having two or more active hydrogen atoms.Specific examples of initiators include aliphatic polyhydric alcohols, such as glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexylene glycol, and cyclohexanedimethanol, triols such as trimethylolpropane and glycerin, tetrafunctional alcohols such as pentaerythritol, and highly functional alcohols such as sucrose and sorbitol. The initiator also includes aliphatic amines, such as alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, and neopentyldiamine; alkanolamines such as monoethanolamine and diethanolamine; and aromatic amines such as aniline, tolylenediamine, xylylenediamine, diphenylmethanediamine, and Mannich condensation products. Among these, polyether polyols produced using an initiator having an aromatic ring are polyether polyols having an aromatic ring, for example, polyether polyols produced using an aromatic amine as an initiator are polyether polyols having an aromatic ring. Among polyether polyols having an aromatic ring, tolylenediamine-based polyether polyols, Mannich-based polyether polyols, etc. can be preferably used.

[0015] The tolylenediamine-based polyether polyol is a tolylenediamine-based polyether polyol produced using tolylenediamine as an initiator. The Mannich polyether polyol is a polyether polyol obtained by utilizing the Mannich reaction, which is a Mannich condensation product having two or more hydroxyl groups in the molecule, or a polyether polyol obtained by adding an alkylene oxide to such a Mannich condensation product. More specifically, it is a Mannich condensation product obtained by the Mannich reaction of at least one of phenol and its alkyl-substituted derivatives, formaldehyde, and alkanolamine, or a polyether polyol obtained by ring-opening addition polymerization of this compound with at least one of ethylene oxide and propylene oxide.

[0016] Examples of polylactone polyols include polypropiolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol. Examples of polycarbonate polyols include polyols obtained by dealcoholization reaction of hydroxyl group-containing compounds such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, and nonanediol with ethylene carbonate, propylene carbonate, and the like.

[0017] Examples of polymer polyols include polymers obtained by graft polymerizing an ethylenically unsaturated compound such as acrylonitrile, styrene, methyl acrylate, or methacrylate with an aromatic polyol, alicyclic polyol, aliphatic polyol, or polyester polyol, polybutadiene polyol, or hydrogenated products thereof.

[0018] The polyol content in the urethane resin composition of the present invention is preferably 8 to 60 mass%, more preferably 10 to 50 mass%, and even more preferably 15 to 40 mass%. When the polyol content is within the above range, polyurethane foam can be appropriately formed.

[0019] [Polyisocyanate compounds] Examples of the polyisocyanate compound include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates. Examples of aromatic polyisocyanates include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanates such as 4,4'-diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate (polymeric MDI).

[0020] Examples of alicyclic polyisocyanates include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate. Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

[0021] Among these, from the viewpoints of reactivity and availability, aromatic polyisocyanates are preferred, and diphenylmethane diisocyanate, polymeric MDI, or a mixture thereof is more preferred. One type of polyisocyanate may be used alone, or two or more types may be used in combination.

[0022] The content of the isocyanate compound in the urethane resin composition is preferably adjusted so that the isocyanate index is 200 or more. If the isocyanate index is equal to or greater than the lower limit, the amount of the polyisocyanate compound relative to the polyol compound becomes excessive, which facilitates the formation of isocyanurate bonds due to trimerization of the polyisocyanate compound. As a result, an isocyanurate foam can be appropriately formed, and the foam's residual rate and shape retention after high-temperature heating are likely to be increased, leading to improved fire resistance. The isocyanate index is more preferably 250 or more, even more preferably 300 or more, and even more preferably 350 or more, from the viewpoint of improving fire resistance by increasing the residual rate of residue after high-temperature heating and shape retention. The isocyanate index is, for example, not more than 1000, preferably not more than 800, more preferably not more than 600, and even more preferably not more than 550. When the isocyanate index is not more than the upper limit, performance commensurate with the production cost can be obtained.

[0023] The isocyanate index can be calculated by the following method. Isocyanate Index = number of equivalents of polyisocyanate compound ÷ (number of equivalents of polyol compound + number of equivalents of water) × 100 Here, each equivalent number can be calculated as follows: Equivalent number of polyisocyanate compound = Amount of polyisocyanate compound used (g) × NCO content (mass%) / Molecular weight of NCO (mol) × 100 Equivalent weight of polyol compound = OHV × amount of polyol compound used (g) ÷ molecular weight of KOH (mmol) OHV is the hydroxyl value (mgKOH / g) of the polyol compound. Equivalents of water = Amount of water used (g) / Molecular weight of water (moles) × Number of OH groups in water In the above formulas, the molecular weight of NCO is 42 (mol), the molecular weight of KOH is 56,100 (mmol), the molecular weight of water is 18 (mol), and the number of OH groups in water is 2.

[0024] [catalyst] (trimerization catalyst) The catalyst preferably contains at least a trimerization catalyst. The trimerization catalyst is a catalyst that reacts isocyanate groups contained in a polyisocyanate compound to trimerize them and promote the formation of isocyanurate rings. By containing the trimerization catalyst, the urethane resin composition undergoes isocyanuration, making it possible to easily form an isocyanurate foam. By forming an isocyanurate foam, it becomes easier to improve fire resistance. Examples of trimerization catalysts include nitrogen-containing aromatic compounds, alkali metal carboxylates, tertiary ammonium salts, and quaternary ammonium salts. These may be used alone or in combination of two or more. Among these, it is preferable to use at least one of alkali metal carboxylates and quaternary ammonium salts as the trimerization catalyst, and it is also preferable to use both of these. Furthermore, it is more preferable to use alkali metal carboxylates as the trimerization catalyst.

[0025] Examples of the nitrogen-containing aromatic compound used in the trimerization catalyst include tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, and 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine. Examples of alkali metal carboxylates include potassium organic acids, and preferred examples include potassium octylate such as potassium 2-ethylhexanoate, potassium acetate, potassium propionate, potassium butanoate, potassium benzoate, and other potassium carboxylates having 2 to 8 carbon atoms.

[0026] Examples of tertiary ammonium salts include triethylammonium salts and triphenylammonium salts. Examples of quaternary ammonium salts include tetramethylammonium salts, tetraethylammonium salts, tetraphenylammonium salts, triethylmethylammonium salts, hydroxybutyltrimethylammonium salts, and hydroxypropyltrimethylammonium salts. The ammonium salt is, for example, an ammonium salt of a carboxylic acid. Examples of the carboxylic acid in the ammonium salt include saturated fatty acids having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms. The saturated fatty acid may have a hydrocarbon group that is linear or branched, but preferably branched. Specific examples of the carboxylic acid include 2-ethylhexanoic acid, 2,2-dimethylpropanoic acid, acetic acid, and formic acid.

[0027] The content of the trimerization catalyst is preferably 0.1 to 15 parts by mass, more preferably 0.5 to 10 parts by mass, even more preferably 1 to 10 parts by mass, and even more preferably 2 to 7 parts by mass, relative to 100 parts by mass of the polyol. When the content of the trimerization catalyst is within this range, the trimerization reaction can proceed appropriately at a rate commensurate with the amount of catalyst, and isocyanurate rings can be appropriately formed. This facilitates the formation of a core material with excellent fire resistance.

[0028] (resinification catalyst) A resinification catalyst may be used as the catalyst. The resinification catalyst is a catalyst that promotes the reaction between a polyol compound and a polyisocyanate compound. Use of the resinification catalyst allows polyurethane to be appropriately produced at a good reaction rate, making it easier to appropriately form a polyurethane foam, for example, by the production method described below. The catalyst preferably contains a resinification catalyst in addition to a trimerization catalyst. Use of both the trimerization catalyst and the resinification catalyst as catalysts allows both the urethanization reaction and the trimerization reaction to proceed appropriately, making it easier to appropriately form an isocyanurate foam, for example, by the production method described below.

[0029] Examples of the resinification catalyst include amine catalysts such as imidazole compounds and piperazine compounds, and metal catalysts. Examples of imidazole compounds include tertiary amines in which the secondary amine at the 1-position of the imidazole ring is substituted with an alkyl group, an alkenyl group, or the like. Specific examples include N-methylimidazole, 1,2-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-methyl-2-ethylimidazole, 1,2-diethylimidazole, and 1-isobutyl-2-methylimidazole. Other examples include imidazole compounds in which the secondary amine in the imidazole ring is substituted with a cyanoethyl group. Furthermore, examples of the piperazine compound include tertiary amines such as N-methyl-N',N'-dimethylaminoethylpiperazine and trimethylaminoethylpiperazine. Examples of the amine catalyst include, in addition to imidazole compounds and piperazine compounds, various tertiary amines such as pentamethyldiethylenetriamine, triethylamine, N-methylmorpholinebis(2-dimethylaminoethyl)ether, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N'-trimethylaminoethyl-ethanolamine, bis(2-dimethylaminoethyl)ether, N,N-dimethylcyclohexylamine, diazabicycloundecene, triethylenediamine, tetramethylhexamethylenediamine, and tripropylamine.

[0030] Examples of metal catalysts used as resinification catalysts include metal salts of lead, tin, bismuth, copper, zinc, cobalt, nickel, etc., and are preferably organic acid metal salts of lead, tin, bismuth, copper, zinc, cobalt, nickel, etc. More preferred are organic acid tin salts such as dibutyltin dilaurate, dioctyltin dilaurate, and dioctyltin versatate, and organic acid bismuth salts such as bismuth trioctate and bismuth tris(2-ethylhexanoate), and among these, organic acid bismuth salts are preferred. The resinification catalyst may be used alone or in combination of two or more. The resinification catalyst is preferably at least one selected from amine catalysts and metal catalysts, more preferably amine catalysts, and even more preferably imidazole compounds.

[0031] The content of the resinification catalyst in the urethane resin composition is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 7.5 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the polyol. When the content of the resinification catalyst is within this range, the reaction between the polyol and the isocyanate tends to proceed appropriately.

[0032] The total content of catalysts in the urethane resin composition is not particularly limited, but is preferably 0.1 to 30 parts by mass, more preferably 1 to 15 parts by mass, and even more preferably 2 to 12 parts by mass, relative to 100 parts by mass of polyol. When the total content of catalysts is within this range, the reaction between polyol and isocyanate and the trimerization reaction tend to proceed appropriately.

[0033] [Foaming agent] The blowing agent promotes foaming of the urethane resin composition. Examples of the blowing agent include organic physical blowing agents such as low-boiling hydrocarbons such as water, propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cycloheptane, chlorinated aliphatic hydrocarbon compounds such as dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, and isopentyl chloride, ether compounds such as hydrofluoroolefins (hereinafter sometimes referred to as "HFO") and diisopropyl ether, and mixtures of these compounds, and inorganic physical blowing agents such as nitrogen gas, oxygen gas, argon gas, and carbon dioxide gas. Of the above-mentioned blowing agents, it is preferable to use hydrofluoroolefins (HFOs) which are highly stable as blowing agents, do not easily reduce catalytic activity, and have a low environmental impact.

[0034] Suitable HFOs include fluoroalkenes having about 3 to 6 carbon atoms. The HFO may be a hydrochlorofluoroolefin having a chlorine atom, and therefore may be a chlorofluoroalkene having about 3 to 6 carbon atoms. Examples of HFOs include trifluoropropene, tetrafluoropropenes such as HFO-1234, pentafluoropropenes such as HFO-1225, chlorodifluoropropene, chlorotrifluoropropenes such as HFO-1233, and chlorotetrafluoropropene. More specifically, 3,3,3-trifluoropropene (HFO-1243zf), trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), cis-1,3,3,3-tetrafluoropropene (HFO-1234ze(Z)), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,1,3,3-tetrafluoropropene, cis-1,3,3,3-tetrafluoropropene (HFO-1234ze(Z)), trans-1,2,3,3,3-tetrafluoropropene Examples of suitable fluoropropenes include 1,2,3,3,3-pentafluoropropene (HFO-1225ye(E)), cis-1,2,3,3,3-pentafluoropropene (HFO-1225ye(Z)), 1,1,3,3,3-pentafluoropropene (HFO-1225zc), 1,1,2,3,3-pentafluoropropene (HFO-1225yc), trans-1-chloro-3,3,3-trifluoropropene (HFO-1233zd(E)), and 1,1,1,4,4,4-hexafluorobut-2-ene (HFO-1336mzz). Of these, HFO-1233zd(E) is preferred.

[0035] The amount of foaming agent in the urethane resin composition is not particularly limited, and is preferably 10 to 100 parts by mass, more preferably 15 to 85 parts by mass, and even more preferably 20 to 70 parts by mass, per 100 parts by mass of polyol. When the content of the foaming agent is equal to or greater than the lower limit, foaming is promoted, foamability is improved, the density of the polyurethane foam is reduced, and good heat insulating performance can be imparted. When the content of the foaming agent is equal to or less than the upper limit, excessive foaming can be suppressed.

[0036] The blowing agents may be used alone or in combination of two or more. In the urethane resin composition of the present invention, it is preferable to use the above-mentioned HFO in combination with another blowing agent. For example, HFO may be used in combination with water, oxygen gas, or carbon dioxide gas, which is easy to handle. Water is particularly preferable from the viewpoints of adjusting the isocyanate index and ease of handling. The content of HFO is preferably from 10 to 100 parts by mass, more preferably from 15 to 85 parts by mass, and even more preferably from 20 to 70 parts by mass, relative to 100 parts by mass of polyol. The content of water is preferably from 0.1 to 10 parts by mass, more preferably from 0.2 to 5 parts by mass, and even more preferably from 0.5 to 3 parts by mass, relative to 100 parts by mass of polyol.

[0037] [mica] The urethane resin composition of the present invention contains mica, a type of clay mineral. When the urethane resin composition contains mica, a certain amount of residue remains when a polyurethane foam formed from the urethane resin composition is burned, thereby enhancing fire resistance. While the mechanism behind this is unclear, it is presumed that the mica is sintered by heating, for example, at 800 to 1000°C, and the mica bonds together, maintaining the shape of the residue, thereby ensuring fire resistance. Examples of mica include, but are not limited to, muscovite, phlogopite, and margarite.

[0038] The shape of the mica is not particularly limited, but is preferably scaly. A scaly shape facilitates improved fire resistance. The average particle size of the mica is not particularly limited, but is, for example, 1 to 100 μm, preferably 5 to 50 μm, more preferably 10 to 40 μm, and even more preferably 12 to 30 μm. When the particle size of the mica is within the above range, it is easy to improve fire resistance. The average particle size is a volume average diameter determined by a laser diffraction / scattering method.

[0039] The content of mica in the urethane resin composition may be, for example, 1 to 30 mass% based on the total amount of the urethane resin composition. By setting the content of mica at or above the lower limit, it becomes easier to increase the residue remaining rate and shape retention after high-temperature heating, and it becomes easier to improve fire resistance. Furthermore, by setting the content at or below the upper limit, it becomes possible to contain components such as polyol compounds and polyisocyanate compounds in certain amounts in the urethane resin composition, and it becomes possible to properly form a foam. The content of mica is preferably 2 to 25 mass %, more preferably 3 to 22 mass %, and even more preferably 4 to 20 mass %, from the viewpoint of increasing the rate of residue remaining after high-temperature heating and shape retention.

[0040] The content of mica is not particularly limited as long as it is based on 100 parts by mass of the polyol compound, but is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, even more preferably 50 parts by mass or more, and even more preferably 80 parts by mass or more, relative to 100 parts by mass of the polyol compound. Increasing the amount of mica makes it easier to impart high fire resistance. On the other hand, setting the amount of mica to a certain level or less can also prevent the viscosity from increasing. Since the fire resistance improves as the content of mica increases, the upper limit of the content of mica is not particularly limited, and is, for example, 200 parts by mass.

[0041] [Phosphate ester] The urethane resin composition may contain a phosphate ester. It is preferable to use a phosphate ester that is liquid at room temperature (23°C) and normal pressure (1 atmosphere). The use of a phosphate ester reduces the viscosity of the urethane resin composition and the polyol liquid agent described below, making them easier to handle. Furthermore, the phosphate ester is also a liquid flame retardant, which makes it easier to improve the flame retardancy and fire resistance of polyurethane foam.

[0042] Examples of the phosphate ester that can be used include monophosphate esters and condensed phosphate esters. Monophosphate esters are phosphate esters having one phosphorus atom in the molecule. Examples of the monophosphate ester include trialkyl phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, and tri(2-ethylhexyl)phosphate; halogen-containing phosphate esters such as tris(β-chloropropyl)phosphate; trialkoxy phosphates such as tributoxyethyl phosphate; aromatic ring-containing phosphate esters such as tricresyl phosphate, trixylenyl phosphate, tris(isopropylphenyl)phosphate, cresyl diphenyl phosphate, and diphenyl(2-ethylhexyl)phosphate; and acidic phosphate esters such as monoisodecyl phosphate and diisodecyl phosphate.

[0043] Examples of the condensed phosphate ester include aromatic condensed phosphate esters such as trialkyl polyphosphate, resorcinol polyphenyl phosphate, bisphenol A polycresyl phosphate, and bisphenol A polyphenyl phosphate. Commercially available condensed phosphate esters include, for example, "CR-733S," "CR-741," and "CR747" manufactured by Daihachi Chemical Industry Co., Ltd., and "ADEKA STAB PFR" and "FP-600" manufactured by ADEKA Corporation.

[0044] The phosphate ester may be used singly or in combination of two or more of the above-mentioned phosphate esters. Among these, monophosphate esters are preferred, and halogen-containing phosphate esters such as tris(β-chloropropyl)phosphate are more preferred, from the viewpoint of easily reducing the viscosity and improving the flame retardancy and fire resistance of the polyurethane foam. The content of the phosphate ester in the urethane resin composition is, for example, 5 to 150 parts by mass, preferably 15 to 130 parts by mass, more preferably 20 to 120 parts by mass, and even more preferably 30 to 110 parts by mass, relative to 100 parts by mass of the polyol.

[0045] [Foam stabilizer] The urethane resin composition may contain a foam stabilizer. The inclusion of a foam stabilizer can improve the foamability of the polyurethane foam, and can appropriately promote foaming in the production method described below, for example. Specific examples of the foam stabilizer include surfactants, more specifically, polyoxyalkylene foam stabilizers such as polyoxyalkylene alkyl ethers, and silicone foam stabilizers such as organopolysiloxanes. The foam stabilizer used in the present invention is not particularly limited, but silicone foam stabilizers are preferred from the viewpoint of foaming properties. The foam stabilizers may be used alone or in combination of two or more.

[0046] The content of the foam stabilizer in the urethane resin composition of the present invention is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, and even more preferably 0.5 to 3 parts by mass, per 100 parts by mass of polyol. When the content of the foam stabilizer is at least the above-mentioned lower limit, the urethane resin composition becomes easier to foam, making it possible to obtain a homogeneous polyurethane foam. Furthermore, when the content of the foam stabilizer is at most the above-mentioned upper limit, an optimal balance between production costs and the obtained effects is achieved.

[0047] [Other ingredients] In addition to the above, the urethane resin composition of the present invention may contain at least one of a flame retardant other than phosphate ester, a filler other than mica, etc. Examples of flame retardants other than phosphate ester include solid flame retardants that are solid at room temperature (23°C) and normal pressure (1 atmosphere). Examples of flame retardants other than phosphate ester include red phosphorus-based flame retardants, phosphate-containing flame retardants, bromine-containing flame retardants, boron-containing flame retardants, antimony-containing flame retardants, metal hydroxides, etc.

[0048] The red phosphorus-based flame retardant may be red phosphorus alone, red phosphorus coated with a resin, metal hydroxide, metal oxide or the like, or red phosphorus mixed with a resin, metal hydroxide, metal oxide or the like. Examples of phosphate-containing flame retardants include phosphates formed from salts of various phosphoric acids such as phosphoric acid, phosphorous acid, hypophosphorous acid, monophosphoric acid, pyrophosphoric acid, and polyphosphoric acid with at least one metal or compound selected from metals of Groups IA to IVB of the periodic table, ammonia, aliphatic amines, aromatic amines, and heterocyclic compounds containing nitrogen in the ring. Specific examples include aluminum phosphate, aluminum phosphite, ammonium polyphosphate, and aluminum polyphosphate.

[0049] Examples of bromine-containing flame retardants include monomeric organic bromine compounds such as hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromophenoxy)ethane, ethylene bis(pentabromophenyl), ethylene bis(tetrabromophthalimide), and tetrabromobisphenol A, as well as polymeric organic bromine compounds. Examples of boron-containing flame retardants include borax, boron oxide, boric acid, and borates such as zinc borate. Examples of antimony-containing flame retardants include antimony oxides such as antimony trioxide and antimony pentoxide, antimonates, and pyroantimonates. Examples of metal hydroxides include magnesium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, vanadium hydroxide, and tin hydroxide. The above flame retardants other than phosphate esters may be used alone or in combination of two or more.

[0050] Examples of fillers other than mica include calcium sulfate, barium sulfate, calcium silicate, wollastonite, sepiolite, montmorillonite, saponite, stevensite, hectorite, activated clay, glass beads, aluminum nitride, boron nitride, silicon nitride, various metal powders, magnesium sulfate, lead zirconate titanate, molybdenum sulfide, silicon carbide, various magnetic powders, fly ash, etc. Fillers other than mica may be used alone or in combination of two or more.

[0051] In addition to the above, the urethane resin composition may contain one or more selected from phenolic, amine, sulfur-based and other antioxidants, heat stabilizers, metal inhibitors (metal deactivators), antistatic agents, crosslinking agents, lubricants, softeners, pigments, dyes, tackifiers, and the like, as needed, provided that the object of the present invention is not impaired.

[0052] The urethane resin composition of the present invention may be a one-component type, or may be divided into two or more parts and mixed for use. When divided into two or more parts, it is preferable to divide it into at least a polyol liquid agent containing a polyol compound and an isocyanate liquid agent containing a polyisocyanate compound. The urethane resin composition is preferably a two-component type. In the two-component type, it is preferable to be composed of a polyol liquid agent and a polyisocyanate liquid agent. In the two-component type, various components such as catalyst, blowing agent, and mica may be contained in either the polyol liquid or the polyisocyanate liquid, but are preferably contained in the polyol liquid from the viewpoint of storage stability, etc. Furthermore, components other than the catalyst, blowing agent, and mica, such as phosphate ester, foam stabilizer, flame retardant, filler, and other components, are also preferably contained in the polyol liquid.

[0053] The urethane resin composition of the present invention can be produced by mixing the components that make up the urethane resin composition. Furthermore, in the case of a two-component type, it can be obtained by mixing a polyol liquid and a polyisocyanate liquid. When each of these liquids contains two or more components, it can be obtained by mixing the components that make up each liquid.

[0054] <Polyurethane foam> The polyurethane foam constituting the core material of the present invention can be formed by foaming and curing the above-described urethane resin composition. The foaming and curing of the urethane resin composition may be performed by a known method. For example, in the case of a two-component type, the polyurethane foam can be obtained by mixing a polyol liquid agent and a polyisocyanate liquid agent prepared in advance as described above, and foaming and curing the resulting urethane resin composition. The polyurethane foam is preferably an isocyanurate foam isocyanurated with an excess amount of a polyisocyanate compound as described above.

[0055] The core material made of polyurethane foam has a density of, for example, 40 to 210 kg / m 3 However, preferably 60 to 180 kg / m 3 , more preferably 60 to 160 kg / m 3 The core material tends to have good fire resistance if its density is set to a certain level or higher, for example, 60 kg / m 3 By setting the density to a certain level or less, the core material has a low thermal conductivity and good heat insulation properties, for example, 160 kg / m 3 The density of the core material made of polyurethane foam is set to 65 to 140 kg / m from the viewpoint of improving fire resistance and insulation in a balanced manner. 3 is more preferably 70 to 100 kg / m 3 is even more preferred.

[0056] The core material made of polyurethane foam has a thermal conductivity of, for example, 0.035 W / (m·K) or less. When the thermal conductivity of the polyurethane foam is equal to or less than the above upper limit, it exhibits good thermal insulation. From the viewpoint of achieving a target level of thermal insulation or higher, the thermal conductivity is preferably 0.03 W / (m·K) or less, more preferably 0.028 W / (m·K) or less, and even more preferably 0.024 W / (m·K) or less. The thermal conductivity is not particularly limited, but from the viewpoint of easily ensuring a certain level of fire resistance, it is preferably 0.01 W / (m·K) or more, more preferably 0.015 W / (m·K) or more, and even more preferably 0.018 W / (m·K) or more. The thermal conductivity can be measured by the method described in the Examples below.

[0057] The core material made of polyurethane foam may have a volume retention rate of, for example, more than 20%, preferably 40% or more, more preferably 50% or more, and even more preferably 70% or more after being heated from 600°C to 800°C over 6 minutes and maintained at 800°C for 14 minutes. By ensuring that the volume retention rate of the polyurethane foam is at least a certain level as described above, it becomes easier to improve fire resistance. The volume retention rate may be 100% or less, but in practical terms, it may be 97% or less. The volume retention rate can be measured by the method described in the Examples below.

[0058] <Panel with non-flammable surface on both sides> The panel with double-sided non-combustible face material of the present invention has a core material formed from the above-mentioned urethane resin composition. As shown in Figure 1, the panel with double-sided non-combustible face material 10 has a pair of opposing face materials 20, 21 and a core material 11 sandwiched between them. The thickness of the core material 11 is preferably 5 to 300 mm, more preferably 10 to 200 mm, and even more preferably 25 to 150 mm. When the thickness of the core material 11 is within the above range, it has high fire resistance and heat insulation properties and can be made lighter.

[0059] The face materials 20 and 21 are non-combustible face materials. Examples of non-combustible face materials include calcium silicate board, gypsum board, FRP, and metal plate, with metal plate being preferred. Therefore, it is preferable that the face materials 20 and 21 are metal face materials. Using metal plate as the face material can improve fire resistance. There are no particular limitations on the metal face material, but various steel plates such as galvanized steel plate, Galvalume steel plate (registered trademark), stainless steel plate, and aluminum steel plate can be used. In other words, it is more preferable that the panel 10 with double-sided non-combustible face material is a panel with double-sided steel plate. The face materials 20 and 21 are adhered to the front and back surfaces of the core material 11, respectively. The thickness of each of the face materials 20, 21 is preferably 0.1 to 5 mm, more preferably 0.2 to 3 mm, and even more preferably 0.3 to 1 mm. When the thickness of the face materials 20, 21 is equal to or greater than the above-mentioned lower limit, high fire resistance can be imparted. Furthermore, when the thickness of the face materials 20, 21 is equal to or less than the above-mentioned upper limit, the weight of the panel 10 with double-sided noncombustible face materials can be reduced. The surface materials 20, 21 may be flat plate-like members, or if a surface material is provided that covers the side surface of the core material 11 described below, the surface materials 20, 21 may be U-shaped or L-shaped members, in which case it is preferable that a portion of the U-shaped or L-shaped member constitutes a surface material that covers the side surface.

[0060] Between the face materials 20, 21 and the core material 11, there may be further another face material, such as a paper face material, an aluminum face material, an aluminum craft face material, a polyethylene laminate face material, a cross laminate face material, or the like. To further improve fire resistance, core material 11 may be combined with an inorganic core material. Examples of inorganic core materials include core materials containing mineral fibers such as rock wool, glass wool, long glass fibers, special-purpose glass microfibers, ceramic wool, alkaline earth silicate wool (AES), refractory ceramic fibers (RCF), alumina fibers, potassium titanate whiskers, and silicon carbide whiskers, calcium silicate boards, and ALC panels. The inorganic core material may be laminated on only one side of core material 11, or may be laminated on both sides of core material 11, resulting in a configuration in which the core material has three or more layers in total. Furthermore, two or more layers of inorganic core material may be laminated on at least one side of core material 11.

[0061] In a panel with double-sided non-combustible facings, the surfaces (side surfaces) other than the surfaces constituting the front and back surfaces of the core material 11, which are covered in addition to the facings 20 and 21, may also be covered with a facing material as appropriate. The material of the facing material covering the side surfaces is not limited to a specific material, and may be metal, a resin such as FRP, or other non-combustible facing materials. The metal facing material may be any of various steel plates, as with the metal facing material. Furthermore, the resin facing material is not particularly limited, and may be formed from, for example, FRP. The panel 10 with non-combustible facing on both sides is generally roughly rectangular and preferably has four sides, but all four sides may be covered with facing material, or only two opposing sides may be covered with facing material.

[0062] A plurality of panels 10 with double-sided non-combustible face materials may be connected together for use. When a plurality of panels 10 are connected, it is preferable that the side surfaces of the panels 10 with double-sided non-combustible face materials are connected together. When the side surfaces are connected together, the surface materials of the side surfaces of the panels may be formed with irregularities or the like, and the panels may be connected by fitting or the like.

[0063] The panels with double-sided non-combustible facings are installed in partitions of buildings to separate them into compartments. Examples of partitions of buildings where the panels with double-sided non-combustible facings can be installed include walls, partitions, floors, ceilings, and roofs, and are preferably walls and partitions, and more preferably fire-resistant exterior walls and fire-resistant partitions. The fire-resistant outer wall and fire-resistant partition are preferably used as a fire-resistant outer wall and fire-resistant partition of a refrigerating compartment, and more preferably as a fire-resistant partition of a refrigerating compartment. The fire-resistant partition may be used as a fire-resistant partition between a refrigerating compartment and a room temperature compartment, or as a fire-resistant partition between refrigerating compartments.

[0064] <Manufacturing method for panels with non-combustible surfaces on both sides> The panel with double-sided non-flammable face materials of the present invention can be manufactured by filling a urethane resin composition between the face materials, foaming and curing the urethane resin composition to form a polyurethane foam, and integrating the polyurethane foam with the face materials.

[0065] For example, a laminated structure of a panel with double-sided non-flammable face materials can be manufactured by supplying a urethane resin composition onto one face material, while arranging the other face material so that it covers the top of the supplied urethane resin composition and is spaced a predetermined distance from the one face material, and foaming the urethane resin composition to form a polyurethane foam. In this method, the panels with double-sided non-combustible facings are preferably produced continuously. Specifically, in a production line, a urethane resin composition is discharged from a discharge head installed on the production line onto one of the conveyed facings, while the other facing is supplied so as to cover the top of the discharged urethane resin composition. The urethane resin composition is then foamed and cured between the two facings flowing on the production line, forming a polyurethane foam between the two facings.

[0066] Alternatively, a panel with non-combustible facings on both sides may be manufactured using a mold. Specifically, the facings are set at a predetermined interval inside a mold such as a press, a urethane resin composition is poured into the mold, and the urethane resin composition is foamed and cured between the facings to form a polyurethane foam between the two facings. A facing material for covering the side surfaces may also be set inside the mold as appropriate to provide a facing material for covering the side surfaces. The laminate of the face material, polyurethane foam, and face material obtained by each of the above methods may be used as a panel with non-combustible face materials on both sides as is, or may be cut appropriately as needed to form a panel with non-combustible face materials on both sides.

[0067] Furthermore, the panel with double-sided non-combustible face material of the present invention may be manufactured by combining a pre-manufactured core material with face materials. For example, a panel with double-sided non-combustible face material may be manufactured by bonding face materials to a pre-manufactured core material. In this case, the core material may be obtained, for example, by foaming and curing the resin composition to form a polyurethane foam, and then processing the polyurethane foam into the desired shape by cutting or the like, or by injecting the urethane resin composition into a mold or the like, foaming and curing it inside the mold or the like, and then releasing it from the mold to obtain a core material having the desired shape.

[0068] Furthermore, when a panel with double-sided non-combustible face materials has face materials that cover both side surfaces of the opposing core material in addition to face materials that cover the front and back surfaces of the core material, a rectangular frame-shaped member consisting of a pair of face materials and a pair of face materials that form the side surfaces can be obtained by bending metal material or joining appropriate non-combustible face materials, and then inserting a core material into the rectangular frame-shaped member to obtain a panel with double-sided non-combustible face materials.A panel with double-sided non-combustible face materials can also be obtained by fitting a core material between two U-shaped face materials. [Example]

[0069] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples in any way.

[0070] The evaluation methods used in each of the examples and comparative examples are as follows. [Fire resistance] As shown in Figure 2, a heating furnace 30 with a rectangular parallelepiped interior was prepared, and a panel with non-combustible surface material on both sides, measuring 800 mm x 800 mm and 100 mm thick, was placed on the back side of the heating furnace 30. The interior of the heating furnace 30 was heated by flame F generated by a heat source on the front side of the heating furnace 30, and heating was carried out for 1 hour so that the temperature inside the heating furnace 30 rose in accordance with the ISO 834 curve. The temperature inside the heating furnace 30 was measured by a thermocouple 31 placed approximately in the center of the heating furnace 30. Additionally, nine thermocouples 32 were arranged in a 3 x 3 pattern on the back of the heating furnace 30 to measure the temperature on the back of the panel 10 with double-sided non-combustible surface material. At this time, the average value of the temperatures measured by the nine thermocouples 32 and the maximum temperature among the nine thermocouples 32 were calculated. If the average temperature was equal to or lower than the initial temperature (23°C) + 140°C and the maximum temperature was equal to or lower than the initial temperature (23°C) + 180°C, the fire resistance was deemed excellent and rated "A", otherwise rated "C".

[0071] [Thermal Conductivity] A 200mm x 200mm, 25mm thick sample was cut from the center of the core material of the obtained double-sided non-combustible facing panel, and the thermal conductivity was measured using a thermal conductivity measuring device (product name "HC-074") manufactured by Eiko Seiki Co., Ltd. Based on the measured thermal conductivity, the heat insulation was evaluated according to the following evaluation criteria. AA: 0.024W / (m·K) or less A: Greater than 0.024W / (m K) and less than or equal to 0.030W / (m K) B: Greater than 0.030W / (m K) and less than or equal to 0.035W / (m K) C: Greater than 0.035W / (m·K)

[0072] [Volume retention rate and residue retention] One of the face materials was peeled off, and the core material, cut to a thickness of 20 mm and dimensions of 50 mm x 50 mm, was placed on a thin steel plate and placed in an electric furnace heated to 600°C. After the sample was placed in the electric furnace, the temperature was raised from 600°C to 800°C over 6 minutes, and the temperature was maintained at 800°C for 14 minutes, after which the heated residue was removed from the electric furnace. The volume residual rate was calculated by calculating the ratio of the volume of the residue after removal from the electric furnace to the volume of the polyurethane foam before it was placed in the electric furnace. Volume residual rates of over 50% were rated as "A," those over 20% but not exceeding 50% as "B," and those not exceeding 20% ​​as "C."

[0073] Regarding residue retention, when the residue removed from the electric furnace was picked up by hand from both sides and lifted, those that could be lifted with almost no change in shape were rated as "AA", those that had some damage but did not change shape significantly were rated as "A", those that retained their shape but fell apart when picked up by hand and could not be lifted were rated as "B", and those that did not retain their shape at all were rated as "C".

[0074] The components used in each of the examples and comparative examples are as follows. (Polyol compound) Polyester polyol, manufactured by WOOJO HIGHTECH, product name: WJESOPOL6201, hydroxyl value = 235 mg KOH / g (Isocyanate compounds) Polymeric MDI, manufactured by Tosoh Corporation, product name: Millionate MR-200 (Foam stabilizer) Silicone foam stabilizer, manufactured by Dow Toray, product name: SH193

[0075] (catalyst) Trimerization catalyst: Toei Chemical Industry Co., Ltd., product name: potassium hexoate, potassium 2-ethylhexanoate (concentration: 75% by mass) Resinification catalyst: Kao Corporation, product name: Kao Raiser No. 120, 1-isobutyl-2-methylimidazole (concentration 98-100% by mass) (Flame retardant) Phosphate ester: Tris(β-chloropropyl)phosphate, manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP

[0076] (clay minerals) Mica 1: Osaka Mica Co., Ltd., product name: H-2000, average particle size 12.5 μm Mica 2: Yamaguchi Mica Co., Ltd., product name: A-21S, average particle size 23 μm Mica 3: Yamaguchi Mica Co., Ltd., product name: TM-10, average particle size 11 μm Sepiolite: Manufactured by Omi Mining Co., Ltd., Product name: Miraclay P-300, average particle size 5 μm Montmorillonite: Kunimine Industries Co., Ltd., product name: Kunipia F Saponite: Manufactured by Kunimine Kogyo Co., Ltd. Product name: Sumecton-SA Stevensite: Manufactured by Kunimine Kogyo Co., Ltd. Product name: Sumecton-ST Hectorite: Kunimine Industries Co., Ltd., Product name: Sumecton-SWN

[0077] (foaming agent) water Hydrofluoroolefin (HFO): trans-1-chloro-3,3,3-trifluoropropene (Honeywell Japan, product name: Soltis LBA)

[0078] [Examples 1 to 9, Comparative Examples 1 to 6] A polyol premix (polyol liquid) was prepared by premixing the raw materials, except for the isocyanate compound, according to the formulations in Tables 1 and 2. A press with upper and lower heatable metal press plates was prepared. 0.5 mm thick steel plates were placed on the upper and lower sides of the press as face plates, and the distance between the metal press plates was adjusted so that the overall panel thickness was 100 mm. With the metal press plates heated to 60°C, a urethane resin composition obtained by mixing the polyol liquid with the polyisocyanate compound was filled between the two face plates. The composition was then foamed and cured in the press for 30 minutes to obtain a double-sided non-combustible panel consisting of a steel plate, polyurethane foam, and steel plate. The resulting double-sided non-combustible panel was cut into an 800 mm x 800 mm piece, resulting in a double-sided non-combustible panel with an overall thickness of 100 mm. The density, fire resistance, and thermal conductivity of the double-sided non-combustible panel manufactured in each example and comparative example were evaluated. The results are shown in Tables 1 and 2.

[0079] [Table 1]

[0080] [Table 2] *In Tables 1 and 2, the amount of catalyst used is the amount in the product.

[0081] As shown in Tables 1 and 2, the panels with double-sided non-flammable facings in each of the above examples have a core material obtained by foaming and curing a urethane resin composition containing a polyol compound, a polyisocyanate compound, a catalyst, a foaming agent, and mica. Therefore, they have low thermal conductivity, good insulation properties, good residue retention rate, and excellent fire resistance. In contrast, the polyurethane foams obtained by foaming and curing the urethane resin compositions of each comparative example did not contain clay minerals, and even if they did contain clay minerals, they were not mica, making it difficult to improve fire resistance. [Explanation of symbols]

[0082] 10 Panel with non-combustible surface material on both sides 11 Core material 20,21 Surface material 30 Furnace 31,32 Thermocouple

Claims

1. A panel with double-sided non-flammable face materials, comprising a pair of opposing face materials and a core material disposed between the face materials, the core material being a foam formed from a urethane resin composition containing a polyol compound, a polyisocyanate compound, a catalyst, a foaming agent, and mica.

2. 2. A panel with double-sided non-combustible face materials according to claim 1, wherein the mica is flaky.

3. 3. A panel with double-sided non-combustible surface material as described in claim 1 or 2, wherein the catalyst comprises a trimerization catalyst, and the trimerization catalyst comprises at least one selected from the group consisting of a nitrogen-containing aromatic compound, an alkali metal carboxylic acid salt, a tertiary ammonium salt, and a quaternary ammonium salt.

4. The density of the core material is 60 to 180 kg / m ３ 3. A panel with double-sided non-combustible face materials according to claim 1 or 2.

5. 3. A panel with double-sided non-combustible face materials according to claim 1, wherein the core material has a thermal conductivity of 0.035 W / (m·K) or less.

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