JP2020070712A - Fire resistant panel and manufacturing method of the same - Google Patents

Abstract

To provide a fire resistant panel having an excellent fire resistance and a structural stability and its manufacturing method.SOLUTION: A fire resistant panel comprises a fibrous layer, a thermoplastic resin layer and a fire resistant layer arranged in order, in which the fire resistant layer contains a polyisocyanurate resin as a main component and is bonded with the thermoplastic resin layer, and a basis weight of the fibrous layer is less than 45 g/m.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a fire resistant panel and a method for manufacturing the same.

  With the revision of the Building Standards Act in 2000, various materials and structural methods can be adopted if they meet certain fire resistance. Conventionally, the fire resistant structure has been limited to a non-combustible material such as a steel frame structure or a reinforced concrete structure, but if a predetermined fire resistance performance can be confirmed, a combustible material such as wood can also be used. Wood, which is a material that can be regenerated by planting trees, is a building material that is kind to the global environment as a measure to reduce carbon dioxide, and in particular, it is hoped that the use of domestic timber, which is a powerful resource in Japan, will be actively expanded. It is rare.

  Fire-resistant buildings under the Building Standards Act are required to continue to be built even after the fire ends, and even after the specified fire-resistant heating is applied, the fire-resistant performance expected of the member ( It is necessary to maintain the load bearing capacity, heat insulation and flame insulation). The specific fire resistance test method is to use a fire resistant heating furnace and perform heating along a standard fire heating temperature curve (ISO-834) defined by the International Organization for Standardization, and then triple the heating time in the furnace. Perform the judgment based on the deformation and the deformation speed while leaving it for a while, and confirm that it will stop burning after the fire resistance test. This is a severe condition for ordinary wooden columns and beams, and it is difficult to satisfy this condition.

  Hitherto, various structural materials have been proposed in order to realize a fire resistant structure by using a laminated material composed of combustible wood. For example, Patent Document 1, Patent Document 2 and Patent Document 3 disclose composite wooden structural materials such as laminated materials and laminated wood. That is, the laminated material with a certain strength is used as the core material, and the outer periphery of the laminated material is an inorganic material such as gypsum board, mortar and cement, various flame retardant components, wood treated with the flame retardant, or high density wood as the fireproof layer. It is a composite wood structure material to be placed as. However, in order to manufacture these structural materials, it is necessary to coat the surface of the core material with a highly viscous material, which makes the process considerably complicated. Further, it is more difficult to make the cross-sectional shape of the structural materials arbitrary (for example, a circular cross-section), and it is very troublesome to manufacture those structural materials.

  Further, Patent Document 4 and Patent Document 5 disclose a refractory article having a refractory layer made of a polyisocyanurate resin.

  On the other hand, there has been no report on a method for stably bonding the polyisocyanurate resin forming the fire resistant layer and other materials such as wood while maintaining excellent fire resistance.

JP 2005-036456 JP 2005-048585 JP JP 2008-031743 Japanese Patent Laid-Open No. 2015-061969 JP 2017-087528 JP

  However, it has become clear from the study by the present inventors that it may be difficult to stably join the polyisocyanurate resin and other members such as wood while maintaining remarkable fire resistance. Furthermore, when the present inventors use a fire resistant panel composed of a fire resistant layer containing a polyisocyanurate resin as a main component and a specific plurality of layers, the present invention stably adheres to members such as wood. In addition, it has been found that excellent fire resistance can be imparted. The present invention is based on such findings.

  The present invention provides a fire resistant panel having excellent fire resistance imparting ability and adhesion to other members such as wood and the like, and a method for producing the same.

According to the present invention, the following [1] to [13] are provided.
[1] a fibrous layer,
A thermoplastic resin layer,
A fire-resistant panel having a fire-resistant layer in order,
The refractory layer contains a polyisocyanurate resin as a main component and is adhered to a thermoplastic resin layer,
A fire resistant panel, wherein the fibrous layer has a basis weight of less than 45 g / m ² .
[2] When the fire-resistant panel and the fire resistance-imparting target are joined on one surface of the fibrous layer side, and the fire-resistant panel is burned and heat-treated from the fire-resistant layer side according to an ISO-834 heating curve, The refractory panel according to [1], wherein it takes 40 minutes or more to reach a temperature of 150 ° C. on one side of the refractory layer.
[3] The fire resistant panel according to [1] or [2], which satisfies at least one of the following (A) and (B):
(A) Japanese Agricultural Standards (JAS) of laminated veneer for structure (JAS Notification No. 1443, September 14, 1988) [Final revision February 27, 2003 Ministry of Agriculture, Forestry and Fisheries Notification 237] No peeling is confirmed in the boiling peeling test according to
(B) The shear strength measured by the horizontal shear test according to the Japanese agricultural and forestry standard test method is 3.0 MPa or more.
[4] The fire resistant panel according to any one of [1] to [3], wherein the amount of the thermoplastic resin layer is 5 g / m ² or more.
[5] The polyisocyanurate resin contains polyisocyanate and an active hydrogen-containing compound as constituent elements,
The active hydrogen-containing compound is one or more polyols having a hydroxyl value of 80 to 2000 mgKOH / g, a functionality of 2 to 4, a molecular weight of 50 to 2000, and two or more hydroxyl groups. ]-[4] Fireproof panel in any one of.
[6] The fire resistant panel according to [5], wherein the amount of the isocyanurate-forming catalyst used for forming the polyisocyanurate resin is 0.5 part by mass or more based on 100 parts by mass of polyisocyanate.
[7] The fire resistant panel according to any one of [1] to [6], wherein the fire resistant layer contains aluminum hydroxide, red phosphorus or a combination thereof.
[8] The fire resistant panel according to any one of [1] to [7], wherein at least a part of the fire resistance imparting target is made of a wood material.
[9] The fire resistant panel according to any one of [1] to [8], wherein the fibrous layer and the thermoplastic resin layer are integrally formed.
[10] The fire resistant panel according to any one of [1] to [9], wherein the fibrous layer is a paper base material layer. [11] The fire-resistant panel according to any one of [1] to [10], wherein the thermoplastic resin layer is a resin layer containing at least polyethylene.
[12] The refractory panel according to any one of [1] to [11], wherein the melting point of the thermoplastic resin layer is 90 ° C. or higher.
[13] A method for manufacturing a fire resistant panel according to any one of [1] to [12],
A laminate having a fibrous layer and a thermoplastic resin layer, a step of preparing a raw material liquid of a polyisocyanurate resin, and one surface of the laminate on the thermoplastic resin layer side and the raw material liquid of the refractory layer are brought into contact with each other, and A method comprising the step of curing a raw material liquid to form a refractory layer.

  According to the present invention, it is possible to easily provide a fire resistant panel having excellent fire resistance imparting ability and adhesiveness to other members such as wood. According to the present invention, since the polyisocyanurate resin and other members such as wood can be stably bound, heating and combustion proceed from a portion where adhesion with the polyisocyanurate resin is poor, and fire resistance performance is not sufficiently exhibited. This is advantageous in avoiding problems. Further, the fire resistant panel of the present invention can exhibit excellent shear strength and anti-stripping property. According to the present invention, since the fireproof performance can be easily adjusted by adjusting the thickness of each layer including the fireproof layer, a wide range of pillars, beams, walls, floors, girders, braces, foundations, etc. It can be advantageously used as a part of a member.

FIG. 4 is a cross-sectional view of one embodiment of a fire resistant panel including a fibrous layer, a thermoplastic resin layer, and a fire resistant layer. It is sectional drawing of one aspect | mode of the fire resistant panel provided with two each of a fibrous layer and a thermoplastic resin layer. FIG. 3 is a cross-sectional view of one embodiment of a fire resistant panel including two fibrous layers and two thermoplastic resin layers and a surface layer. FIG. 4 is a schematic diagram of a fire resistant article obtained by joining the fire resistant panel shown in FIG. 3 and a fire resistance imparting target. 9 is a schematic diagram showing an embodiment of a heating test in Test Example 3. FIG. Standard fire heating temperature curve according to ISO-834, heating temperature curve according to heating test method in Test Examples 3 and 4, temperature change curve of surface B (non-heated surface) of the fire resistant panel in Test Example 3, and fire resistance in Test Example 4. It is a graph which shows the temperature change curve of the surface B (non-heating surface) of a flexible panel.

<Fireproof panel>
The fire resistant panel of the present invention,
A fibrous layer,
A thermoplastic resin layer,
A fire resistant panel having a fire resistant layer in order,
The refractory layer contains a polyisocyanurate resin as a main component and is adhered to the thermoplastic resin layer,
The fibrous layer is characterized by having a basis weight of less than 45 g / m ² .
As in the present invention, when a fire-resistant panel is manufactured by combining a fire-resistant layer containing a polyisocyanurate resin as a main component, a specific fibrous layer and a thermoplastic resin layer, other members including a wood-based material are produced. On the other hand, it is a surprising fact that it can be provided with remarkable fire resistance and exhibit stable adhesiveness.

  The arrangement of each layer in the fire-resistant panel of the present invention will be specifically described below with reference to FIGS. The elements in the drawings may not be to scale. In addition, as described in the following description of the drawings, in the present invention, “include” and “comprise” may include a constituent element other than the constituent element in addition to the constituent element. Means

  FIG. 1 is a cross-sectional view of one embodiment of a fire resistant panel including a fibrous layer, a thermoplastic resin layer, and a fire resistant layer. The fire-resistant panel 1 has a fibrous layer 2, a thermoplastic resin layer 3, and a fire-resistant layer 4 in that order on one surface thereof. An intermediate layer may be provided between the fibrous layer 2 and the thermoplastic resin layer 3, but it is preferable that the laminate 5 is integrally formed from the viewpoint of improving the bondability. Providing the fibrous layer and the thermoplastic resin layer integrally as a laminate is preferable for imparting structural stability to the fire resistant panel while maintaining excellent fire resistance. Further, the thermoplastic resin layer 3 is bonded to the fireproof layer 4. It is preferable that the thermoplastic resin layer 3 and the refractory layer 4 are directly bonded from the viewpoint of compatibility and bondability.

The basis weight of the fibrous layer 2 is less than 45 g / m ² . Arranging such a basis weight fibrous layer in combination with the thermoplastic resin layer is particularly advantageous for imparting excellent shear strength and anti-peeling property to the fire resistant panel.

  In addition, FIG. 2 is a cross-sectional view of one aspect of a fire resistant panel including two fibrous layers and two thermoplastic resin layers. That is, the fire-resistant panel of FIG. 2 is such that the second thermoplastic resin layer 3 ′ and the fibrous layer 2 ′ are further arranged on one surface of the fire-resistant layer 2 of the fire-resistant panel 1 of FIG. 1. The amount and material of the second thermoplastic resin layer 3'and the fibrous layer 2'may be the same as or different from those of the first thermoplastic resin layer 3 and the fibrous layer 2. An intermediate layer may be provided between the second fibrous layer 2 ′ and the thermoplastic resin layer 3 ′, but from the viewpoint of imparting structural stability, the fibrous layer 2 ′ and the thermoplastic resin layer 3 are provided. It is preferable that the'constituting the laminate 5'integrally. Further, the second thermoplastic resin layer 3 ′ is bonded to the refractory layer 4. It is preferable that the thermoplastic resin layer 3 and the refractory layer 4 are directly bonded from the viewpoint of compatibility and bondability. Further, although not shown, the outer surface of the second fibrous layer 2 ′ has a repeating structure of a thermoplastic resin layer, a fibrous layer, and a fireproof layer (for example, thermoplastic resin layer-fireproof layer-thermoplastic resin layer- Fibrous layers, etc.) may be further disposed.

  FIG. 3 is a cross-sectional view of one embodiment of a fire-resistant panel including two fibrous layers and two thermoplastic resin layers and a surface layer. That is, the fire-resistant panel of FIG. 3 is obtained by further disposing the surface layer 6 on the outer surface of the first laminate 5 of the fire-resistant panel of FIG. An intermediate layer (not shown) may be present between the first laminate 5 and the surface layer 6. The surface layer 6 may have a function as a burn-up layer. The surface layer 6 is carbonized in the event of a fire and can block heat transfer and oxygen supply to the inside. Moreover, the surface layer may have a function as a decoration. Note that the first laminate 5 may not be present in the fire resistant panel of FIG.

  The fire resistant panel as shown in FIGS. 1 to 3 can be used for imparting fire resistance by joining with a fire resistance imparting target such as a wood material. FIG. 4 is a schematic diagram of a refractory article formed by joining the refractory panel shown in FIG. 2 to a fire resistance imparting target 7. As shown in FIG. 4, the fire resistant panel 1 ′ is joined to the fire resistance imparting target 7 through the fibrous layer 2 ′ to form the fire resistant article 8. As described above, according to the present invention, it is possible to easily impart excellent fire resistance by combining a fire resistance-imparting object such as a wood material with a fire resistant panel.

  The shape of the fire resistant panel is not particularly limited, and may be appropriately changed depending on the shape of the fire resistance imparting target. The shape of the cross section, the upper surface and the lower surface of the article may be, for example, a square, a rectangle (for example, a plate shape), a polygon other than a quadrangle, a circle, an ellipse, or the like.

  According to the present invention, it is possible to impart excellent fire resistance and structural stability to a fire resistant panel by applying the above-mentioned layer structure. According to a preferred embodiment of the present invention, a fire resistant panel and a fire resistance-imparting object are joined on one side of the fibrous layer side, and the fire resistant panel is burned from the fire resistant layer side according to an ISO-834 heating curve. In the case of heat treatment, the time required for the temperature of one surface of the refractory layer side to reach 150 ° C. is preferably 30 minutes or more, more preferably 40 minutes or more, and further preferably 80 minutes or more. . More specifically, the time required to reach the temperature of 150 ° C. is preferably 30 minutes to 100 minutes, more preferably 40 minutes to 100 minutes or more, and further preferably 40 minutes to 90 minutes. .

  In addition, the fire-resistant article of the present invention is the Japanese Agriculture and Forestry Standard (all revised: September 25, 2007 Ministry of Agriculture, Forestry and Fisheries Notification No. 1152 and some revisions: June 21, 2012 Ministry of Agriculture, Forestry and Fisheries Notification No. 1587). The shear strength measured by the block shear test method according to (4) is preferably 1.0 MPa or more. More specifically, the shear strength is, for example, 1.0 to 10.0 MPa, and more preferably 1.0 to 5.0 MPa.

  Further, the fire-resistant article of the present invention preferably has a peeling rate (%) measured by a decompression / pressure peeling test in accordance with the above-mentioned Japanese agricultural and forestry standard test method, which is preferably less than 1%. More specifically, the release rate (%) is preferably 0 to less than 1%, more preferably 0 to 0.5%.

<Lamination of fibrous layer and thermoplastic resin layer>
As described above, the fire resistant panel of the present invention includes the fibrous layer and the thermoplastic resin layer.

[Fibrous layer]
As the fibrous layer used in the present invention, those usually used as a paper substrate can be used. The paper base material is advantageous for stable alignment with the wooden core material. Further, the fibrous layer may contain a flame retardant, an inorganic agent, a dry paper strength enhancer, a wet paper strength enhancer, a colorant, a sizing agent, a fixing agent and the like, if necessary. Preferable examples of the paper base material include thin paper, kraft paper and titanium paper. These paper base materials are used to strengthen the interlaminar strength between the paper base fibers or other layers of the paper base material and the paper base material, and in order to prevent flickering, these paper base materials are further provided with an acrylic resin, a styrene-butadiene rubber, Resins such as melamine resin and urethane resin may be added (impregnated with resin after paper making, or internally filled during paper making). For example, inter-paper reinforced paper, resin-impregnated paper, and the like. The fibrous layer used in the present invention also includes those that correspond to non-woven fabrics in terms of classification.

Regarding the basis weight of the fibrous layer, from the viewpoint of structural stability, the basis weight is less than 45 g / m ² , preferably 40 g / m ² or less, more preferably 5 to 40 g / m ² , and still more preferably 10 g / m ² . to 40 g / m ^2, more preferably 10 to 30 g / m ^2, more preferably 10 to 25 g / m ^2, more preferably from 12~23g / m ^2.

  The thickness of the fibrous layer is not particularly limited, but is preferably 5 to 200 μm, more preferably 10 to 100 μm.

[Thermoplastic resin layer]
The thermoplastic resin layer is a layer provided on one surface of the fibrous layer and containing at least a thermoplastic resin.

The basis weight of the thermoplastic resin layer is not particularly limited, and may be 20 g / m ² or less, preferably less than 15 g / m ² , more preferably 14 g / m ² or less, and further preferably 2 a ~14g / ^{m 2,} more preferably from 5~14g / ^{m 2,} more preferably from 8~14g / ^{m 2.}

  The thickness of the thermoplastic resin layer is not particularly limited, but is preferably 5 to 200 μm. More preferably, it is 10 to 100 μm.

  Although the melting point of the thermoplastic resin is not particularly limited, it is preferably 120 ° C. or lower, more preferably 110 ° C. or lower, still more preferably 100 ° C. or lower, in consideration of easiness of production.

The melting point of the thermoplastic resin can be measured by the following method.
A differential scanning calorimeter (DSC analyzer, DSC6220 manufactured by SII Nano Technology Co., Ltd.) is used for measurement under the following conditions.
(I) About 5 mg of the sample is heated from room temperature to 200 ° C. at a temperature rising rate of 30 ° C./minute, and is held for 5 minutes after the temperature rising is completed.
(Ii) Next, the temperature is decreased from 200 ° C. to −100 ° C. at a temperature decrease rate of 10 ° C./min, and after the completion of the temperature decrease, the temperature is maintained for 5 minutes.
(Iii) Next, the temperature was raised from −100 ° C. to 200 ° C. at a heating rate of 10 ° C./min. The temperature at which the melting peak is observed is the melting point.

  The resin in the thermoplastic resin layer is not particularly limited, but from the viewpoint of forming a stable bond with the refractory layer, polyethylene, polyvinyl chloride, polyvinylidene chloride, polyolefin, acrylate, and a mixed resin or copolymer of these. Resins may be mentioned, with polyethylene being preferred. Therefore, the thermoplastic resin layer of the present invention is preferably a polyethylene resin layer.

  The polyethylene used in the thermoplastic resin layer may be a homopolymer of ethylene or a copolymer of ethylene and α-olefin. Examples of the α-olefin used as a comonomer of the copolymer include a linear or branched α-olefin having 3 to 20 carbon atoms, preferably 3 to 8 carbon atoms.

  Examples of the monomer (comonomer) other than the α-olefin that constitutes the ethylene copolymer include vinyl carboxylate, unsaturated carboxylic acid, unsaturated carboxylic acid ester, and the like. Specific examples of vinyl carboxylate include vinyl acetate. Specific examples of the unsaturated carboxylic acid include acrylic acid and methacrylic acid. Specific examples of the unsaturated carboxylic acid ester include methyl acrylate and methyl methacrylate.

  Among these comonomers, vinyl carboxylate is preferable, and vinyl acetate is more preferable, from the viewpoint of imparting fire resistance and bondability with the fire resistant layer.

  Examples of the ethylene copolymer used as the resin component of the thermoplastic resin layer include ethylene-vinyl carboxylate copolymer, ethylene-unsaturated carboxylic acid copolymer, and ethylene-unsaturated carboxylic acid ester copolymer. .. More specifically, ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate copolymer (EMA), Examples thereof include ethylene- (meth) acrylic acid copolymer (EMAA). In addition, in this specification, "(meth) acrylic acid" means acrylic acid or methacrylic acid. These ethylene copolymers may be used alone or in combination of two or more.

  Further, in the ethylene copolymer, the ratio of ethylene and comonomer is not particularly limited, but, for example, as a comonomer content based on the total mass of the ethylene copolymer, usually 5 to 42% by mass, preferably 5 to 35%. A mass% is mentioned.

  Regarding the content of the resin component in the thermoplastic resin layer, it is appropriately set in consideration of the type and combination of the resin components to be used, but from the viewpoint of maintaining the balance between the above-mentioned fire resistance and the provision of the adhesiveness with the fire resistant layer. Therefore, the total amount of the resin component is usually 50 to 100% by mass, preferably 50 to 90% by mass, and more preferably 55 to 85% by mass with respect to the total mass of the thermoplastic resin layer.

  The thermoplastic resin layer may be manufactured using a foaming agent. The foaming agent is not particularly limited and can be selected from known foaming agents. For example, azo compounds such as azodicarbonamide (ADCA) and azobisformamide; organic pyrolyzable foaming agents such as oxybenzenesulfonyl hydrazide (OBSH) and hydrazide compounds such as paratoluenesulfonyl hydrazide; microcapsule type foaming agents; baking soda. And the like inorganic foaming agents. These foaming agents may be used alone or in combination of two or more.

  The content of the foaming agent can be appropriately set according to the type of foaming agent, the expansion ratio, and the like. The foaming agent may be, for example, about 1 to 20 parts by mass with respect to 100 parts by mass of the resin component.

  The thermoplastic resin layer may contain a foaming aid, if necessary, in order to improve the foaming effect of the foaming agent. The foaming aid is not particularly limited, but examples thereof include metal oxides and fatty acid metal salts. More specifically, zinc stearate, calcium stearate, magnesium stearate, zinc octylate, calcium octylate, magnesium octylate, zinc laurate, calcium laurate, magnesium laurate, zinc oxide, magnesium oxide and the like can be mentioned. These foaming aids may be used alone or in combination of two or more. The content of these foaming aids is appropriately set according to the type of foaming aid, the type and content of the foaming agent, and, for example, 0.3 to 10 parts by mass with respect to 100 parts by mass of the resin component. Parts, and preferably about 1 to 5 parts by mass.

  In addition, the thermoplastic resin layer may contain a flame retardancy-imparting agent (inorganic filler), if necessary, in order to impart flame retardancy, suppress penetration, improve surface properties, and the like. The inorganic filler is not particularly limited, and examples thereof include calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, molybdenum compounds and the like. These inorganic fillers may be used alone or in combination of two or more.

  Further, the thermoplastic resin layer may contain additives such as an antioxidant, a cross-linking agent, a cross-linking aid, and a surface treatment agent, if necessary.

  The mass ratio between the fibrous layer and the thermoplastic resin layer as described above (fibrous layer: thermoplastic resin layer) is not particularly limited, but is, for example, 1: 0.45 to 1: 3. However, it is preferably 1: 0.45 to 1: 1, more preferably 1: 0.45 to 1: 0.9, and further preferably 1: 0.45 to 1: 0. 8

  Further, in the fire resistant panel, it is preferable that the fibrous layer and the thermoplastic resin layer are integrally molded to have a laminated structure.

  The thickness of the laminate of the fibrous layer and the thermoplastic resin layer is not particularly limited, but is preferably 10 to 300 μm, more preferably 20 to 200 μm, and further preferably 30 to 150 μm. ..

As the laminate, a commercially available product can be used. Such commercial products include thin paper 14 g / PE 10 g (grammage: paper 14 g / m ² / polyethylene 10 g / m ² , manufactured by Koshihara), tissue paper 20 g / PE 13.8 g (grammage: paper 20 g / m ² / polyethylene 13.8 g). / M ² , manufactured by Koshihara, and 21 g of thin paper / 10 g of PE (basis weight: 21 g / m ^{2 of} paper / 10 g / m ^{2 of} polyethylene, manufactured by Daishowa Paper Co., Ltd.).

<Fireproof layer>
As described above, the fire resistant layer of the present invention contains the polyisocyanurate resin as a main component. Here, "containing as a main component" means containing 50 mass% or more with respect to the total mass of all components of the refractory layer, preferably 70 mass% or more, and more preferably 50 mass% to 100 mass%. , More preferably 70% by mass to 95% by mass, further preferably 75% by mass to 90% by mass.

The polyisocyanurate resin is a resin containing an isocyanurate ring structure obtained by trimerization of polyisocyanate. Usually, it can be obtained by reacting a polyisocyanate in the presence of an isocyanurate-forming (trimerization) catalyst or the like. In the present invention, it is preferable to polyisocyanate the polyisocyanate in the presence of a compound having an isocyanate-reactive active hydrogen (eg, a polyol). The polyisocyanurate resin is preferably solid at room temperature (20 ° C.). Further, the polyisocyanurate resin is preferably a non-foaming material.
In the present invention, a part of the polyisocyanate reacts with a compound having an isocyanate-reactive active hydrogen (urethane reaction). The urethanization and isocyanurate formation may be performed before or after (separately) or simultaneously. The molar ratio of isocyanurate-forming isocyanate groups to urethane-forming isocyanate groups may be 1.0: 0.018 to 0.59, preferably 1.0: 0.02 to 0.50.

  As the polyisocyanate, those generally used for producing a polyurethane resin are used. As such an isocyanate, aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate, modified products thereof (for example, urethane group, carbodiimide group, allophanate group, urea group, buret group, isocyanurate group, or Oxazolidone group-containing modified products) and mixtures of two or more thereof.

  Examples of the aromatic polyisocyanate include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), and polymeric TDI (crude TDI or crude TDI). ), 2,4′- and / or 4,4′-diphenylmethane diisocyanate (MDI), polymethylene polyphenyl polyisocyanate (also referred to as crude MDI or polymeric MDI), polyaryl polyisocyanate (PAPI) and the like.

  Examples of the aliphatic polyisocyanate include aliphatic diisocyanates having 2 to 18 carbon atoms. Specific examples include 1,6-hexamethylene diisocyanate and lysine diisocyanate. Examples of the alicyclic polyisocyanate include alicyclic diisocyanates having 4 to 16 carbon atoms. Specific examples include isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate, norbornane diisocyanate and the like.

  The polyisocyanate is preferably an aromatic polyisocyanate, for example polymethylene polyphenylene polyisocyanate (Polymeric MDI).

  The polyisocyanate as described above is preferably liquid at room temperature (20 to 25 ° C.) from the viewpoint of easily producing a fire resistant panel having a desired shape. The viscosity of the polyisocyanate is, for example, about 1 to 5000 mPa · s at room temperature.

  Generally, a catalyst (isocyanurate-forming catalyst) is used to promote the formation of isocyanurate rings. As an isocyanurate-forming catalyst, for example, aromatic compounds such as tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol, 2,4,6-tris (dialkylaminoalkyl) hexahydro-S-triazine Alkali metal salts of carboxylic acids such as potassium acetate, potassium 2-ethylhexanoate and potassium octylate, and quaternary ammonium salts of carboxylic acids can be used. The amount of the isocyanurate-forming catalyst may be 0.01 to 10 parts by mass based on 100 parts by mass of polyisocyanate.

  In the present invention, it is essential to contain a compound having an isocyanate-reactive active hydrogen. The compound having isocyanate-reactive active hydrogen is preferably a polyol having two or more hydroxyl groups in one molecule.

The number of hydroxyl groups (functionality) in the above-mentioned polyol is 2 to 4 in one molecule. The hydroxyl value is 80 to 2000 mgKOH / g, for example 100 to 1500 mgKOH / g. The molecular weight (number average molecular weight) is 50 to 2000, for example 60 to 1500. Examples of the low molecular weight compound include glycols such as ethylene glycol, propylene glycol, diethylene glycol and glycerin.
Further, it may be a compound in which a hydrogen atom of hydrocarbon is substituted with a hydroxyl group or an amino group, or a compound in which a polyoxyalkylene group is added to this substituted compound, that is, a polyether polyol. The oxyalkylene preferably has 2 to 5 carbon atoms, and examples thereof include propylene oxide and ethylene oxide.
In the present invention, the polyol may be polyester polyol. The composition of the polyester polyol is not limited, and may be aromatic or aliphatic.
The polyether polyol and the polyester polyol may be used alone or in combination of two or more.
The viscosity of the polyol is preferably low, considering that it is mixed with other components to form a polyisocyanurate resin. The viscosity of the polyol is, for example, 100 to 3000 mPa · s / 25 ° C.

In the present invention, it has been found that by using the above-mentioned polyol, the isocyanurate-forming reaction is smoothly promoted, the brittleness of the polyisocyanurate resin produced is improved, and the flame-retardant performance is greatly improved. Further, since these compounds have relatively low viscosities, they also have an effect of facilitating handling such as mixing with various additives and polyisocyanates described later.
The amount of the polyol used is 5 to 30 parts by mass, preferably 6 to 25 parts by mass with respect to 100 parts by mass of the polyisocyanate. When the amount of the polyol used is 30 parts by mass or less, the urethane bond group ratio in the resin produced is low, which is advantageous in increasing the heat resistance.

If necessary, additives such as plasticizers, flame retardants, inorganic fillers, reinforcing agents, surfactants, organic and inorganic pigments, colorants, UV and heat stabilizers, or antifungal or antibacterial agents. Use substances that have an effect.
The additive may react with the isocyanate group of the polyisocyanate, but preferably does not react with the isocyanate group. Therefore, the additive preferably has no active hydrogen that reacts with the isocyanate group.

  Examples of plasticizers are carboxylic acid esters (eg, alkanedicarboxylic acid ester, arylcarboxylic acid ester), and phosphoric acid esters, halogenated phosphoric acid esters (eg, tris (chloroethyl) phosphate, tris (β-chloropropyl) phosphate). ) And so on. Specific examples of the plasticizer include dioctyl phthalate, dibutyl phthalate, dioctyl adipate, tricresyl phosphate and the like. By adding a plasticizer, the brittleness of the polyisocyanurate resin is improved.

  Examples of flame retardants include metal oxides (eg iron oxide, titanium oxide, cerium oxide), metal hydroxides (eg aluminum hydroxide), brominated compounds (eg brominated diphenyl ether, brominated diphenyl). Alkanes, brominated phthalimides), phosphorus compounds (eg red phosphorus, phosphoric acid esters, phosphoric acid ester salts, phosphoric acid amides, organic phosphine oxides), nitrogenous compounds (eg ammonium polyphosphate, phosphazenes, triazines, melamines) Cyanurate). These flame retardancy-imparting agents may be used alone or in combination of plural kinds.

  In the present invention, the flame retardancy can be further improved by using the above-mentioned polyol in combination with these flame retardancy-imparting agents. In that case, the combination of aluminum hydroxide and red phosphorus is particularly effective in selecting the flame retardancy-imparting agent.

  In the present invention, the details of the combination of aluminum hydroxide and red phosphorus, which are particularly effective for improving the flame retardant performance, are as follows. That is, the flame retardancy-imparting agent contains aluminum hydroxide and red phosphorus, and the amount of aluminum hydroxide is 10 to 20 parts by mass with respect to 100 parts by mass of polyisocyanate as a raw material of the polyisocyanurate resin. When the amount is 5 to 10 parts by mass and the mass ratio of aluminum hydroxide and red phosphorus is 1 to 4: 1 and the flame retardancy-imparting agent is within this range, the flame retardancy is significantly improved. Is.

  The red phosphorus used in the present invention is not limited, and various commercially available products can be selected and used. Examples of commercially available products are Nova Red 120, 120UF, 120UFA and Nova Excel 140, 140F manufactured by Rin Kagaku Kogyo Co., Ltd. The aluminum hydroxide used in the present invention is not limited, and various commercially available products can be selected and used. Commercially available products are, for example, C-12, C-31 and C-F-1 manufactured by Sumitomo Chemical Co., Ltd. However, in selecting the flame retardant, in consideration of the need for stirring and mixing with the polyol or polyisocyanate, a shape that inhibits mixing (for example, solid pellet shape) or a shape that increases viscosity (for example, fibrous shape) The flame retardancy-imparting agent of) is not preferable. These choices should be made according to the actual usage. The shape of the flame retardant agent may be, for example, powder, liquid or the like.

Examples of inorganic fillers and reinforcements are barium sulphate, porous diatomaceous earth, whiting, mica, talc, especially glass fibres, glass flakes, glass spheres, aramid fibers or carbon fibres.
The amount of the additive may be 0 to 100 parts by weight, for example 1 to 50 parts by weight, based on 100 parts by weight of polyisocyanate.

  The polyisocyanurate resin in the present invention is a resin containing an isocyanurate ring structure obtained by trimerization of polyisocyanate using an isocyanurate (trimerization) catalyst.

  The amount of the catalyst used is not particularly limited, but is preferably 0.5 parts by mass or more, and more preferably 0.5 to 1.5 parts by mass with respect to 100 parts by mass of polyisocyanate. , More preferably 0.5 to 1.0 part by mass, and further preferably 0.6 to 1.0 part by mass.

  In the present invention, the polyol compound and the polyisocyanate react with each other, and the isocyanate index (NCO Index) at that time is preferably 170 to 5600, more preferably 200 to 5000, and further preferably 500 to 2000. Yes, more preferably 800 to 1800, and even more preferably 1000 to 1500.

  In the present invention, the isocyanate index is a value obtained by multiplying a value obtained by dividing the total number of isocyanate groups in polyisocyanate by the total number of active hydrogen that reacts with a hydroxyl group of poly (mono) ol or an isocyanate group of an amino group by 100. That is, when the number of active hydrogens that react with an isocyanate group and the isocyanate group in polyisocyanate are stoichiometrically equal, the isocyanate index becomes 100.

  The isocyanurate ring structure is particularly preferable for the use of the present invention because it has excellent heat resistance, but it is also possible to introduce other compositions provided that the heat resistance of the resulting resin is not significantly reduced. In the present invention, the urethane linking group is partially introduced by using the above-mentioned specific polyol in combination. In the present invention, by introducing these appropriate urethane bonding groups, the effect of compensating the brittleness of the isocyanurate ring structure is produced, and by suppressing the cracking of the test piece during the combustion test, the fire resistance (flame retardancy) is improved. It is speculated that it is improving. (When the test piece breaks during the combustion test, flame and heat are transmitted quickly through the gap, so the fire resistance (flame retardancy) tends to decrease). Also, other types of bonding groups such as biuret groups and allophanate groups, A carbodiimide group or the like may be introduced to such an extent that the fire resistance is not significantly deteriorated.

  The thickness of the refractory layer is not particularly limited and may be appropriately adjusted depending on desired fire resistance and use of the article, for example, 1 to 200 mm, preferably 2 to 50 mm, and more preferably It is 5 to 45 mm. The thickness of the fireproof layer is preferably substantially constant in one fireproof panel from the viewpoint of avoiding a partial difference in fireproof performance in the fireproof panel.

  At the time of manufacturing the refractory layer, the above-mentioned various raw materials are put into a mold and mixed to cause a polymerization reaction. The reaction temperature (preferably the highest temperature reached) of the mixed liquid during the reaction is not particularly limited, but is preferably 85 ° C. or higher, more preferably 85 to 150 ° C., and further preferably 90 to It is 120 ° C., and more preferably 95 to 115 ° C.

<Surface layer>
The fire resistant panel of the present invention may be provided with a surface layer from the viewpoint of decorativeness or burning margin layer addition, as shown in FIG. The material forming the surface layer is not particularly limited, and examples thereof include wood, paper, plastic, and the like, with wood being preferable.

  The thickness of the surface layer of the present invention is not particularly limited, but is, for example, 0.1 to 100 mm, preferably 0.2 to 50 mm, more preferably 1 to 30 mm.

<Objects with fire resistance>
The fire resistance imparting target is not particularly limited as long as it is a material that can be applied to a member, but it is preferable that at least a part thereof is made of a wood material. More specifically, the fire resistance imparting target can be composed of ordinary wood, solid wood, laminated wood, CLT (Cross Laminated Timber), and the like. The size of the fire resistance imparting target is not particularly limited and may be variously adjusted depending on the application.

<Fireproof panel / Production method of fireproof panel>
In the present invention, as shown in FIGS. 1 to 3, a fibrous layer, a thermoplastic resin layer and a fireproof layer are laminated to form a fireproof panel, which can be used by being joined to a fireproof object.

More specifically, the fire resistant panel can be manufactured by, for example, the following method. 1. A laminate of the fibrous layer and the thermoplastic resin layer (resin-laminated paper) is placed so that the fibrous layer side (paper side) faces the surface of the mold.
2. Various raw materials for manufacturing the refractory layer are mixed by stirring and charged into the above mold.
3. The mold is allowed to stand for a predetermined time to raise the surface temperature of the mold.
4. After the reaction is completed, the refractory layer covered with the laminate is taken out of the mold.

  Further, the method for manufacturing the refractory article is not particularly limited, but the refractory-imparting object and the one surface on the fibrous layer side of the refractory panel are bonded so that the arrangement shown in FIG. 4 is obtained. Can be easily produced. Therefore, according to a preferred embodiment, the method for manufacturing a refractory article includes a step of preparing a refractory panel including a fibrous layer, a thermoplastic resin layer, and a refractory layer in that order, and a fireproof object, The method includes a step of joining one surface on the fibrous layer side of the panel and the fire resistance imparting target.

  An adhesive may be used to join the fire resistance imparting target and the one surface on the fibrous layer side. The type of adhesive is not particularly limited, but from the viewpoint of adhesion of wood materials, preferably a resorcinol-based adhesive, a urethane-based adhesive, an aqueous polymer isocyanate-based adhesive, a urea-based adhesive, a melamine-based adhesive. , Phenol-based adhesives, vinyl acetate-based adhesives, and the like, and more preferably resorcinol-based adhesives. Such an adhesive may form an intermediate layer between the fire resistance imparting target and the fibrous layer.

<Use>
Fire resistant panels can be used in a wide variety of applications where fire resistance is required. By selecting a material having a strength required as a fire resistance imparting target, it can be used as a part of a building member, for example, a pillar, a beam, a wall, a floor, a girder, a bracing, a base or the like.

Hereinafter, the present invention will be described in detail with reference to examples.
In addition, unless otherwise specified, the unit and the measuring method of the present invention comply with the Japanese Industrial Standard (JIS). Further, unless otherwise specified, "part" and "%" mean "part by mass" and "mass%", respectively, and temperature means Celsius.

<Raw materials and their preparation>
The raw materials used in this example were as follows.
[Polyisocyanurate resin raw material]
Polyisocyanate 1: Sumidule 44V20L (manufactured by Sumika Covestrourethane Co., Ltd .; NCO content 31.5%, viscosity 180 mPa · s / 25 ° C, polymeric MDI)
Polyol 1: SBU Polyol 0497 (manufactured by Sumika Covestrourethane Co., Ltd .; hydroxyl value 500 mg KOH / g, number of functional groups 2, molecular weight 220, propylene oxide addition type polyether polyol with viscosity of about 50 mPa · s / 25 ° C.)
Polyol 2: Maximol RLK-085 (manufactured by Kawasaki Kasei Co., Ltd .; polyester polyol with hydroxyl value of 200 mgKOH / g, number of functional groups of 2, molecular weight of 560, viscosity of about 900 mPa · s / 25 ° C.)
Flame retardant 1: Aluminum hydroxide C-31 (Sumitomo Chemical Co., Ltd.)
Flame-retardant agent 2: Novarred 120UFA (red phosphorus) (manufactured by Rin Kagaku Kogyo Co., Ltd.)
Catalyst: Kaorizer No. 14 (Kao Corporation; isocyanurate-forming catalyst; N, N ', N''-tris (3-dimethylaminopropyl) hexahydro-s-triazine)

[adhesive]
Dianol D-300 (resorcinol type) (manufactured by OSHIKA CORPORATION)

[Polyisocyanurate resin stock solutions A and B]
Polyisocyanurate resin stock solutions A and B were prepared according to the following procedure.
1) Polyisocyanate 1 (10 kg), flame retardant 1 (1500 g) and flame retardant 2 (750 g) were weighed and placed in a 20 L container. Next, the contents in the container were sufficiently stirred and mixed with a hand mixer under the conditions of 300 rpm × 3 minutes.
2) Predetermined amounts of polyol 1 and polyol 2 and 180 g of catalyst were placed in a 3 L container. Next, the contents in the container were sufficiently stirred and mixed with a hand mixer under the conditions of 300 rpm × 3 minutes.
3) The mixture obtained in the above 2 was put into a container accommodating the mixture of the above 1, and sufficiently stirred and mixed with a hand mixer under the conditions of 400 rpm × 20 seconds.
4) The mixture obtained in 3 above was used as a polyisocyanurate resin stock solution and poured into a mold for a fireproof panel described later. When the materials 1) and 2) are mixed, the isocyanurate-forming reaction and the urethane-forming reaction start. Therefore, the mixing 3) was performed immediately before forming the polyisocyanurate resin.

The compositions of the polyisocyanurate resin stock solutions A and B are as follows.

[Resin laminated paper]
The resin laminated paper used in the following experiments is as shown in Table 2.

<Test Example 1: Evaluation of Adhesiveness between Polyisocyanurate Resin and Resin Laminated Paper>

<Manufacture of fire resistant panels>
[Test Area 1]
1) An aluminum mold having the following size was prepared and heated to 40 ° C.
Size: 1500 (length) x 50 (width) x 200 (height) mm
2) Using a double-sided tape, a paper layer of the coating material 1 was arranged on both inner sides of the vertical surface of the mold (1500 (length) x 200 (height) mm).
3) The polyisocyanurate resin undiluted solution A prepared in [Preparation of polyisocyanurate resin] was charged into the mold of 2) above (calculated as isocyanate index 1300, density 1.15, and 17.25 kg was charged). ).
4) The mold was kept at 40 ° C. for 30 minutes to accelerate the reaction of the polyisocyanurate resin stock solution. At this time, the surface temperature of the polyisocyanurate resin produced reached the maximum temperature of 105 ° C. due to the isocyanurate-forming reaction and the urethane-forming reaction in the mixed resin stock solution.
5) After 60 minutes, the mold was disassembled to obtain a fire resistant panel in which two surfaces of the polyisocyanurate resin were covered with resin laminated paper.

[Test area 2-5]
A fire resistant panel was manufactured in the same procedure as in the test section 1 except that the coating material 1 was replaced with the coating materials 2 to 5.

[Test area 6-8]
In place of the coating materials 1 to 6 instead of the coating materials 6 to 8, polyethylene of the coating materials 6 to 8 is formed on both inner sides of the vertical surface (1500 (width) x 200 (height) mm) of the mold in the manufacturing process 2) of [Test area 1]. The layers were arranged. Other than that, the fire resistant panel was manufactured in the same procedure as in the test section 1.

[Test area 9-11]
Replacing the coating material 1 with the coating materials 6 to 8, the paper of the coating materials 6 to 8 is formed on both inner sides of the vertical surface of the mold (1500 (width) x 200 (height) mm) in the manufacturing process 2) of [Test area 1]. The layers were arranged. Other than that, the fire resistant panel was manufactured in the same procedure as in the test section 1.

[Test area 12-14]
The coating materials 1 to 9 were replaced with the coating materials 9 to 11, and polyethylene of the coating materials 9 to 11 was formed on both inner sides of the vertical surface of the mold (1500 (width) x 200 (height) mm) in the manufacturing process 2) of [Test area 1]. The layers were arranged. Other than that, the fire resistant panel was manufactured in the same procedure as in the test section 1.

[Test area 15-17]
Instead of the covering materials 1 to 9 to 11, the papers of the covering materials 9 to 11 are formed on both inner sides of the vertical surface of the mold (1500 (width) x 200 (height) mm) in the manufacturing process 2) of [Test area 1]. The layers were arranged. Other than that, the fire resistant panel was manufactured in the same procedure as in the test section 1.

[Test area 18-20]
In Test Groups 6 to 8, fire resistant panels were manufactured by the same procedure except that the polyisocyanurate resin stock solution B was used.

[Adhesion evaluation]
After arranging the fire resistant panels of test sections 1 to 20 in a room at a temperature of 25 ° C. and a humidity of 50% RH for 24 hours, polyisocyanate was used according to JIS K 5600 5-6: 1999 Adhesion (Crosscut method). Adhesion evaluation between the nurate resin and the resin laminated paper was performed.
The judgment was based on the following evaluation criteria.
If there is no peeling in any of the grids: Good adhesion (○)
If any of the grids are peeled off: Poor adhesion (x)

The results are as shown in Table 3.

  In Table 3, when the material of the coating material on the adhesive surface with the polyisocyanurate resin was paper, the adhesiveness was poor (test groups 1-5, 9-11, 15-17). On the other hand, when the material of the coating material on the adhesion surface with the polyisocyanurate resin is polyethylene, using Polyisocyanurate resin undiluted solution A (maximum temperature reached at the time of production is 105 ° C) gives good adhesion. There was (test section 6-8, 12-14). However, when the polyisocyanurate resin undiluted solution B (the highest temperature reached in the production was 80 ° C.) was used, the adhesion was poor (test groups 18 to 20).

<Test Example 2: Evaluation of adhesiveness of fire resistant panel>
According to the test method shown below, the adhesiveness between the fire-resistant panel manufactured in Test Sections 6 to 8 and Test Sections 12 to 14 and Lauan plywood (thickness 15 mm: manufactured by Asahi Corporation) was evaluated.

[Boiling and peeling test]
Test piece: The above fire-resistant panel and a lauan plywood (thickness 15 mm: manufactured by Asahi Co., Ltd.) were bonded together using a resorcinol-based adhesive to form a square body having a side of 75 mm.
Test method: Japanese Agricultural Standards (JAS) for laminated structural veneer (JAS) (Ministry of Agriculture, Forestry and Fisheries Notification No. 1443, September 14, 1988) [Final revision February 27, 2003 Ministry of Agriculture, Forestry and Fisheries Notification No. 237] The test was conducted in accordance with.
The judgment was based on the following evaluation criteria.
Even a slight amount of peeling is observed-poor (x)
No peeling observed-good (○)

[Horizontal shear test]
Test piece: The fire-resistant panel and the lauan plywood were bonded together using a resorcinol-based adhesive to prepare a test piece having a width of 40 mm, a length of 240 mm, and a thickness of 40 mm. At this time, the fire resistant panel had a thickness of 25 mm.
Test method: Japanese Agricultural Standards (JAS) for laminated structural veneer (JAS) (Ministry of Agriculture, Forestry and Fisheries Notification No. 1443, September 14, 1988) [Final revision February 27, 2003 Ministry of Agriculture, Forestry and Fisheries Notification No. 237] The test was conducted in accordance with.
The judgment was based on the following evaluation criteria.
Horizontal shear strength less than 3.0 MPa-poor (x)
Horizontal shear strength of 3.0 MPa or more-Good (○)

The results are as shown in Table 4.

In the test plots 21 to 23, both the boiling peel test and the horizontal shear test were good.
On the other hand, in the test plots 24 to 26 (using resin-laminated paper having a paper basis weight of 45 to 50 g / m ² ), both the boiling peel test and the horizontal shear test were poor.

<Test Example 3: Heating test 1>
[Manufacture of fire resistant panels]
In accordance with the procedure of Test Zone 21, the fireproof panel of Test Zone 6 (that is, the isocyanurate resin stock solution is Liquid A, the resin-laminated paper is thin paper 14g / PE10g, and the thickness is 50mm) is attached to the lauan material. The following heating tests were performed using the combined samples.

  FIG. 5 is a schematic diagram of a heating test. The sample specimen is placed above the strong gas burner NRD10 (natural gas, tip caliber 28 mm, obtained from Tech Jam Co., Ltd.) and tripod 11 so that the fire-resistant panel 1 is on the lower side and the Lauan plywood 9 is on the upper side. Further, in the sample sample, the temperature measurement point 12 on the surface A (burner heating surface) side of the refractory panel 1 and the temperature measurement on the surface B (non-heated surface) are checked so that the temperature change of the sample sample during heating can be confirmed. A thermocouple is attached at location 13. Also, the flame from the gas burner 14 is shown by the dotted line.

  As shown in FIG. 5, the sample sample was placed directly on a tripod, and the lower surface of the sample was heated by a strong gas burner 10 with a flame of 1000 ° C. to 1100 ° C. In the thermocouple attached to the temperature measurement point 12 (Surface A), it was confirmed that the temperature of the sample surface hit by the flame from the burner was 1000 ° C to 1100 ° C. With the thermocouple attached to the temperature measurement location 13 (Surface B), the temperature change of the surface B (non-heated surface) of the refractory panel 1 due to heating was observed. Assuming that 150 ° C. is the upper limit temperature that is considered not to affect the Lauan plywood 9, heating was stopped when the temperature of the surface B (non-heated surface) reached 200 ° C.

The result was as shown in FIG.
It took 80 minutes for the temperature of the surface B (non-heated surface) to reach 150 ° C. Further, during the heating test, the sample specimen maintained its almost initial shape, and no large deformation was observed.

  As shown in FIG. 6, although the heating test method in Test Example 3 is different from the test method (heating according to the standard fire heating temperature curve according to ISO-834) required for a refractory building under the Building Standard Act, The temperature rise curve shows more severe heating conditions than that of ISO-834. Even under such heating conditions, in the sample sample using the fire resistant panel, the time required to reach 150 ° C. on the surface B (non-heated surface) was 80 minutes or more. Further, after the heating was stopped, the sample sample extinguished itself, the spread of flame stopped, and the burning portion was carbonized. From these results, it is considered that the fire-resistant panel constituting the sample sample provided sufficient fire resistance to the lauan plywood.

<Test Example 4: Heating test 2>
A heating test was performed in the same manner as in Test Example 3 except that the thickness of the fire-resistant panel was 25 mm (used aluminum mold size: 1500 (width) x 25 (width) x 200 (height) mm).

The result was as shown in FIG.
It took 40 minutes for the temperature of the surface B (non-heated surface) to reach 150 ° C. Further, during the heating test, the sample specimen maintained its almost initial shape, and no large deformation was observed.

<Test Example 5>
The same tests as in Test Examples 2 to 4 were performed using various members (paper prints, paper wallpaper, plastic wallpaper, cotton fabric) instead of the lauan plywood. As a result, almost the same results as in Test Examples 2 to 4 were obtained. From these results, it was confirmed that the fire resistant panel constituting the sample sample has excellent fire resistance imparting ability and adhesiveness with other members.

1,1 'Fireproof panel 2,2' Fibrous layer 3,3 'Thermoplastic resin layer 4 Fireproof layer 5,5' Laminate 6 Surface layer 7 Fireproof object 8 Fireproof article 9 Lauan plywood 10 Strong gas burner NRD
11 Tripod 12 Temperature measurement point (side A of fireproof panel)
13 Temperature measurement points (side B of fireproof panel)
14 Flame with gas burner A Burner heating surface of refractory panel B Non-heating surface of refractory panel

Claims (13)

A fibrous layer,
A thermoplastic resin layer,
A fire resistant panel having a fire resistant layer in order,
The refractory layer contains a polyisocyanurate resin as a main component and is bonded to the thermoplastic resin layer,
A fire resistant panel, wherein the fibrous layer has a basis weight of less than 45 g / m ² .   When the fire-resistant panel and the fire resistance-imparting target are joined on one side of the fibrous layer side, and the fire-resistant panel is subjected to combustion heat treatment from the fire-resistant layer side in accordance with an ISO-834 heating curve, the fire-resistant layer The refractory panel according to claim 1, wherein the time required for the temperature of one side on one side to reach 150 ° C is 40 minutes or more. The fire resistant panel according to claim 1 or 2, which satisfies at least one of the following (A) and (B):
(A) Japanese Agricultural Standards (JAS) of laminated veneer for structure (JAS Notification No. 1443, September 14, 1988) [Final revision February 27, 2003 Ministry of Agriculture, Forestry and Fisheries Notification 237] No peeling is confirmed in the boiling peeling test according to
(B) The shear strength measured by the horizontal shear test according to the Japanese agricultural and forestry standard test method is 3.0 MPa or more. The fire resistant panel according to claim 1, wherein the amount of the thermoplastic resin layer is 5 g / m ² or more. The polyisocyanurate resin contains a polyisocyanate and an active hydrogen-containing compound as constituent elements,
The active hydrogen-containing compound is one or more polyols having a hydroxyl value of 80 to 2000 mgKOH / g, a functionality of 2 to 4, a molecular weight of 50 to 2000, and having two or more hydroxyl groups. The fire resistant panel according to any one of claims 1 to 4.   The fire resistant panel according to claim 5, wherein the amount of the isocyanurate-forming catalyst used for forming the polyisocyanurate resin is 0.5 part by mass or more based on 100 parts by mass of the polyisocyanate.   7. The refractory panel according to any one of claims 1 to 6, wherein the refractory layer contains aluminum hydroxide, red phosphorus or a combination thereof.   The fire resistant panel according to claim 1, wherein at least a part of the fire resistance imparting target is made of a wood material.   The fire resistant panel according to any one of claims 1 to 8, wherein the fibrous layer and the thermoplastic resin layer are integrally formed.   The fire resistant panel according to any one of claims 1 to 9, wherein the fibrous layer is a paper base layer.   The fire resistant panel according to any one of claims 1 to 10, wherein the thermoplastic resin layer is a resin layer containing at least polyethylene.   The refractory panel according to claim 1, wherein the thermoplastic resin layer has a melting point of 90 ° C. or lower. A method for manufacturing a fire resistant panel according to any one of claims 1 to 12,
A laminate having a fibrous layer and a thermoplastic resin layer, a step of preparing a raw material liquid of a polyisocyanurate resin, and one surface of the laminate on the thermoplastic resin layer side and the raw material liquid of the refractory layer are brought into contact with each other, and A method comprising the step of curing a raw material liquid to form a refractory layer.