JP7617990B2 - Laminate and covering structure - Google Patents

Description

The present invention relates to a novel laminate and a covering structure.

When buildings, civil engineering structures, and other structures are exposed to high temperatures due to fire or other causes, there is a problem in that the physical strength of the steel framework that constitutes the columns, beams, etc. drops rapidly. In response to this problem, a coating structure is known in which the steel framework is covered with a heat-resistant protective coating material, which delays the temperature rise of the steel framework during a fire and suppresses the drop in the physical strength of the steel framework.

One method of covering such a structure is to attach a thermally foamable sheet to a steel frame with an adhesive. Thermally foamable sheets are made by forming a mixture of synthetic resin, flame-retardant foaming agent, polyhydric alcohol, etc. into a sheet shape. They are thin and lightweight under normal conditions, but when the temperature rises due to a fire or the like, they foam and carbonize to form a carbonized insulating layer, which has the effect of providing heat-resistant protection (for example, Patent Document 1, etc.). Such thermally foamable sheets are characterized by being relatively easy to install by simply attaching them with a regular adhesive, not requiring extra space, and being able to achieve a uniform thickness. In addition, the surface side can be colored or painted to improve the design, so there is a high demand for them to be installed in areas that require aesthetics or design.

JP 2002-201733 A

However, the thermally foamable sheet of Patent Document 1 may cause damage such as cracks or chips in the carbonized insulation layer formed due to hot air during a fire or physical impact. In such damaged areas of the carbonized insulation layer, the surface of the steel frame is likely to be exposed, making it difficult to maintain the desired heat-resistant protective performance.

As a result of intensive research into achieving the above object, the inventors came up with the idea of a laminate and covering structure having a thermally foamed layer and a decorative layer on its surface, and having inorganic fiber nonwoven fabric in a specific form on the back side of the thermally foamed layer, and completed the present invention.

That is, the present invention has the following features.
1. A laminate having a thermally foamed layer and a decorative layer on the surface side thereof,
The thermally foamable layer has an inorganic fiber nonwoven fabric on a back surface side thereof, and an adhesive layer on the back surface side of the inorganic fiber nonwoven fabric,
the inorganic fiber nonwoven fabric is laminated so as to be semi-embedded in the thermally foamed layer, and the exposed inorganic fiber nonwoven fabric is semi-embedded in the adhesive layer;
The laminate is characterized in that the decorative layer contains a resin component and granular inorganic particles, and a reinforcing layer is laminated on the back surface of the decorative layer so as to be partially or completely embedded therein.
2. The laminate according to 1., wherein the inorganic fiber nonwoven fabric has a basis weight of 10 to 150 g/ ^m2 .
3. The laminate according to 1. or 2., wherein the inorganic fiber nonwoven fabric is formed by bonding randomly arranged inorganic fibers with a resin component.
4. The laminate according to 1., wherein the reinforcing layer is at least one of a nonwoven fabric, a woven fabric, and a woven fabric, and contains inorganic fibers as a main component.
5. A covering structure having the laminate according to 1. on the surface of a steel frame,
A covered structure characterized in that the inorganic fiber nonwoven fabric is installed facing the steel frame.

The present invention has excellent design and can maintain stable heat-resistant protection when the steel frame is exposed to high temperatures due to a fire or other event.

FIG. 1 is a cross-sectional view showing an example of a laminate of the present invention. FIG. 2 is a cross-sectional view showing an example of a thermally foamable layer used in the present invention. FIG. 2 is a cross-sectional view showing an example of a thermally foamable layer used in the present invention. FIG. 2 is a cross-sectional view showing an example of a decorative layer used in the present invention. FIG. 1 is a cross-sectional view showing an example of a laminate of the present invention. FIG. 1 is a cross-sectional view showing an example of a laminate of the present invention. FIG. 1 is a cross-sectional view showing an example of a laminate of the present invention. FIG. 1 is a cross-sectional view showing an example of a covering structure of the present invention. FIG. 1 is a cross-sectional view showing an example of a covering structure of the present invention. FIG. 1 is a cross-sectional view showing an example of a covering structure of the present invention.

A: Laminate 1, 11, 11a: Thermally foamable layer (thermally foamable sheet)
1a: inorganic fiber nonwoven fabric 1b: adhesive layer 1c: release sheet 2: decorative layer (decorative sheet)
2b: adhesive layer 2c: release sheet 2d: surface protective layer 3: reinforcing layer 13: thermal foam layer (thermal foam sheet)
23: Decorative layer (decorative sheet)
B: Steel frame X: Joint section

The following describes how to implement the present invention.

Figure 1 shows a cross-sectional view of laminate A of the present invention. Laminate A of the present invention has heat-resistant protection properties, design properties, etc., and as shown in Figure 1, is a laminate having thermally foamed layer 1 and decorative layer 2 laminated on its surface, with decorative layer 2 laminated on the surface side of thermally foamed layer 1 so that it can be seen.

(Thermal foam layer)
The thermally foamed layer 1 of the present invention foams when the ambient temperature rises due to a fire or the like and the temperature of the layer reaches a predetermined foaming temperature (preferably 180°C or higher, more preferably 200 to 400°C), and forms a carbonized insulating layer in that temperature range.

The thermal foam layer 1 is preferably formed from a mixed composition containing a resin component, a flame retardant, a foaming agent, a carbonizing agent, and a filler as constituent components. In the event of a fire, these components exert functions such as layer expansion, formation of a carbonized insulating layer, and generation of non-flammable gas through their combined mutual actions, thereby providing excellent insulation and heat-resistant protection.

As the resin component, for example, thermoplastic resins such as vinyl resin, polystyrene resin, polypropylene resin, acrylic resin, acrylic-styrene resin, polyamide resin, polyurethane resin, vinyl acetate resin, ethylene-vinyl acetate resin, etc. can be used. In addition, rubber substances such as natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, chlorinated butyl rubber, ethylene-propylene rubber, chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, multi-vulcanized rubber, silicone rubber, fluororubber, urethane rubber, etc. can also be used. These can be used alone or in combination of two or more. Of these, acrylic resin, acrylic-styrene resin, vinyl acetate resin, ethylene-vinyl acetate resin, etc. are preferably used.

Flame retardants generally exert at least one of the following effects in the event of a fire: dehydrating and cooling effect, non-flammable gas generation effect, and promoting carbonization of thermoplastic resins, and have the effect of suppressing the combustion of resin components. The flame retardants used in the present invention are not particularly limited as long as they have such effects, and known flame retardants can be used. Examples include chlorine compounds, antimony compounds, phosphorus compounds, boron compounds, etc. These can be used alone or in combination of two or more. These may be either uncoated or coated. Among these, phosphorus compounds such as ammonium phosphate and ammonium polyphosphate are preferably used.

The mixing ratio of the flame retardant is preferably 50 to 1000 parts by weight, more preferably 100 to 800 parts by weight, and even more preferably 200 to 600 parts by weight, per 100 parts by weight (solid content) of the resin component. In the present invention, by including a relatively high ratio of flame retardant in this way, good performance in terms of heat resistance protection can be obtained.

The foaming agent generally has the effect of generating a non-flammable gas in the event of a fire, foaming the resin component and carbonizing agent that are carbonizing, and forming a carbonized insulation layer with pores. There are no particular limitations on the foaming agent as long as it has this effect, and any known foaming agent can be used. Examples include melamine and its derivatives, dicyandiamide and its derivatives, azodicarbonamide, urea, and thiourea. These can be used alone or in combination of two or more. Among these, melamine, dicyandiamide, azodicarbonamide, etc. are preferably used.

The mixing ratio of the foaming agent is preferably 5 to 500 parts by weight, more preferably 30 to 200 parts by weight, and even more preferably 40 to 150 parts by weight, per 100 parts by weight (solid content) of the resin component. By keeping the mixing ratio within this range, excellent foaming properties can be achieved, and good performance can be obtained in terms of insulation and heat resistance protection.

Generally, the carbonizing agent has the effect of forming a thick carbonized insulation layer with excellent insulation properties by carbonizing the thermoplastic resin and dehydrating and carbonizing itself during a fire. The carbonizing agent used in the present invention is not particularly limited as long as it has such an effect, and any known carbonizing agent can be used. Examples include polyhydric alcohols such as pentaerythritol, dipentaerythritol, and trimethylolpropane; starch, casein, and the like. The carbonizing agent can be used alone or in combination of two or more kinds. Among these, pentaerythritol, dipentaerythritol, and the like are preferably used.

The mixing ratio of the carbonizing agent is preferably 5 to 600 parts by weight, more preferably 20 to 300 parts by weight, and even more preferably 40 to 150 parts by weight, per 100 parts by weight (solid content) of the resin component. By using this range, the dehydration and cooling effect and the carbonization and insulation layer formation effect can be achieved, and good performance can be obtained in terms of insulation and heat resistance protection.

The filler generally has the effect of maintaining the strength of the carbonized insulation layer. There are no particular limitations on the filler as long as it has such an effect, and known fillers can be used. Examples include carbonates such as calcium carbonate, sodium carbonate, magnesium carbonate, and aluminum oxide; metal oxides such as titanium dioxide and zinc oxide; and inorganic powders such as silica, clay, talc, kaolin, diatomaceous earth, shirasu, mica, wollastonite, silica sand, silica stone, quartz, vermiculite, alumina, and fly ash. These can be used alone or in combination. The shape of the filler is not particularly limited, and examples include spherical, granular, plate-like, rod-like, scaly, and needle-like.

The blending ratio of the filler is preferably 10 to 300 parts by weight, more preferably 20 to 250 parts by weight, and even more preferably 50 to 160 parts by weight, per 100 parts by weight (solid content) of the resin component. By keeping the blending ratio in this range, the strength of the carbonized insulation layer can be maintained, and good performance in terms of heat resistance protection can be obtained.

The thermally foamed layer 1 of the present invention preferably contains a fibrous material in addition to the above components. The inclusion of a fibrous material prevents the carbonized insulation layer from falling off and enhances the effect of maintaining the shape of the carbonized insulation layer. The mechanism of action is not limited to the following, but it is believed that the carbonized insulation layer is formed while the fibrous material is entangled with the inorganic fiber nonwoven fabric 1a laminated on the back side of the thermally foamed layer 1, thereby preventing the carbonized insulation layer from falling off and forming a uniform carbonized insulation layer on the surface of the inorganic fiber nonwoven fabric 1a. As a result, stable heat resistance protection can be obtained.

Examples of fibrous materials include inorganic fibers such as rock wool, glass fiber, silica-alumina fiber, ceramic fiber, potassium titanate fiber, and carbon fiber, and organic fibers such as pulp fiber, polypropylene fiber, vinyl fiber, and aramid fiber. These can be used alone or in combination of two or more. Among these, heat-resistant inorganic fibers and carbon fibers are preferred, and rock wool, glass fiber, and the like are particularly suitable. The fiber length is preferably 1 to 30 mm, more preferably 2 to 20 mm, and the fiber diameter is preferably 1 to 20 μm, more preferably 2 to 15 μm.

The mixing ratio of the fibrous material is preferably 0.1 to 50 parts by weight, and more preferably 0.5 to 30 parts by weight, per 100 parts by weight (solid content) of the resin component.

In addition to the above-mentioned components, the thermally foamed layer 1 may contain various additives as necessary. Any additives may be used as long as they do not significantly impair the effects of the present invention, and examples of such additives include pigments, wetting agents, plasticizers, lubricants, preservatives, antifungal agents, anti-algae agents, antibacterial agents, thickeners, dispersants, defoamers, crosslinking agents, UV absorbers, light stabilizers, antioxidants, diluting solvents, etc.

The thickness of the thermally foamed layer 1 can be set appropriately depending on the application area, etc., but is preferably about 0.2 to 10 mm, and more preferably about 0.3 to 6 mm.

As shown in Fig. 2, the present invention is characterized in that an inorganic fiber nonwoven fabric 1a is laminated on the back side of the thermally foamed layer 1, and the surface on which the inorganic fiber nonwoven fabric 1a is laminated becomes the back side of the laminate A. Examples of the lamination mode of the thermally foamed layer 1 and the inorganic fiber nonwoven fabric 1a include the following:
(I) Semi-embedded [FIG. 2(I)]: the surface of the inorganic fiber nonwoven fabric 1a on the thermally foamed layer 1 side is embedded, and the opposite surface is exposed.
(II) Fully embedded [FIG. 2(II)]: the inorganic fiber nonwoven fabric 1a is entirely embedded in the thermally foamed layer 1;
In the above embodiment (II), the fully embedded inorganic fiber nonwoven fabric 1a is located on the back side of the center of the thickness of the thermally foamed layer 1, and the surface on which the inorganic fiber nonwoven fabric 1a is embedded becomes the back side and is installed facing the steel frame. (Hereinafter, the thermally foamed layer 1 in the part where the inorganic fiber nonwoven fabric 1a is partially or fully embedded (the part biting into the inorganic fiber nonwoven fabric 1a) is also referred to as the "thermally foamed layer 11a", and the other part is also referred to as the "thermally foamed layer 11".)

In the present invention, the above aspects (I) and (II) can enhance the effect of preventing the carbonized insulation layer from falling off, and the effects of the present invention can be fully achieved. In addition, in the case of the above aspect (I), when the insulation layer is installed on a steel frame via an adhesive material described below, the adhesion to the steel frame surface can be enhanced, and the effect of preventing the carbonized insulation layer from falling off can be further enhanced.

The thermal foam layer 1 having the above-mentioned embodiment (I) [Fig. 2(I)] or (II) [Fig. 2(II)] forms a structure having at least two layers, the thermal foam layer 11 and the thermal foam layer 11a, and when exposed to high temperatures due to a fire or the like, the thermal foam layer 11 and the thermal foam layer 11a each form a carbonized insulation layer. In particular, in the carbonized insulation layer formed by the thermal foam layer 11a, it is presumed that the inorganic fibers contained in the inorganic fiber nonwoven fabric 1a act as a carbonized layer reinforcing component, forming a strong carbonized insulation layer. Even if the thermal foam layer 11 is damaged, the carbonized insulation layer formed by the thermal foam layer 11a prevents the steel frame from being exposed, and as a result, stable heat-resistant protection can be maintained without the risk of the steel frame being exposed.

The inorganic fiber nonwoven fabric 1a preferably has a basis weight of 10 to 150 g/m ² (more preferably 15 to 100 g/m ² ). In this case, the thermally foamable layer 1 is easily filled into the gaps between the inorganic fibers of the inorganic fiber nonwoven fabric 1a, and the thermally foamable sheet of the above embodiment (I) or (II) is easily obtained. By satisfying the above basis weight, a strong carbonized insulation layer can be formed near the steel frame, and as a result, there is no risk of the steel frame 1 being exposed, and stable heat-resistant protection can be maintained.

The inorganic fiber nonwoven fabric 1a is a cloth (sheet) made of independent inorganic fibers (formed without weaving), and examples of such fabrics include inorganic fibers arranged in one direction, inorganic fibers arranged in a crossed manner, and inorganic fibers arranged randomly. In the present invention, inorganic fibers arranged randomly are preferred. In addition, examples of methods for bonding inorganic fibers include chemical adhesion using a resin component (chemical bonding), fusion by heating (thermal bonding), mechanical entanglement (needle punching), and sewing (stitch bonding). In the present invention, inorganic fiber nonwoven fabrics in which inorganic fibers are bonded to each other using a resin component (chemical bonding) are preferred.

In this way, by using inorganic fiber nonwoven fabric 1a in which the randomly arranged inorganic fibers are bonded together with a resin component, it is presumed that when exposed to high temperatures due to a fire or the like, the inorganic fibers contained in inorganic fiber nonwoven fabric 1a act as reinforcing components of the carbonized insulation layer formed by thermal foam layer 11a, and furthermore, the resin component has an effect similar to that of a carbonizing agent, so that an even stronger carbonized insulation layer can be formed. As a result, there is no risk of the steel frame being exposed, and more stable heat-resistant protection can be maintained.

The inorganic fibers constituting the inorganic fiber nonwoven fabric 1a are not particularly limited, but examples thereof include rock wool, glass fiber, silica fiber, silica-alumina fiber, carbon fiber, silicon carbide fiber, and the like, as well as metal fine wires such as iron and copper. In the present invention, glass fiber is preferred. The inorganic fibers may also be subjected to some surface treatment. Furthermore, the cross-sectional shape of the fibers is not particularly limited, and any shape such as a circle, a polygon, or a flat shape can be used. Furthermore, the resin component that bonds the inorganic fibers is not particularly limited, but examples thereof include acrylic resin, polyurethane resin, polyester resin, vinyl acetate, polyvinyl alcohol, SBR resin, NBR resin, epoxy resin, and melamine resin. The thickness of such inorganic fiber nonwoven fabric 1a may be set appropriately, but is preferably about 0.1 to 2 mm, and more preferably about 0.15 to 1 mm.

In addition, in the present invention, the inorganic fiber nonwoven fabric 1a may contain organic fibers in addition to inorganic fibers, so long as the effects of the present invention are not impaired. Examples of organic fibers include pulp fibers, polyester fibers, polypropylene fibers, aramid fibers, vinylon fibers, polyethylene fibers, polyarylate fibers, PBO fibers, nylon fibers, acrylic fibers, polyvinyl chloride fibers, and cellulose fibers. The organic fibers may be those that melt and become liquid in a temperature range of about 150°C, but it is preferable that they do not melt in such a temperature range. Two or more of these may also be used in combination.

The thermally foamed layer 1 may be produced by any method as long as the inorganic fiber nonwoven fabric 1a is laminated so as to be partially or completely embedded in the thermally foamed layer 1. For example, the following methods may be mentioned.
A method in which a mixed composition of the components of the thermally foamed layer 1 is poured into a mold, and then the inorganic fiber nonwoven fabric 1a is laminated thereon, and the mixture is dried and then removed from the mold.
A method in which a mixed composition of the components constituting the thermally foamed layer 1 is prepared, and then the mixed composition is applied to the inorganic fiber nonwoven fabric 1a and laminated.
A method in which the components of the thermally foamable layer 1 are kneaded using a kneader or the like to prepare a kneaded product (hereinafter also referred to as "kneaded product for thermally foamable layer"), and then the kneaded product is laminated on the inorganic fiber nonwoven fabric 1a and processed into a sheet using a rolling roller or the like.
The thermally foamable layer 1 of the present invention is preferably a sheet-like thermally foamable layer (hereinafter also referred to as "thermally foamable sheet") obtained by the above-mentioned method or the like.

As shown in FIG. 3, the thermally foamable layer 1 (thermally foamable sheet) of the present invention can have an adhesive layer 1b laminated on the outer side (back side) of the inorganic fiber nonwoven fabric 1a [FIG. 3(I)]. In this case, the inorganic fiber nonwoven fabric 1a is laminated so as to be semi-embedded in the thermally foamable layer 1 (above (I)), and it is preferable that the exposed inorganic fiber nonwoven fabric 1a is semi-embedded in the adhesive layer 1b. This can further enhance the effects of the present invention. Furthermore, the surface of the adhesive layer 1b can be covered with a release sheet 1c [FIG. 3(II)]. By using such a thermally foamable layer 1, the work efficiency can be improved.

The method of laminating the adhesive layer 1b and the release sheet 1c is not particularly limited, but examples include a method of applying an adhesive to the inorganic fiber nonwoven fabric 1a side of the thermally foamed layer 1 and laminating the release sheet 1c on top of that, or a method of applying an adhesive to the release sheet 1c in advance to form the adhesive layer 1b, and laminating the adhesive layer 1b on the inorganic fiber nonwoven fabric 1a side of the thermally foamed layer 1.

The adhesive layer 1b may be formed from known adhesives such as water-dispersible, water-soluble, and solvent-based adhesives made mainly from acrylic resin, silicon resin, epoxy resin, vinyl resin, phenolic resin, polyester resin, urethane resin, and paraffin. If necessary, the adhesive may contain a flame retardant, foaming agent, carbonizing agent, filler, and the like that are blended in the above-mentioned thermally foamable resin sheet. In the present invention, the adhesive also includes a pressure-sensitive adhesive. The adhesive layer 1b preferably has a thickness of 25 to 200 μm, or a coating amount of 0.05 to 0.5 kg/ ^m2 .

The release sheet 1c protects the adhesive layer 1b during storage or transportation of the thermally foamable layer 1, and can be easily peeled off from the adhesive layer 1b when the thermally foamable sheet is used. Such a release sheet can be a known one, such as paper or film coated or impregnated with a release agent such as silicone, wax, or fluorine resin, or a synthetic resin film such as polypropylene or polyethylene that does not contain the release agent and has releasability by itself.

(Decorative Layer)
The decorative layer 2 of the present invention is not particularly limited as long as it can impart design properties, but is preferably formed from a composition containing a resin component and colored powder or granules (hereinafter also referred to as a "composition for decorative layer").

The resin component mainly serves to fix the colored powder particles. Various synthetic resins can be used as such resin components. Examples of the types of resin include acrylic resin, silicone resin, acrylic silicone resin, fluororesin, vinyl acetate resin, acrylic-vinyl acetate resin, vinyl chloride resin, urethane resin, acrylic urethane resin, epoxy resin, alkyd resin, polyvinyl alcohol resin, polyester resin, ethylene resin, polyvinyl alcohol, cellulose and its derivatives, and composites of these. Such synthetic resins may have the property of causing a crosslinking reaction.

The glass transition temperature of the resin component is preferably -60°C to 60°C, more preferably -40°C to 30°C, and even more preferably -30°C to 20°C. Within such a range, it is possible to impart appropriate flexibility. The glass transition temperature is a value calculated using Fox's formula.

The colored powders and granules serve to impart color, patterns, etc. to the decorative layer. As such colored powders and granules, for example, known materials such as color pigments, extender pigments, and aggregates can be used, and these can be used alone or in combination of two or more kinds.

The decorative layer 2 of the present invention preferably contains granular inorganic particles as the colored powder. As a result, the granular inorganic particles are fixed by the resin component, and the decorative layer 2 exhibits a color tone based on the granular inorganic particles and a design due to the connection (aggregation) of the granular inorganic particles is obtained. That is, the color tone of the decorative layer 2 is based on the color tone of the granular inorganic particles. The decorative layer 2 may also have a plurality of colored regions having different colors. In this case, the decorative layer 2 can be formed by hardening a plurality of decorative layer compositions having different colors. Such a decorative layer 2 not only enhances the design due to the granular inorganic particles, but also has excellent surface strength, so that it can prevent dents and scratches on the thermal foaming layer 1. Furthermore, the granular inorganic particles can enhance heat resistance protection. Although the mechanism of action is not limited, it is considered that the heat reflectivity, heat resistance, etc. of the granular inorganic particles can suppress a sudden rise in the steel frame temperature until the foaming start temperature of the thermal foaming layer 1 is reached under high temperatures such as during a fire.

As the granular inorganic particles, either natural or artificial products can be used as long as the base material is inorganic. As the granular inorganic particles, an embodiment containing at least granular colored inorganic particles is preferable. As such granular colored inorganic particles, particularly opaque ones with a light transmittance of less than 3% are preferable, and those with a light transmittance of 2% or less are more preferable. Specific examples of such granular colored inorganic particles include marble, granite, serpentine, granite, sandstone, slate, basalt, gabbro, diorite, andesite, limestone, and crushed products thereof, crushed ceramics, crushed ceramics, metal particles, etc. In addition, fluorite, galespar, feldspar, silica, silica sand, and crushed products thereof, crushed glass, glass beads, etc., colored to satisfy the above conditions can also be used.

The light transmittance mentioned above is the total light transmittance measured by a turbidimeter. In this measurement, a sample of granular inorganic particles is filled into a transparent glass cell with an inner thickness of 5 mm, and then water is gradually added, after which air bubbles in the cell are removed by vibration.

In addition to the above-mentioned granular colored inorganic particles, granular transparent inorganic particles may also be included. The use of such granular transparent inorganic particles is preferable in terms of improving aesthetics. Suitable granular transparent inorganic particles have a light transmittance of 3% or more (more preferably 3 to 50%, and even more preferably 10 to 30%). Examples of granular transparent inorganic particles include silica, sappanite, feldspar, quartz stone, etc., and crushed products thereof, crushed glass, glass beads, etc., and both colorless and colored types can be used as long as they satisfy the above-mentioned light transmittance.

The particle size of the granular inorganic particles is preferably 0.01 mm to 5 mm, more preferably 0.02 mm to 2 mm, and even more preferably 0.03 to 0.8 mm. The range of design possibilities can be expanded by combining various granular inorganic particles with different particle sizes. The particle size of the granular inorganic particles is measured by sieving using a metal mesh sieve as specified in JIS Z8801-1:2000.

The mixing ratio of the resin component and the colored powder is preferably 2 to 50 parts by weight (more preferably 3 to 30 parts by weight, even more preferably 4 to 20 parts by weight, and most preferably 5 to 19 parts by weight) of the resin component per 100 parts by weight of the total amount of the colored powder, calculated as solid content. With such a ratio, it is easy to obtain a decorative layer 2 consisting of a connected body (aggregate) of the colored powder. As a result, a sudden temperature rise is suppressed under high temperatures such as during a fire, and gases generated by the expansion of the thermal expansion layer 1 can be efficiently transmitted, forming a uniform carbonized insulation layer without impeding the expansion.

The cosmetic layer composition may contain other components (additives) as necessary, as long as they do not significantly impair the effects of the present invention. Examples of such components include plasticizers, anti-algae agents, antibacterial agents, deodorants, adsorbents, flame retardants, thickeners, defoamers, crosslinking agents, coloring pigments, extender pigments, photoluminescent pigments, phosphorescent pigments, fluorescent pigments, aggregates, fibers, UV absorbers, light stabilizers, antioxidants, catalysts, etc.

The decorative layer 2 of the present invention preferably has an uneven pattern on its surface. The pattern of the decorative layer 2 is not particularly limited, and may have a variety of shapes, such as a stone-like pattern, a wood-grain pattern, and a joint pattern. The thickness of the decorative layer 2 is preferably 0.2 to 30 mm (more preferably 0.5 to 20 mm).

The decorative layer 2 may be formed by applying the above-mentioned composition for the decorative layer, but in the present invention, it is preferable to use a composition that has been molded into a sheet shape in advance (hereinafter, also referred to as a "decorative sheet"). The method for manufacturing the decorative sheet is not particularly limited, but examples include a method in which the composition for the decorative layer is poured into the inner surface of a mold and then removed after hardening.

As shown in Figure 4, the decorative layer 2 (decorative sheet) of the present invention can have an adhesive layer 2b laminated on the back surface, if necessary [Figure 4(I)]. Furthermore, the surface of the adhesive layer 2b can be covered with a release sheet 2c [Figure 4(II)]. By using such a decorative layer 2, work efficiency can be improved.

The method of laminating the adhesive layer 2b and the release sheet 2c is not particularly limited, but examples include a method of applying an adhesive to the back surface of the decorative layer 2 and laminating the release sheet 2c on top of it, or a method of applying an adhesive to the release sheet 2c in advance to form an adhesive layer 2b and laminating the back surface of the decorative layer 2 on the adhesive layer 2b. The adhesive and release sheet 2c that form the adhesive layer 2b can be the same as those that can be used for the thermally foamable sheet 1 described above.

Furthermore, the decorative layer 2 of the present invention may have a clear layer 2d [Fig. 4 (III)] on the outermost surface for the purpose of surface protection (water resistance, weather resistance, etc.), contamination prevention, etc. A known clear paint can be used as the clear layer.

It is preferable to laminate a reinforcing layer 3 inside the laminate A of the present invention. This can prevent cracks and falling off of the carbonized insulation layer that is formed. Furthermore, it can also improve the physical properties of the laminate A, such as flexibility and strength.

(Reinforcing layer)
Examples of the reinforcing layer 3 include nonwoven fabrics, woven fabrics, and woven fabrics. These may be used in combination of two or more kinds. Furthermore, two or more layers may be laminated as long as the present invention is not adversely affected.
In the present invention, the term "nonwoven fabric" refers to a fabric (sheet) made by entangling or bonding individual fibers using heat or adhesives as described above (a fabric formed without weaving). The term "braided fabric" refers to a laminated and bonded fabric made by entangling a group of fiber threads aligned in one direction with a group of fiber threads aligned in a different direction vertically, horizontally, or diagonally. The structure of the woven fabric may be any structure having a mesh structure, and may include multi-axis woven fabrics such as biaxial woven fabrics, triaxial woven fabrics, and quadraxial woven fabrics depending on the number of axes of the fiber threads. The term "woven fabric" refers to a fabric formed by a group of fiber threads in the same manner as the woven fabric, and woven by interlacing warp threads and weft threads vertically. The structure of the woven fabric may include plain weave, twill weave, satin weave, double warp weave, double weft weave, double warp and weft weave, pile weave, twill weave, patterned weave, etc.

In the present invention, it is preferable to use a woven fabric and/or a woven material as the reinforcing layer 3. In addition, the woven fabric and/or the woven material preferably has a warp and weft density of 3 threads/25 mm or more and 20 threads/25 mm or less (more preferably 5 threads/25 mm or more and 18 threads/25 mm or less), and a basis weight of 5 to 150 g/m ² (more preferably 8 to 130 g/m ² , more preferably 10 to 100 g/m ² ). When such a range is satisfied, the foaming of the thermally foamable layer 1 is not inhibited, and a uniform heat insulating layer can be formed.

Furthermore, it is preferable to use a woven fabric (more preferably a tangled fabric) as the reinforcing layer 3. This can further enhance the effect of preventing cracks and falling off of the carbonized insulation layer formed by the foaming of the thermal foaming layer 1 under high temperatures such as during a fire. Although the mechanism of action is not limited to the following, the fabric is woven by intersecting the warp threads and weft threads up and down, so there is little misalignment or deformation. As a result, it is believed that the carbonized insulation layer can be stably supported and cracks and falling off can be prevented. Furthermore, a tangled fabric is a fabric in which the weft threads are woven while the warp threads are intertwined with each other (a fabric with a mesh like the weft threads are tied with the warp threads), and has extensibility in the diagonal direction. Therefore, it is believed that the above effect can be exerted without inhibiting the foaming of the thermal foaming layer 1, and the effect of the present invention can be further enhanced.

The fibers used in the reinforcing layer 3 are not particularly limited, and various fibers such as organic fibers and inorganic fibers that can be used in the inorganic fiber nonwoven fabric 1a described above can be used. It is preferable that the reinforcing layer 3 contains, as a main component, inorganic fibers (especially glass fibers) that have excellent heat resistance and are not easily melted even at high temperatures.

The thickness of the reinforcing layer 3 is preferably 0.01 to 3 mm (more preferably 0.05 to 1 mm). By keeping it in this range, the effects of the present invention are more easily obtained.

(Laminate)
The laminate A of the present invention is a laminate having a thermally foamed layer 1 and a decorative layer 2 laminated on its surface, as shown in Fig. 1, in which an inorganic fiber nonwoven fabric 1a is provided on the back side of the thermally foamed layer 1, and the decorative layer 2 is laminated on the front side so that it can be visually recognized. When laminating the thermally foamed layer 1 and the decorative layer 2, for example, they can be laminated by the following method.
A method in which a composition for a decorative layer is applied to the surface of a thermally foamed layer 1 and then a decorative layer 2 is laminated thereon.
A method in which a decorative layer 2 (decorative sheet) prepared by previously molding a composition for a decorative layer is laminated on the surface of a thermally foamed layer 1 via an adhesive.

When the reinforcing layer 3 is laminated on the laminate A of the present invention, the reinforcing layer 3 can be laminated at any position inside the laminate except the back surface of the thermally foamed layer 1 and the front surface of the decorative layer 2. Examples of the manner in which the reinforcing layer 3 is laminated include a manner in which the reinforcing layer 3 is laminated between the thermally foamed layer 1 and the decorative layer 2, or a manner in which the reinforcing layer 3 is laminated so as to be partially or completely embedded on the front surface side of the thermally foamed layer 1 and/or the back surface side of the decorative layer 2.

5 to 7 show an example of the laminate A in which the reinforcing layer 3 is laminated.
5 shows an embodiment in which the reinforcing layer 3 is interposed between the thermally foamed layer 1 and the decorative layer 2. In this case, the reinforcing layer 3 is not embedded in either the thermally foamed layer 1 or the decorative layer 2.
Such a laminate can be laminated, for example, by the following method.
A method in which the reinforcing layer 3 is bonded to the surface of the thermally foamed layer 1 via an adhesive, and then the decorative layer composition is applied to laminate the decorative layer 2.
A method in which a reinforcing layer 3 is bonded to the surface of a thermally foamed layer 1 via an adhesive, and then a decorative layer 2 (decorative sheet) formed in advance from a decorative layer composition is laminated thereon via an adhesive.

Fig. 6 shows an embodiment in which the reinforcing layer 3 is laminated so as to be partially embedded [Fig. 6(I)] or fully embedded [Fig. 6(II)] on the surface side of the thermally foamed layer 1, and the decorative layer 2 is laminated on the surface side of the reinforcing layer 3. In the embodiment of Fig. 6(II), the fully embedded reinforcing layer 3 is located on the surface side with respect to the center of the thickness of the thermally foamed layer 1.
For such a laminate, it is preferable to use a thermally foamed layer 13 (thermally foamable sheet 13) in which the reinforcing layer 3 is pre-laminated so as to be partially or completely embedded on the surface side of the thermally foamed layer 1, and the laminate can be laminated, for example, by the following method.
A method in which a composition for a decorative layer is applied to the surface of the thermally foamed layer 13 and then the decorative layer 2 is laminated thereon.
A method in which a decorative layer 2 (decorative sheet) prepared by previously molding a composition for a decorative layer is laminated on the surface of a thermally foamed layer 13 via an adhesive.

The thermally foamable layer 13 (thermally foamable sheet 13) can be produced, for example, by the following method.
A method in which the reinforcing layer 3 is laid in a formwork, then a mixed composition of the components of the thermally foamable layer 1 is poured in, and then the inorganic fiber nonwoven fabric 1a is laminated thereon, followed by drying and then demolding.
A method in which a mixed composition of the components of the thermally foamed layer 1 is prepared, then applied to the inorganic fiber nonwoven fabric 1a, and then the reinforcing layer 3 is laminated thereon.
A method in which the components of the thermally foamed layer 1 are kneaded by a kneader or the like to prepare a kneaded mixture, and then the kneaded mixture is filled between the inorganic fiber nonwoven fabric 1a and the reinforcing layer 3, and processed into a sheet shape by a pressure roller or the like.

Fig. 7 shows an embodiment in which a decorative layer 2 is laminated on the front side of a thermally foamed layer 1, and a reinforcing layer 3 is laminated so as to be partially embedded [Fig. 7(I)] or completely embedded [Fig. 7(II)] on the back side of the decorative layer 2. In the embodiment of Fig. 7(II), the completely embedded reinforcing layer 3 may not be exposed on the front side of the decorative layer 2, but it is preferable that it is located on the back side of the thickness center of the decorative layer 2.
Such a laminate can be laminated, for example, by the following method.
A method in which a reinforcing layer 3 is placed on the surface of a thermally foamed layer 1, a composition for a decorative layer is applied, and then a decorative layer 2 is laminated.
A method of laminating a decorative layer 23 (decorative sheet 23) having a reinforcing layer 3 pre-laminated on the back side of the decorative layer 2 so as to be partially or completely embedded on the surface of the thermally foamed layer 1 via an adhesive.

The decorative layer 23 (decorative sheet 23) can be produced, for example, by the following method.
A method of applying a composition for a decorative layer to the reinforcing layer 3.
A method in which the decorative layer composition is poured into a formwork, the reinforcing layer 3 is then laminated, and the composition is removed after drying.
A method in which the decorative layer composition is poured into a formwork, the reinforcing layer 3 is laminated, and then the decorative layer composition is poured again, and the formwork is removed after drying.

The laminate A of the present invention is particularly preferably in the form shown in FIG. 7. In this case, the effect of preventing cracks, falling off, etc. of the carbonized insulation layer formed is enhanced, and better heat resistance protection can be achieved. Furthermore, the physical properties of the laminate A, such as flexibility and strength, can also be improved. The thickness of the laminate A is preferably 1.2 to 65 mm (more preferably 1.5 to 50 mm).

(Covering structure)
The covered structure of the present invention has the above-mentioned laminate A on the surface of a steel frame.
An example of the covered structure of the present invention is shown in Fig. 8. As shown in Fig. 8, the covered structure of the present invention is a covered structure in which a thermally foamed layer 1 and a decorative layer 2 are laminated on a steel frame B, and the present invention is characterized in that the inorganic fiber nonwoven fabric 1a of the thermally foamed layer 1 is covered facing the steel frame B, and the decorative layer 2 is disposed on the surface side. Such a covered structure is covered so that the decorative layer 2 can be seen, and is excellent in design and can maintain stable heat-resistant protection when the steel frame is exposed to high temperatures due to a fire or the like.

In addition, Figure 9 shows another example of the coated structure of the present invention. As shown in Figure 9, the coated structure of the present invention is a coated structure in which a thermally foamed layer 1, a reinforcing layer 3, and a decorative layer 2 are laminated on a steel frame B, and is characterized in that the inorganic fiber nonwoven fabric 1a of the thermally foamed layer 1 is coated facing the steel frame B, and the decorative layer 2 is arranged on the surface side. This type of coated structure is coated so that the decorative layer 2 can be seen, and is excellent in design and can maintain more stable heat-resistant protection when the steel frame is exposed to high temperatures due to a fire, etc.

The steel frame B is not particularly limited, but examples include square, round, H-shaped, I-shaped, and other steel frame materials, which are used as columns, beams, etc. that make up the structure.

Examples of the coating method for such a coated structure include the following methods.
(1) A method of covering a steel frame B with a thermal foaming layer 1 (reinforcing layer 3) and a decorative layer 2 in that order.
(2) A method of covering the steel frame B with a thermal foaming layer 13 and a decorative layer 2 in that order.
(3) A method of covering the steel frame B with a thermal foam layer 1 and a decorative layer 23 in that order.
(4) A method of covering a steel frame B with a laminate A in which a thermal foam layer 1, (reinforcing layer 3) and decorative layer 2 are laminated in advance.
In the above methods (1) to (4), when the thermally foamed layer 1 (thermally foamed layer 13, or laminate A) is coated on the steel frame B, the surface (rear surface) on which the inorganic fiber nonwoven fabric 1a is laminated is placed facing the steel frame B.

Specific methods for covering the steel frame B with the thermally foamed layer 1 (thermally foamed layer 13, or laminate A) include, for example, the following methods.
(a) The thermally foamed layer 1 (thermally foamed layer 13, or laminate A) is wrapped around a steel frame B with the inorganic fiber nonwoven fabric 1a side facing, and the ends are fixed with fixing members.
(b) After applying an adhesive to the surface of the steel frame B and/or the surface of the inorganic fiber nonwoven fabric 1a, the thermally foamed layer 1 (thermally foamed layer 13, or laminate A) is attached with the inorganic fiber nonwoven fabric 1a side facing the steel frame B.
(c) In the case where the thermally foamed layer 1 (thermally foamed layer 13, or laminate A) has an adhesive layer 1b and a release sheet 1c, the release sheet 1c is peeled off to expose the adhesive layer 1b, and the exposed adhesive layer 1b is attached to a steel frame B (to which an adhesive may be applied in advance).
The covering structure of the present invention is suitable for directly (adhering closely) covering (covering by adhesion) these steel frames B.

In (i) above, the fixing members for fixing the ends of the thermally foamed layer 1 (thermally foamed layer 13, or laminate A) are not particularly limited, but for example, fasteners such as washers (screws), tackers, welding pins, bolts, tapping screws, etc. can be used. In addition, the materials for these are preferably non-flammable, such as metals.

When applying the adhesive to the steel frame B and/or the surface of the inorganic fiber nonwoven fabric 1a, tools such as a brush, roller, trowel, spatula, spray, etc. can be used. The amount of adhesive applied may be set appropriately, but is preferably 0.1 to 0.5 kg/ ^m2 . When attaching the thermally foamed layer 1 (thermally foamed layer 13, or laminate A) to the steel frame B, it is preferable to apply pressure. When applying pressure, a pressing tool such as a roller or trowel can be used as necessary.

In the above methods (1) to (4), the method for laminating each layer is the same as the manufacturing method for the laminate shown in Figures 5 to 7.

As a method for covering the covered structure of the present invention, the above method (3) is particularly suitable. In this case, workability and finish are excellent. Furthermore, as shown in FIG. 10, it is preferable to provide a joint portion X. The location of the joint portion X is not particularly limited, but it is preferably a location other than the corners of the steel frame B. By providing the joint portion X, the thermal foaming layer 1 can be efficiently foamed, further enhancing the effect of the present invention.

The following examples will clarify the features of the present invention.

<Production of thermally foamable layer (thermally foamable sheet)>
・Kneaded material for thermal foaming layer 1
A mixture mainly composed of 100 parts by weight of thermoplastic resin (acrylic resin), 90 parts by weight of melamine, 90 parts by weight of dipentaerythritol, 320 parts by weight of ammonium polyphosphate, and 100 parts by weight of titanium oxide was kneaded in a pressure kneader set at a temperature of 120°C to prepare a kneaded material 1 for a thermally foamed layer.
・Kneaded material for thermal foaming layer 2
A mixture mainly composed of 100 parts by weight of thermoplastic resin (acrylic resin), 90 parts by weight of melamine, 90 parts by weight of dipentaerythritol, 320 parts by weight of ammonium polyphosphate, 100 parts by weight of titanium oxide, and 4 parts by weight of glass fiber (fiber diameter 7 μm, fiber length 6 mm) was kneaded in a pressure kneader set at a temperature of 120° C. to prepare a kneaded material 2 for a thermally foamed layer.

Nonwoven fabric 1: inorganic fiber nonwoven fabric in which glass fibers are randomly arranged and bonded with polyvinyl alcohol resin, basis weight 25 g/m ² , thickness 0.2 mm
Nonwoven fabric 2: inorganic fiber nonwoven fabric in which glass fibers are randomly arranged and bonded with polyvinyl alcohol resin, basis weight 50 g/m ² , thickness 0.4 mm
Nonwoven fabric 3: inorganic fiber nonwoven fabric in which glass fibers are randomly arranged and bonded with polyvinyl alcohol resin, basis weight 140 g/m ² , thickness 1.0 mm
Nonwoven fabric 4: polyester (organic fiber) nonwoven fabric in which polyester long fibers are randomly arranged and bonded with polyvinyl alcohol resin, basis weight 60 g/m ² , thickness 0.5 mm

The kneaded material for the thermally foamable layer was laminated on the nonwoven fabric in the combination shown in Table 1, and the nonwoven fabric was processed into a sheet shape using a rolling roller so that the nonwoven fabric was (I) semi-embedded or (II) fully embedded, to produce eight types of thermally foamable sheets (450 mm x 1200 mm) with a thickness of 2 mm.
In addition, the kneaded material for the thermally foamable layer was formed into a sheet shape using a rolling roller, and then laminated to the thermally foamable layer and nonwoven fabric via an acrylic adhesive to produce one type of thermally foamable sheet (450 mm x 1200 mm) [(III) No embedding].

(Reinforcing layer)
Inorganic fiber fabric: glass fiber, leno weave, warp density 10x2 threads/25 mm, weft density 10 threads/25 mm, basis weight 60 g/m ² , thickness 0.2 mm

(Composition for decorative layer 1)
Composition 1 for decorative layer was prepared by uniformly mixing 200 parts by weight of acrylic resin emulsion (solid content 50% by weight), 1,000 parts by weight of granular colored inorganic particles (brown) having an average particle size of 150 μm, water, and additives (thickener, defoamer, etc.) in a standard manner.
(Composition for decorative layer 2)
Composition 2 for cosmetic layer was produced in the same manner as above, except that the granular colored inorganic particles of Composition 1 for cosmetic layer were replaced with granular colored inorganic particles (brown:black=1:4) having an average particle size of 100 μm.

<Production of decorative layer (decorative sheet) 1>
The decorative layer compositions 1 and 2 were poured into a wood grain mold, cured at 23° C. for 24 hours, and then demolded to produce a wood grain sheet (600 mm×1200 mm, thickness 3 mm). Next, a clear coating was applied to the outermost surface at a coating amount of 0.3 kg/ ^m2 .

<Production of decorative layer (decorative sheet) 2>
The decorative layer compositions 1 and 2 were poured into a wood grain mold, the reinforcing layer (I) was laminated so as to be semi-embedded, and the mold was removed after curing for 24 hours at 23°C to produce a wood grain sheet (600 mm x 1200 mm, thickness 3 mm). Next, a clear coating was applied to the outermost surface at a coating amount of 0.3 kg/ ^m2 .

(Manufacturing of test specimens)
The above nine types of thermally foamable sheets and the above two types of decorative sheets were used to produce the following covered structures.
The prepared thermally foamable sheet 1 was attached to a square steel frame (300 mm x 300 mm, thickness 9 mm, length 1200 mm) via an adhesive so that the inorganic fiber nonwoven fabric side faced the square steel frame, and then a decorative sheet was attached via an adhesive to form a covered structure, which was used as a test specimen.

The prepared specimens were subjected to a one-hour heating test according to the standard heating curve of ISO834. 20 minutes after the start of the test (at about 280°C), an impact was applied to a part of the carbonized insulation layer in the process of being formed to cause a crack, and the test was continued. The temperature of the steel frame (steel temperature) at this time was measured, and after the test, the shape of the carbonized insulation layer other than the cracked part and the shape of the carbonized insulation layer at the cracked part were evaluated. The evaluation criteria are as follows. The results are shown in Table 1.
(Evaluation 1: Steel temperature)
(Steel temperature)
AA: Less than 475°C A: 475°C or more and less than 500°C B: 500°C or more and less than 525°C C: 525°C or more and less than 550°C D: 550°C or more (Evaluation 2: Shape of carbonized insulation layer)
The shape of the carbonized insulation layer other than the cracked portion was visually confirmed. The evaluation criteria were a five-level evaluation (excellent: AA>A>B>C>D: poor), with "AA" being a uniform carbonized insulation layer without any falling off and "D" being a layer in which the carbonized insulation layer had fallen off.
(Evaluation 3: Carbonized insulation layer at cracked area)
The shape of the carbonized insulation layer at the cracked area was visually confirmed. The evaluation criteria were a five-level evaluation (excellent: AA>A>B>C>D: poor), with "AA" being the one where the carbonized insulation layer was formed and "D" being the one where the steel frame was exposed.

Claims (5)

A laminate having a thermally foamed layer and a decorative layer on the surface side thereof,
The thermally foamable layer has an inorganic fiber nonwoven fabric on a back surface side thereof, and an adhesive layer on the back surface side of the inorganic fiber nonwoven fabric,
the inorganic fiber nonwoven fabric is laminated so as to be semi-embedded in the thermally foamed layer, and the exposed inorganic fiber nonwoven fabric is semi-embedded in the adhesive layer;
The laminate is characterized in that the decorative layer contains a resin component and granular inorganic particles, and a reinforcing layer is laminated on the back surface of the decorative layer so as to be partially or completely embedded therein. The laminate according to claim 1, wherein the inorganic fiber nonwoven fabric has a basis weight of 10 to 150 g/ ^m2 . The laminate according to claim 1 or 2, characterized in that the inorganic fiber nonwoven fabric is made of randomly arranged inorganic fibers bonded together with a resin component. 2. The laminate according to claim 1, wherein the reinforcing layer is at least one of a nonwoven fabric, a woven fabric, and a woven material, and contains inorganic fibers as a main component. A covering structure having the laminate according to claim 1 on a surface of a steel frame,
A covered structure characterized in that the inorganic fiber nonwoven fabric is installed facing the steel frame.

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