JP2021014032A - Laminate and coating structure - Google Patents

Abstract

To provide a laminate having a heat foamable layer and a decorative layer, wherein the laminate has excellent designability; and, when exposed to high temperature in a fire or the like, stable heat-resistant protection is ensured.SOLUTION: A laminate has a heat foamable layer and a decorative layer on its surface side, wherein the decorative layer has a reinforcement layer inside it or on its back side, and the reinforcement layer is a fiber layer with a basis weight 5-150 g/m2.SELECTED DRAWING: Figure 1

Description

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

When a structure such as a building or a civil engineering structure is exposed to a high temperature due to a fire or the like, there is a problem that the physical strength of the steel frame constituting the columns, beams, etc. is sharply reduced. On the other hand, there is known a coating structure in which a steel frame is coated with a heat-resistant protective coating material to delay the temperature rise of the steel frame in the event of a fire and suppress a decrease in the physical strength of the steel frame.

As such a coating structure, there is a method of attaching a heat-foamable sheet to a steel frame via an adhesive. The heat-foamable sheet is a sheet formed by molding a mixture of synthetic resin, flame-retardant foaming agent, polyhydric alcohol, etc., and is thin and lightweight in normal times, and foams when the temperature rises due to a fire or the like. -It has the effect of carbonizing to form a carbonized heat insulating layer and exhibiting heat resistance (for example, Patent Document 1 and the like). Such a heat-foamable sheet usually has a feature that it can be installed relatively easily by simply attaching it with an adhesive or the like, does not require an extra space, and can have a uniform thickness. Further, since the surface side can be colored or painted to improve the design, there are many requests for construction on a part that imparts aesthetics and design.

JP-A-2002-201733

However, the heat-foamable sheet of Patent Document 1 may cause damage such as cracks or chips in the formed carbonized heat insulating layer due to hot air such as in a fire or physical impact. The surface of the steel frame is easily exposed at such a damaged portion of the carbonized heat insulating layer, and it may be difficult to maintain the desired heat resistance protection performance. Further, in order to impart aesthetics or design to the heat-foamable sheet, it is necessary to provide a decorative layer or the like, but depending on the type of the decorative layer, the formation of the carbonized heat-insulating layer of the heat-foamable sheet may be hindered. In some cases, the desired heat-resistant protection performance may be lowered.

As a result of diligent studies to achieve the above object, the present inventor has come up with a heat foam layer, a laminate having a decorative layer on the surface thereof, and a coating structure, and completed the present invention.

That is, the present invention has the following features.
1. 1. A laminate having a heat foam layer and a decorative layer on the surface side thereof.
The decorative layer has a reinforcing layer inside or on the back surface side thereof.
A laminate characterized in that the reinforcing layer is a fiber layer having a basis weight of 5 to 150 g / m ² .
2. 2. The reinforcing layer is a braided fabric and / or a woven fabric. The laminate described in.
3. 3. The reinforcing layer is characterized by containing inorganic fibers. Or 2. The laminate described in.
4. The heat foam layer has an inorganic fiber non-woven fabric on the back surface side.
1. The inorganic fiber non-woven fabric is laminated so as to be semi-embedded or fully embedded in the heat-foamed layer. ~ 3. The laminate according to any one of.
5. On the surface of the steel frame, 1. ~ 4. A covering structure having the laminate according to any one of.

The present invention is excellent in design and can maintain stable heat resistance when the steel frame is exposed to a high temperature due to a fire or the like.

It is sectional drawing which shows an example of the laminated body of this invention. It is sectional drawing which shows an example of the thermal foaming layer used in this invention. It is sectional drawing which shows an example of the thermal foaming layer used in this invention. It is sectional drawing which shows an example of the decorative layer used in this invention. It is sectional drawing which shows an example of the decorative layer of this invention. It is sectional drawing which shows an example of the laminated body of this invention. It is sectional drawing which shows an example of the covering structure of this invention. It is sectional drawing which shows an example of the covering structure of this invention. It is sectional drawing which shows an example of the covering structure of this invention.

A: Laminated bodies 1, 11, 11a: Heat-foaming layer (heat-foaming sheet)
1a: Inorganic fiber non-woven fabric 1b: Adhesive layer 1c: Releasable sheet 2: Decorative layer (decorative sheet)
2a: Reinforcing layer 2b: Adhesive layer 2c: Releasable sheet 2d: Surface protective layer 13: Thermal foaming layer (thermally foamable sheet)
23: Cosmetic layer (decorative sheet)
B: Steel frame X: Joint

Hereinafter, modes for carrying out the present invention will be described.

FIG. 1 shows a cross-sectional view of the laminated body A of the present invention. The laminate A of the present invention has heat resistance protection, design properties, etc., and as shown in FIG. 1, is a laminate in which a heat foam layer 1 and a decorative layer 2 are laminated on the surface thereof, and is cosmetic. The layer 2 is laminated on the surface side of the heat foam layer 1 so that the layer 2 can be visually recognized.

(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 the temperature range thereof. It forms a carbonized heat insulating layer in.

It is preferable that the heat foam layer 1 is formed of 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, each of these components exhibits excellent heat insulating properties and heat resistance by exhibiting functions such as layer expansion, carbonized heat insulating layer formation, and generation of nonflammable gas through mutual combined action. be able to.

As the resin component, for example, a thermoplastic resin such as vinyl resin, polystyrene resin, polypropylene resin, acrylic resin, acrylic styrene resin, polyamide resin, polyurethane resin, vinyl acetate resin, ethylene vinyl acetate resin can be used. In addition, 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, polyvulverized rubber, silicon rubber. , Fluorine rubber, urethane rubber and other rubber substances can also be used. These can be used alone or in combination of two or more. Among these, acrylic resin, acrylic styrene resin, vinyl acetate resin, ethylene vinyl acetate resin and the like are preferably used.

The flame retardant generally exerts at least one effect such as a dehydration cooling effect, a nonflammable gas generating effect, and a carbonization promoting effect of a thermoplastic resin in the event of a fire, and has an effect of suppressing combustion of a resin component. The flame retardant used in the present invention is not particularly limited as long as it has such an action, and a known flame retardant can be used. For example, chlorine compounds, antimony compounds, phosphorus compounds, boron compounds and the like can be mentioned. These can be used alone or in combination of two or more. Further, these may be either an uncoated product or a coated product. 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 further preferably 200 to 600 parts by weight with respect to 100 parts by weight (solid content) of the resin component. In the present invention, since the flame retardant is contained in such a relatively high ratio, good performance in heat resistance can be obtained.

The foaming agent generally has an action of generating a nonflammable gas in the event of a fire to foam a carbonizing resin component and a carbonizing agent to form a carbonized heat insulating layer having pores. The foaming agent is not particularly limited as long as it has such an action, and a known foaming agent can be used. For example, melamine and its derivatives, dicyandiamide and its derivatives, azodicarbonamide, urea, thiourea and the like can be mentioned. These can be used alone or in combination of two or more. Among these, melamine, dicyandiamide, azodicarbonamide and the like 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 further preferably 40 to 150 parts by weight with respect to 100 parts by weight (solid content) of the resin component. Within such a range, excellent foaming property can be exhibited, and good performance in heat insulating property and heat resistance protection can be obtained.

The carbonizing agent generally has an action of forming a thick carbonized heat insulating layer having excellent heat insulating properties by dehydrating and carbonizing itself together with carbonization of the thermoplastic resin in the event of a fire. The carbonizing agent used in the present invention is not particularly limited as long as it has such an action, and known carbonizing agents can be used. For example, polyhydric alcohols such as pentaerythritol, dipentaerythritol and trimethylolpropane; starch, casein and the like can be mentioned. The carbonizing agent can be used alone or in combination of two or more. Of 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 further preferably 40 to 150 parts by weight with respect to 100 parts by weight (solid content) of the resin component. Within such a range, it is possible to exert a dehydration cooling effect and a carbonized heat insulating layer forming action, and to obtain good performance in heat insulating property and heat resistant protection.

The filler generally has an action of maintaining the strength of the carbonized heat insulating layer. The filler is not particularly limited as long as it has such an action, and a known filler can be used. For example, carbonates such as calcium carbonate, sodium carbonate, magnesium carbonate, aluminum oxide; metal oxides such as titanium dioxide, zinc oxide; silica, clay, talc, clay, kaolin, silica stone, silas, mica, wallastnite, Examples thereof include inorganic powders such as silica sand, silica stone, quartz, hirustone, alumina, and fly ash. These may be used alone or in combination of two or more. The shape of the filler is not particularly limited, and examples thereof include a spherical shape, a granular shape, a plate shape, a rod shape, a phosphorus piece shape, and a needle shape.

The blending ratio of the filler is preferably 10 to 300 parts by weight, more preferably 20 to 250 parts by weight, and further preferably 50 to 160 parts by weight with respect to 100 parts by weight (solid content) of the resin component. Within such a range, the strength of the carbonized heat insulating layer can be maintained, and good performance in heat resistance can be obtained.

The heat foam layer 1 of the present invention preferably contains a fibrous substance in addition to the above components. By containing the fibrous substance, the effect of preventing the carbonized heat insulating layer from falling off and maintaining the shape of the carbonized heat insulating layer is enhanced. This mechanism of action is not limited to the following, but the carbonized heat insulating layer is formed while the fibrous material is entwined with the inorganic fibrous nonwoven fabric 1a laminated on the back surface side of the heat foam layer 1, so that the carbonized heat insulating layer falls off. It is considered that a uniform carbonized heat insulating layer is formed on the surface of the inorganic fiber non-woven fabric 1a. As a result, stable heat resistance can be obtained.

Examples of the fiber material include inorganic fibers such as rock wool, glass fiber, silica-alumina fiber, ceramic fiber, potassium titanate fiber and carbon fiber, and organic fiber such as pulp fiber, polypropylene fiber, vinyl fiber and aramid fiber. Be done. These may be used alone or in combination of two or more. Among these, inorganic fibers and carbon fibers having heat resistance are preferable, and rock wool, glass fibers and the like are particularly preferably used. 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 substance is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 30 parts by weight, based on 100 parts by weight (solid content) of the resin component.

Further, the heat foam layer 1 may contain various additives in addition to the above-mentioned constituent components, if necessary. The additive may be any additive that does not significantly impair the effects of the present invention, for example, pigments, wetting agents, plasticizing agents, lubricants, preservatives, fungicides, algae-proofing agents, antibacterial agents, thickeners, and dispersions. Examples thereof include agents, antifoaming agents, cross-linking agents, ultraviolet absorbers, light stabilizers, antioxidants, diluting solvents and the like.

The thickness of the heat foam layer 1 may be appropriately set depending on the application site and the like, but is preferably about 0.2 to 10 mm, more preferably about 0.3 to 6 mm.

In the present invention, as shown in FIG. 2, it is preferable that the inorganic fiber nonwoven fabric 1a is laminated on the back surface side of the heat foam layer 1. The surface side on which the inorganic fiber nonwoven fabric 1a is laminated is the back surface of the laminated body A. As a mode of laminating the heat foam layer 1 and the inorganic fiber non-woven fabric 1a, for example,
(I) Semi-embedded [FIG. 2 (I)]: The surface of the inorganic fiber nonwoven fabric 1a on the heat foam layer 1 side is buried, and the surface on the opposite side is exposed.
(II) Fully embedded [FIG. 2 (II)]: An embodiment in which the entire inorganic fiber nonwoven fabric 1a is embedded in the heat foam layer 1.
And so on. In the aspect of (II) above, the inorganic fiber nonwoven fabric 1a to be completely embedded is located on the back surface side with respect to the central portion of the thickness of the heat foam layer 1, and the inorganic fiber nonwoven fabric 1a is embedded. It is installed with the front side facing the back side and facing the steel frame side. (Hereinafter, the heat-foamed layer 1 of the portion where the inorganic fiber non-woven fabric 1a is semi-embedded or completely embedded (the portion that bites into the inorganic fiber non-woven fabric 1a) is referred to as the "heat-foamed layer 11a", and the other portion is also referred to as the "heat-foamed layer 11". Say.)

In the present invention, the effect of preventing the carbonized heat insulating layer from falling off is enhanced by the embodiment as described in (I) [FIG. 2 (I)] or (II) [FIG. 2 (II)], and the effect of the present invention is enhanced. It can be further enhanced. Further, in the case of the above aspect (I), when the steel frame is installed via an adhesive described later, the adhesion to the steel frame surface can be enhanced, and the effect of preventing the carbonized heat insulating layer from falling off is further enhanced. Can be enhanced.

The heat-foaming layer 1 having the aspect (I) or (II) above forms a structure having at least two layers of the heat-foaming layer 11 and the heat-foaming layer 11a, and when exposed to a high temperature by a fire or the like, The heat foam layer 11 and the heat foam layer 11a form a carbonized heat insulating layer, respectively. In particular, in the carbonized heat insulating layer formed by the heat 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 to form a strong carbonized heat insulating layer. Even if the heat foam layer 11 is damaged, the carbonized heat insulating layer formed by the heat foam layer 11a prevents the steel frame from being exposed, and as a result, the steel frame is not exposed and stable heat resistance is maintained. Can be done.

The basis weight of such an inorganic fiber nonwoven fabric 1a is preferably 10 to 150 g / m ² (more preferably 15 to 100 g / m ² ). In such a case, the heat-foaming layer 1 is likely to be filled in the voids between the inorganic fibers of the inorganic fiber nonwoven fabric 1a, and the heat-foamable sheet according to the above (I) or (II) can be easily obtained, satisfying the above basis weight. As a result, a strong carbonized heat insulating layer can be formed in the vicinity of the steel frame, and as a result, the steel frame 1 is not likely to be exposed, and stable heat-resistant protection can be maintained.

Further, the inorganic fiber non-woven fabric 1a is a cloth-like (sheet-like) one in which independent inorganic fibers are arranged one by one (formed without weaving), for example, an inorganic fiber arranged in one direction. , The one in which the arrangement of the inorganic fibers is crossed, the one in which the arrangement of the inorganic fibers is randomly arranged, and the like. In the present invention, those in which inorganic fibers are randomly arranged are preferable. Further, as a bonding method between inorganic fibers, for example, chemical adhesion by a resin component (chemical bond), fusion by heating (thermal bond), mechanical entanglement (needle punch), stitching (stitch bond) and the like are used. In the present invention, an inorganic fiber non-woven fabric in which the fibers of the inorganic fibers are bonded with a resin component (chemical bond) is preferable.

By using the inorganic fiber non-woven fabric 1a in which the fibers of the inorganic fibers arranged at random are bonded with a resin component in this way, a carbonized heat insulating layer formed by the heat foam layer 11a when exposed to a high temperature due to a fire or the like. Then, since the inorganic fibers contained in the inorganic fiber non-woven fabric 1a act as a reinforcing component of the carbonized heat insulating layer and the resin component has an effect like a carbonizing agent, a stronger carbonized heat insulating layer can be formed. It is inferred that. As a result, there is no possibility that the steel frame is exposed, and more stable heat resistance can be maintained.

The inorganic fiber constituting the inorganic fiber non-woven fabric 1a is not particularly limited, and for example, rock wool, glass fiber, silica fiber, silica-alumina fiber, carbon fiber, silicon carbide fiber and the like, and fine metal wire such as iron and copper are used. Can be mentioned. In the present invention, glass fiber is suitable. Further, the inorganic fiber may be one that has been subjected to some kind of surface treatment. Further, the cross-sectional shape of the fiber is not particularly limited, and any of a circular shape, a polygonal shape, a flat shape and the like can be used. The resin component for adhering the inorganic fibers is not particularly limited, and 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 an inorganic fiber nonwoven fabric 1a may be appropriately set, but is preferably about 0.1 to 2 mm, more preferably about 0.15 to 1 mm.

Further, in the present invention, the inorganic fiber nonwoven fabric 1a may contain organic fibers in addition to the inorganic fibers as long as the effects of the present invention are not impaired. Examples of the organic fiber include pulp fiber, polyester fiber, polypropylene fiber, aramid fiber, vinylon fiber, polyethylene fiber, polyarylate fiber, PBO fiber, nylon fiber, acrylic fiber, vinyl chloride fiber, cellulose fiber and the like. The organic fiber may be such that it melts in a temperature range of about 150 ° C. to become a liquid state, but it is preferable that the organic fiber does not melt in such a temperature range. These can also be used in combination of two or more.

The heat-foaming layer 1 may be formed by a mixture of the components of the heat-foaming layer 1, and as a method for producing the same, for example, a method of applying a mixture containing the components of the heat-foaming layer 1 Alternatively, a method of molding a mixture containing the constituent components of the heat foam layer 1 into a sheet or the like can be mentioned. Further, when the inorganic fiber nonwoven fabric 1a is laminated so as to be semi-embedded or completely embedded in the heat-foamed layer 1, for example, the following method and the like can be mentioned.
A method in which a mixture containing the constituent components of the heat foam layer 1 is applied to the inorganic fiber nonwoven fabric 1a and laminated.
-A method in which a mixture of the constituent components of the heat foam layer 1 is poured into a mold, an inorganic fiber non-woven fabric 1a is further laminated, and the mold is removed after drying.
-After preparing a kneaded product in which the constituent components of the heat foam layer 1 are kneaded with a kneader or the like (hereinafter, also referred to as "kneaded product for heat foam layer"), the kneaded product is laminated on the inorganic fiber non-woven fabric 1a, and a rolling roller or the like is used. How to process into a sheet by.
The heat-foaming layer 1 of the present invention is preferably a sheet-like heat-foaming layer (hereinafter, also referred to as "heat-foaming sheet") obtained by the above method or the like.

As shown in FIG. 3, in the heat-foaming layer 1 (particularly, the heat-foaming sheet) of the present invention, the adhesive layer 1b can be laminated on the outside (back surface 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 heat foam layer 1 (the aspect (I) above), and the exposed inorganic fibrous nonwoven fabric 1a is semi-embedded in the adhesive layer 1b. Is preferable. Thereby, the effect of the present invention can be further enhanced. Further, the surface of the adhesive layer 1b can be covered with the releasable sheet 1c [FIG. 3 (II)]. By using such a heat foam layer 1, work efficiency can be improved.

The method of laminating the adhesive layer 1b and the releasable sheet 1c is not particularly limited, but for example, the adhesive is applied to the inorganic fiber non-woven fabric 1a side of the heat foam layer 1 and the releasable sheet 1c is laminated on the adhesive. Or a method in which an adhesive is previously applied onto the releasable sheet 1c to form an adhesive layer 1b, and the adhesive layer 1b is laminated on the inorganic fiber non-woven fabric 1a side of the heat foam layer 1. Can be mentioned.

Examples of the adhesive material forming the adhesive layer 1b include water-dispersible type and water-soluble type using acrylic resin, silicon resin, epoxy resin, vinyl resin, phenol resin, polyester resin, urethane resin, paraffin and the like as main raw materials. Known materials such as solvent-type adhesives can be used. If necessary, a flame retardant, a foaming agent, a carbonizing agent, a filler, or the like, which is blended in the above-mentioned thermosetting resin sheet, can be added to the adhesive. Further, in the present invention, the adhesive material also includes an adhesive. The thickness of the adhesive layer 1b is preferably 25 to 200 μm, or the coating amount is preferably 0.05 to 0.5 kg / m ² .

The releasable sheet 1c protects the adhesive layer 1b during storage or transportation of the heat-foaming layer 1, and can be easily peeled off from the adhesive layer 1b when the heat-foaming sheet is used. As such a releasable sheet, a known one can be used, and for example, a paper or film coated or impregnated with a releasing agent such as silicone, wax, or fluororesin, or the releasable agent is not included. Examples thereof include synthetic resin films such as polypropylene and polyethylene which have releasability by themselves.

(Cosmetic layer)
The decorative layer 2 of the present invention is not particularly limited as long as it can impart designability, but is preferably a composition containing a resin component and colored powder particles (hereinafter, also referred to as "composition for decorative layer"). It is formed by (referred to as), and is characterized by having a reinforcing layer inside or on the back surface side thereof.

The resin component mainly plays a role of immobilizing colored powder particles. As such a resin component, various synthetic resins can be used. Examples of the type of resin include acrylic resin, silicone resin, acrylic silicon resin, fluororesin, vinyl acetate resin, acrylic / vinyl acetate resin, vinyl chloride resin, urethane resin, acrylic urethane resin, epoxy resin, alkyd resin, and polyvinyl alcohol. Examples thereof include resins, polyester resins, ethylene resins, polyvinyl alcohols, celluloses and derivatives thereof, or composites thereof. Such a synthetic resin may have a property of causing a cross-linking 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. In the case of such a range, it is possible to impart appropriate flexibility. The glass transition temperature is a value obtained by the Fox calculation formula.

The colored powder granules play a role of imparting a color, a pattern, etc. to the decorative layer. As such colored powder granules, for example, known ones such as coloring pigments, extender pigments and aggregates can be used, and these can be used by one kind or two or more kinds.

The decorative layer 2 of the present invention preferably contains granular inorganic particles as the colored powder particles. As a result, the granular inorganic particles are immobilized by the resin component, and a decorative layer 2 exhibiting a color tone based on the granular inorganic particles and a design property due to the concatenation (aggregation) of the granular inorganic particles can be obtained. That is, the color tone of the decorative layer 2 is based on the color tone of the granular inorganic particles. Further, the decorative layer 2 may have a plurality of colored regions having different color tones. In this case, the decorative layer 2 can be formed by curing a plurality of decorative layer compositions having different color tones. Since such a decorative layer 2 not only enhances the design property but also has excellent surface strength due to the granular inorganic particles, it is possible to prevent dents and scratches on the heat foam layer 1. Furthermore, the heat resistance can be enhanced by the granular inorganic particles. The mechanism of action is not limited, but the steel frame temperature rapidly rises due to the heat reflectivity, heat resistance, etc. of the granular inorganic particles until the foaming start temperature of the heat foam layer 1 is reached under a high temperature such as in a fire. It is considered that the rise to the temperature can be suppressed.

As the granular inorganic particles, both natural products and artificial products can be used as long as the material of 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, opaque particles having a light transmittance of less than 3% are particularly preferable, and those having a light transmittance of 2% or less are more preferable. Specific examples of such granular colored inorganic particles include marble, granite, serpentine, granite, sandstone, mucilage, basalt, gabbro, diorite, andesite, limestone, crushed products thereof, and crushed ceramic products. , Ceramic crushed product, metal grains and the like. Further, fluorite, cold water stone, feldspar, silica stone, silica sand, and crushed products, crushed glass products, glass beads, etc. thereof, which are colored so as to satisfy the above conditions, can also be used.

The light transmittance is a value of the total light transmittance by the turbidity meter. In this measurement, a sample of granular inorganic particles is filled in a transparent glass cell having an inner thickness of 5 mm, then gradually filled with water, and then bubbles in the cell are removed by vibration.

In addition to the above-mentioned granular colored inorganic particles, a form containing granular transparent inorganic particles can also be used. The use of such granular transparent inorganic particles is preferable in terms of improving aesthetics. As the granular transparent inorganic particles, those having a light transmittance of 3% or more (more preferably 3 to 50%, further preferably 10 to 30%) are preferable. Examples of the granular transparent inorganic particles include silica, cold water stone, slag stone, silica stone and the like, crushed products thereof, crushed glass products, glass beads and the like, and are colorless and colored as long as they satisfy the above light transmittance. Both types can be used.

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

The mixing ratio of the resin component and the colored powder or granular material is preferably 2 parts by weight or more and 50 parts by weight or less (more preferably 3 weight by weight) with respect to 100 parts by weight of the total amount of the colored powder or granular material in terms of solid content. 3 parts or more and 30 parts by weight or less, more preferably 4 parts by weight or more and 20 parts by weight or less, and particularly preferably 5 parts by weight or more and 19 parts by weight or less). With such a ratio, it is easy to obtain a decorative layer 2 made of an articulated body (aggregate) of colored powder particles. As a result, in a high temperature such as in a fire, a rapid temperature rise is suppressed, and gas and the like generated by the foaming of the heat foam layer 1 are efficiently permeated, and a uniform carbonized heat insulating layer is formed without inhibiting the foaming. Can be formed.

The composition for a decorative layer may contain components (additives) other than the above, if necessary, as long as the effects of the present invention are not significantly impaired. Examples of such components include plasticizers, algae-proofing agents, antibacterial agents, deodorants, adsorbents, flame retardants, thickeners, defoaming agents, cross-linking agents, coloring pigments, extender pigments, and bright pigments. Examples thereof include phosphorescent pigments, fluorescent pigments, aggregates, fibers, ultraviolet absorbers, light stabilizers, antioxidants, catalysts and the like.

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 examples thereof include stone-like patterns, wood-grain patterns, joint patterns, and the like. The thickness of the decorative layer 2 is preferably 0.2 to 30 mm (more preferably 0.5 to 20 mm).

As shown in FIG. 4, the present invention is characterized in that the reinforcing layer 2a is laminated on the inside or the back surface side of the decorative layer 2. As a mode of laminating the decorative layer 2 and the reinforcing layer 2a,
(I) Semi-embedded [FIG. 4 (I)]: The surface of the reinforcing layer 2a on the decorative layer 2 side is buried, and the surface on the opposite side is exposed.
(II) Fully embedded [FIG. 4 (II)]: A mode in which the entire reinforcing layer 2a is embedded in the decorative layer 2.
And so on. In the aspect of FIG. 4 (II), the reinforcing layer 2a to be completely embedded does not have to be exposed on the surface of the decorative layer 2, but is located on the back surface side with respect to the central portion of the thickness of the decorative layer 2. Is preferable.

In the present invention, by having the reinforcing layer 2a inside or on the back surface side of the decorative layer 2 as described in (I) [FIG. 4 (I)] and (II) [FIG. 4 (II)], the temperature is high due to a fire or the like. When exposed to, the carbonized heat insulating layer formed by the heat foam layer 1 can be prevented from cracking or falling off, and excellent heat resistance can be exhibited. Furthermore, it is possible to enhance physical properties such as flexibility and strength of the laminated body A.

Such a reinforcing layer 2a is characterized in that it is a fiber layer having a basis weight of 5 to 150 g / m ² (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 heat foam layer 1 is not hindered, a uniform heat insulating layer can be formed, and the effect of preventing cracks in the carbonized heat insulating layer can be exhibited.

Examples of such a fiber layer include non-woven fabrics, braids, and woven fabrics. These can also be used in combination of two or more. Further, two or more layers can be laminated as long as the present invention is not impaired.
In the present invention, the "nonwoven fabric" is a cloth-like (sheet-like) material obtained by entwining independent fibers one by one or adhering them with heat or an adhesive as described above. It is formed in). Further, the "braided cloth" is a group of fiber yarns aligned in one direction and a group of fiber yarns aligned in a different direction, assembled horizontally or diagonally, and laminated and bonded. The structure of the braid may be any one having a mesh structure, and depending on the number of axes of the fiber yarn group, there are many braids such as 2-axle cloth, 3-axis cloth, and 4-axis cloth. Examples include frame cloth. The "woven fabric" is formed by a group of fiber threads like a braided cloth, and is woven by vertically interlacing warp threads and weft threads. Examples of the structure of the woven fabric include plain weave, twill weave, red woven fabric, vertical double weave, horizontal double weave, vertical and horizontal double weave, pile weave, entangled weave, and crest weave.

In the present invention, it is preferable to use a braided cloth and / or a woven fabric as the reinforcing layer 2a. Further, as the braid and / or woven fabric, it is preferable that the densities of the warp threads and the weft threads are both 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). When such a range is satisfied, the foaming of the heat foam layer 1 is not hindered, and a more uniform heat insulating layer can be formed.

Furthermore, it is preferable to use a woven fabric (more preferably, an entwined woven fabric) as the reinforcing layer 2a. This makes it possible to further enhance the effect of preventing the carbonized heat insulating layer formed by the foaming of the heat foam layer 1 from cracking or falling off under a high temperature such as in a fire. This mechanism of action is not limited to the following, but the woven fabric is woven by vertically interlacing the warp threads and the weft threads, so that the woven fabric has less misalignment and deformation. As a result, it is considered that the carbonized heat insulating layer can be stably supported and cracks and falling off can be prevented. Further, the entangled woven fabric is a woven fabric in which weft threads are woven while the warp threads are entwined with each other (a woven fabric having eyes as if the weft threads are tied with warp threads), and has elasticity in the diagonal direction. Therefore, it is considered that the effect of the present invention can be further enhanced because the above effect can be exhibited without inhibiting the foaming of the heat foam layer 1.

The fibers used for the reinforcing layer 2a are not particularly limited, and various fibers such as organic fibers and inorganic fibers that can be used for the above-mentioned inorganic fiber nonwoven fabric 1a can be used. The reinforcing layer 2a preferably contains an inorganic fiber (particularly glass fiber) as a main component, which has excellent heat resistance and is difficult to melt even at high temperatures.

The thickness of the reinforcing layer 2a is preferably 0.01 to 3 mm (more preferably 0.05 to 1 mm). Within such a range, the effect of the present invention can be more easily obtained.

The decorative layer 2 may be one in which the reinforcing layer 2a is laminated on the back surface of the decorative layer 2, and examples of the manufacturing method thereof include the following methods.
-A method of applying the composition for a decorative layer to the reinforcing layer 2a and laminating it.
-A method in which a decorative layer composition is poured into a mold, a reinforcing layer 2a is further laminated, and the mold is removed after drying.
-A method in which a decorative layer composition is poured into a mold, a reinforcing layer 2a is laminated, a decorative layer composition is further poured, and the mold is removed after drying.

As shown in FIG. 5, the decorative layer 2 (decorative sheet) of the present invention can have an adhesive layer 2b laminated on the back surface as needed [FIG. 5 (I)]. Further, the surface of the adhesive layer 2b can be covered with the releasable sheet 2c [FIG. 5 (II)]. By using such a decorative layer 2, work efficiency can be improved.

The method of laminating the adhesive layer 2b and the releasable sheet 2c is not particularly limited, but for example, a method of applying an adhesive to the back surface of the decorative layer 2 and laminating the releasable sheet 2c on the adhesive layer 2 or Examples thereof include a method in which an adhesive is applied to the releasable sheet 2c in advance to form an adhesive layer 2b, and the back surface of the decorative layer 2 is laminated on the adhesive layer 2b. As the adhesive and the releasable sheet 2c forming the adhesive layer 2b, the same ones that can be used in the above-mentioned heat-foamable sheet 1 can be used.

Further, the decorative layer 2 of the present invention may have a clear layer 2d [FIG. 5 (III)] on the outermost surface for the purpose of surface protection (water resistance, weather resistance, etc.), stain prevention, and the like. .. As the clear layer, a known clear paint can be used.

(Laminate)
As shown in FIG. 1, the laminate A of the present invention is a laminate in which a heat foam layer 1 and a decorative layer 2 are laminated on the surface thereof, and as shown in FIG. 6, the inside or the back surface of the decorative layer 2 is laminated. A reinforcing layer 2a is provided on the side, and the decorative layer 2 is laminated on the surface side so that it can be visually recognized. When such a heat foam layer 1 and a decorative layer 2 are laminated, they can be laminated by, for example, the following method.
A method in which a reinforcing layer 2a is placed on the surface of the heat foam layer 1, a composition for a decorative layer is applied, and the decorative layer 2 is laminated.
-A decorative layer 2 (decorative sheet 2) in which a reinforcing layer 2a is previously laminated on the front surface of the thermal foam layer 1 so as to be semi-embedded or fully embedded on the inside or the back surface side of the decorative layer 2 is provided via an adhesive. How to stack.
The thickness of the laminated body A is preferably 1.2 to 65 mm (more preferably 1.5 to 50 mm).

(Coating structure)
The coating structure of the present invention has the above-mentioned laminate A on the surface of the steel frame.
FIG. 7 shows an example of the coating structure of the present invention. As shown in FIG. 7, the coating structure of the present invention is a coating structure in which a heat foam layer 1 and a decorative layer 2 are laminated on the surface side of the steel frame B. Such a coating structure is coated so that the decorative layer 2 can be visually recognized, and is excellent in design and maintains stable heat-resistant protection when the steel frame is exposed to a high temperature due to a fire or the like. be able to.

Further, FIG. 8 shows another example of the covering structure of the present invention. As shown in FIG. 8, the coating structure of the present invention is a coating structure in which a heat foam layer 1 and a decorative layer 2 are laminated on a steel frame B, and the inorganic fiber nonwoven fabric 1a of the heat foam layer 1 is a steel frame. It is characterized in that it is coated toward the B side and the decorative layer 2 is arranged so as to be on the surface side. Such a covering structure is coated so that the decorative layer 2 can be visually recognized, and has excellent designability and more stable heat protection when the steel frame is exposed to a high temperature due to a fire or the like. Can be maintained.

The steel frame B is not particularly limited, and examples thereof include steel frame steel materials such as square type, round type, H type, and I type, which are used as columns, beams, and the like constituting a structure. ..

Examples of the coating method for such a covering structure include the following methods.
(1) A method of sequentially coating a heat foam layer 1 and a decorative layer 2 on a steel frame B.
(2) A method of coating a laminated body A on which a heat foam layer 1 and a decorative layer 2 are laminated in advance on a steel frame B.
In the above methods (1) and (2), when the heat-foamed layer 1 (laminated body A) having the inorganic fiber non-woven fabric 1a on the back surface side is coated as the heat-foamed layer 1, the inorganic fiber non-woven fabric is applied to the steel frame B. It is preferable to install the surface (back surface) on which 1a is laminated so as to face the steel frame B side.

Specific methods for coating the heat foam layer 1 on the steel frame B include, for example, the following methods.
(A) The steel frame B is coated with a mixture containing the constituent components of the heat foam layer 1.
(B) After applying an adhesive to the front surface of the steel frame B and / or the back surface of the inorganic fiber non-woven fabric 1a, the inorganic fiber non-woven fabric 1a is attached, and the mixture containing the constituent components of the heat foam layer 1 is applied.
(C) A sheet-shaped heat-foaming layer 1 (heat-foaming sheet) (or laminate A) is wound around the steel frame B, and the end portion is fixed with a fixing member.
(D) After applying an adhesive to the front surface of the steel frame B and / or the back surface of the sheet-shaped heat-foaming layer 1 (heat-foamable sheet), the heat-foaming layer 1 (or laminate A) is attached.
(E) When the sheet-shaped heat-foaming layer 1 (heat-foaming sheet) (or laminate A) has the adhesive layer 1b and the releasable sheet 1c, the releasable sheet 1c is peeled off and the adhesive layer is peeled off. 1b is exposed and attached to the steel frame B (adhesive may be applied in advance).
The coating structure of the present invention is suitable for a mode in which the steel frame B is directly (adheredly) coated (attached and coated).

In the above (a) and (b), when applying the mixture containing the constituent components of the heat foam layer 1, for example, an instrument such as a brush, a roller, a trowel, a spatula, or a spray can be used.

In the above (c), the fixing member for fixing the end portion of the heat foam layer 1 (or the laminated body A) is not particularly limited, but for example, a washer (screw), a tacker, a welding pin, a bolt, a tapping screw, or the like. Stoppers can be used. Further, as these materials, nonflammable materials such as metal are preferable.

In the above (b) and (d), when applying the adhesive to the back surface of the steel frame B, the heat foam layer 1 or the inorganic fiber non-woven fabric 1a, for example, an instrument such as a brush, a roller, a trowel, a spatula, or a spray can be used. it can. The amount of the adhesive applied may be appropriately set, but is preferably 0.1 to 0.5 kg / m ² . Further, when the heat foam layer 1 (or the laminated body A) is attached to the steel frame B, it is desirable to crimp it. When crimping, a pressing tool such as a roller or a trowel can be used if necessary.

As the coating method for the covering structure of the present invention, the method (1) above is particularly suitable. In this case, workability and finish are excellent. Further, as shown in FIG. 9, it is preferable to provide the joint portion X. The place where the joint portion X is provided is not particularly limited, but is preferably a place other than the corner portion of the steel frame B. By providing the joint portion X, the heat foam layer 1 can be efficiently foamed, and the effect of the present invention can be further enhanced.

Examples are shown below to clarify the features of the present invention.

<Manufacturing of heat foam layer (heat foamable sheet)>
・ Kneaded product for thermal foam layer 1
Pressurization of a mixture containing 100 parts by weight of a 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 at a temperature of 120 ° C. Kneaded with a kneader to prepare a kneaded product 1 for a heat-foamable sheet.
・ Kneaded product for thermal foam layer 2
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, 4 parts by weight of glass fiber (fiber diameter 7 μm, fiber length 6 mm) The kneaded product 2 for a heat-foamable sheet was prepared by kneading a mixture containing

-Nonwoven fabric 1: Inorganic fiber non-woven 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 non-woven 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 non-woven 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) non-woven fabric in which polyester filaments are randomly arranged and bonded with polyvinyl alcohol resin, basis weight 60 g / m ² , thickness 0.5 mm

In the combination shown in Table 1, the kneaded material for the heat-foaming layer is laminated on the non-woven fabric and processed into a sheet so that the non-woven fabric is (I) semi-embedded or (II) fully embedded by a rolling roller. Eight kinds of sheets (450 mm × 1200 mm) were prepared.
Further, the heat-foamable sheet (450 mm × 1200 mm) of the embodiment [(III) without burying] in which the kneaded product for the heat-foaming layer is formed into a sheet by a rolling roller and then laminated on the heat-foaming layer and the non-woven fabric via an acrylic adhesive. ) Was prepared.

(Reinforcement layer)
-Inorganic fiber woven fabric: glass fiber, entwined weave, warp yarn density 10 x 2/25 mm, weft density 10/25 mm, basis weight 60 g / m ² , thickness 0.2 mm

(Composition for decorative layer 1)
Acrylic resin emulsion (solid content 50% by weight) 200 parts by weight, granular colored inorganic particles (brown) with an average particle diameter of 150 μm, 1000 parts by weight, water, and additives (thickener, defoamer, etc.) are uniformly added by a conventional method. The composition 1 for a decorative layer was produced by mixing.
(Composition for decorative layer 2)
The decorative layer composition 2 was produced in the same manner except that the granular colored inorganic particles of the decorative layer composition 1 were replaced with granular colored inorganic particles (brown: black = 1: 4) having an average particle diameter of 100 μm.

<Manufacturing of decorative layer (decorative sheet) 1>
The above-mentioned 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 paint was applied to the outermost surface at an application amount of 0.3 kg / m ² .

<Manufacturing of decorative layer (decorative sheet) 2>
The decorative layer compositions 1 and 2 are poured into a wood grain formwork, the reinforcing layers are laminated so as to be semi-embedded, cured at 23 ° C. for 24 hours, and then demolded to form a wood grain sheet (600 mm × 1200 mm). , Thickness 3 mm) was manufactured. Next, a clear paint was applied to the outermost surface at an application amount of 0.3 kg / m ² .

(Manufacturing of test specimen)
The following coating structure was manufactured using the above 9 types of heat-foamable sheets and the above 2 types of decorative sheets.
It is attached to a square steel frame (300 mm × 300 mm, thickness 9 mm, length 1200 mm) via an adhesive so that the inorganic fiber non-woven fabric side of the produced heat-foamable sheet 1 is on the square steel frame side, and then a decorative sheet is attached. The coated structure attached via the adhesive was used as a test piece.

In the process of conducting a heating test for 1 hour according to the standard heating curve of ISO834 for the prepared test piece, a part of the carbonized heat insulating layer in the process of formation is impacted 20 minutes after the start of the test (around 280 ° C.). After the crack was generated, the test was continued, the temperature of the steel frame (steel material temperature) at this time was measured, and after the test, the shape of the carbonized heat insulating layer other than the crack and the shape of the carbonized heat insulating layer of the crack were evaluated. .. Each evaluation standard is 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 heat insulating layer)
The shape of the carbonized heat insulating layer other than the cracked portion was visually confirmed. The evaluation criteria are a five-grade evaluation (excellent: AA>A> B) in which the carbonized heat insulating layer is not dropped and a uniform carbonized heat insulating layer is formed as "AA" and the carbonized heat insulating layer is dropped as "D". >C> D: Inferior).
(Evaluation 3: Carbonized heat insulating layer in cracks)
The shape of the carbonized heat insulating layer at the crack was visually confirmed. The evaluation criteria were a five-grade evaluation (excellent: AA>A>B>C> D: inferior), with the carbonized heat insulating layer formed as "AA" and the exposed steel frame as "D".

Claims (5)

A laminate having a heat foam layer and a decorative layer on the surface side thereof.
The decorative layer has a reinforcing layer inside or on the back surface side thereof.
A laminate characterized in that the reinforcing layer is a fiber layer having a basis weight of 5 to 150 g / m ² . The laminate according to claim 1, wherein the reinforcing layer is a braided fabric and / or a woven fabric. The laminate according to claim 1 or 2, wherein the reinforcing layer contains inorganic fibers. The heat foam layer has an inorganic fiber non-woven fabric on the back surface side.
The laminate according to any one of claims 1 to 3, wherein the inorganic fiber nonwoven fabric is laminated so as to be semi-embedded or fully embedded in the heat-foamed layer. A coating structure having a laminate according to any one of claims 1 to 4 on the surface of a steel frame.

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