JP7439389B2 - noncombustible sheet - Google Patents

Description

The present invention relates to a noncombustible sheet.

Some noncombustible sheets, which are noncombustible or flame retardant sheets, contain an inorganic material in a raw fabric layer that serves as a base material. As a technique related to this sheet, there is one described in Patent Document 1, for example.

JP 2018-48229 Publication

Some noncombustible sheets containing an inorganic material in the raw material layer have the inorganic material falling off the surface of the raw material layer when printing or the like is performed on the surface of the raw material layer, so-called powder falling. If the inorganic material falls off from the sheet after printing or the like, it may contaminate the inside of the printing system, specifically, the inside of the printing device, for example.
In addition, when a printing layer is directly formed on the surface of a noncombustible sheet containing an inorganic material in the original fabric layer, the adhesion between the original fabric layer and the ink for forming the printing layer is low, and printing In some cases, peeling occurs within the layer or between the original fabric layer and the printed layer. Such a noncombustible sheet is unsuitable for use as a building material, for example, because the printed layer and the like may peel off during use.

Therefore, an object of the present invention is to provide a noncombustible sheet that can prevent the inorganic material contained in the raw fabric layer from falling off and improve the interlayer strength between the raw fabric layer and the printed layer.

In order to achieve the above object, a noncombustible sheet according to one aspect of the present invention includes a raw fabric layer, a first anchor layer formed on a first surface of the raw fabric layer, and a first anchor layer formed on the first surface of the raw fabric layer. a second anchor layer formed on a second surface opposite to the first surface, the raw fabric layer containing a thermoplastic resin and an inorganic material; The anchor layer contains a urethane resin containing vinyl acetate or an acrylic resin containing vinyl acetate in an amount of 15% by mass or more and 100% by mass or less based on the entire mass of the first anchor layer. The surface of the inorganic material is treated with at least one of an organic phosphorus surface treatment agent, an inorganic phosphoric acid surface treatment agent, a polycarboxylic acid surface treatment agent, and a coupling agent surface treatment agent. Features.

According to the present invention, it is possible to provide a noncombustible sheet that can prevent the inorganic material contained in the raw fabric layer from falling off, and can improve the interlayer strength between the raw fabric layer and the printed layer.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows the structure of the noncombustible sheet and noncombustible material based on 1st Embodiment of this invention. It is a sectional view showing composition of a noncombustible sheet and a noncombustible material concerning a modification of a 1st embodiment of the present invention. It is a sectional view showing composition of a noncombustible sheet and a noncombustible material according to a second embodiment of the present invention.

Next, embodiments of the present invention will be described with reference to the drawings.
Here, the drawings are schematic, and the relationship between the thickness and the planar dimension, the ratio of the thickness of each layer, etc. are different from the actual one. In addition, the embodiments shown below illustrate configurations for embodying the technical idea of the present invention, and the technical idea of the present invention is that the materials, shapes, structures, etc. of the component parts are It is not something specific. The technical idea of the present invention can be modified in various ways within the technical scope defined by the claims.

<First embodiment>
[Composition of noncombustible sheet]
As shown in FIG. 1, the noncombustible sheet 10 of the first embodiment includes, from the back side to the top side, a primer layer 6, a back anchor layer 5, a raw fabric layer 1, and a front anchor layer 2. , a pattern layer 3 and a top coat layer 4. Further, the noncombustible material 12 of the first embodiment includes the noncombustible sheet 10 of the first embodiment and a substrate 11.
Each layer constituting the noncombustible sheet 10 will be explained below. In addition, the content of various materials mentioned below means the content ratio (mass %) with respect to the mass of the whole corresponding layer in a dry state. For example, the content of the inorganic material in this embodiment, which will be described later, means the content ratio (mass %) with respect to the mass of the entire raw fabric layer 1 in a dry state. In addition, the content of the urethane resin containing vinyl acetate salt or the acrylic resin containing vinyl acetate salt in the surface anchor layer 2, which will be described later, is the content ratio (mass%) with respect to the entire mass of the surface anchor layer 2 in a dry state. means. In addition, the content of the urethane resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the back anchor layer 5, which will be described later, is the content ratio (mass%) with respect to the entire weight of the back anchor layer 5 in a dry state. means.

(Original fabric layer)
The raw fabric layer 1 is a layer (sheet) serving as a base material of the noncombustible sheet 10, and is a layer containing a thermoplastic resin and an inorganic material.

<Inorganic materials>
The content of the inorganic material of this embodiment may be within the range of 15% by mass or more and 90% by mass or less, and may be within the range of 20% by mass or more and 80% by mass or less, based on the mass of the raw fabric layer 1. It is more preferable if it is within the range of 60% by mass or more and 80% by mass or less. When the content of the inorganic material is less than 15% by mass with respect to the mass of the raw fabric layer 1, the proportion of the thermoplastic resin becomes relatively large, so that it tends to be difficult to obtain nonflammability or flame retardance. Furthermore, when the surface of the raw fabric layer 1 is scratched using a Hoffman scratch tester, visible scratches may occur, that is, sufficient surface hardness may not be obtained. On the other hand, when the content of the inorganic material exceeds 90% by mass with respect to the mass of the raw fabric layer 1, the proportion of the thermoplastic resin becomes relatively small. For this reason, when an anchor layer is coated or printed on the surface of the raw fabric layer 1, so-called "powder blowing" may occur on the surface of the raw fabric layer 1. Here, "powder blowing" means that the inorganic material contained in the raw fabric layer 1 comes out onto the surface of the raw fabric layer 1. Further, when forming the picture pattern layer 3, the inorganic material that stands out from the original fabric layer 1 may make it difficult for ink to be laminated, that is, the printability may deteriorate. Also, when laminating a sheet on which at least one of the front anchor layer 2, the back anchor layer 5, the picture pattern layer 3, and the top coat layer 4 is formed on a wood base material or a stone base material in a roll or sheet form, It becomes difficult to laminate, that is, the suitability for lamination tends to decrease. Furthermore, when the sheet on which at least one of the front anchor layer 2, the back anchor layer 5, the picture pattern layer 3, and the top coat layer 4 is formed is folded and opened again, cracks may occur from the folded portion, and inorganic Materials may fall. In addition, after pressing the cellophane tape on the surface of the sheet on which the picture pattern layer 3 is formed, peel it off strongly and peel it off within the picture pattern layer 3 or between the raw fabric layer 1 (surface anchor layer 2) and the picture pattern layer 3. may occur, that is, ink adhesion may deteriorate.

As described above, the content of the inorganic material of this embodiment is 15% by mass or more and 90% by mass or less, preferably 20% by mass or more and 80% by mass or less, and more preferably 60% by mass, based on the mass of the raw fabric layer 1. If the content is within the above range of 80% by mass or less, non-flammability or flame retardance can be achieved, the occurrence of powder blowing can be reduced, printing suitability can be improved, lamination suitability can be improved, and cracking at the folded part of the sheet can be prevented. It is possible to reduce the occurrence of ink, obtain sufficient surface hardness, and improve ink adhesion.

Further, the inorganic material of this embodiment is preferably in powder form (powder shape), and preferably has an average particle size in the range of 1 μm or more and 3 μm or less, and a maximum particle size of 50 μm or less. . If the average particle size and maximum particle size of the inorganic material are within the above numerical ranges, the flatness of the surface of the original fabric layer 1 can be maintained while improving the dispersibility of the inorganic material in the thermoplastic resin. When the average particle diameter of the inorganic material is less than 1 μm, the cohesive force between the inorganic materials increases, and the dispersibility in the thermoplastic resin described below may decrease. In addition, when the average particle diameter of the inorganic material exceeds 3 μm, the flatness of the surface of the raw fabric layer 1 decreases, and the thickness of the surface anchor layer 2 or the back surface anchor layer 5, which will be described later, may become uneven, uneven, or chipped. It may occur. Furthermore, if the maximum particle size of the inorganic material exceeds 50 μm, the flatness of the surface of the raw fabric layer 1 will decrease, and the thickness of the surface anchor layer 2 or the back surface anchor layer 5, which will be described later, may become uneven, uneven, or chipped. It may occur. In addition, in this embodiment, "average particle diameter" means a mode diameter.

The inorganic material is, for example, a powder containing at least one of calcium carbonate and calcium carbonate salt. The powder containing at least one of calcium carbonate and calcium carbonate salt preferably contains 50% by mass or more and 100% by mass or less. That is, the purity of the powder containing at least one of calcium carbonate and calcium carbonate salt is preferably in the range of 50% by mass or more and 100% by mass or less of calcium carbonate. If the powder contains at least one of calcium carbonate and calcium carbonate salt containing 50% by mass or more of calcium carbonate, it is possible to impart sufficient nonflammability or sufficient flame retardancy to the raw fabric layer 1. At the same time, sufficient mechanical strength can be imparted.

In addition to powders containing at least one of the calcium carbonate and calcium carbonate salts, examples of inorganic materials include silica (especially hollow silica), alumina, antimony trioxide, antimony soda, zirconium silicate, and zirconium oxide. compounds, such as magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, borax, zinc borate, molybdenum trioxide or complexes of antimony dimolybdate and aluminum hydroxide, complexes of antimony trioxide and silica, antimony trioxide and zinc Examples include at least one of a complex of zirconium, silicic acid of zirconium, a complex of a zirconium compound and antimony trioxide, and salts thereof. In particular, calcium carbonate and calcium carbonate salts are easy to control particle size and compatibility with thermoplastic resin through manufacturing methods, and are also inexpensive in terms of material cost, so they are useful from the perspective of reducing the cost of noncombustible sheets. suitable.

Further, the inorganic material may be a powder material having crystallinity, a so-called crystalline powder, or a powder material having no crystallinity, a so-called amorphous type powder material. If the inorganic material is a powder material having crystallinity, the powder itself is homogeneous and has isotropy, so the mechanical strength of the powder itself is improved, and the scratch resistance and durability of the noncombustible sheet tend to be improved. In addition, if the inorganic material is an amorphous type powder material, it is possible to adjust the electrical conductivity and thermal conductivity of the powder itself, as well as the light transmittance and light absorption rate, resulting in variations in texture, gloss, etc. This makes it possible to provide a rich variety of designs.

Inorganic materials such as calcium carbonate whose surfaces are not coated generally have low powder fluidity and do not have high alkali resistance, so they tend to change color easily.
On the other hand, when an inorganic material such as calcium carbonate that has been pretreated, that is, surface treated, is used, the fluidity of the powder is generally improved, and the alkali resistance and hue tend to be improved. Furthermore, weather resistance can also be improved by selecting an appropriate treatment agent for pretreatment.
Therefore, in this embodiment, various surface treatment agents are applied to inorganic materials such as calcium carbonate, as necessary, for the purpose of improving powder fluidity, alkali resistance, hue improvement, and other properties of calcium carbonate fillers. surface treatment (coating). This point will be explained below.

The surface of the inorganic material of this embodiment is treated with at least one of an organic phosphorus surface treatment agent, an inorganic phosphoric acid surface treatment agent, a polycarboxylic acid surface treatment agent, and a coupling agent surface treatment agent. It is something. Note that in this embodiment, "surface treatment" refers to the surface being covered with a surface treatment agent, that is, the surface is coated.

Examples of organic phosphorus surface treatment agents that can be used for surface treatment of inorganic materials include 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilotrismethylenephosphonic acid, trimethyl phosphate, triethyl phosphate, tributyl phosphate, Examples include organic phosphoric acids such as triphenyl phosphate, methyl phosphate, and ethyl phosphate, and their salts.
Furthermore, examples of inorganic phosphoric acid surface treatment agents that can be used for surface treatment of inorganic materials include condensed phosphoric acids represented by pyrophosphoric acid, polyphosphoric acids, hexametaphosphoric acid, and salts thereof.
Incidentally, these surface treating agents can be used alone or in combination of two or more as necessary.

Polycarboxylic acid surface treatment agents that can be used for surface treatment of inorganic materials include, for example, monocarboxylic acids such as polyacrylic acid, methacrylic acid, and crotonic acid, and dicarboxylic acids such as itaconic acid, maleic acid, and fumaric acid. Examples include acids. These may be used alone or in combination of two or more. Further, copolymers with compounds having functional groups such as polypropylene glycol (PPG) and polyethylene glycol (PEG) can also be used without problems.
Coupling agent-based surface treatment agents that can be used for surface treatment of inorganic materials include, for example, silane-based coupling agents such as vinyltrimethoxysilane and N-2-(aminoethyl)-3-aminopropyltrimethoxysilane. titanate coupling agents typified by isopropyl triisostearoyl titanate, silicone oils typified by methyl hydrogen, and the like. These may be used alone or in combination of two or more.

Among these surface treatment agents, trimethyl phosphate (TMP) and triethyl phosphate (TEP) are used from the viewpoint of compatibility with resins, heat resistance, inactivation of inorganic materials such as calcium carbonate, and dehydration/deaeration properties. , condensed phosphoric acids, and silicone-based treatments are preferred. In particular, in the case of a polyester resin having an ester bond, a surface treatment agent is suitable since the resin has low alkali resistance.
The amount of surface treatment agent to be used varies depending on the specific surface area of the inorganic material such as calcium carbonate, the compounding conditions, etc., so it is difficult to specify it unconditionally, but from the purpose of this embodiment, it is usually It is preferably within the range of 0.01% by weight or more and 5% by weight or less based on the material. If the amount used is less than 0.01% by weight, it is difficult to obtain a sufficient surface treatment effect, while if it is added in excess of 5% by weight, the hue of the resin will change to yellow due to decomposition and volatilization of the surface treatment agent during resin kneading. Since such problems may occur, the content is more preferably in the range of 0.05% by weight or more and 3% by weight or less, and even more preferably in the range of 0.1% by weight or more and 1.5% by weight or less.

As a surface treatment method for inorganic materials such as calcium carbonate, for example, a mixer such as a super mixer, a Henschel mixer, a tumbler mixer, a kneader mixer, or a Banbury mixer is used to mix the surface treatment agent directly into the powder of an inorganic material such as calcium carbonate. There is a dry treatment method in which the surface is treated by heating if necessary, or a surface treatment agent is dissolved in an aqueous solvent, etc., and the surface is treated in an inorganic material suspension such as calcium carbonate by heating if necessary. A cake obtained by dehydrating a suspension of an inorganic material such as calcium carbonate may be surface-treated by wet treatment methods such as dehydration and drying, or a combination of both.
In addition, as necessary, for example, a lubricant, an antioxidant, a fluorescent whitening agent, a heat stabilizer, a light stabilizer, an ultraviolet absorber, a neutralizing agent, and an antifogging agent may be added to the extent that the effectiveness of the raw fabric layer 1 is not impaired. , an anti-blocking agent, an antistatic agent, a slip agent, a coloring agent, etc. may be added.

<Thermoplastic resin>
The thermoplastic resin of this embodiment preferably contains at least one of polypropylene, polyethylene, and polyester, and more preferably contains polypropylene. By using at least one of polypropylene, polyethylene, and polyester as the thermoplastic resin, the dispersibility of the inorganic material is improved. Further, by using polypropylene as the thermoplastic resin, the dispersibility of the inorganic material is further improved.

Further, the total content of the thermoplastic resin and the inorganic material is preferably in the range of 90% by mass or more and 100% by mass or less based on the mass of the raw fabric layer 1. If the total content of thermoplastic resin and inorganic material is within the above numerical range, sufficient non-flammability or sufficient flame retardance can be obtained, printability and lamination suitability can be improved, and the problem can be prevented from occurring at the folded portion of the sheet. cracking can be reduced. If the total content of the thermoplastic resin and the inorganic material is less than 90% by mass based on the mass of the raw fabric layer 1, sufficient nonflammability or sufficient flame retardance may not be obtained. In addition, printability and lamination suitability may deteriorate, and cracks may occur at the folded portion of the sheet.

In addition, when the total content of the thermoplastic resin and the inorganic material is 100% by mass with respect to the mass of the raw fabric layer 1, the content of the thermoplastic resin is 10% by mass or more and 85% by mass or less. The content of the inorganic material is preferably within the range of 15% by mass or more and 90% by mass or less. Further, it is more preferable that the content of the thermoplastic resin be within the range of 20% by mass to 80% by mass, and the content of the inorganic material be within the range of 20% by mass to 80% by mass. Further, it is more preferable that the content of the thermoplastic resin be within the range of 20% by mass to 40% by mass, and the content of the inorganic material be within the range of 60% by mass to 80% by mass. If the total content of the thermoplastic resin and inorganic material is within the above numerical range, sufficient nonflammability or sufficient flame retardance will be reliably obtained, printability and lamination suitability will be reliably improved, and the sheet will be It is possible to reliably reduce cracks occurring in the bent portion.

Further, the thickness of the raw fabric layer 1 is preferably within the range of 50 μm or more and 250 μm or less, and more preferably within the range of 70 μm or more and 200 μm or less. If the thickness of the raw fabric layer 1 is within the above numerical range, lamination suitability can be improved and cracks occurring at the folded portion of the sheet can be reduced. If the thickness of the raw fabric layer 1 is less than 50 μm, lamination suitability tends to decrease. Moreover, if the thickness of the original fabric layer 1 exceeds 250 μm, cracks may occur at the folded portion of the sheet.
Moreover, it is preferable that the raw fabric layer 1 is a monoaxially stretched or biaxially stretched raw fabric layer. If the raw fabric layer 1 is a monoaxially stretched or biaxially stretched raw fabric layer, the versatility of the noncombustible sheet 10 can be increased.

In addition, on at least one of the front surface (first surface) and back surface (second surface) of the raw fabric layer 1, for example, a surface anchor layer (first anchor layer) 2 and a back surface anchor layer (second surface), which will be described later, are coated. Before forming the anchor layer 5, it is preferable to perform surface treatment such as corona treatment or plasma treatment. By performing surface treatment such as corona treatment or plasma treatment on at least one of the front and back surfaces of the raw fabric layer 1, the adhesiveness (adhesion) between the front anchor layer 2 and the back anchor layer 5 and the raw fabric layer 1 is improved. will improve.
In addition, before forming the front anchor layer 2 and the back anchor layer 5, for example, at least one of the front surface and the back surface of the raw fabric layer 1 is brushed, and at least one of powdered inorganic materials such as calcium carbonate and calcium carbonate salts is applied. The powder containing one of the two may be dropped in advance.

(Surface anchor layer)
The surface anchor layer 2 is a layer formed so as to cover the entire surface of the raw fabric layer 1, and is a layer for preventing the inorganic material contained in the raw fabric layer 1 from falling off. If the inorganic material contained in the original fabric layer 1 falls off within the printing system, specifically within the printing device, during printing or resin coating, the inside of the printing system may be contaminated. Further, if the inorganic material contained in the original fabric layer 1 falls off, problems such as ink omission may occur. Here, "ink omission" refers to ink not being printed partially.

The surface anchor layer 2 also has a function of improving the adhesion between the original fabric layer 1 and the ink forming the picture pattern layer 3, which will be described later. If the surface anchor layer 2 is not provided, the ink forming the pattern layer 3 may not adhere to the original fabric layer 1 and may peel off.
The surface anchor layer 2 preferably contains a urethane resin containing vinyl acetate or an acrylic resin containing vinyl acetate. Here, "salted vinyl acetate" means a copolymer of vinyl chloride and vinyl acetate. In addition, "urethane resin containing salt vinyl acetate" is a composition containing salt vinyl acetate and urethane resin, and the ratio of the content of salt vinyl acetate to the content of urethane resin (salt vinyl acetate content and urethane resin content) Bi content (mass)/urethane resin content (mass)) may be within the range of 80/20 to 1/99, preferably within the range of 50/50 to 5/95, and 20 It is more preferable if it is within the range of /80 to 10/90.

Further, the "urethane resin containing salt vinyl acetate" may contain a curing agent in addition to the salt vinyl acetate and urethane resin described above. This hardening agent is added to reliably harden the urethane resin containing vinyl acetate, and its content is not particularly limited. For example, the ratio of the content of urethane resin containing salt vinyl acetate to the content of curing agent (content (mass) of urethane resin containing salt vinyl acetate/content (mass) of curing agent) is 99 It may be within the range of /1 to 1/99, preferably within the range of 99/1 to 50/50, and more preferably within the range of 95/5 to 90/10.

The content of the urethane resin containing salt vinyl acetate or the acrylic resin containing salt vinyl acetate in the surface anchor layer 2 is within the range of 15% by mass or more and 100% by mass or less based on the mass of the surface anchor layer 2. It is preferably in the range of 80% by mass or more and 100% by mass or less, and even more preferably in the range of 85% by mass or more and 95% by mass or less. If the content of the urethane resin containing salt-vinyl acetate or the acrylic resin containing salt-vinyl acetate in the surface anchor layer 2 is within the above numerical range, the interlayer strength between the surface anchor layer 2 and the pattern layer 3 will be reduced. It is possible to form a uniform surface anchor layer 2 without any unevenness or chipping while making it sufficient. If the content of the urethane resin containing salt vinyl acetate or the acrylic resin containing salt vinyl acetate in the surface anchor layer 2 is less than 15% by mass with respect to the weight of the surface anchor layer 2, the surface anchor layer 2 The interlayer strength with the pattern layer 3 may be insufficient. Furthermore, if the content of the urethane resin containing salt-vinyl acetate or the acrylic resin containing salt-vinyl acetate in the surface anchor layer 2 is less than 80% by mass with respect to the mass of the surface anchor layer 2, there will be no problem in use. Although there is no problem, the penetration ratio of the surface anchor layer 2 into the raw fabric layer 1 may be reduced, and the interlayer strength between the surface anchor layer 2 and the raw fabric layer 1 may be slightly reduced. Note that if the content of the urethane resin containing vinyl acetate salt or the acrylic resin containing vinyl acetate salt in the surface anchor layer 2 is 100% by mass or less based on the mass of the surface anchor layer 2, there will be no problem in use. However, if it exceeds 95% by mass, more precisely 98% by mass, the surface anchor layer 2 may be chipped due to insufficient curing, or the surface anchor layer 2 and the original fabric layer 1, or the surface anchor layer 2 and the pattern may The interlayer strength with layer 3 may decrease.

The content of the urethane resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the front anchor layer 2 is the same as the content of the urethane resin containing vinyl salt or vinyl acetate in the back anchor layer 5, which will be described later. It may be the same as the content of the acrylic resin containing. That is, the content of the urethane resin containing vinyl acetate salt or the acrylic resin containing vinyl acetate salt in the front anchor layer 2 is the same as the content of the urethane resin containing vinyl acetate salt or the acrylic resin containing vinyl acetate salt in the back anchor layer 5. The content may be 1.0 times (within a range of 0.95 times or more and 1.04 times or less) the content of the acrylic resin. The content of the urethane resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the front anchor layer 2 is higher than that of the urethane resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the back anchor layer 5. When the resin content is the same, the physical properties of the front anchor layer 2 and the back anchor layer 5 are almost the same, so the raw fabric layer 1 is equipped with the front anchor layer 2 and the back anchor layer 5. In this case, the occurrence of distortion, warpage, etc. can be reduced. Therefore, the occurrence of distortion, warpage, etc. of the entire noncombustible sheet can be reduced. In addition, since the coating liquid for forming the front surface anchor layer 2 and the coating liquid for forming the back surface anchor layer 5 can be shared, manufacturing costs are reduced and work efficiency is improved. be able to.

Further, the content of the urethane resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the front anchor layer 2 is the same as the content of the urethane resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the back anchor layer 5. The content may be greater or less than the content of the acrylic resin. The content of the urethane resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the front anchor layer 2 is higher than that of the urethane resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the back anchor layer 5. If the content is higher or lower than the resin content, the physical properties of the front anchor layer 2 and the back anchor layer 5 will be different, so the original fabric layer 1 with the front anchor layer 2 and the back anchor layer 5 will be strained. It is possible to add warpage, warpage, etc. In this way, by imparting distortion, warping, etc. to the raw fabric layer 1 provided with the front anchor layer 2 and the back anchor layer 5, the raw fabric layer 1 can be bonded to a base material etc. with a curved surface without any gaps. be able to. For example, the content of the urethane resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the front anchor layer 2 is the same as the content of the urethane resin containing vinyl acetate or vinyl acetate in the back anchor layer 5. The content of the acrylic resin may be 1.1 times or more and 10 times or less, or 0.1 times or more and 0.9 times or less.

The thickness of the surface anchor layer 2 is, for example, in the range of 0.5 μm or more and 20 μm or less, preferably in the range of 0.5 μm or more and 10 μm or less. Further, the thickness of the front anchor layer 2 may be the same as the thickness of the back anchor layer 5. When the thickness of the front anchor layer 2 is the same as the thickness of the back anchor layer 5, the physical properties of the front anchor layer 2 and the back anchor layer 5 are almost the same. And in a state where the back anchor layer 5 is provided, the occurrence of distortion, warping, etc. can be reduced.
Moreover, the thickness of the front surface anchor layer 2 may be thicker or thinner than the thickness of the back surface anchor layer 5. By making the thickness of the front surface anchor layer 2 and the thickness of the back surface anchor layer 5 different, a difference in gloss is generated, so that the front surface side and the back surface side of the original fabric layer 1 can be easily recognized visually. By doing so, the picture pattern layer 3 can be printed on the surface of the original fabric layer 1 without forming, for example, an identification mark or the like indicating that it is a printing surface. As a result, product loss caused by forming the picture pattern layer 3 on the back surface (non-printing surface) side of the original fabric layer 1 can be reduced.

(Picture pattern layer)
The pattern layer 3 is a layer that imparts a pattern to the noncombustible sheet 10, and is formed on the surface anchor layer 2.
There are no particular restrictions on the type of picture pattern formed by the picture pattern layer 3, and for example, wood grain patterns, stone grain patterns, cloth grain patterns, abstract patterns, geometric figures, characters, symbols, etc. may be used singly or in combination. It may be formed by combining the above.

The pattern layer 3 is a layer formed by applying an ink containing an acrylic resin as a binder (hereinafter also referred to as a pattern layer forming ink) to one surface of the surface anchor layer 2. Examples of acrylic resins included as binders in the ink for forming pattern layers include ethylene-methyl acrylate copolymer resin (EMA), ethylene-ethyl acrylate copolymer resin (EEA), and ethylene-methacrylate copolymer resin. Polymer resins (EMAA), ethylene-acrylic acid copolymer resins (EAA), ionomer resins, or mixtures thereof, which are based on acrylate copolymer resins, can be used. Here, the term "main component" refers to the component with the highest content among the components constituting the picture pattern layer 3.
Note that the picture pattern layer 3 may be a layer formed by applying ink containing urethane resin as a binder to one surface of the surface anchor layer 2. As the urethane resin, a urethane resin obtained by reacting an acrylic polyol and an isocyanate may be used. Examples of isocyanates include tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), diphenylmethane diisocyanate (MDI), lysine diisocyanate (LDI), isophorone diisocyanate (IPDI), and methylhexane diisocyanate (HTDI). ), methylcyclohexanone diisocyanate (HXDI), trimethylhexamethylene diisocyanate (TMDI), etc.; however, in consideration of weather resistance, it is preferable to use hexamethylene diisocyanate (HMDI), which has a linear molecular structure. preferable.

The ink for forming a picture pattern layer may contain, together with the acrylic resin, a crosslinking agent that crosslinks the acrylic resin. Since this crosslinking agent has the function of crosslinking the acrylic resin and imparting mechanical strength to the entire picture pattern layer 3, it is also generally referred to as a "curing agent." Examples of the crosslinking agent (curing agent) that can be added to the ink for forming a picture pattern layer include a urethane curing agent. More specifically, examples of the urethane curing agent that can be added to the ink for forming a pattern layer include IPDA (isofluorone diamine) and HDI (hexamethylene diisocyanate). In this embodiment, these can be used alone or in combination.

When the ink for forming a picture pattern layer contains a crosslinking agent, the content of the crosslinking agent is in the range of more than 0 parts by mass and not more than 10 parts by mass, when the content of the acrylic resin in the picture pattern layer 3 is 100 parts by mass. It is preferable that it be within. If the content of the crosslinking agent is within the above numerical range, the coatability of the ink for forming a picture pattern layer will be improved. Preferably, the content of the crosslinking agent is 3 parts by mass when the content of the acrylic resin in the picture pattern layer 3 is 100 parts by mass.

In addition to the above-mentioned binder, the ink for forming a pattern layer may contain, for example, organic or inorganic dyes or pigments, extender pigments, fillers, tackifiers, dispersants, antifoaming agents, stabilizers, and other additives as necessary. Agents may be added as appropriate. Further, the ink for forming the picture pattern layer is adjusted to a desired viscosity using a suitable diluting solvent.
There are no particular restrictions on the method of forming the picture pattern layer 3, and for example, any printing method such as gravure printing, offset printing, screen printing, flexo printing, letterpress printing, inkjet printing, etc. can be used. It is possible.

In addition, when a solid ink layer (not shown) is provided between the surface anchor layer 2 and the picture pattern layer 3 for the purpose of base coloring, the solid ink layer can be formed by using the various printing methods described above. For example, any coating method can be used, such as a roll coating method, a gravure coating method, a rod coating method, a knife coating method, an air knife coating method, a spray coating method, a lip coating method, a die coating method, and the like.

(Top coat layer)
A top coat layer 4 is provided on the outermost surface of the noncombustible sheet 10, which serves to protect the surface and adjust gloss. The thickness of the top coat layer 4 is preferably 2 μm or more and 10 μm or less. If the thickness of the top coat layer 4 is within the above range, flexibility can be maintained while obtaining sufficient mechanical properties such as abrasion resistance and surface hardness. If the thickness of the top coat layer 4 is less than 2 μm, sufficient mechanical properties such as abrasion resistance and surface hardness may not be obtained. Moreover, when the thickness of the top coat layer 4 exceeds 10 μm, the flexibility may decrease.
The resin material that is the main component of the top coat layer 4 may be selected from among resin materials such as polyurethane, acrylic silicone, fluorine, epoxy, vinyl, polyester, melamine, aminoalkyd, and urea. It can be used selectively. The form of the resin material is not particularly limited, and may be water-based, emulsion, solvent-based, or the like. The curing method can be appropriately selected from one-liquid type, two-liquid type, ultraviolet curing method, etc.

As the resin material that is the main component of the top coat layer 4, a urethane-based resin material using isocyanate is preferable from the viewpoints of workability, price, and cohesive force of the resin itself. Examples of isocyanates include tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), diphenylmethane diisocyanate (MDI), lysine diisocyanate (LDI), isophorone diisocyanate (IPDI), and bis(methyl isocyanate). The curing agent can be appropriately selected from adducts, burettes, isocyanurates, etc. of derivatives such as cyclohexane (HXDI) and trimethylhexamethylene diisocyanate (TMDI). Curing agents based on hexamethylene diisocyanate (HMDI) or isophorone diisocyanate (IPDI), which have a linear molecular structure, are suitable. In addition, in order to improve the surface hardness, it is preferable to use a resin that is cured by active energy rays such as ultraviolet rays and electron beams. Note that these resins can be used in combination with each other; for example, a hybrid type of thermosetting type and photocuring type can be used to improve surface hardness, suppress curing shrinkage, and improve adhesion. can be achieved.

Further, in order to improve the weather resistance of the noncombustible sheet 10, an ultraviolet absorber and a light stabilizer may be added as appropriate. Furthermore, functional additives such as antibacterial agents and antifungal agents can be optionally added to impart various functions. Furthermore, alumina, silica, silicon nitride, silicon carbide, glass beads, etc. can be optionally added to adjust the surface design and gloss, or to further impart wear resistance.

(backside anchor layer)
The back anchor layer 5 is a layer formed to cover the entire back surface of the raw fabric layer 1, and is a layer for preventing the inorganic material contained in the raw fabric layer 1 from falling off. If the inorganic material contained in the original fabric layer 1 falls off within the printing system, specifically within the printing device, during printing or resin coating, the inside of the printing system may be contaminated.
In addition, the back anchor layer 5 also has a function of improving the adhesion between the raw fabric layer 1 and the primer layer 6, which will be described later. If the back anchor layer 5 is not provided, the coating liquid forming the primer layer 6 may not adhere to the base layer 1 and may peel off.
The back anchor layer 5 preferably contains a urethane resin containing vinyl acetate or an acrylic resin containing vinyl acetate.

The content of the urethane resin containing vinyl acetate salt or the acrylic resin containing vinyl acetate salt in the back anchor layer 5 is, for example, in the range of 15% by mass or more and 100% by mass or less based on the mass of the back anchor layer 5. It is preferably in the range of 80% by mass or more and 100% by mass or less, and even more preferably in the range of 85% by mass or more and 95% by mass or less. If the content of the urethane resin containing salt-vinyl acetate or the acrylic resin containing salt-vinyl acetate in the back anchor layer 5 is within the above numerical range, the interlayer strength between the back anchor layer 5 and the primer layer 6 can be sufficiently increased. It is possible to form a uniform back anchor layer 5 without any unevenness or chipping while maintaining the same quality. If the content of the urethane resin containing salt-vinyl acetate or the acrylic resin containing salt-vinyl acetate in the back anchor layer 5 is less than 15% by mass with respect to the mass of the back anchor layer 5, the back anchor layer 5 The interlayer strength with the primer layer 6 may be insufficient. Furthermore, if the content of the urethane resin containing salt-vinyl acetate or the acrylic resin containing salt-vinyl acetate in the back anchor layer 5 is less than 80% by mass with respect to the mass of the back anchor layer 5, there will be no problem in use. Although there is no problem, the penetration ratio of the back anchor layer 5 into the web layer 1 may be reduced, and the interlayer strength between the back anchor layer 5 and the web layer 1 may be slightly reduced. Note that if the content of the urethane resin containing salt-vinyl acetate or the acrylic resin containing salt-vinyl acetate in the back anchor layer 5 is 100% by mass or less based on the mass of the back anchor layer 5, there will be no problem in use. However, if it exceeds 95% by mass, more precisely 98% by mass, the back anchor layer 5 may be chipped due to insufficient curing, or the back anchor layer 5 and the original fabric layer 1, or the back anchor layer 5 and the primer layer may be damaged. The interlayer strength with 6 may decrease.
Further, the thickness of the back anchor layer 5 is, for example, in the range of 0.5 μm or more and 20 μm or less, preferably in the range of 0.5 μm or more and 10 μm or less.

(Primer layer)
The material for the primer layer 6 may be appropriately selected from, for example, nitrified cotton as a binder, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyester, etc. alone or modified from each of them. Can be used. These may be of any particular form, such as water-based, solvent-based, or emulsion type. Furthermore, the curing method can be appropriately selected from among a one-component type that is cured alone, a two-component type that uses a curing agent together with the main agent, and a type that is cured by irradiation with ultraviolet rays, electron beams, etc. The general curing method is a two-component type in which a urethane-based base resin is combined with an isocyanate-based curing agent. It is suitable from this point of view. In addition to the binder described above, colorants such as pigments and dyes, extender pigments, solvents, and various additives are added. In particular, since the primer layer 6 is located on the backmost side of the non-combustible sheet 10, considering that the non-combustible sheet 10 is rolled up as a continuous plastic film (web-like), the films stick together and are difficult to slip. Inorganic fillers such as silica, alumina, magnesia, titanium oxide, barium sulfate, etc. may be added to prevent blocking such as peeling or failure to peel, and to improve adhesion with the adhesive. . The layer thickness is preferably within the range of 0.1 μm or more and 3.0 μm or less since the purpose is to ensure adhesion with the substrate 11 described later.

(adhesive resin layer)
The noncombustible sheet 10 of this embodiment may include an adhesive resin layer (not shown) between the picture pattern layer 3 and the top coat layer 4 or the transparent resin layer 7 described below. By providing the adhesive resin layer, the adhesion between the picture pattern layer 3 and the top coat layer 4 can be improved. The material for the adhesive resin layer is not particularly limited, but can be appropriately selected from acrylic, polyester, polyurethane, epoxy, and the like. The coating method can be selected as appropriate depending on the viscosity of the adhesive, etc., but generally gravure coating is used, and after coating on the pattern layer 3 by gravure coating, the top coat layer 4 or It is formed so as to be laminated with the transparent resin layer 7.

[Method for manufacturing noncombustible sheet]
An example of a method for manufacturing the noncombustible sheet 10 will be briefly described.
First, a surface anchor layer forming ink for forming the surface anchor layer 2 is applied to one surface of the raw fabric layer 1 to form the surface anchor layer 2.
Next, on the surface of the surface anchor layer 2, a picture pattern layer forming ink for forming the picture pattern layer 3 is applied to form the picture pattern layer 3.
Next, a top coat layer forming ink for forming the top coat layer 4 is applied onto the surface of the picture pattern layer 3 to form the top coat layer 4.

Next, a back anchor layer forming ink for forming the back anchor layer 5 is applied to the back surface, which is the other surface of the original fabric layer 1, to form the back anchor layer 5.
Finally, a primer layer forming ink for forming the primer layer 6 is applied onto the surface of the back anchor layer 5 to form the primer layer 6.
In this way, the noncombustible sheet 10 according to this embodiment is manufactured.
Note that the back anchor layer 5 may be formed simultaneously with the front anchor layer 2. Further, the primer layer 6 may be formed before the pattern layer 3 and the top coat layer 4 are formed.

[Composition of noncombustible material]
The configuration of the noncombustible material 12 will be explained using FIG. 1.
As shown in FIG. 1, the noncombustible material 12 includes a substrate 11 and the above-mentioned noncombustible sheet 10. Therefore, the substrate 11 will be explained below, and the explanation of the above-mentioned noncombustible sheet 10 will be omitted.

(substrate)
The substrate 11 of this embodiment is a plate-shaped member formed using, for example, a metal material, a wood material, or an inorganic material.
As the metal material, for example, aluminum, steel, stainless steel, composite panel, etc. can be used.
As a composite panel, for example, one including a resin layer serving as a core material and metal plates (aluminum, galvalume, stainless steel, etc.) attached to both surfaces of the resin layer can be used.
As the wood-based material, for example, MDF (Medium Density Fiberboard), plywood, particle board, etc. can be used.
As the inorganic material, for example, gypsum board, fiber-mixed calcium silicate board, etc. can be used.

[Method for manufacturing noncombustible material]
An example of a method for manufacturing the noncombustible material 12 will be briefly described.
First, the primer layer 6 of the noncombustible sheet 10 is placed facing the substrate 11 side.
Next, this laminate is thermally laminated, for example.
In this way, the primer layer 6 and the substrate 11 are welded together, and the noncombustible material 12 is manufactured.
As a method for thermally laminating the above-mentioned laminate, in addition to the method of flat-pressing metal plates in contact with each other, it is also possible to use a continuous lamination method using circular pressure. In particular, if a continuous lamination method using an endless metal belt or a metal or hardening resin heat drum is used, the surface will not warp or wave, and the adhesion between the layers will be good, resulting in a densely cured and integrated structure. There is an advantage that high-quality noncombustible material 12 can be manufactured continuously at high speed.

According to the technical standards for noncombustible materials stipulated in the Building Standards Act Construction Order, the following requirements must be met in a heat generation test using a cone calorimeter tester compliant with ISO 5660-1 (Building Standards Act Construction Order Article 108-2 Items 1 and 2). In order for the non-combustible sheet 10 of this embodiment to be certified as a non-combustible material, the following conditions 1 to 3 must be met when the non-combustible sheet 10 is heated for 20 minutes with 50 kW/m ² radiant heat while bonded to a non-combustible base material. All required items must be met.
1. Total calorific value is 8MJ/ ^m2 or less 2. Maximum heat generation rate does not exceed 200kW/ ^m2 for 10 seconds or more 3. Cracks and holes penetrating to the back surface that are detrimental to flame resistance do not occur.The noncombustible base material can be selected from gypsum board, fiber-mixed calcium silicate board, or galvanized steel board.

The noncombustible sheet 10 of this embodiment, which includes the above-mentioned original fabric layer 1, was tested for heat generation by a cone calorimeter tester in accordance with ISO 5660-1 in a state where it was bonded to the above-mentioned noncombustible base material. A non-combustible material has been created that satisfies both the requirements set forth in Article 108-2, Items 1 and 2 of the Construction Order.

<Modified example>
In this embodiment, the case where the top coat layer 4 is a single layer has been described, but it may be a multilayer. Therefore, a case will be described below in which the top coat layer 4 includes two layers, a first top coat layer 4a and a second top coat layer 4b.
As shown in FIG. 2, the first top coat layer 4a is a layer that is provided on the surface side of the picture pattern layer 3 and covers the whole picture pattern layer 3. The first top coat layer 4a is made of a material (resin) that is transparent or translucent to such an extent that the pattern of the picture pattern layer 3 can be seen through the first top coat layer 4a. The first top coat layer 4a may be a single layer or a layer formed by stacking a plurality of layers. Further, the thickness of the first top coat layer 4a is preferably within a range of, for example, 2 μm or more and 10 μm or less.

The second top coat layer 4b is a layer that is partially provided on the surface side of the first top coat layer 4a and covers a part of the surface of the first top coat layer 4a. The part of the surface of the first top coat layer 4a includes, for example, the part of the picture pattern layer 3 that faces the printing ink. Further, as the material for the second top coat layer 4b, for example, the same resin as the first top coat layer 4a can be used. A filler may be added to the second top coat layer 4b. By adding a filler, mechanical properties such as gloss, touch, texture, surface strength, and friction that are different from those of the first top coat layer 4a can be imparted. The filler is preferably a material that consumes a small amount of oxygen during combustion, such as calcium carbonate, antimony trioxide, antimony soda, zirconium compounds such as zirconium silicate, zirconium oxide, magnesium hydroxide, aluminum hydroxide, and bases. Magnesium carbonate, borax, zinc borate, complexes of molybdenum trioxide or antimony dimolybdate and aluminum hydroxide, complexes of antimony trioxide and silica, complexes of antimony trioxide and zinc white, silicic acid of zirconium, zirconium compounds and antimony trioxide complexes. In particular, calcium carbonate is suitable for reducing the cost of decorative sheets because it is easy to control the particle size through manufacturing methods and the compatibility with polyolefin resin through surface treatment, and the material cost is low. It is. Furthermore, beads and irregularly shaped particles of resin such as acrylic, polyolefin, and silicone, and beads and irregularly shaped particles of inorganic materials such as silica (particularly hollow silica), alumina, and metal oxides can be used. Further, the method of forming the second top coat layer 4b is not particularly limited, and any known printing method can be employed. Note that the second top coat layer 4b is also generally referred to as a "tactile coat layer" or a "matte conduit printing layer."

<Second embodiment>
[Composition of noncombustible sheet]
As shown in FIG. 3, the noncombustible sheet 10 of the second embodiment includes, from the back side to the top side, a primer layer 6, a back anchor layer 5, a raw fabric layer 1, and a front anchor layer 2. , a picture pattern layer 3, a transparent resin layer 7, and a top coat layer 4. The top coat layer 4 of the second embodiment includes a first top coat layer 4a and a second top coat layer 4b. Further, the noncombustible material 12 of the second embodiment includes the noncombustible sheet 10 of the second embodiment and a substrate 11. That is, the noncombustible sheet 10 of the second embodiment differs from the noncombustible sheet 10 of the first embodiment in that it includes the transparent resin layer 7 and the top coat layer 4 made up of multiple layers. Therefore, hereinafter, the transparent resin layer 7 and the top coat layer 4, which are different parts, will be explained, and the explanation of the other layers will be omitted.

(Transparent resin layer)
The transparent resin layer 7 is a sheet-like layer formed using a transparent resin so that the pattern of the pattern layer 3 can be seen through, and is formed by being laminated on the top surface of the pattern layer 3.
As a method for laminating the transparent resin layer 7, for example, it is possible to use a method of laminating the transparent resin layer 7 on a laminate including the raw fabric layer 1, the surface anchor layer 2, and the picture pattern layer 3 by lamination processing. It is.
The transparent resin forming the transparent resin layer 7 is not particularly limited, and any known transparent resin can be used.

Therefore, examples of the transparent resin forming the transparent resin layer 7 include polyolefin resins, ethylene-vinyl acetate copolymers, saponified products thereof, polyolefin copolymers, polyester resins, polymethyl methacrylates, etc. Acrylic resin, polyamide resin, styrene resin, cellulose derivative, chlorine resin, fluorine resin, etc. alone, or a mixture, copolymer, composite, or laminate of two or more selected from these materials. It is possible to use the body etc. as appropriate.
In particular, in manufacturing using melt extrusion equipment, it is recommended to use polyolefin resin as the transparent resin forming the transparent resin layer 7, considering productivity, environmental compatibility, mechanical strength, durability, cost, etc. More preferred.

As the polyolefin resin, for example, polyethylene, polypropylene, polybutene, polymethylpentene, etc. can be used, and polypropylene is most preferred. Further, as the polyolefin copolymer, for example, ethylene-(meth)acrylic acid (ester) copolymer or the like can be used.
Examples of polyester resins include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, polycarbonate, and copolymerized polyester (typically, 1,4-cyclohexanedimethanol copolymerized polyethylene terephthalate resin commonly known as PET-). G) etc. can be used.
As the polyamide resin, for example, 6-nylon, 6,6-nylon, 6,10-nylon, 12-nylon, etc. can be used.
As the styrene resin, for example, polystyrene, AS resin, ABS resin, etc. can be used.

As the cellulose derivative, for example, cellulose acetate, nitrocellulose, etc. can be used.
As the chlorine-based resin, for example, polyvinyl chloride, polyvinylidene chloride, etc. can be used.
As the fluororesin, for example, polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, etc. can be used.

The thickness of the transparent resin layer 7 is preferably within the range of 20 μm or more and 150 μm or less, and preferably within the range of 45 μm or more and 90 μm or less, in order to improve both the strength and transparency of the transparent resin layer 7. is more preferable.
The transparent resin layer 7 may contain existing heat stabilizers, flame retardants, ultraviolet absorbers, light stabilizers, antiblocking agents, catalyst scavengers, colorants, light scattering agents, and gloss adjusters as necessary. Various additives such as can be added. In order to improve the surface strength, it is preferable to use a highly crystalline polypropylene resin. Note that, as the thermal stabilizer, for example, a phenol type, sulfur type, phosphorus type, hydrazine type, etc. can be used. As the flame retardant, for example, aluminum hydroxide, magnesium hydroxide, etc. can be used. As the ultraviolet absorber, for example, benzotriazole type, benzoate type, benzophenone type, triazine type, etc. can be used. As the light stabilizer, for example, a hindered amine type or the like can be used. Furthermore, an embossed pattern 7a having a predetermined uneven pattern as shown in FIG. 3 may be formed on the surface of the transparent resin layer 7, if necessary.

(embossed pattern)
The embossed pattern 7a is, for example, a pattern consisting of concave portions and convex portions that are synchronized with the pattern of the picture pattern layer 3. The concave portions and convex portions of the embossed pattern 7a can provide a three-dimensional effect through tactile sensation. It is preferable that the deviation between the embossed pattern 7a and the pattern of the pattern layer 3 be within the range of, for example, 10 mm or less in the longitudinal direction and 3 mm or less in the lateral direction (width direction) with respect to the shape of the pattern. . For example, if the picture pattern is wood grain, the direction in which the wood grain conduit extends is the "longitudinal direction with respect to the shape of the picture pattern," and the direction perpendicular to the longitudinal direction is the "short direction with respect to the shape of the picture pattern." Become. In particular, when the wood grain conduit extends along the longitudinal direction of the noncombustible sheet 10, the longitudinal direction of the noncombustible sheet 10 becomes the "longitudinal direction with respect to the shape of the pattern", and the transverse direction (width direction) of the noncombustible sheet 10 ) is the "short direction with respect to the shape of the picture pattern". Since the transparent resin layer 7 and the top coat layer 4 are transparent, the embossed pattern 7a is only strongly visible due to the reflection of oblique light. For example, it is difficult to visually recognize the transmitted light of the picture pattern layer 3 at the same time as the reflected light, so there is no discomfort. By suppressing the deviation between the embossed pattern 7a and the pattern of the patterned pattern layer 3 within a certain range, it is possible to obtain a noncombustible sheet 10 in which the shape and distribution of the pattern are uniform and accurately matched over the entire surface of the sheet. Further, the height difference between the concave portion and the convex portion of the embossed pattern 7a is, for example, within a range of 3 μm or more and 200 μm or less. For the height difference, a value suitable for the intended design of the noncombustible sheet 10 can be selected. For example, it is also possible to take a continuous multi-stage shape within the maximum height difference (200 μm). In particular, in order to obtain a shape as a macroscopic three-dimensional object, the height difference is more preferably in a range of 10 μm or more and 150 μm or less.

(Top coat layer)
The top coat layer 4 includes a first top coat layer 4a and a second top coat layer 4b.
The first top coat layer 4a is a layer that is provided on the surface side of the transparent resin layer 7 and covers the entire transparent resin layer 7. The first top coat layer 4a is made of a material (resin) that is transparent or translucent to such an extent that the pattern of the picture pattern layer 3 can be seen through the first top coat layer 4a. The first top coat layer 4a may be a single layer or a layer formed by stacking a plurality of layers. In addition, the thickness of the first top coat layer 4a is, for example, 3 μm or more and 100 μm or less in order to obtain sufficient strength to completely fill the embossed pattern 7a and protect the surface of the transparent resin layer 7 without impairing the design. It is preferable that it is within the range of . Further, as the material for the first top coat layer 4a, a thermosetting resin is preferable, for example, from the viewpoints of adhesion to the transparent resin layer 7, deformation followability of the noncombustible sheet 10, scratch resistance, and the like. In particular, from the viewpoint of cost and versatility, a thermosetting resin (binder) having a urethane bond such as a two-component curable urethane resin is more preferable. For example, a matting agent such as silica particles or a scratch-resistant agent may be added to the thermosetting resin.

As the two-component curable urethane resin, for example, a urethane resin containing a polyol as a main component and an isocyanate as a crosslinking agent (curing agent) can be used. The polyol has two or more hydroxyl groups in the molecule, and for example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol, polycarbonate polyol, and polyurethane polyol can be used.
Further, as the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in the molecule can be used. For example, aromatic isocyanates such as 2,4-tolylene diisocyanate, xylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. aliphatic (or cycloaliphatic) isocyanates can be used. Further, adducts or multimers of the various isocyanates mentioned above can be used. Examples include tolylene diisocyanate adducts, tolylene diisocyanate trimers, and the like. In addition, among the above-mentioned isocyanates, aliphatic (or alicyclic) isocyanates are preferable because they have good weather resistance and resistance to heat yellowing, and for example, 1,6-hexamethylene diisocyanate can be used.

Moreover, when abrasion resistance is important, an ionizing radiation-curable resin is preferable from the viewpoint of hardness. As the ionizing radiation curable resin, for example, an ultraviolet ray curable resin can be used. For example, (meth)acrylic resin, silicone resin, polyester resin, urethane resin, amide resin, and epoxy resin can be used. By using the ultraviolet curable resin, the hardness of the top coat layer 4, that is, the outermost layer of the noncombustible sheet 10, can be improved, and the surface physical properties of the noncombustible sheet 10, such as abrasion resistance, scratch resistance, and solvent resistance, can be improved. . Further, as the material for the first top coat layer 4a, for example, a mixture of a thermosetting resin and an ionizing radiation curable resin may be used.

The second top coat layer 4b is a layer that is partially provided on the surface side of the first top coat layer 4a and covers a part of the surface of the first top coat layer 4a. The part of the surface of the first top coat layer 4a includes, for example, the part of the picture pattern layer 3 that faces the printing ink. Further, as the material for the second top coat layer 4b, for example, the same resin as the first top coat layer 4a can be used. A filler may be added to the second top coat layer 4b. By adding a filler, mechanical properties such as gloss, touch, texture, surface strength, and friction that are different from those of the first top coat layer 4a can be imparted. As the filler, for example, beads or irregularly shaped particles of resin such as acrylic, polyolefin, or silicone, or beads or irregularly shaped particles of inorganic material such as silica, alumina, or metal oxide can be used. Further, the method for forming the second top coat layer 4b is not particularly limited, and any known printing method can be employed. Note that the second top coat layer 4b is also generally referred to as a "tactile coat layer" or a "matte conduit printing layer."
The above-described embodiment is an example of the present invention, and the present invention is not limited to the above-described embodiment, and even forms other than this embodiment may incorporate the technical idea of the present invention. Various changes can be made according to the design, etc., as long as they do not deviate from the range.

[Example]
(Examples 1 to 16, Comparative Examples 1 to 2)
First, a raw fabric layer composed of calcium carbonate powder and polypropylene resin, which is a thermoplastic resin, was formed. The composition ratio of the raw fabric layer was 60% by mass of calcium carbonate powder and 40% by mass of polypropylene resin. The thickness of the original fabric layer was 200 μm. The purity of the calcium carbonate powder used was 90% by mass of calcium carbonate. Further, the calcium carbonate powder used had an average particle diameter (mode diameter) of 2 μm and a maximum particle diameter of 50 μm or less. The calcium carbonate powder used had its surface treated (coated) with 1-hydroxyethylidene-1,1-diphosphonic acid, which is an organic phosphorus-based surface treatment agent.

Next, the front and back surfaces of the original fabric layer were subjected to corona treatment.
Next, a urethane-based anchor layer forming ink containing salt-vinyl acetate or an acrylic-based anchor layer-forming ink containing salt-vinyl acetate is applied to the front and back surfaces of the corona-treated original fabric layer to a film thickness of 1 μm to 2 μm. It was coated and dried under conditions of a drying temperature of 40° C. and a drying time of 30 seconds. In this way, anchor layers were formed on the front and back surfaces of the original fabric layer. The content of urethane resin containing vinyl acetate and the content of acrylic resin containing vinyl acetate in the anchor layer forming ink used in each example and each comparative example are as shown in Table 1 below. . Note that the urethane resin containing vinyl acetate salt and the acrylic resin containing vinyl acetate salt are expressed in "% by mass" based on the mass of the entire anchor layer. Moreover, as the urethane-based resin containing salt-vinyl acetate, one in which the mass ratio of salt-vinyl acetate and urethane-based resin (salt-vinyl acetate: urethane-based resin) was 20:80 was used. Furthermore, as the acrylic resin containing salt vinyl acetate, one having a mass ratio of salt vinyl acetate and acrylic resin (salt vinyl acetate:acrylic resin) was used.

Next, on the anchor layer on the surface side of the original fabric layer, a urethane-based pattern layer forming ink is coated (printed) so that the coating film thickness is 1 μm to 2 μm, and the drying temperature is 40°C and the drying time is 30°C. It was dried under conditions of seconds. In this way, a picture pattern layer was formed on the anchor layer on the surface side of the original fabric layer.
Thereafter, the laminate (sheet) including the original fabric layer, the anchor layer, and the picture pattern layer was aged at room temperature for one day to prepare samples for each evaluation.

(Examples 17-22, Comparative Examples 3-4)
In Examples 17 to 22 and Comparative Examples 3 to 4, the content of the urethane-based resin containing salt-vinyl acetate with respect to the mass of the anchor layer was 85% by mass, and the mass of salt-vinyl acetate and the urethane-based resin in the anchor layer forming ink were A laminate (sheet ) was obtained.

(Examples 23 to 26)
In Examples 23 to 26, the content of the urethane-based resin containing salt-vinyl acetate with respect to the mass of the anchor layer was 85% by mass, and the ratio of the mass of salt-vinyl acetate to the urethane-based resin in the anchor layer forming ink ( A laminate (sheet) was prepared in the same manner as in Examples 1 to 16, except that the ratio (mass of salt-vinyl acetate/mass of urethane resin) was 20/80, and the type of surface treatment agent was as shown in Table 3 below. I got it.
The evaluation items in this example are as follows.

<Ink adhesion>
After pressing cellophane tape manufactured by Nichiban onto the surface of the printed sheet, it was strongly peeled off with a constant force, and the presence or absence of peeling inside the picture pattern layer or between the original fabric layer and the picture pattern layer was visually evaluated. The evaluation criteria are as follows.
◎: When peeled off with a force of 15N (Newton), no peeling occurred inside the pattern layer or between the original fabric layer and the pattern layer. ○: When peeled off with a force of 10N, the pattern did not peel off. No peeling occurred inside the layer or between the raw fabric layer and the patterned layer. △: When peeled off with a force of 10N, no peeling occurred inside the patterned layer or in a part of the layer between the raw fabric layer and the patterned layer. Peeling occurs ×: The picture pattern layer adheres to the entire surface of the cellophane tape, and significant peeling occurs inside the picture pattern layer or between the original fabric layer and the picture pattern layer. In the above evaluation, "◎", "○", and " △” was considered a pass.

<Print suitability>
Visual evaluation was made to determine whether the ink could be laminated without powder falling from the original fabric layer during printing. The evaluation criteria are as follows.
○: Plate jams due to falling powder do not occur, and it is possible to form a uniform coated surface without unevenness or omissions. △: Plate jamming, unevenness, or omissions due to falling powder may occur depending on the printing conditions or equipment conditions of the printing machine. ×: Plate clogging occurred due to falling powder, or it was extremely difficult to form a uniform coated surface. In the above evaluation, "○" and "△" were considered acceptable.

<Surface dusting after printing>
After printing, the surface of the sheet was dry-rubbed by hand or with cotton, and the presence or absence of powder blowing and shedding of calcium carbonate powder was visually evaluated. The evaluation criteria are as follows.
○: No calcium carbonate powder was observed on the surface of the hand or cotton. △: Calcium carbonate powder was observed on part of the surface of the hand or cotton. ×: The entire surface of the hand or cotton was observed. In the above evaluation, "○" and "△" were considered to be acceptable.

<Nonflammability test>
It was evaluated whether the following requirements were met in a heat generation test using a cone calorimeter tester in accordance with ISO5660-1.
1. Total calorific value is 8MJ/ ^m2 or less 2. Maximum heat generation rate does not exceed 200kW/ ^m2 for 10 seconds or more 3. No cracks or holes penetrating the back surface, which would be detrimental to flame protection, were created. As the noncombustible base material, gypsum board was used. Moreover, the evaluation criteria are as follows.
○: All of the above requirements are met. ×: At least one of the above requirements is not met. In each of the above evaluations, a sheet with an evaluation of "x" was judged as a failure as a whole.

<Weather resistance test>
The sheets obtained in each Example and each Comparative Example were set in Metal Weather manufactured by Daipura Wintes Co., Ltd. under light conditions (illuminance: 60 mW/cm ² , black panel temperature 63°C, inner humidity 50% RH). 20 hours, 4 hours under dew condensation conditions (illuminance: 0 mW/cm ² , black panel temperature 30°C, layer humidity 98% RH), 98 hours under water spray conditions (10 seconds before and after dew condensation conditions), 200 hours , 300 hours, 500 hours, and 1000 hours of weather resistance tests were conducted. After the above test, the sheet was kept under conditions of 25° C. and 50% RH for 2 days, and then the appearance of the sheet surface, such as cracks and yellowing, was visually evaluated according to the following criteria.

(exterior)
◎: There was no change at all compared to the initial stage even after 200 hours.
○: After 200 hours, there was a change in appearance compared to the initial stage, but no cracks were observed.
Δ: Although there were fine cracks on the surface after 200 hours, there were no problems in use.
×: After 200 hours, there were numerous cracks on the surface.
In the above evaluation, "◎", "○", and "△" were regarded as passing.

(yellowing)
◎: There was no change at all compared to the initial state even after 98 hours.
○: After 98 hours, some yellowing was observed compared to the initial stage.
△: Although yellowing was observed after 98 hours, it was not a problem in use.
x: Significant yellowing occurred after 98 hours.
In the above evaluation, "◎", "○", and "△" were regarded as passing.

As described above, the sheet includes the raw fabric layer 1, the front anchor layer 2 formed on the surface of the raw fabric layer 1, and the back anchor layer 5 formed on the back side of the raw fabric layer 1, The raw fabric layer 1 contains a thermoplastic resin and an inorganic material, and the surface anchor layer 2 contains a urethane resin containing salt-vinyl acetate or an acrylic resin containing salt-vinyl acetate in the total mass of the surface anchor layer 2. In contrast, it contains within the range of 15% by mass or more and 100% by mass or less, and the surface of the inorganic material is treated with an organic phosphorus surface treatment agent, an inorganic phosphoric acid surface treatment agent, a polycarboxylic acid surface treatment agent, and a coupling agent. When treated with at least one type of surface treatment agent, it is possible to prevent the inorganic material contained in the raw fabric layer 1 from falling off while providing nonflammability, and the raw fabric layer 1 and the pattern layer 3 It is possible to improve the interlayer strength between the two layers, and furthermore, it is possible to impart weather resistance.

1 Original fabric layer 2 Surface anchor layer 3 Pattern layer 4 Top coat layer 4a First top coat layer 4b Second top coat layer 5 Back anchor layer 6 Primer layer 7 Transparent resin layer 7a Embossed pattern 10 Noncombustible sheet 11 Substrate 12 Noncombustible material

Claims (22)

a raw fabric layer, a first anchor layer formed on a first surface of the raw fabric layer, and a second anchor layer formed on a second surface of the raw fabric layer that is a surface opposite to the first surface. a second anchor layer;
The raw fabric layer contains a thermoplastic resin and an inorganic material,
The first anchor layer contains an acrylic resin containing vinyl acetate in an amount of 15% by mass or more and 100% by mass or less based on the entire mass of the first anchor layer,
The surface of the inorganic material is treated with at least one of an organic phosphorus surface treatment agent, an inorganic phosphoric acid surface treatment agent, a polycarboxylic acid surface treatment agent, and a coupling agent surface treatment agent,
A noncombustible sheet characterized in that the content of the inorganic material is within a range of 15% by mass or more and 90% by mass or less based on the mass of the raw fabric layer . The first anchor layer contains the acrylic resin containing vinyl acetate in an amount of 80% by mass or more and 100% by mass or less based on the entire mass of the first anchor layer. The noncombustible sheet according to claim 1. The second anchor layer contains a urethane resin containing vinyl acetate or an acrylic resin containing vinyl acetate in an amount of 15% by mass or more and 100% by mass or less based on the entire mass of the second anchor layer. The noncombustible sheet according to claim 1 or 2, characterized in that the content is within a range. The second anchor layer contains a urethane resin containing vinyl acetate or an acrylic resin containing vinyl acetate in an amount of 80% by mass or more and 100% by mass or less based on the entire mass of the second anchor layer. The noncombustible sheet according to claim 3, characterized in that the content is within a range. The content of the acrylic resin containing the salt vinyl acetate in the first anchor layer is equal to the content of the urethane resin containing the salt vinyl acetate in the second anchor layer, or the content of the acrylic resin containing the salt vinyl acetate in the second anchor layer. The noncombustible sheet according to claim 3 or 4, characterized in that the amount is the same. The content of the acrylic resin containing the salt vinyl acetate in the first anchor layer is equal to the content of the urethane resin containing the salt vinyl acetate in the second anchor layer, or the content of the acrylic resin containing the salt vinyl acetate in the second anchor layer. The noncombustible sheet according to claim 3 or 4, characterized in that the amount of the noncombustible sheet is larger than the amount. The content of the acrylic resin containing the salt vinyl acetate in the first anchor layer is equal to the content of the urethane resin containing the salt vinyl acetate in the second anchor layer, or the content of the acrylic resin containing the salt vinyl acetate in the second anchor layer. 5. The noncombustible sheet according to claim 3 or 4, characterized in that the amount of the noncombustible sheet is less than the amount. Any one of claims 1 to 7, wherein the inorganic material is in a powder form, has an average particle size in a range of 1 μm or more and 3 μm or less, and has a maximum particle size of 50 μm or less. Noncombustible sheet as described in . The inorganic materials include antimony trioxide, antimony soda, zircon silicate, zircon oxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, borax, zinc borate, calcium carbonate, molybdenum trioxide, or antimony dimolybdate and water. Contains at least one of a complex of aluminum oxide, a complex of antimony trioxide and silica, a complex of antimony trioxide and zinc white, a silicic acid of zirconium, a complex of a zirconium compound and antimony trioxide, and a salt thereof. The noncombustible sheet according to any one of claims 1 to 8 . The noncombustible sheet according to any one of claims 1 to 9 , wherein the thermoplastic resin contains at least one of polypropylene, polyethylene, and polyester. The total content of the thermoplastic resin and the inorganic material is within a range of 90% by mass or more and 100% by mass or less based on the mass of the raw fabric layer. 1. The noncombustible sheet according to any one of 10 . The noncombustible sheet according to any one of claims 1 to 11 , wherein the thickness of the original fabric layer is within a range of 50 μm or more and 250 μm or less. The noncombustible sheet according to any one of claims 1 to 12 , comprising the raw fabric layer, the first anchor layer, and a top coat layer in this order. The noncombustible material according to any one of claims 1 to 13 , characterized in that the raw fabric layer, the first anchor layer, a picture pattern layer, and a top coat layer are provided in this order. sheet. The noncombustible sheet according to any one of claims 1 to 14 , comprising the raw fabric layer, the second anchor layer, and a primer layer in this order. The noncombustible sheet according to any one of claims 1 to 15 , characterized in that it satisfies requirements for obtaining noncombustibility certification in a heat generation test based on ISO5660-1. The second anchor layer is characterized in that it contains an acrylic resin containing vinyl acetate in an amount of 15% by mass or more and 100% by mass or less based on the entire mass of the second anchor layer. The noncombustible sheet according to any one of claims 1 to 16 . The inorganic materials include antimony soda, zircon silicate, zircon oxide, basic magnesium carbonate, borax, zinc borate, a complex of antimony dimolybdate and aluminum hydroxide, a complex of antimony trioxide and silica, and a complex of antimony trioxide and zinc. Claims 1 to 17 , characterized in that the composition contains at least one of a complex of zirconium, silicic acid of zirconium, a complex of a zirconium compound and antimony trioxide, and a salt thereof. nonflammable sheet. The surface of the inorganic material is treated with at least one of the organic phosphorus surface treatment agent, the inorganic phosphate surface treatment agent, and the coupling agent surface treatment agent. The noncombustible sheet according to any one of claims 1 to 8 . The surface of the inorganic material is treated with at least one of the organic phosphorus surface treatment agent and the inorganic phosphate surface treatment agent,
The organic phosphorus surface treatment agent includes 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilotrismethylenephosphonic acid, trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, methyl phosphoric acid, and phosphoric acid. acid ethyl acid or their salts,
20. The noncombustible sheet according to claim 1, wherein the inorganic phosphoric acid surface treatment agent is pyrophosphoric acid, polyphosphoric acids, hexametaphosphoric acid, or a salt thereof. The inorganic material is calcium carbonate,
20. The surface of the inorganic material is coated with 1-hydroxyethylidene- 1,1 -diphosphonic acid, which is the organic phosphorus surface treatment agent. Noncombustible sheet as described in . The noncombustible sheet according to any one of claims 1 to 21, wherein at least one of the first anchor layer and the second anchor layer does not contain an inorganic material.

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