JP2020163777A - Method for producing non-flammable sheet and non-flammable sheet - Google Patents

Abstract

To provide a non-flammable sheet having heat insulation property.SOLUTION: A non-flammable sheet 10 includes a raw fabric layer 1 and a surface anchor layer 2 formed on one surface of the raw fabric layer 1, in which the raw fabric layer 1 is formed by uniaxially stretching or biaxially stretching a mixture containing a thermoplastic resin, an inorganic material and a foaming agent and foaming the foaming agent, and the surface anchor layer 2 is formed by containing an urethane-based resin containing vinyl acetate or an acrylic resin containing vinyl acetate. A planar gap is formed by uniaxially stretching or biaxially stretching, and a gap having such a shape as to extend in a thickness direction of the raw fabric layer 1 is formed by heating and foaming the foaming agent. Thus, heat insulation property can be imparted to the non-flammable sheet 10 by having the gap in the raw-fabric layer 1.SELECTED DRAWING: Figure 1

Description

The present invention relates to a method for producing a non-combustible sheet and a non-combustible sheet.

Non-combustible materials are used for interiors such as walls, floors, and ceilings of buildings. As a laminated material having high non-combustibility, for example, a non-combustible laminated material in which a heat insulating base material, a non-combustible reinforcing layer, a paper layer, a metal layer, and a decorative layer are bonded in this order has been proposed (for example). , Patent Document 1).

Japanese Unexamined Patent Publication No. 2017-035898

By the way, flooring materials such as around water and dressing rooms can easily convey coldness, and in winter, it is easy to catch a cold, which may be harmful to health, and in the case of elderly people, it may put a burden on the heart and the like.
As a method for ensuring heat insulating properties, for example, laminating a heat insulating material, a heat insulating sheet, or the like on a nonflammable floor material can be mentioned. However, since it takes time and effort to laminate a heat insulating material, a heat insulating sheet, or the like on the floor, a non-combustible sheet capable of sufficiently ensuring heat insulating properties without laminating these heat insulating materials or the like has been desired.
Therefore, an object of the present invention is to provide a method for producing a non-combustible sheet having heat insulating properties and a non-combustible sheet.

In order to achieve the above object, the method for producing a non-combustible sheet according to one aspect of the present invention is a method for producing a non-combustible sheet including a raw fabric layer and an anchor layer formed on one surface of the raw fabric layer. The raw fabric layer is formed by uniaxially or biaxially stretching a mixture containing a thermoplastic resin, an inorganic material, and a foaming agent, and foaming the foaming agent, and the anchor layer is formed of salt and vinegar. It is characterized in that it is formed by containing a urethane resin containing salt or an acrylic resin containing salt and vinegar.
Further, the non-combustible sheet according to another aspect of the present invention has a raw fabric layer and an anchor layer formed on one surface of the raw fabric layer, and the raw fabric layer is made of a thermoplastic resin and an inorganic material. It contains a material and a foaming agent, and has a plurality of voids formed between the inorganic material and the thermoplastic resin scattered throughout, and the voids formed by the foamed foaming agent are scattered throughout. The anchor layer is characterized by containing a urethane resin containing salt and vinegar or an acrylic resin containing salt and vinegar.

According to the present invention, a non-combustible sheet having heat insulating properties can be realized.

It is sectional drawing which shows the structure of the noncombustible sheet and noncombustible material which concerns on 1st Embodiment of this invention. It is sectional drawing which shows the structure of the noncombustible sheet and the noncombustible material which concerns on the modification of 1st Embodiment of this invention. It is sectional drawing which shows the structure of the noncombustible sheet and the noncombustible material which concerns on 2nd Embodiment of this invention.

Next, an embodiment 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 plane dimension, the ratio of the thickness of each layer, and the like are different from the actual ones. Further, the embodiments shown below exemplify a configuration for embodying the technical idea of the present invention, and the technical idea of the present invention describes the materials, shapes, structures, etc. of the constituent parts as follows. It is not something that is specific to something. The technical idea of the present invention may be modified in various ways within the technical scope specified by the claims stated in the claims.

<First Embodiment>
[Composition of non-combustible sheet]
As shown in FIG. 1, the non-combustible sheet 10 of the first embodiment has a primer layer 6, a back surface anchor layer 5, a raw fabric layer 1, and a surface anchor layer (patented) from the backmost surface side to the outermost surface side. (Corresponding to the anchor layer in the claims) 2, the pattern layer 3 and the surface protection layer 4 are provided. Although FIG. 1 is a cross-sectional view of the non-combustible sheet 10, the raw fabric layer 1 is not hatched. Further, the non-combustible material 12 of the first embodiment includes the non-combustible sheet 10 of the first embodiment and the substrate 11.

Hereinafter, each layer constituting the non-combustible sheet 10 will be described. The content of various materials described later means the content ratio (mass%) with respect to the mass of the entire corresponding layer in the dry state. For example, the content of the inorganic material of the present embodiment, which will be described later, means the content ratio (mass%) with respect to the total mass of the raw fabric layer 1 in the dry state. Further, the content of the urethane resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the surface anchor layer 2 described later is the content ratio (mass%) with respect to the total mass of the surface anchor layer 2 in the dry state. Means. Further, the content of the urethane resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the back surface anchor layer 5 described later is the content ratio (mass%) with respect to the total mass of the back surface anchor layer 5 in the dry state. Means.

(Original layer)
The raw fabric layer 1 is a layer (sheet) that serves as a base material for the non-combustible sheet 10, and is a layer containing a thermoplastic resin, an inorganic material, and a foaming agent.
The content of the inorganic material of the present embodiment may be in the range of 15% by mass or more and 90% by mass or less with respect to the mass of the raw fabric layer 1, and may be in the range of 20% by mass or more and 80% by mass or less. It is more preferable, and more preferably in 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 is relatively large, so that it tends to be difficult to obtain nonflammability or flame retardancy. Further, when the surface of the raw fabric layer 1 is scratched with a Hoffman scratch tester, it may be scratched to a visible extent, 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, so-called "powder blowing" may occur on the surface of the raw fabric layer 1 when the anchor layer is applied or printed on the surface of the raw fabric layer 1. Here, "powder blowing" means that the inorganic material contained in the raw fabric layer 1 emerges on the surface of the raw fabric layer 1. Further, when the pattern layer 3 is formed, the inorganic material that emerges from the raw fabric layer 1 may make it difficult for the ink to be laminated, that is, the printability may be lowered. Further, when laminating a sheet forming at least one of a front surface anchor layer 2, a back surface anchor layer 5, a pattern layer 3, and a surface protection layer 4 on a wood-based base material and a stone-based base material in a roll shape or a single leaf. It becomes difficult to laminate, that is, the laminating suitability tends to decrease. Further, after the cellophane tape is pressure-bonded to the surface of the sheet on which the pattern pattern layer 3 is formed, it is strongly peeled off and peeled off in the pattern pattern layer 3 or between the original fabric layer 1 (surface anchor layer 2) and the pattern pattern layer 3. That is, the ink adhesion may decrease.

As described above, the content of the inorganic material of the present 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 with respect to the mass of the raw fabric layer 1. If it is within the range of 80% by mass or more, it is possible to reduce the occurrence of powder blowing, improve the printability, improve the laminating suitability, and further have sufficient surface hardness while obtaining nonflammability or flame retardancy. Can be obtained, and ink adhesion can be improved.

Further, the inorganic material of the present embodiment is preferably in a powder shape (powder shape), and its average particle diameter is preferably in the range of 1 μm or more and 3 μm or less, and the maximum particle diameter is preferably 50 μm or less. .. When the average particle size and the maximum particle size of the inorganic material are within the above numerical ranges, the flatness of the surface of the raw fabric layer 1 can be maintained while improving the dispersibility of the inorganic material with respect to the thermoplastic resin. If the average particle size of the inorganic material is less than 1 μm, the cohesive force between the inorganic materials may increase, and the dispersibility in the thermoplastic resin described later may decrease. Further, when the average particle size of the inorganic material exceeds 3 μm, the flatness of the surface of the raw fabric layer 1 is lowered, and the thickness of the front surface anchor layer 2 or the back surface anchor layer 5 described later becomes uneven, or unevenness or chipping occurs. It may occur. Further, when the maximum particle size of the inorganic material exceeds 50 μm, the flatness of the surface of the raw fabric layer 1 is lowered, and the thickness of the front surface anchor layer 2 or the back surface anchor layer 5 described later becomes uneven, or unevenness or chipping occurs. It may occur. In this embodiment, the "average particle size" means the mode diameter.

The inorganic material is, for example, a powder containing calcium carbonate. The inorganic material preferably contains calcium carbonate in the range of 50% by mass or more and 100% by mass or less. If it is an inorganic material having a calcium carbonate content of 50% by mass or more, it is possible to impart sufficient nonflammability or sufficient flame retardancy to the raw fabric layer 1 and impart sufficient mechanical strength. Can be done.
In addition to calcium carbonate, examples of inorganic materials include calcium carbonate salts, silica (particularly hollow silica), alumina, antimony trioxide, antimony soda, zirconite silicate, zirconium oxide compounds such as zirconium oxide, magnesium hydroxide, and hydroxide. Antimony trioxide and silica complex, antimony trioxide and zinc flower complex, zirconium silicic acid, such as aluminum, basic magnesium carbonate, borosand, zinc borate, molybdenum trioxide or antimony dimolybate and aluminum hydroxide complex. , Complexes of zirconium compounds and antimony trioxide, and at least one salt thereof. In particular, calcium carbonate and calcium carbonate salt can easily control the particle size and compatibility with the thermoplastic resin by the manufacturing method, and also because the material cost is low, from the viewpoint of reducing the cost of the non-combustible sheet. Suitable.

Further, the inorganic material may be a powder material having crystallinity, so-called crystalline powder, or a powder material having no crystallinity, so-called amorphous type powder material. If the inorganic material is a crystalline powder material, the powder itself is homogeneous and hasotropic, so that the mechanical strength of the powder itself is improved, and the scratch resistance and durability of the non-combustible sheet tend to be improved. Further, if the inorganic material is an amorphous type powder material, the electrical conductivity and thermal conductivity of the powder itself, or the light transmittance and light absorption rate can be appropriately adjusted, so that there are variations in tactile sensation and luster. It is possible to give abundant design.

Further, the inorganic material may be hollow glass beads or acrylic beads.
The thermoplastic resin of the present embodiment includes an ethylene homopolymer, a propylene homopolymer, an ethylene and / or a copolymer of propylene and another α-olefin copolymerizable therewith, an ethylene-ethyl acrylate copolymer and It is at least one selected from the group consisting of ethylene-vinyl acetate copolymers, that is, polyolefin-based resins. Specifically, polyethylene, polypropylene, polybutene, polymethylpentene and the like can be used, and polypropylene is most preferable. By using at least one of polypropylene and polyethylene 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 95% by mass or less with respect to the mass of the raw fabric layer 1. When the total content of the thermoplastic resin and the inorganic material is within the above numerical range, printability and laminating suitability can be improved while obtaining sufficient nonflammability or sufficient flame retardancy. If the total content of the thermoplastic resin and the inorganic material is less than 90% by mass with respect to the mass of the raw fabric layer 1, sufficient nonflammability or sufficient flame retardancy may not be obtained. In addition, printability and laminating suitability may decrease.

When the total content of the thermoplastic resin and the inorganic material is 95% 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. It is preferably within the range, and 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 is in the range of 20% by mass or more and 80% by mass or less, and the content of the inorganic material is in the range of 20% by mass or more and 80% by mass or less. Further, it is more preferable that the content of the thermoplastic resin is in the range of 20% by mass or more and 40% by mass or less, and the content of the inorganic material is in the range of 60% by mass or more and 80% by mass or less. When the total content of the thermoplastic resin and the inorganic material is within the above numerical range, it is possible to surely improve printability and laminate suitability while surely obtaining sufficient nonflammability or sufficient flame retardancy.

As the foaming agent of the present embodiment, at least one of a decomposition gas generating foaming agent, an expandable capsule foaming agent and the like can be used. Preferred examples of the decomposition gas generating foaming agent are azodicarboxylic amide, dinitrosopentamethylenetetramine, paratoluenesulfonyl hydrazide, benzenesulfonylhydrazide, sodium bicarbonate and ammonium carbonate, azobisisobutyronitrile, 4,4-oxybis. (Benzerosulfonic acid hydrazide), diphenylsulfon-3,3'-disulfohydrazide, benzene-1,3-disulfohydrazide, p-toluenesulfonyl semicarbazide, and at least one of effervescent hollow microspheres. .. The expandable capsule foaming agent includes hydrocarbons such as ethane, butane, pentane, neopentane, hexane, and heptane in fine particles coated with a thermoplastic resin such as acrylic acid ester, vinylidene chloride, acrylonitrile, and urethane. Examples include those containing the volatile expansion component of.

By including the foaming agent in the raw fabric layer 1, as shown in FIG. 1, it is possible to obtain the raw fabric layer 1 in which a plurality of voids 1a formed by the foaming agent are scattered throughout.
The content of the foaming agent may be any amount as long as it can obtain heat insulating properties as the floor material and has the interlayer strength of the resin composition and the strength as the floor material, and may be adjusted as necessary. For example, the amount of foaming agent foams at least 10%, 25%, 50%, 100%, 150%, 200% or more in volume when the non-combustible sheet 10 is heated. You just have to do it. The content of the foaming agent is, for example, in the range of 5% by mass or more and 10% by mass or less with respect to the mass of the raw fabric layer 1.

The raw fabric layer 1 may contain at least one or more fillers in an amount in the range of 10% by weight or more and 60% by weight or less in order to improve corrosion resistance, surface adhesiveness and the like.
The raw fabric layer 1 may contain at least one selected from the group consisting of mica filler, glass fiber, calcium carbonate and hollow glass microspheres as the filler. The hollow glass microspheres preferably have a diameter in the range of, for example, 5 μm or more and 200 μm or less, and more preferably 70 μm or less.
Further, the raw fabric layer 1 may contain fibers selected from the group consisting of carbon fibers, metal fibers (for example, aluminum), glass fibers, polyamide fibers, polyethylene fibers or polyester fibers, and mixtures thereof. Further, the raw fabric layer 1 may contain cellulose fibers such as cellulose nanofibers.

Further, the raw fabric layer 1 may contain one or more kinds of ultrafine thermoplastic polymer powders. In principle, the thermoplastic polymer powder can be selected from a large number of ultrafine polymer powders, for example, vinyl acetate pomopolymer, vinyl acetate copolymer, ethylene vinyl acetate copolymer, vinyl chloride homopolymer (PVC), vinyl chloride and acetic acid. Copolymers with at least one of vinyl and (meth) acrylate, styrene homo or copolymers, (meth) acrylate homo or copolymers (eg, polymethylmethacrylate, butyl acrylate / methyl acrylate copolymers), polyolefins, polyethers, polyvinyl butyral and the like. .. In particular, a thermoplastic polymer containing a functional group such as a carboxyl group, a carboxylic acid anhydride group or an imidazole group and / or having a core / shell structure is preferable. The thermoplastic polymer powder generally has an average particle size of 1 mm or less, preferably 350 μm or less, more preferably 100 μm or less.

The thickness of the raw fabric layer 1 is preferably in the range of 50 μm or more and 12500 μm or less, and more preferably in the range of 70 μm or more and 10000 μm or less. When the thickness of the raw fabric layer 1 is within the above numerical range, the laminating suitability can be improved. If the thickness of the raw fabric layer 1 is less than 50 μm, the laminating suitability tends to decrease. Further, if the thickness of the raw fabric layer 1 exceeds 12500 μm, it becomes difficult to handle in terms of workability and workability.
Further, the raw fabric layer 1 is a uniaxially stretched or biaxially stretched raw fabric layer. If the raw fabric layer 1 is a uniaxially stretched or biaxially stretched raw fabric layer, the versatility of the noncombustible sheet 10 can be enhanced. Further, in the case of a uniaxially stretched or biaxially stretched raw fabric layer, as shown in FIG. 1, by including the inorganic material 1b, the front and back surfaces of the raw fabric layer 1 are placed between the inorganic material 1b and the thermoplastic resin. It is possible to obtain the original fabric layer 1 in which a plurality of voids 1c having a planar (horizontal direction) shape extending in a direction parallel to the above are scattered throughout.

That is, since the raw fabric layer 1 contains a foaming agent and is formed by uniaxial stretching or biaxial stretching, as shown in FIG. 1, the void 1a having a shape extending in the thickness direction in FIG. 1 due to the foaming agent. And has a void 1c having a shape extending in the lateral direction in FIG. 1 due to the inorganic material 1b, and as a result, a void having a shape extending in the lateral direction and a shape extending in the thickness direction in FIG. It is possible to obtain the raw fabric layer 1 in which a plurality of voids are scattered throughout.
It is preferable to perform surface treatment such as corona treatment or plasma treatment on at least the surface of the raw fabric layer 1 before forming the surface anchor layer 2 described later. Adhesion (adhesion) between the surface anchor layer 2 formed on the surface treated surface by applying surface treatment such as corona treatment or plasma treatment to at least the surface of the raw fabric layer 1 and the raw fabric layer 1. Gender) improves. When the back surface anchor layer 5 is also formed on the back surface of the raw fabric layer 1, the back surface of the raw fabric layer 1 may be subjected to surface treatment such as corona treatment or plasma treatment before forming the back surface anchor layer 5. preferable.

Further, before forming the front surface anchor layer 2 and the back surface anchor layer 5, the front surface of the raw fabric layer 1 on which the front surface anchor layer 2 is formed, and the back surface when the back surface anchor layer 5 is formed are also brushed. , The powdered inorganic material may be removed in advance.
A surface anchor layer 2 is provided between the pattern layer 3 and the original fabric layer 1, that is, on the surface side of the original fabric layer 1 in order to bring the pattern pattern layer 3 into close contact with one surface of the original fabric layer 1. There is a need. On the other hand, the back surface anchor layer 5 and the primer layer 6 do not necessarily have to be provided on the back surface side of the raw fabric layer 1 because it depends on the method of constructing the noncombustible sheet 10.

(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 powder falling of the inorganic material contained in the raw fabric layer 1. If the inorganic material contained in the raw fabric layer 1 falls off in the printing system, specifically, in the printing apparatus during printing or resin coating, the inside of the printing system may be contaminated. Further, if the inorganic material contained in the raw fabric layer 1 is powdered off, problems such as ink loss may occur. Here, "ink missing" means that the ink is not partially printed.

Further, the surface anchor layer 2 also has a function of improving the adhesion between the raw fabric layer 1 and the ink forming the pattern layer 3 described later. If the surface anchor layer 2 is not provided, the ink forming the pattern layer 3 may peel off without adhering to the original fabric layer 1.
The surface anchor layer 2 preferably contains a urethane-based resin containing vinyl acetate or an acrylic resin containing vinyl acetate. Here, "salt vinegar bi" means a copolymer of vinyl chloride and vinyl acetate. The "urethane resin containing salt vinegar" is a composition containing salt vinegar and urethane resin, and the ratio of the content of salt vinegar to the content of urethane resin (salt vinegar). The bi content (mass) / urethane resin content (mass)) may be in the range of 80/20 or more and 1/99 or less, and preferably in the range of 50/50 or more and 5/95 or less. , 20/80 or more and 10/90 or less is more preferable.

Further, the "urethane-based resin containing vinyl acetate" may contain a curing agent in addition to the above-mentioned vinyl acetate and urethane-based resin. This curing agent is added to reliably cure the urethane-based resin containing vinyl acetate, and the content thereof is not particularly limited. For example, the ratio of the content of the urethane resin containing salt and vinegar to the content of the curing agent (content of urethane resin containing salt and vinegar (mass) / content of curing agent (mass)) is 99. It may be in the range of 1/1 or more and 1/99 or less, preferably in the range of 99/1 or more and 50/50 or less, and more preferably in the range of 95/5 or more and 90/10 or less.

The content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the surface anchor layer 2 is in the range of 15% by mass or more and 100% by mass or less with respect to the mass of the surface anchor layer 2. It is more preferably in the range of 80% by mass or more and 100% by mass or less, and further 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 and vinegar or the acrylic resin containing salt and vinegar 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 is increased. It is possible to form the surface anchor layer 2 which is uniform and has no unevenness or chipping while making it sufficient. When the content of the urethane resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the surface anchor layer 2 is less than 15% by mass with respect to the mass of the surface anchor layer 2, the surface anchor layer 2 and the surface anchor layer 2 The interlayer strength with the pattern layer 3 may be insufficient. Further, when the content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the surface anchor layer 2 is less than 80% by mass in a dry state with respect to the mass of the surface anchor layer 2. Although there is no problem in use, the ratio of the surface anchor layer 2 to the raw fabric layer 1 is lowered, and the interlayer strength between the surface anchor layer 2 and the raw fabric layer 1 is slightly lowered. If the content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the surface anchor layer 2 is 100% by mass or less with respect to the mass of the surface anchor layer 2, there is no problem in use. However, if it exceeds 95% by mass, or more accurately 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 pattern. The interlayer strength with the 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 urethane resin containing vinyl acetate or the vinyl acetate in the back anchor layer 5 described later. It may be the same as the content of the acrylic resin containing. That is, the content of the urethane-based resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the front surface anchor layer 2 includes the urethane-based resin containing vinyl acetate or the vinyl acetate in the back surface anchor layer 5. The content of the acrylic resin may be 1.0 times (within the range of 0.95 times or more and 1.04 times or less). The content of the urethane resin containing salt and vinegar in the front surface anchor layer 2 or the acrylic resin containing salt and vinegar is the urethane resin containing salt and vinegar in the back surface anchor layer 5, or the acrylic resin containing salt and vinegar. When the content of the resin is the same, the physical properties of the front surface anchor layer 2 and the physical properties of the back surface anchor layer 5 are almost the same, so that the raw fabric layer 1 is provided with the front surface anchor layer 2 and the back surface anchor layer 5. In, the occurrence of distortion, warpage, etc. can be reduced. Therefore, it is possible to reduce the occurrence of distortion and warpage of the entire non-combustible sheet. Further, 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, the manufacturing cost can be reduced and the work efficiency can be improved. be able to.

The content of the urethane-based resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the front surface anchor layer 2 includes the urethane-based resin containing vinyl acetate or the vinyl acetate in the back surface anchor layer 5. It may be higher or lower than the content of the acrylic resin. The content of the urethane resin containing salt and vinegar in the front surface anchor layer 2 or the acrylic resin containing salt and vinegar is the urethane resin containing salt and vinegar in the back surface anchor layer 5, or the acrylic resin containing salt and vinegar. When the content is higher or lower than the resin content, the physical properties of the front surface anchor layer 2 and the back surface anchor layer 5 are different, so that the raw fabric layer 1 provided with the front surface anchor layer 2 and the back surface anchor layer 5 is distorted. And warpage can be added. In this way, by imparting distortion, warpage, etc. to the raw fabric layer 1 provided with the front surface anchor layer 2 and the back surface anchor layer 5, the raw fabric layer 1 is bonded to the base material or the like having a curved surface without gaps. be able to. For example, the content of the urethane-based resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the front surface anchor layer 2 includes the urethane-based resin containing vinyl acetate or the vinyl acetate in the back surface 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 surface anchor layer 2 may be the same as the thickness of the back surface anchor layer 5. When the thickness of the front surface anchor layer 2 is the same as the thickness of the back surface anchor layer 5, the physical properties of the front surface anchor layer 2 and the physical properties of the back surface anchor layer 5 are almost the same, so that the original fabric layer 1 is the surface anchor layer 2. In the state where the back surface anchor layer 5 is provided, it is possible to reduce the occurrence of distortion, warpage, and the like.
Further, 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 different from the thickness of the back surface anchor layer 5, 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 visually recognized. By doing so, the pattern pattern layer 3 can be printed on the surface of the original fabric layer 1 without forming, for example, an identification mark indicating that it is a printing surface. As a result, product loss caused by forming the pattern layer 3 on the back surface (non-printing surface) side of the original fabric layer 1 can be reduced.

(Pattern pattern layer)
The pattern pattern layer 3 is a layer for imparting a pattern to the non-combustible sheet 10 and is formed on the surface anchor layer 2.
There are no particular restrictions on the type of pattern pattern formed by the pattern pattern layer 3, for example, wood grain pattern, stone pattern, cloth pattern, abstract pattern, geometric figure, character, symbol, etc. alone or in two types. The above may be combined and formed. Further, the pattern pattern layer 3 may be multicolored or monochromatic.
The pattern layer 3 is a layer formed by applying an ink containing an acrylic resin as a binder (hereinafter, also referred to as an ink for forming a pattern layer) to one surface of the surface anchor layer 2. Examples of the acrylic resin contained as a binder in the pattern layer forming ink include ethylene-methyl acrylate copolymer resin (EMA), ethylene-ethyl acrylate copolymer resin (EEA), and ethylene-methacrylic acid. A polymer resin (EMAA), an ethylene-acrylic acid copolymer resin (EAA), an ionomer resin, or a mixture thereof, which is mainly composed of an acrylate-based copolymer resin, can be used. Here, the "main component" refers to the component having the highest content among the components constituting the pattern pattern layer 3.

The pattern layer 3 may be a layer formed by applying an ink containing a urethane resin as a binder to one surface of the surface anchor layer 2. As the urethane-based resin, a urethane-based resin obtained by reacting an acrylic polyol with 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). ), Methylcyclohexamethylene diisocyanate, trimethylhexamethylene diisocyanate (TMDI) and the like can be appropriately selected, but in consideration of weather resistance, hexamethylene diisocyanate (HMDI) having a linear molecular structure is preferably used.

The pattern layer forming ink may contain a cross-linking agent for cross-linking the acrylic resin together with the acrylic resin. Since this cross-linking agent has a function of cross-linking an acrylic resin to impart mechanical strength to the entire pattern layer 3, it is also generally referred to as a "hardener". Examples of the cross-linking agent (curing agent) that can be added to the pattern layer forming ink include urethane curing agents. More specifically, examples of the urethane curing agent that can be added to the pattern layer forming ink include IPDA (isofluorodiamine) and HDI (hexamethylene diisocyanate). In the present embodiment, these can be used alone or in combination thereof.

When the pattern layer forming ink contains a cross-linking agent, the content of the cross-linking agent is in the range of more than 0 parts by mass and 10 parts by mass or less when the content of the acrylic resin in the pattern layer 3 is 100 parts by mass. It is preferably inside. When the content of the cross-linking agent is within the above numerical range, the coatability of the pattern layer forming ink is improved. The content of the cross-linking agent is preferably 3 parts by mass when the content of the acrylic resin in the pattern layer 3 is 100 parts by mass.
In addition to the above binders, the pattern layer forming ink includes, for example, organic or inorganic dyes or pigments, and if necessary, extender pigments, fillers, tackifiers, dispersants, defoamers, stabilizers and the like. The agent may be added as appropriate. Further, the pattern layer forming ink is adjusted to a desired viscosity with an appropriate diluting solvent.

The method for forming the pattern layer 3 is not particularly limited, and any printing method such as a gravure printing method, an offset printing method, a screen printing method, a flexo printing method, a letterpress printing method, or an inkjet printing method can be used. It is possible.
Further, when a solid ink layer (not shown) is provided between the surface anchor layer 2 and the pattern layer 3 for the purpose of coloring the base, as a method for forming the solid ink layer, in addition to the above-mentioned various printing methods, For example, any coating method 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, and a die coating method can be used.

(Surface protective layer)
A surface protective layer 4 that serves as surface protection and gloss adjustment is provided on the outermost surface of the non-combustible sheet 10. The thickness of the surface protective layer 4 is preferably in the range of 2 μm or more and 10 μm or less. When the thickness of the surface protective layer 4 is within the above range, flexibility can be maintained while sufficiently obtaining mechanical properties such as wear resistance and surface hardness. If the thickness of the surface protective layer 4 is less than 2 μm, it may not be possible to sufficiently obtain mechanical properties such as wear resistance and surface hardness. Further, if the thickness of the surface protective layer 4 exceeds 10 μm, the flexibility may decrease.
The resin material that is the main component of the surface protective layer 4 is appropriately selected from, for example, polyurethane-based, acrylic silicon-based, fluorine-based, epoxy-based, vinyl-based, polyester-based, melamine-based, aminoalkyd-based, and urea-based resin materials. It can be selected and used. The form of the resin material is not particularly limited, such as water-based, emulsion, and solvent-based. As for the curing method, a one-component type, a two-component type, an ultraviolet curing method, or the like can be appropriately selected.

As the resin material that is the main component of the surface protective layer 4, a urethane-based resin material using isocyanate is suitable 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 (isocyanate methyl). It can be appropriately selected from curing agents such as adduct, buretto, and isocyanurate, which are derivatives such as cyclohexane (HXDI) and trimethylhexamethylene diisocyanate (TMDI), but it is linear in consideration of weather resistance. Hexamethylene diisocyanate (HMDI) or isophorone diisocyanate (IPDI) -based curing agent having the above molecular structure is suitable. In addition to this, when improving the surface hardness, it is preferable to use a resin that is cured by active energy rays such as ultraviolet rays and electron beams. These resins can be used in combination with each other. For example, by using a hybrid type of a thermosetting type and a photocuring type, the surface hardness can be improved, the curing shrinkage can be suppressed, and the adhesion can be improved. Can be planned.

When the non-combustible sheet 10 is used as a floor material, a certain level of strength is required. Therefore, the surface protective layer 4 must be a resin capable of obtaining sufficient strength, such as an acrylic UV resin. Is preferable.
Further, an ultraviolet absorber and a light stabilizer may be appropriately added in order to improve the weather resistance of the non-combustible sheet 10. Further, in order to impart various functions, functional additives such as antibacterial agents and antifungal agents can be arbitrarily added. Further, alumina, silica, silicon nitride, silicon carbide, glass beads and the like can be optionally added in order to adjust the gloss from the design of the surface or to impart wear resistance.

(Back anchor layer)
The back surface anchor layer 5 is a layer formed so as to cover the entire back surface of the raw fabric layer 1, and is a layer for preventing powder falling off of the inorganic material contained in the raw fabric layer 1. If the inorganic material contained in the raw fabric layer 1 falls off in the printing system, specifically, in the printing apparatus during printing or resin coating, the inside of the printing system may be contaminated.
Further, the back surface anchor layer 5 also has a function for improving the adhesion between the raw fabric layer 1 and the primer layer 6 described later. If the back surface anchor layer 5 is not provided, the coating liquid forming the primer layer 6 may peel off without adhering to the raw fabric layer 1.
The back surface 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 salt and vinegar or the acrylic resin containing salt and vinegar in the back surface anchor layer 5 is, for example, in the range of 15% by mass or more and 100% by mass or less with respect to the mass of the back surface anchor layer 5. Is preferable, the range of 80% by mass or more and 100% by mass or less is more preferable, and the range of 85% by mass or more and 95% by mass or less is further preferable. If the content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the back surface anchor layer 5 is within the above numerical range, the interlayer strength between the back surface anchor layer 5 and the primer layer 6 is sufficient. It is possible to form the back surface anchor layer 5 which is uniform and has no unevenness or chipping. When the content of the urethane resin containing vinyl acetate or the acrylic resin containing vinyl acetate in the back surface anchor layer 5 is less than 15% by mass with respect to the mass of the back surface anchor layer 5, the back surface anchor layer 5 and the back surface anchor layer 5 The interlayer strength with the primer layer 6 may be insufficient. Further, if the content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the back surface anchor layer 5 is less than 80% by mass with respect to the mass of the back surface anchor layer 5, nothing will happen in use. Although there is no problem, the ratio of the back surface anchor layer 5 to the original fabric layer 1 decreases, and the interlayer strength between the back surface anchor layer 5 and the original fabric layer 1 decreases slightly. If the content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the back surface anchor layer 5 is 100% by mass or less with respect to the mass of the back surface anchor layer 5, there is no problem in use. However, if it exceeds 95% by mass, or more accurately 98% by mass, the back surface anchor layer 5 may be chipped due to insufficient curing, or the back surface anchor layer 5 and the original fabric layer 1, or the back surface anchor layer 5 and the pattern pattern. The interlayer strength with the layer 3 may decrease.
The thickness of the back surface 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)
As the material of the primer layer 6, for example, nitrocellulose as a binder, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyester, etc. alone or each modified product are appropriately selected. Can be used. These are not particularly limited in their form such as water-based, solvent-based, and emulsion type. The curing method can also be appropriately selected from a one-component type that cures independently, a two-component type that uses a curing agent in combination with the main agent, and a type that cures by irradiation with ultraviolet rays or electron beams. As a general curing method, a two-component type that cures by combining an isocyanate-based curing agent with a urethane-based main agent is used, and this method has workability, price, and cohesive force of the resin itself. It is suitable from the viewpoint. In addition to the above binders, colorants such as pigments and dyes, extender pigments, solvents, various additives and the like are added. In particular, since the primer layer 6 is located on the backmost surface of the non-combustible sheet 10, considering that the non-combustible sheet 10 is wound as a continuous plastic film (web-like), the films adhere to each other and are not slippery. Inorganic fillers such as silica, alumina, magnesia, titanium oxide, and barium sulfate may be added in order to prevent the film from becoming peeled off and to prevent the film from peeling off and to improve the adhesion with the adhesive. .. The layer thickness is preferably in the range of 0.1 μm or more and 3.0 μm or less because the purpose is to secure the adhesion with the substrate 11 described later.

(Adhesive resin layer)
The non-combustible sheet 10 of the present embodiment may include an adhesive resin layer (not shown) between the pattern layer 3 and the surface protective layer 4 or the transparent resin layer 7 described later. By providing the adhesive resin layer, the adhesion between the pattern pattern layer 3 and the surface protective layer 4 can be improved. The material of 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 appropriately selected depending on the viscosity of the adhesive and the like, but generally, a gravure coat is used, and after being applied by the gravure coat on the pattern layer 3, the surface protective layer 4 or the surface protective layer 4 or It is formed so as to be laminated with the transparent resin layer 7.

[Manufacturing method of non-combustible sheet]
An example of a method for manufacturing the non-combustible sheet 10 will be briefly described.
First, the raw fabric layer 1 is formed. That is, an inorganic material, a thermoplastic resin, a foaming agent, and other components contained in the raw fabric layer 1 are blended. These components are mixed using, for example, a known mixer such as a super mixer, a Henschel mixer, a tumbler mixer, or a ribbon blender.
After mixing each component contained in the raw fabric layer 1, heat kneading is performed with a single-screw or twin-screw extruder to prepare a pellet composed of a mixture of each component contained in the raw fabric layer 1 to prepare a T-die. It is melted and formed into a film using a known molding machine such as extrusion. Then, it is stretched uniaxially or biaxially to form a raw fabric layer 1 having a uniform micropore diameter. Next, the raw fabric layer 1 is heated to heat and foam the foaming agent.

Next, the surface anchor layer 2 is formed by applying a surface anchor layer forming ink for forming the surface anchor layer 2 on the surface which is one surface of the raw fabric layer 1.
Next, the pattern layer 3 is formed by applying the pattern layer forming ink for forming the pattern layer 3 on the surface of the surface anchor layer 2.
Next, an ink for forming a surface protective layer 4 for forming the surface protective layer 4 is applied on the surface of the pattern layer 3 to form the surface protective layer 4.
Next, an ink for forming a back surface anchor layer 5 for forming the back surface anchor layer 5 is applied to the back surface, which is the other surface of the original fabric layer 1, to form the back surface anchor layer 5.
Finally, a primer layer forming ink for forming the primer layer 6 is applied on the front surface of the back surface anchor layer 5 to form the primer layer 6.
In this way, the non-combustible sheet 10 according to the present embodiment is manufactured.
The back surface anchor layer 5 may be formed at the same time as the front surface anchor layer 2. Further, the primer layer 6 may be formed before the pattern layer 3 and the surface protection layer 4 are formed.

[Composition of non-combustible material]
In the non-combustible sheet 10 of the present embodiment, the non-combustible material 12 may be formed by arranging the non-combustible sheet 10 on the substrate 11. That is, the heat insulating effect may be obtained by laying the non-combustible material 12 on the floor material or the like.
The configuration of the non-combustible material 12 will be described with reference to FIG.
As shown in FIG. 1, the non-combustible material 12 includes a substrate 11 and the non-combustible sheet 10 described above. Therefore, the substrate 11 will be described below, and the description of the non-combustible sheet 10 described above will be omitted.

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

[Manufacturing method of non-combustible material]
An example of a method for producing the non-combustible material 12 will be briefly described.
First, the primer layer 6 of the non-combustible sheet 10 is arranged toward the substrate 11.
Next, this laminate is heat-laminated, for example.
In this way, the primer layer 6 and the substrate 11 are welded together to produce the non-combustible material 12.
As a method for heat laminating the laminated body, a circular pressure type continuous laminating method can be used in addition to the method of abutting a metal plate and pressing it under flat pressure. In particular, when a continuous laminating method using a metal endless belt or a heat drum made of metal or a curable resin is used, there is no surface warpage or waviness, and the adhesion between layers is good, and the layers are densely cured. There is an advantage that the high-quality non-combustible material 12 can be continuously produced at a high speed.

Here, in the technical standards for non-combustible materials specified in the Building Standards Law Construction Ordinance, it is necessary to meet the following requirements in the heat generation test using a cone calorimeter tester conforming to ISO5660-1 (Building Standards Law). Construction Ordinance Article 108-2 No. 1 and No. 2). In order for the non-combustible sheet 10 of the present embodiment to be certified as a non-combustible material, the following 1 to 3 can be obtained by heating with radiant heat of 50 kW / m ^{2 in} a state of being bonded to a non-combustible base material for 20 minutes. All requirements must be met.
1. 1. Total calorific value is 8MJ / m ² or less 2. 2. The maximum heat generation rate does not exceed 200 kW / m ² continuously for 10 seconds or more. No cracks or holes that penetrate to the back surface, which is harmful for flame protection

As the nonflammable base material, gypsum board, fiber-mixed calcium silicate board or galvanized steel sheet can be selected and used.
Then, the non-combustible sheet 10 of the present embodiment provided with the above-mentioned raw fabric layer 1 is subjected to a heat generation test by a cone calorimeter tester conforming to ISO5660-1 in a state of being bonded to the above-mentioned non-combustible base material. We have realized a non-combustible material that meets both the requirements described in Article 108-2, Item 1 and Item 2 of the above-mentioned Construction Ordinance.
The ratio of the individual components of the non-combustible sheet 10 can be changed so as to obtain desired characteristics according to the processing characteristics, flexibility, required rigidity, heat insulating properties, and the like.

<Effect>
The non-combustible sheet 10 according to the present embodiment has a void in the raw fabric layer 1. Therefore, it has excellent heat insulating properties, as well as shielding properties and strength. Therefore, a heat insulating effect can be obtained by using it as a floor material or the like in a place where heat insulating properties are required, such as a dressing room or a water area. At this time, the heat insulating effect can be obtained only by arranging the floor material without separately providing a heat insulating sheet or a heat insulating material.
Further, by stretching the raw fabric layer 1 uniaxially or biaxially, a plurality of planar voids having a shape extending in a direction parallel to the front and back surfaces of the raw fabric layer 1 are only formed scattered throughout. However, since the foaming agent is blended in the raw fabric layer 1 within a range that does not impair the interlayer strength of the resin composition, voids having a shape extending in the thickness direction of the raw fabric layer 1 are formed. Therefore, a three-dimensional void is formed in the raw fabric layer 1, and the heat insulating effect can be further enhanced.
Further, the voids formed by the foaming agent are connected to each other and become larger than the voids formed alone. Therefore, by using a flooring material containing such voids in the raw fabric layer 1, it is possible to further provide heat insulating properties.

Further, since the voids formed by the foaming agent and the voids formed by the uniaxial or biaxial stretching are mixed, by adjusting the amount of the foaming agent and the inorganic material, the foaming agent can be used in the thickness direction. The ratio of the voids formed and the voids formed in the direction parallel to the front and back surfaces of the raw fabric layer 1 by stretching can be adjusted, and the interlayer strength can be not impaired and the heat insulating effect can be further improved. The raw fabric layer 1 can be easily obtained.
Further, since the heat insulating property is improved by forming the voids, the non-combustible sheet 10 having more excellent heat insulating property can be realized without significantly increasing the weight.

<Modification example>
In the present embodiment, the case where the surface protection layer 4 is a single layer has been described, but it may be a plurality of layers. Therefore, a case where the surface protective layer 4 includes two layers, a first surface protective layer 4a and a second surface protective layer 4b, will be described below.
As shown in FIG. 2, the first surface protective layer 4a is a layer provided on the surface side of the pattern layer 3 and covering the entire pattern layer 3. The first surface protective layer 4a is formed of a transparent or translucent material (resin) to the extent that the pattern of the pattern pattern layer 3 can be seen through the first surface protective layer 4a. The first surface protection layer 4a may be a single layer or a layer formed by stacking a plurality of layers. Further, the thickness of the first surface protective layer 4a is preferably in the range of, for example, 2 μm or more and 10 μm or less.

The second surface protective layer 4b is a layer that is partially provided on the surface side of the first surface protective layer 4a and covers a part of the surface of the first surface protective layer 4a. As a part of the surface of the first surface protective layer 4a, for example, a portion of the pattern layer 3 facing the printing ink can be mentioned. Further, as the material of the second surface protective layer 4b, for example, the same resin as that of the first surface protective layer 4a can be adopted. A filler may be added to the second surface protective layer 4b. By adding the filler, mechanical properties such as gloss, touch, texture, surface strength, and friction different from those of the first surface protective layer 4a can be imparted. As the filler, for example, a material that consumes less oxygen during combustion is preferable, and for example, zirconium compounds such as calcium carbonate, antimony trioxide, antimony soda, zircon silicate, and zircon oxide, magnesium hydroxide, aluminum hydroxide, and base. Antimony trioxide and silica complex, antimony trioxide and zinc flower complex, zirconium silicic acid, zirconium compounds, such as magnesium carbonate, borosand, zinc borate, molybdenum trioxide or antimony dimolybate and aluminum hydroxide complex. And antimony trioxide complex and the like. In particular, calcium carbonate is suitable from the viewpoint of reducing the cost of the decorative sheet because it is easy to control the particle size by the manufacturing method and the compatibility with the polyolefin resin by the surface treatment, and the material cost is low. Is. Further, resin beads and amorphous particles such as acrylic, polyolefin and silicone, and inorganic beads and amorphous particles such as silica (particularly hollow silica), alumina and metal oxide can be used. Further, the method for forming the second surface protective layer 4b is not particularly limited, and a known printing method can be adopted. The second surface protective layer 4b is also generally referred to as a "tactile coat layer" or a "matte conduit printing layer".

<Second Embodiment>
[Composition of non-combustible sheet]
As shown in FIG. 3, the non-combustible sheet 10 of the second embodiment has a primer layer 6, a back surface anchor layer 5, a raw fabric layer 1, and a surface anchor layer 2 from the backmost side to the outermost surface side. A pattern layer 3, a transparent resin layer 7, and a surface protective layer 4 are provided. The surface protective layer 4 of the second embodiment includes a first surface protective layer 4a and a second surface protective layer 4b. Further, the non-combustible material 12 of the second embodiment includes the non-combustible sheet 10 of the second embodiment and the substrate 11. That is, the non-combustible sheet 10 of the second embodiment is different from the non-combustible sheet 10 of the first embodiment in that it includes a transparent resin layer 7 and a surface protective layer 4 composed of a plurality of layers. Therefore, the transparent resin layer 7 and the surface protective layer 4 composed of a plurality of layers, which are different portions thereof, will be described below, and the description of the other layers will be omitted.

(Transparent resin layer)
The transparent resin layer 7 is a sheet-like layer formed by 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 upper surface of the pattern layer 3.
As a method of laminating the transparent resin layer 7, for example, it is possible to use a method of laminating the transparent resin layer 7 on the laminated body including the raw fabric layer 1, the surface anchor layer 2 and the pattern layer 3 by laminating. Is.
The transparent resin forming the transparent resin layer 7 is not particularly limited, and a 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, or sachets thereof, polyolefin-based copolymers, polyester-based resins, polymethyl methacrylate, and the like. Acrylic resin, polyamide resin, styrene resin, fibrous derivative, chlorine resin, fluorine resin, etc. alone or a mixture, copolymer, composite, laminate of two or more kinds selected from these materials It is possible to use the body and the like as appropriate.

In particular, in the production using the melt extrusion device, in consideration of productivity, environmental compatibility, mechanical strength, durability, price, etc., it is possible to use a polyolefin resin as the transparent resin forming the transparent resin layer 7. More preferred.
As the polyolefin-based resin, for example, polyethylene, polypropylene, polybutene, polymethylpentene and the like can be used, and polypropylene is most preferable. Further, as the polyolefin-based copolymer, for example, an ethylene- (meth) acrylic acid (ester) copolymer or the like can be used.

Examples of the polyester-based resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, polycarbonate, and copolymerized polyester (typically, PET-, which is a 1,4-cyclohexanedimethanol copolymerized polyethylene terephthalate resin. G) and the like can be used.
As the polyamide resin, for example, 6-nylon, 6,6-nylon, 6,10-nylon, 12-nylon and the like can be used.

As the styrene resin, for example, polystyrene, AS resin, ABS resin and the like can be used.
As the fibrous derivative, for example, cellulose acetate, nitrocellulose and the like can be used.
As the chlorine-based resin, for example, polyvinyl chloride, polyvinylidene chloride or the like can be used.
As the fluororesin and the like, for example, polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer and the like can be used.
The thickness of the transparent resin layer 7 is preferably in the range of 20 μm or more and 150 μm or less, and preferably in the range of 45 μm or more and 90 μm or less, from the viewpoint of improving both the strength and the transparency of the transparent resin layer 7. Is more preferable.

The transparent resin layer 7 contains existing heat stabilizers, flame retardants, ultraviolet absorbers, light stabilizers, blocking inhibitors, catalyst scavengers, colorants, light scattering agents and gloss adjusters, if necessary. Various additives such as these can be added. When improving the surface strength, it is preferable to use a highly crystalline polypropylene resin. As the heat stabilizer, for example, a phenol-based, sulfur-based, phosphorus-based, hydrazine-based, or the like can be used. As the flame retardant, for example, aluminum hydroxide, magnesium hydroxide and the like can be used. As the ultraviolet absorber, for example, benzotriazole type, benzoate type, benzophenone type, triazine type and the like can be used. As the light stabilizer, for example, a hindered amine type can be used. Further, if necessary, 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.

(Embossed pattern)
The embossed pattern 7a is, for example, a pattern composed of concave portions and convex portions synchronized with the pattern of the pattern pattern layer 3. The concave and convex portions of the embossed pattern 7a make it possible to give a three-dimensional effect by touch. The deviation between the embossed pattern 7a and the pattern of the pattern pattern layer 3 is preferably within a range of 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, when the pattern is wood grain, the direction in which the wood grain conduit extends is the "longitudinal direction with respect to the shape of the pattern", and the direction orthogonal to the longitudinal direction is the "short direction with respect to the shape of the pattern". Become. In particular, when the wood grain conduit extends along the longitudinal direction of the non-combustible sheet 10, the longitudinal direction of the non-combustible sheet 10 is the "longitudinal direction with respect to the shape of the pattern", and the lateral direction (width direction) of the non-combustible sheet 10 ) Is the "short direction with respect to the shape of the pattern". Since the transparent resin layer 7 and the surface protection layer 4 are transparent, the embossed pattern 7a is strongly visible for the first time due to the reflection of oblique light. However, if the deviation between the embossed pattern 7a and the pattern of the pattern layer 3 is within the above range. For example, since it is difficult to visually recognize the transmitted light of the pattern layer 3 at the same time as the reflected light, there is no sense of discomfort. By suppressing the deviation between the embossed pattern 7a and the pattern of the pattern pattern layer 3 within a certain range, it is possible to obtain a non-combustible sheet 10 in which the shape and distribution of the patterns are equal and accurately matched on 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 the range of 3 μm or more and 200 μm or less. For the height difference, a numerical value suitable for the design of the target non-combustible sheet 10 can be selected. For example, it is 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 the range of 10 μm or more and 150 μm or less.

(Surface protective layer)
The surface protective layer 4 includes a first surface protective layer 4a and a second surface protective layer 4b.
The first surface protective layer 4a is a layer provided on the surface side of the transparent resin layer 7 and covering the entire transparent resin layer 7. The first surface protective layer 4a is formed of a transparent or translucent material (resin) to the extent that the pattern of the pattern pattern layer 3 can be seen through the first surface protective layer 4a. The first surface protection layer 4a may be a single layer or a layer formed by stacking a plurality of layers. Further, the thickness of the first surface protective layer 4a is, for example, 3 μm or more and 100 μm or less from the viewpoint of obtaining strength sufficient to completely fill the embossed pattern 7a and protect the surface of the transparent resin layer 7 without impairing the design feeling. It is preferable that it is within the range of. Further, as the material of the first surface protective layer 4a, a thermosetting resin is preferable in terms of, for example, adhesiveness 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 cross-linking agent (curing agent) can be used. As the polyol, those having two or more hydroxyl groups in the molecule, for example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol, polycarbonate polyol, polyurethane polyol can be used.
Further, as the isocyanate, a multivalent 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 and 4,4'-diphenylmethane diisocyanate, or 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate and the like. (Or alicyclic) isocyanate can be used. Further, an adduct or a multimer of the above-mentioned various isocyanates can be used. For example, there are adducts of tolylene diisocyanate, trimer trimer and the like. Among the above-mentioned isocyanates, the aliphatic (or alicyclic) isocyanate is preferable in that it can also have good weather resistance and heat-resistant yellowing, and for example, 1,6-hexamethylene diisocyanate can be used.

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

The second surface protective layer 4b is a layer that is partially provided on the surface side of the first surface protective layer 4a and covers a part of the surface of the first surface protective layer 4a. As a part of the surface of the first surface protective layer 4a, for example, a portion of the pattern layer 3 facing the printing ink can be mentioned. Further, as the material of the second surface protective layer 4b, for example, the same resin as that of the first surface protective layer 4a can be adopted. A filler may be added to the second surface protective layer 4b. By adding the filler, mechanical properties such as gloss, touch, texture, surface strength, and friction different from those of the first surface protective layer 4a can be imparted. As the filler, for example, resin beads or amorphous particles such as acrylic, polyolefin, or silicone, or inorganic beads or amorphous particles such as silica, alumina, or metal oxide can be used. Further, the method for forming the second surface protective layer 4b is not particularly limited, and a known printing method can be adopted. The second surface protective layer 4b is also generally referred to as a "tactile coat layer" or a "matte conduit printing layer".

In the above embodiment, the case where the non-combustible sheet 10 is used as the floor material has been described, but the present invention is not limited to this, and may be applied to other uses such as walls, ceilings, interior fittings, furniture, and doors. It is possible.
Further, the above-described embodiment is an example of the present invention, and the present invention is not limited to the above-mentioned embodiment, and even in a mode other than this embodiment, the technical idea relating to the present invention can be applied. As long as it does not deviate, various changes can be made according to the design and the like.

[Example]
The non-combustible sheet 10 in the examples is a raw fabric layer 1 containing a foaming agent.
Here, as a comparative example, a non-combustible sheet containing no foaming agent in the raw fabric layer will be described first, and then the non-combustible sheet 10 in the examples will be described.
The non-combustible sheet in the comparative example was prepared by the following procedure. That is, first, a raw fabric layer composed of an inorganic material containing calcium carbonate and a polypropylene resin which is a thermoplastic resin was formed. The composition ratio of the raw fabric layer was 60% by mass of the inorganic material and 40% by mass of the polypropylene resin. The thickness of the raw fabric layer was 200 μm. The purity of the inorganic material used was 90% by mass of calcium carbonate. Further, as the inorganic material, a material having an average particle diameter (mode diameter) of 2 μm and a maximum particle diameter of 50 μm or less was used.

Next, the front surface and the back surface of the raw fabric layer were corona-treated.
Next, an ink for forming a urethane-based anchor layer containing vinyl acetate is applied on the front surface and the back surface of the corona-treated raw fabric layer so that the coating film thickness is within the range of 1 μm or more and 2 μm or less, and dried. It was dried under the conditions of a temperature of 40 ° C. and a drying time of 30 seconds. In this way, anchor layers were formed on the front surface and the back surface of the raw fabric layer.
Next, urethane-based pattern layer forming ink is applied (printed) on the anchor layer on the surface side of the raw fabric layer so that the coating film thickness is within the range of 1 μm or more and 2 μm or less, and the drying temperature is 40 ° C. , The drying time was 30 seconds. In this way, a pattern layer was formed on the anchor layer on the surface side of the original fabric layer.

Then, the laminate (sheet) provided with the raw fabric layer, the anchor layer and the pattern layer was aged at room temperature for one day, and a sample of a non-combustible sheet as a comparative example for performing each evaluation was prepared.
In the non-combustible sheet in the example, in Comparative Example, a mixture of an inorganic material containing calcium carbonate, a polypropylene resin as a thermoplastic resin, and azobisisobutyronitrile as a foaming agent was first-stretched to obtain a foaming agent. It was prepared under the same conditions as the non-combustible sheet in the comparative example except that the raw fabric layer was formed by foaming. The composition ratio of the inorganic material, the polypropylene resin which is a thermoplastic resin, and the azobisisobutyronitrile as the foaming agent is 60% by mass of the inorganic material, 10% by mass of the polypropylene resin, and the foaming agent (azobisisobutyronitrile). ) 10% by mass.
The evaluation items in this example are as follows.

<Ink adhesion>
After the Nichiban cellophane tape was pressure-bonded to the surface of the printed sheet, it was strongly peeled off with a constant force, and the presence or absence of peeling inside the pattern layer or between the original fabric layer and the pattern layer was visually evaluated.
<Printability>
It was visually evaluated whether or not the ink could be laminated without powder falling from the original fabric layer during printing.
<Surface powder blowing after printing>
The surface of the sheet after printing was dry-rubbed by hand or cotton, and the presence or absence of powder blowing or dropping of the inorganic material was visually evaluated.
<Non-flammable test>
It was evaluated whether or not the following requirements were satisfied in the heat generation test by the cone calorimeter tester conforming to ISO5660-1.
1. 1. Total calorific value is 8MJ / m ² or less 2. 2. The maximum heat generation rate does not exceed 200 kW / m ² continuously for 10 seconds or more. No cracks or holes penetrate to the back surface, which is harmful for flameproofing. A gypsum board was used as the nonflammable base material.

<Insulation effect>
The non-combustible sheet of Example and the non-combustible sheet of Comparative Example were attached to the dressing room and evaluated by a sensory test by 100 examiners. (Evaluation criteria)
◯: No problem occurs during sheet preparation and sheet processing for each item.
X: A problem occurs for each item.
Regarding the heat insulating effect, the case where the number of people judged to feel the heat insulating effect was 70 or more was evaluated as ◯, the case of 50 or more and less than 70 was evaluated as Δ, and the case of less than 50 was evaluated as ×.
The evaluation results of the non-combustible sheet of the example and the non-combustible sheet of the comparative example are as shown in Table 1. It has been confirmed that the non-combustible sheet containing a foaming agent (Example) can obtain the same characteristics as the conventional non-combustible sheet containing no foaming agent (Comparative Example) and further improves the heat insulating property. Was done.

As described above, the sheet includes the raw fabric layer 1 and the surface anchor layer 2 formed on the surface of the raw fabric layer 1, and the raw fabric layer 1 contains a thermoplastic resin, an inorganic material, and a foaming agent. The surface anchor layer 2 contains a urethane resin containing salt and vinegar, or an acrylic resin containing salt and vinegar, and the raw fabric layer is a mixture containing a thermoplastic resin, an inorganic material, and a foaming agent. When formed by axial stretching or biaxial stretching, it is possible to form a sheet having excellent heat insulating properties while having nonflammability.

1 Raw fabric layer 1a Void 1b Inorganic material 1c Void 2 Surface anchor layer 3 Pattern layer 4 Surface protection layer 4a First surface protection layer 4b Second surface protection layer 5 Back surface anchor layer 6 Primer layer 7 Transparent resin layer 7a Embossing Pattern 10 Non-combustible sheet 11 Substrate 12 Non-combustible material

Claims (11)

A method for producing a non-combustible sheet including a raw fabric layer and an anchor layer formed on one surface of the raw fabric layer.
The raw fabric layer is formed by uniaxially or biaxially stretching a mixture containing a thermoplastic resin, an inorganic material, and a foaming agent, and foaming the foaming agent.
A method for producing a non-combustible sheet, characterized in that the anchor layer is formed by containing a urethane resin containing vinyl acetate or an acrylic resin containing vinyl acetate. The method for producing a non-combustible sheet according to claim 1, wherein the foaming agent is at least one of a decomposition gas generating foaming agent and an expandable capsule foaming agent. The decomposition gas-generating foaming agent includes azodicarboxylic amide, dinitrosopentamethylenetetramine, paratoluenesulfonyl hydrazide, benzenesulfonylhydrazide, sodium bicarbonate and ammonium carbonate, azobisisobutyronitrile, and 4,4-oxybis (benzenesulfon). Acid hydrazide), diphenylsulfon-3,3'-disulfohydrazide, benzene-1,3-disulfohydrazide, p-toluenesulfonyl semicarbazide, and at least one of the effervescent hollow microspheres, said expandable. The capsule foaming agent is a hydrocarbon-based volatile expansion component such as ethane, butane, pentane, neopentane, hexane, and heptan in fine particles coated with a thermoplastic resin such as acrylic acid ester, vinylidene chloride, acrylonitrile, and urethane. The method for producing a non-combustible sheet according to claim 2, wherein the non-combustible sheet is contained. The method for producing a non-combustible sheet according to any one of claims 1 to 3, wherein the raw fabric layer contains one or more types of thermoplastic polymer powder. The thermoplastic polymer powder is a vinyl acetate pomopolymer, a vinyl acetate copolymer, an ethylene vinyl acetate copolymer, a vinyl chloride homopolymer, a copolymer of vinyl chloride and vinyl acetate and at least one of (meth) acrylate, a styrene homo or copolymer, (meth). The method for producing a non-combustible sheet according to claim 4, wherein the non-combustible sheet is any one of acrylate homo or polymer, polyolefin, polyether or polyvinyl butyral. The method for producing a non-combustible sheet according to any one of claims 1 to 5, wherein the thermoplastic resin contains at least one of polypropylene, polyethylene, polybutene and polymethylpentene. The inorganic materials include antimony trioxide, antimony soda, zircon silicate, zircon oxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, borosand, zinc borate, calcium carbonate, molybdenum trioxide or antimony dimolybate and water. Aluminum oxide complex, antimony trioxide and silica complex, antimony trioxide and zinc flower complex, silicic acid of zirconium, zirconium compound and antimony trioxide complex, and salts thereof, as well as silica, alumina, hollow glass. The method for producing a non-combustible sheet according to any one of claims 1 to 6, which comprises at least one of beads and acrylic beads. The method for producing a non-combustible sheet according to any one of claims 1 to 7, wherein the raw fabric layer contains at least one kind of filler. The method for producing a non-combustible sheet according to claim 8, wherein the filler is any one of mica filler, glass fiber, metal fiber, calcium carbonate and hollow glass microspheres. Claim 1 to claim 1, wherein the raw fabric layer contains any one of carbon fiber, metal fiber, glass fiber, polyamide fiber, polyethylene fiber, polyester fiber, cellulose fiber and a mixture thereof. The method for producing a non-combustible sheet according to any one of 9. It has a raw fabric layer and an anchor layer formed on one surface of the raw fabric layer.
The raw fabric layer contains a thermoplastic resin, an inorganic material, and a foaming agent, and has a plurality of voids formed between the inorganic material and the thermoplastic resin scattered throughout, and the foamed foam. Multiple voids formed by the agent are scattered throughout,
The anchor layer is a non-combustible sheet containing a urethane resin containing vinyl acetate or an acrylic resin containing vinyl acetate.

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