JP6061659B2 - Decorative sheet - Google Patents

Description

  Since the present invention has high incombustibility, does not deteriorate excellent design properties, and is lightweight and flexible, it is used independently as a highly incombustible building sheet member. The present invention relates to a decorative sheet that can cover various building elements such as a floor, a wall, a ceiling, and a pillar, or a surface of a door, joinery, furniture, and the like, and can simultaneously improve designability, incombustibility, and flameproof performance.

  Conventionally, attempts have been made to improve the nonflammable performance of films and sheet members for building interiors, to prevent the occurrence of fire and to suppress the spread of fire when a fire occurs. For example, an impact-resistant thermoplastic resin sheet is laminated on both sides of a fiber reinforced resin sheet obtained by impregnating and curing an acrylic ester thermosetting resin composition on a glass fiber substrate such as glass cloth. Has been devised (see Patent Document 1), and it is described that the sheet can be used as a curtain excellent in fire resistance, fire resistance, and flameproof performance. However, this sheet is made for the purpose of preventing the penetration of sparks generated during work at the construction site where welding and fusing operations are performed, and the designability that can be used for building interiors is not assumed from the beginning. .

In addition, the decorative sheet itself is not highly incombustible, but it is laminated on a thick incombustible base material to cover the floor, ceiling, wall, etc. to improve fire resistance, fire resistance, and flameproof performance. Study and development as a board has been made. For example, a decorative sheet impregnated with a thermosetting resin such as a melamine resin is used as a decorative layer, and a non-combustible decorative board in which the decorative sheet is bonded to an inorganic base material is manufactured (see Reference 2). When bonding to an inorganic base material, it was necessary to apply an adhesive of 50 g / m ² or more to avoid the influence of the unevenness of the base material in order to exhibit the original high design properties of a conventional decorative sheet. Furthermore, since the main part of the decorative layer is flammable paper and resin, and the decorative sheet itself is not treated to be incombustible, it is difficult to significantly improve the incombustible performance in this respect as well. For this reason, it has been difficult to impart high incombustibility to the decorative plate produced using the decorative sheet.
On the other hand, when a decorative layer is formed by applying a coating for a decorative layer containing a colorant on the surface of an inorganic base material without using a decorative sheet, a complicated printed pattern is given as when a decorative sheet is used. It was difficult to do in the first place.

When an inorganic material having excellent nonflammability is used as described above, the surface roughness of the surface containing the inorganic base material is increased, so that it is sufficient to form a fine printed layer such as gravure printing in the decorative board formation. Maintaining surface smoothness tends to be difficult. If the decorative sheet itself has both high design properties and corresponding non-combustible performance, the required characteristics of the base material for decorative board for non-combustible performance can be reduced, and the design flexibility of the overall decorative board is increased, thus maintaining good non-combustible performance. However, it is considered that higher designability can be imparted. However, in a thin decorative sheet, even if there is no problem with the calorific value, it is difficult to maintain the shape itself after combustion, so it is difficult to give performance considering independent use, It has been more difficult to realize such excellent design as formed by gravure printing.
For example, attempts have been made to improve the incombustibility of a decorative sheet by incorporating glass fibers, incombustible particles, and the like into the base substrate portion of a decorative sheet having a high-design printed layer. However, the base substrate formed in this way is formed by adding glass fiber or the like in a binder resin, and basically it cannot retain the outer shape and strength of the substrate before combustion, and is a decorative sheet. It is difficult to say that it has sufficient incombustible performance.
For example, a vinyl paste layer and a printing layer are sequentially provided on one side of a base material, and a transparent or translucent resin printing layer made of a mat resin and a gloss resin is provided on the entire surface, for example, an interior capable of forming a high-design wood grain pattern. A decorative sheet is formed (see Patent Document 3). And it is supposed that a flame-retardant backing paper can be used as a base material sheet. However, it is difficult to ensure sufficient nonflammability of the decorative sheet itself only by using such flame retardant paper.

From the viewpoint of incombustibility of the sheet-like substrate, a glass woven fabric such as a glass cloth in Patent Document 1 is extremely excellent. However, since such a glass woven fabric has large irregularities, the contact area with the resin film is small at the time of lamination, and adhesion is difficult. Further, the glass woven fabric made of a bundle of glass filaments forms a smooth flat surface on the glass woven fabric so that the resin coated on the glass woven fabric can easily penetrate and a pattern by gravure printing is suitably formed. It is difficult to improve the design.
For example, a makeup having a decorative pattern resin layer obtained by a transfer process of a transfer sheet having a smooth surface by forming an intermediate layer also serving as a waterproof layer on a fiber sheet containing glass fibers and gravure printing thereon A sheet is produced (see Patent Document 4). However, in the examples of this patent document, a non-woven fabric produced by a wet papermaking method consisting of glass fiber, polyester fiber and pulp is used as a fibrous sheet, and a sheet subjected to binder impregnation treatment with an aqueous emulsion resin binder liquid is used. Yes. Therefore, when the fiber sheet is made of a porous glass woven fabric having a higher nonflammability and a high surface roughness, a smooth screen on the intermediate layer can be obtained even if the method described in this document is applied as it is. Therefore, it is difficult to form a fine decorative pattern.
Further, after forming a printing layer on the carrier sheet via vinyl chloride sol, an adhesive layer containing a vinyl chloride-vinyl acetate copolymer is laminated thereon, and a decorative sheet obtained by peeling this from the carrier sheet is obtained. A decorative material is produced by heat laminating with a base layer made of a glass woven fabric (see Patent Document 5). However, with this method, the coating layer and the adhesive layer cannot be sufficiently applied, resulting in insufficient coating thickness and hiding properties, resulting in physical and visual absorption of the concavo-convex pattern of the glass woven fabric. It is not possible to obtain an excellent design.
Further, a glass woven fabric is impregnated with a thermosetting resin and dried to produce a sheet, which is used as a decorative sheet (see Patent Document 6), but the sheet is used only as a reinforcing sheet, Apart from this, it is used by laminating together with a sheet for core material layer containing a thermosetting resin containing inorganic filler mainly composed of aluminum hydroxide on a glass nonwoven fabric and a decorative sheet impregnated with melamine resin. In addition, the decorative sheet using the non-flammability and light weight, thin film property and flexibility of the glass woven fabric has not been formed.

In recent years, flooring has been produced in which a decorative layer with a surface protective layer made of ionizing radiation curable resin is laminated on the surface of the glass paper with an adhesive layer on it, giving an uneven pattern, for example. It is described that it is possible to impart high designability with a fine grain pattern (see Patent Document 7). However, the glass paper is previously bonded to the plywood side that forms the flooring material via an adhesive layer. For this reason, although incombustible performance is acquired as the whole flooring material, incombustible performance is not provided to the decorative sheet stuck to a base material. Glass paper is produced by making a mixture containing glass fiber, pulp, and resin. It is impossible to maintain its shape after combustion, and it cannot be said that its non-flammability and flameproof performance are high. After all, instead of using the conventional non-combustible base material such as calcium silicate in the flooring material of Reference 7, only the plywood with glass paper attached is used, and the non-combustible performance of the decorative sheet itself is improved. This is not necessarily laminated to the substrate.
Furthermore, there is provided an image sheet having a translucent sheet-shaped body made of glass cloth, a first layer coated with a urethane resin on the surface of the sheet-shaped body, and a second layer coated with an acrylic vinyl chloride resin as a binder resin. (See Patent Document 8). The image sheet can be used as an image panel that can be illuminated from the back side, but the image is formed by an ink jet recording method capable of forming an image even on a relatively rough surface. A flat surface having such a surface smoothness as to allow printing is not obtained on the glass cloth.
Thus, a decorative sheet having a light weight, thinness, high design property, and good noncombustibility has not yet been obtained.

JP-A-8-132241 JP2005-030021 JP-A-8-132587 JP-A-6-1115018 JP-A-11-99596 JP-A-11-268186 JP 2006-207346 A JP2010-042587

The objective of this invention is providing the decorative sheet which has the outstanding designability of the design pattern formed by gravure printing, maintaining favorable nonflammable performance.
Furthermore, the object of the present invention is to provide a means for easily producing a decorative sheet having the above-mentioned good non-combustible performance and an excellent design of a pattern formed by gravure printing.

When the support body which is a woven fabric formed from glass fibers such as a glass cloth having high incombustibility is used as a base material for a decorative sheet, the inventor has the surface of the base material inferior in surface smoothness. Investigate a method for forming a design pattern with high designability, such as that produced by gravure printing, without deteriorating good non-combustibility, and make up a laminated layer on a glass woven fabric as a substrate, including a printed layer It is effective to absorb the unevenness of the glass woven fabric and to give the function of smoothing the surface of the decorative layer without the influence of absorbing the unevenness being greatly transmitted in the film thickness direction of the decorative layer. As a result, the present invention has been reached.
That is, the present invention has a printed layer formed by gravure printing on the surface of the glass woven fabric of the substrate having a layer made of glass woven fabric as a surface layer, through the first smoothing layer, The smoothing layer is a resin film, and a decorative sheet is provided.
Furthermore, the present invention provides a decorative layer having a printed layer formed by gravure printing on the first smoothing layer on the surface of the glass woven fabric side of a substrate having a layer made of a glass woven fabric as a surface layer, A method for producing a decorative sheet is provided, wherein a surface opposite to the printed layer is opposed and thermocompression bonded, and the first smoothing layer is a resin film.

Since the decorative sheet of the present invention uses a substrate having a layer made of glass woven fabric as a surface layer as a sheet-like substrate, it has a very good non-flammability performance while being thin and light, and it is under a high temperature environment at the time of fire. It is possible to maintain the strength and shape even when placed in the oven. Furthermore, since it has a printing layer through the 1st smoothing layer which is a resin film, even if a glass woven fabric adhere | attaches on one side of a smoothing layer, surface roughness is large, and also a glass filament of The surface of the glass woven fabric made of a bundle can be efficiently covered, and the unevenness thereof can be absorbed, and a flat surface with high smoothness suitable for high-definition printing can be formed on the other surface of the smoothing layer. Furthermore, in the present invention, the printing layer is formed using gravure printing suitable for forming a high-definition picture. Then, the entire decorative layer including the first smoothing layer absorbs the unevenness of the glass woven fabric, and a decorative sheet on which a complicated and fine print is formed in which the uneven pattern of the woven fabric is not visually recognized can be obtained. Smoothing the surface of the glass woven fabric by the coating process requires a lot of paint for smoothing because the glass woven fabric is permeable, and even if the surface smoothness can be realized at the time of coating, it is a film after drying Since the thickness decreases at a constant rate, it is difficult to maintain the same smooth plane as that immediately after coating.
In addition, the glass woven fabric has good shape stability, and the size and shape of the produced decorative sheet are very rarely deformed by temperature and tension. For this reason, it can be set as the decorative sheet excellent in the dimensional stability with respect to the heat | fever at the time of construction, tension | tensile_strength, and the shape stability with respect to the temperature after construction. In addition, during the production of the decorative sheet, the decorative sheet being produced after heating and after the heating does not undergo thermal deformation even in the curing step and laminating (laminating) step of each layer of the decorative layer.
Further, in producing the decorative sheet of the present invention, a printed layer formed by gravure printing on the first smoothed layer on the surface of the glass woven fabric side of the substrate having a layer made of glass woven fabric on the surface layer is provided. When a laminated decorative layer is thermocompression-bonded with the surface on the first smoothing layer side facing, and the first smoothing layer is used as a decorative sheet manufacturing method, which is a resin film, by gravure printing in advance The entire decorative layer on which the pattern is formed absorbs the irregularities of the glass woven fabric with the resin film on the first smoothing layer side, while the printed layer side is laminated with various layers, Since the rigidity with respect to the deformation | transformation by the unevenness | corrugation of a glass woven fabric can be made high, the decorative sheet which has complicated and fine printing can be manufactured efficiently.

  Although the decorative sheet of the present invention is thin and lightweight, it can have extremely excellent non-combustible performance without being attached to a non-combustible substrate or the like, and is excellent in flexibility and flexibility. Moreover, it is possible to maintain the high designability of the pattern by gravure printing.

It is a schematic sectional drawing which shows the 1st structure which is embodiment of the decorative sheet of this invention. (Decorative sheet having first smoothing layer and printing layer) It is a schematic sectional drawing which shows the 2nd structure which is embodiment of the decorative sheet of this invention. (A decorative sheet having an auxiliary layer on the opposite side of the first smoothing layer and printed layer of the glass woven fabric) It is a schematic sectional drawing which shows the 3rd structure which is embodiment of the decorative sheet of this invention. (A decorative sheet having first and second smoothing layers, a printing layer, and an auxiliary layer) It is a schematic sectional drawing which shows an example of the decorative layer produced in the decorative sheet of this invention. (Makeup layer of wood grain printing by doubling method) It is a schematic sectional drawing which shows the other example of the decorative layer produced in the decorative sheet of this invention. (Glossy-matte decorative layer for grain printing)

The basic structure of the decorative board of the present invention is shown in FIG. The decorative sheet of the present invention has a decorative layer having a printed layer formed by gravure printing on the surface of the substrate having a glass woven fabric layer on the surface of the glass woven fabric side through a first smoothing layer. The first smoothing layer is a decorative sheet that is a resin film. That is, it has a 1st smoothing layer which consists of a resin film, and a decorative layer with the printing layer formed on it by gravure printing. It is preferable to have a second smoothing layer on the first smoothing layer, and it is preferable to have an auxiliary layer on the other side of the glass woven fabric so that an adhesive or a pressure-sensitive adhesive can be satisfactorily applied. Furthermore, as a method for producing a decorative sheet of the present invention, a printed layer formed by gravure printing on the first smoothing layer on the surface of the substrate having a glass woven fabric layer on the surface of the glass woven fabric side. The decorative layer has a surface opposite to the printed layer and is thermocompression bonded, and the first smoothing layer is a resin film. Here, the substrate having a layer made of glass woven fabric as a surface layer means that the glass woven fabric itself or another sheet-like substrate is bonded to one surface of the glass woven fabric to form a new sheet-like substrate as a whole. And at least one surface of the substrate is a glass woven fabric. These substrates themselves have good nonflammability, and are lightweight, thin, excellent in flexibility and flexibility, and give the above-described excellent characteristics to a decorative sheet formed using these as a substrate.
Hereinafter, each structure in the decorative board of this invention is demonstrated in detail.

The glass woven fabric used as a substrate in the decorative sheet of the present invention is woven from warps and wefts using a bundle of glass fibers as a thread. Prior to weaving, a bundle of two or more glass fibers may be pre-twisted. In particular, glass filaments having a monofilament diameter of 3 to 9 μm are 50 to 800 monofilaments, a glass fiber bundle of 2.8 to 135 tex (g / 1000 m) is used as warps and wefts, and the weaving density of warps is 20 to 75. / 25 mm, and weaved with a plain weave so that the weave density of the weft is 20 to 75/25 mm.
Furthermore, it is preferable to use what was surface-treated with the silane compound as the glass fiber used for a glass woven fabric. As the silane compound as the surface treatment agent, a coupling agent or polysiloxane composed of a polymer thereof can be used. Specific examples of such silane coupling agents include aminosilanes such as γ-aminopropyltriethoxysilane, vinyl silanes such as vinyltriethoxysilane, and (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane. , Γ-glycidoxypropyl-removed epoxy silane such as ethoxysilane, and the like.
The method for performing the fiber surface treatment can be performed, for example, by using a solution containing a silane compound and applying and drying the solution on the fiber surface. The adhesion amount of the silane compound is usually in the range of 0.05 to 5 parts by weight with respect to 100 parts by weight of the fiber.

The first smoothing layer laminated on the glass woven fabric in the present invention is a resin film, and can be adhered to the glass woven fabric satisfactorily through an adhesive used as needed, and the glass woven It is preferably a thermoplastic resin film that absorbs unevenness of the surface of the fabric well and can be appropriately deformed along the unevenness to ensure a contact area for good adhesion. On the other hand, considering the properties required for the surface of the first smoothing layer opposite to the side in contact with the glass woven fabric, the surface of the glass woven fabric in the winding process after thermocompression bonding with the glass woven fabric It is preferable that the woven fabric has a hardness that does not form a pressed pattern when it is overlapped. In addition, when the glass woven fabric is bonded, the unevenness of the glass woven fabric does not appear as unevenness on the surface of the surface of the resin film that is the first smoothing layer that is not in contact with the glass woven fabric. It is preferable that it has sufficient thickness and rigidity.
In the case of a vinyl chloride resin, the rigidity of the first smoothing layer can be adjusted by the relationship between the film thickness and the amount of plasticizer added.
The film thickness of the resin film is preferably sufficiently thick so that the deformation of the surface in contact with the irregularities of the glass woven fabric during thermocompression does not appear as a textured pattern on the opposite surface of the resin film, Moreover, in order to fully satisfy workability and durability, although there exists a relationship with the said elongation rate, 50 micrometers-500 micrometers are preferable.

As the resin film to be the smoothing layer, a film made of a thermoplastic resin is preferable. As the thermoplastic resin used for the film, a polyolefin resin such as a vinyl chloride resin, polyethylene, or polypropylene, a polyester resin, an ABS resin, or the like. Can be illustrated. In particular, vinyl chloride resins have excellent nonflammability and flameproofing performance, a wide variety of resin films pre-colored in each color, and surface hardness and elongation (rigidity) depending on the amount of plasticizer added. This is preferable because it can be easily adjusted.
Adhesion between the resin film to be the first smoothing layer and the glass woven fabric may be performed by directly thermocompression bonding the glass woven fabric that has been subjected to a treatment such as immersion in a resin film and a resin having heat-fusibility. . Or it is preferable to carry out the thermocompression bonding with the glass woven fabric of a resin film at the lamination process through an adhesive agent. The adhesive may be previously applied to the adhesive surface of the first smoothing layer with the glass woven fabric, or the glass woven fabric may be impregnated with the adhesive and adhered to the first smoothing layer. Good. At this time, the composition of the adhesive used for the first smoothing layer is vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, polyolefin copolymer resin, acrylic resin, urethane resin, polyester resin, polyethylene. It can be selected according to the type of the resin film used for the first smoothing layer from among the system resins.
Smoothing by adhesion of the resin film as described above is performed together with effective coating of the surface of the glass woven fabric. For this reason, it is possible to significantly reduce the resin layer compared to the smoothing process by the smoothing layer coating process or the smoothing layer transfer process, which is performed by filling the entire space of the glass woven fabric. is there. For this reason, it is extremely advantageous for maintaining nonflammable performance.
When smoothing is performed with a resin film with a uniform film thickness, the film thickness of the smoothing layer is uniform, and when the coating process is used, the film thickness tends to be uneven depending on the unevenness and texture of the glass woven fabric. Compared to the above, there is no variation in hiding performance, and the design properties of the decorative layer are not adversely affected.

In the present invention, it is preferable to have a second smoothing layer between the printing layer and the first smoothing layer. The second smoothing layer may be formed by further laminating a resin film, but is preferably formed through a coating process and a curing process of the second smoothing layer forming paint that can form the resin layer. . In the case of a resin film, it is preferable to use a resin film having a lower elongation (higher rigidity) and higher surface hardness than the first smoothing layer, and the resin layer formed by the coating process is a second smoothing layer. In the case of the formation layer, it is preferable to have a curing step for forming the resin layer.
In this way, when the second smoothing layer has higher rigidity and surface hardness than the first smoothing layer, the unevenness of the glass woven fabric at the portion close to the glass woven fabric as a whole smoothing layer. And the deformation on the side opposite to the glass woven fabric is less likely to be deformed by the unevenness. And, when the laminate of the second smoothing layer is wound up and the surface of the glass woven fabric comes into contact with the second smoothing layer, the texture pattern deformation occurs on the surface of the second smoothing layer. Less is preferable.
Furthermore, even if slight irregularities remain on the first smoothing layer, the first smoothing layer already covers the surface of the glass woven fabric satisfactorily. For this reason, the surface with higher smoothness is effectively formed on the first smoothing layer with a relatively thin coating film thickness without the second smoothing layer forming coating material penetrating into the glass woven fabric. Can do.

The second smoothing layer paint is polyurethane resin, acrylic resin, polyester resin, polyamide resin, butyral resin, polystyrene resin, nitrocellulose resin, cellulose acetate resin, vinyl chloride / vinyl acetate resin. It is adjusted by blending containing an arbitrary resin selected from a copolymer resin, a vinyl chloride / vinyl acetate / acrylic copolymer resin, a chlorinated polypropylene resin, and a solvent capable of dissolving them.
The coating of the second smoothing layer forming paint can use various coating methods excellent in the smoothing function and the film thickness uniforming function. In addition to reverse coating, gravure coating, gravure coating with a smoother, etc., Various coating methods and printing methods excellent in the smoothing function can be used.
As described above, the second smoothing layer has a smoothing function, and in the subsequent manufacturing process of the decorative sheet, in the winding process, when the back surface and the surface of the decorative sheet on the glass woven fabric side are in contact with each other. It is preferable that the surface of the decorative sheet is not affected by the unevenness of the glass woven fabric. In the use of the above-mentioned various resins, the modification of the resin, the use of a curing agent such as a crosslinking agent, and a polymerization initiator or a polymerization accelerator as appropriate. It is preferable to perform a curing treatment for improving the rigidity of the surface, for example, by the addition of.
By including a pigment in the second smoothing layer used in the present invention, it is possible to obtain a ground layer or a colored layer of a printing layer by gravure printing. By using such a second smoothing layer, it is possible to form a flat surface with good smoothness for fine gravure printing and to form an arbitrary background color of the design pattern to improve the design. It is possible to increase it further.

In the decorative sheet of the present invention, an auxiliary layer may be provided on the surface opposite to the first smoothing layer across the glass woven fabric, and the glass woven fabric with the auxiliary layer may be used as a new substrate. By providing the auxiliary layer, it is possible to reinforce the strength of the glass woven fabric that is the base, and the step of laminating each layer of the decorative layer including the smoothing layer can be stably performed. By further covering the gap portion of the weave of the glass woven fabric from the side opposite to the first smoothing layer, the concealability of the entire decorative sheet is also improved. Further, when the glass woven fabric and the first smoothing layer are bonded by providing an auxiliary layer in advance on the side opposite to the smoothing layer of the glass woven fabric, the first smoothing layer and the glass woven fabric Can be prevented from slipping through the glass woven fabric. Moreover, the adhesive force at the time of bonding a decorative sheet with another base material through an adhesive agent and an adhesive can be improved. The auxiliary layer is preferably a resin layer from the viewpoint of ease of formation, more preferably contains a vinyl chloride resin having good nonflammability, and the auxiliary layer is a resin film, and further a vinyl chloride resin film. Is more preferable. When the first smoothing layer is formed on the glass woven fabric by thermocompression bonding, the surface of the glass woven fabric opposite to the smoothing layer is not in direct contact with the hot-pressing roll. It is preferable that the unevenness of the received glass woven fabric is less likely to disturb the smoothness of the surface of the smoothing layer on the opposite side across the glass woven fabric. Such an effect is also exhibited when performing an efficient manufacturing method in which the first smoothing layer and the auxiliary layer are simultaneously thermocompression bonded to both surfaces of the glass woven fabric.
Adhesion to the glass woven fabric when the auxiliary layer is a resin film can use an adhesive as necessary, and it is preferable to use the adhesive used for the adhesion of the first smoothing layer.

The printing layer is formed directly on the first smoothing layer of the decorative sheet of the present invention or via the second smoothing layer formed on the first smoothing layer. These smoothing layers can have a function of defining the background color of the printing layer, and when the printing layer is printed on the first smoothing layer, the background of the color tone of the resin film that is the first smoothing layer. When the second smoothing layer is formed as a color and on the first smoothing layer, the color tone of the second smoothing layer is used as the background color.
For example, a wood grain pattern, a stone pattern, a cloth pattern, a skin pattern, a geometric pattern, a character, a symbol, a line drawing, and various abstract pattern patterns are formed using the color tone of the smoothing layer as a background color. In order to realize high incombustibility, natural wood as a surface material cannot be used, and therefore it is particularly necessary to print a grain pattern very close to natural wood among the above patterns.
In order to produce such a design pattern with a high designability, a further resin film is laminated on a printed layer of a pattern such as a wood grain pattern, and a doubling technique is used in which embossing is formed from the resin film layer. It is possible to form a design with an uneven pattern on the surface to improve the texture of natural wood. In addition, when the matte layer formed on the printed layer of the pattern and the transparent top coat layer are visually uneven by the gloss mat technique that forms a synchronized gloss pattern corresponding to the pattern. In particular, when the design pattern is a wood grain pattern, a more natural grain three-dimensional effect can be imparted and the design is high.

The pattern may be formed on the surface of the base sheet by a printing method using an ink obtained by dissolving (or dispersing) a known colorant (dye or pigment) in a solvent (or dispersion medium) together with a resin. it can.
Examples of the colorant include inorganic pigments such as carbon black, titanium white, zinc white, dial, bitumen, and cadmium red; azo pigments, lake pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, isoindolinone pigments, dioxazine pigments. Organic pigments such as aluminum powder, metal powder pigments such as bronze powder, pearlescent pigments such as titanium oxide-coated mica and bismuth oxide chloride; fluorescent pigments; These colorants can be used alone or in admixture of two or more. These colorants may be used together with fillers such as silica, extender pigments such as organic beads, neutralizing agents, surfactants and the like.

As the resin used for the printing layer, in addition to the polyester-based urethane resin subjected to hydrophilic treatment, polyester, polyacrylate, polyvinyl acetate, polybutadiene, polyvinyl chloride, chlorinated polypropylene, polyethylene, polystyrene, polystyrene-acrylate copolymer, A rosin derivative, an alcohol adduct of a styrene-maleic anhydride copolymer, a cellulose resin, or the like can be used in combination. More specifically, for example, polyacrylamide resins, poly (meth) acrylic resins, polyethylene oxide resins, poly N-vinyl pyrrolidone resins, water-soluble polyester resins, water-soluble polyamide resins, water-soluble amino acids. Also usable are water-based resins, water-soluble phenolic resins, other water-soluble synthetic resins; water-soluble natural polymers such as polynucleotides, polypeptides, polysaccharides, and the like. Also, for example, natural rubber, synthetic rubber, polyvinyl acetate resin, (meth) acrylic resin, polyvinyl chloride resin, polyurethane-polyacrylic resin, etc. modified or a mixture of the above natural rubber, etc. Resin can also be used. The said resin can be used individually or in combination of 2 or more types. Adding a crosslinking agent, polymerization initiator, or polymerization accelerator to the above resin to improve the coating film strength was affected by the improvement of durability and the textured irregularities of the glass woven fabric. It is preferable in terms of suppressing deformation, and among the above resins, the use of an acrylic resin is preferable.
The thickness of the print layer of the pattern is preferably 0.2 μm to 10.0 μm.

  In order to produce a decorative sheet having a high design property and a high scratch resistance on the surface, an additional layer for further improving the design property and a protective layer can be formed on the printed layer. For example, when printing a pattern with a fine grain pattern, a transparent resin sheet layer is further formed on the print layer of the pattern corresponding to the grain pattern in order to express the natural unevenness of the grain pattern, or Furthermore, after forming a protective layer beforehand on it, an uneven | corrugated pattern can be actually formed on this transparent resin layer or this protective layer (doubling method). Alternatively, a matte layer may be formed on the printed pattern, and a gloss pattern by gloss printing that is synchronized with the grain pattern may be formed to give the grain pattern a visual unevenness (gross mat technique). . By using these methods, it is possible to express the three-dimensional effect of the grain with a thin film thickness, so that it is possible to achieve a high design quality close to that of a solid material without deteriorating the good non-combustible performance of the glass woven fabric. . In addition, for the purpose of improving the design or physical properties, even if a slight influence of the unevenness of the glass woven fabric remains due to a new layer sequentially laminated on the printed layer, the influence is not reduced. Every time it can be made smaller. Furthermore, the appearance of the design can be made more complicated by the lamination of the additional layers, and the pattern of the periodic glass woven fabric can be made more difficult to visually recognize. In addition, the hardness on the surface layer side of the decorative layer portion can be further improved for each additional layer. Thus, when each layer is sequentially laminated on the glass woven fabric to form a decorative layer, the pattern becomes complicated, and the rigidity of the decorative layer increases as it approaches the surface. It becomes difficult to reach the surface layer side of the decorative layer.

The above method capable of forming a fine pattern such as a wood grain pattern will be described in detail.
About the doubling method of forming an uneven pattern by embossing on the surface layer after forming the protective layer at the same time as the resin film layer is laminated on the printed layer by thermal lamination on the printed layer representing the wood grain pattern, FIG. 4 shows a schematic cross-sectional view of a decorative sheet produced using the technique.
By forming the concavo-convex pattern by embossing, the texture pattern of the glass woven fabric can be made less visible. However, the resin sheet layer formed on the printing layer by the doubling method is inherently softened by heating, and the texture of the woven glass cloth affects the printed layer of the pattern from the opposite side of the embossing due to the hot press during embossing. Therefore, it is necessary to pay attention to the settings of the shape and physical properties of the first and second smoothing layers with respect to the conditions of the hot press.

By using a gloss matte technique that gives a natural three-dimensional impression by giving a visual unevenness by forming a gloss pattern by gloss printing in sync with the wood grain pattern without embossing. A schematic cross-sectional view of the produced decorative sheet is shown in FIG.
Of the two decorative layer forming methods, the decorative layer is preferably formed by a gloss mat technique. According to the doubling method, an uneven pattern is formed on the transparent resin film formed on the printed layer of the pattern, thereby resembling the appearance of natural wood and improving the texture. However, when forming a concavo-convex pattern by a thermocompression bonding process, there is a possibility that the texture pattern of the glass woven fabric will appear in the pattern depending on the conditions. On the other hand, in the gloss matting method, such a concavo-convex pattern is not formed, and a matte layer is further formed. Therefore, the texture pattern of the glass woven fabric is further invisible.
In order to produce gloss printing, it is preferable to form a matte layer on the printed layer of the pattern. In glossy printing, transparent printing that matches the grain of the pattern printing on the matte layer produces a clearer difference in gloss between the part corresponding to the grain and the other part. By this, it is possible to produce a realistic feeling rich in stereoscopic effect and perspective. The formation of the matte layer is preferable in this respect because the influence of the textured irregularities of the glass woven fabric on the design of the pattern is reduced in appearance.
The matte layer is formed in order to impart a high-quality design to the pattern and to provide a high-quality wood texture when the pattern is a wood grain pattern. Further, it is performed to form a basic mat portion for forming a three-dimensional effect as printing by a gloss mat method in which a gloss difference is formed corresponding to the pattern.
In addition, the top coat layer described later can be applied directly and synchronously without forming the matte layer, and it is possible to form a three-dimensional effect although not as much as when the matte layer is formed. is there. On the other hand, the formation of the patterned topcoat layer itself can also be performed independently of the printing layer in an asynchronous manner, and the printing surface in this case is not limited to the pattern and may be a single color.

  As the resin used for the matte layer, a transparent or transparent colored resin having excellent wear resistance and stain resistance is used, and a matte agent is strongly dispersed and retained, and a film with good film strength is preferable, and thermosetting Resin, ionizing radiation curable resin, etc. are typical, but the film can be formed with existing equipment, the manufacturing cost can be reduced, the rigidity of the decorative layer part is increased, and the influence of the unevenness of the glass woven fabric Thermosetting resins such as unsaturated polyester resins, acrylic resins, and urethane resins are preferable. In particular, it is preferable to use a two-component curable resin such as a two-component curable urethane resin, a polyol such as an acrylic polyol, a polyester polyol, or a polyether polyol is used as a main agent, and an aliphatic or alicyclic polyisocyanate is used as a crosslinking agent. Is preferred. Among them, those using acrylic polyol as the main agent are preferable.

Examples of the matting agent to be used include inorganic matting agents composed of particles such as amorphous silica, spherical silica, alumina, kaolinite, calcium carbonate, barium sulfate, and glass, polycarbonate resin, acrylic resin, and polyamide (nylon). Organic matting agents such as resins, urea resins and silicon resins can be used. The particle shape of the matting agent is spherical, polyhedral, scale-like or the like. The particle size of the matting agent is about 1 to 10 μm. The addition amount of the matting agent may be such that the difference in gloss between the high gloss portion and the low gloss portion can be visually discerned. Further, as the matting agent, it is preferable to select a matting agent having excellent abrasion resistance capable of protecting the printing layer because there is a portion where the matting layer becomes the outermost surface layer. Examples are matting agents such as amorphous silica, spherical silica, and alumina. In addition, the glass transition point Tg of the resin used for ensuring the abrasion resistance of the basic coating film is also used to increase the rigidity in the vicinity of the surface of the decorative layer and make it less susceptible to the textured deformation of the glass woven fabric. 60 ° C. or higher, preferably 70 ° C. or higher, more preferably 80 ° C. or higher, and even more preferably 100 ° C. or higher. The matte layer is formed by coating the matte layer paint containing the above resin and matting agent from the top of the print layer by spray coating, comma coating, flow coating, roll coating, gravure coating, etc. be able to.
The thickness of the matte layer can be appropriately adjusted in consideration of the state of printing by the gloss matting method, but is preferably 3.0 μm to 10 μm, and further printed to be 2.0 μm to 6.0 μm. preferable. The gloss of the matte layer is preferably 15 or less in terms of gloss value.

Of the additional layers formed on the printed layer, the uppermost protective layer having scratch resistance and durability function, or when a matte layer is formed on the printed layer, the matte layer A top coat layer can be formed as a gloss printed layer that is formed in the pattern and forms a gloss pattern. The topcoat layer contains a thermosetting resin as a resin component, and is preferably a thermosetting resin excellent in wear resistance, stain resistance and transparency.
The use of these resins improves the rigidity of the decorative layer near the surface layer, and the effect of absorbing the unevenness of the glass woven fabric due to deformation of the first smoothing layer near the glass woven fabric is affected. Make it harder to reach the film thickness direction. Moreover, it is preferable also in the point which prevents more effectively receiving the texture-form deformation | transformation by contact with a glass woven fabric at the time of winding after coating-film formation.
Thermosetting resins include unsaturated polyester resins, acrylic resins, polyurethane resins (including two-component curable polyurethane), epoxy resins, amino alkyd resins, phenol resins, urea resins, diallyl phthalate resins, and melamine resins. Guanamine resin, melamine-urea co-condensation resin, silicon resin, polysiloxane resin and the like. A curing agent such as a crosslinking agent, a polymerization initiator, or a polymerization accelerator can be added to the resin. For example, as a curing agent, isocyanate or organic sulfonate is added to unsaturated polyester resin or polyurethane resin, organic amine is added to epoxy resin, peroxide such as methyl ethyl ketone peroxide, azoisobutyl nitrile, etc. The radical initiator is added to the unsaturated polyester resin.
Among the above, a two-component polyurethane resin is preferable in terms of easily improving the abrasion resistance, impact resistance, stain resistance, scratch resistance, weather resistance, and the like of the decorative sheet. The two-component curable urethane resin is not particularly limited. Among them, a polyol component (acrylic polyol, polyester polyol, polyether polyol, epoxy polyol, etc.) having an OH group as a main component and an isocyanate component (tolylene diene) which is a curing agent component. Isocyanate, hexamethylene diisocyanate, metaxylene diisocyanate and the like) can be used. In particular, a two-component curable polyurethane resin using an acrylic polyol and an isocyanate curing agent is preferable.

A reactive silicone oil may be added to the topcoat layer in the present invention. The reactive silicone oil is firmly held in the top coat layer, and it is difficult for the back surface to migrate during winding after application during production, so that the adhesiveness of the produced decorative sheet to the coating material is not impaired. Also, it functions as a good lubricant on the surface, and as a result, improves the wear resistance of the decorative sheet surface, especially when the ridges and corners are frequently in contact with people and objects when entrained. Excellent resistance to contamination.
As the reactive silicone oil that can be used, various addition polymerization type silicone oils and condensation polymerization type silicone oils can be used, but the condensation polymerization type silicone oil that can be selected according to the reactive functional group of the resin used together. Oil is preferred. Amino-modified silicone oil, carbinol-modified silicone oil, carboxyl-modified silicone oil, phenol-modified silicone oil, and the like can be used. Of these, amino-modified silicone oil and carboxyl-modified silicone oil are preferable because they have good reactivity. Oil is most preferred. By using these in combination with the two-component polyurethane resin, a top coat layer having excellent wear resistance can be formed.
The content of reactive silicone oil is preferably 0.1 to 20 parts, more preferably 0.2 to 18 parts, and 0.3 parts with respect to 100 parts of resin in the topcoat layer excluding the curing agent. -15 parts are more preferred, 0.5 parts to 12 parts are more preferred, and 1 part to 10 parts are even more preferred.

Examples of the method for forming the topcoat layer with the thermosetting resin include, for example, a solution for the above-described thermosetting resin and adding a reactive silicone oil to the topcoat layer coating material, such as a roll coating method or a gravure coating method. It is formed by coating by a known coating method, or using these as inks, printing using a known printing method such as a gravure printing method, an offset printing method, a screen printing method, etc., drying and curing. be able to.
In the decorative sheet of the present invention, a gloss difference pattern is formed by the top coat layer formed on the matte layer. The gloss difference pattern is used to visually recognize the difference in gloss and gloss between the matte layer and the top coat layer, and is used independently to improve the design of the decorative sheet. By forming in synchronization with the pattern pattern of the layer, it is possible to perform printing by a good gloss matting method. The gloss and gloss of the top coat layer set with a difference to the matte layer can be set high or low for the matte layer, but the gloss and gloss of the entire decorative sheet Since the top coat layer has a higher gloss and gloss than the matte layer, the contrast of the gloss difference that can be expressed by the gloss pattern can be further expanded. It is preferable. Further, at this time, the top coat layer can be laminated so as to form a negative pattern with respect to the pattern of the pattern printing layer.

In the printing by gloss mat method, which uses the top coat layer as the outermost surface, high glossy and glossy parts are raised, and high design is made using the visual three-dimensional effect that the low-gloss parts recede in a matte state. A sex pattern is formed. For example, by changing the gloss and glossy state between the conduit part and the non-conduit part of the grain pattern, a grain pattern having a more natural three-dimensional effect is formed in synchronization with the grain pattern formed on the printed layer of the pattern . Therefore, the formation of the matte layer on the printed layer is preferable in terms of forming a clearer three-dimensional effect. Here, whether to select a stereoscopic effect so that the conduit or non-conduit portion can be seen in the foreground is related to the overall pattern pattern that is assumed, the type of material to be coated, the installation location of the article after coating, etc. Can be selected.
As described above, the decorative layer formed on the glass woven fabric has high rigidity near the surface layer as the entire decorative layer, and the deformation of the coating film due to the texture pattern of the glass woven fabric is a design with a grain pattern. Will not be disturbed.
For example, as in the examples described later, by making the laminated portion of the topcoat layer a non-conduit portion, the gloss state and gloss value are improved compared to the non-laminated portion of the topcoat layer where the matte layer is the outermost surface. , It can be raised to the front and visually recognized. In other words, the non-conduit portion corresponds to the gross portion, the conduit portion corresponds to the mat portion, and the dark brown and black portions, which are wood-grained conduit portions, recede toward the back compared to other non-conduit portions. The Such a visual three-dimensional effect is in agreement with the actual unevenness of the coating surface although the level difference is very small, and is considered a preferable method for forming a more natural visual three-dimensional effect.
In this way, it is possible to produce a decorative sheet having an extremely high design property, a natural wood grain pattern, and excellent nonflammability.

However, although the topcoat layer has a higher gloss than the matte layer, the overall gloss is often designed to be low, so that the gloss will be reduced when an external load is applied or when different materials are rubbed. It changes in the rising direction or the coat layer peels off in some cases. Therefore, it is conceivable to add inorganic fine particles such as an antifriction material, but in the case of printing by the gloss mat method of the present application that receives a load from an external force at the convex portion of the topcoat layer, a load is applied to the convex portion. It is easy to concentrate, and the added inorganic fine particles are easily detached from the surface of the topcoat layer. This is especially true in view of the fact that these inorganic fine particles are not held by a uniformly formed protective layer in the present application. In particular, in the corners and ridges after coating, a slight elongation of the decorative sheet occurs, and considering the fact that contact pressure with a person or article must be received by a line rather than a plane, the above situation is further increased. It tends to occur. In order to prevent this, it is necessary to improve the slipperiness of the topcoat layer. For this purpose, the addition of reactive silicone oil is extremely important for improving the wear resistance.
On the other hand, it is difficult to add reactive silicone oil in the matte layer that is partially the outermost layer. This is because the silicone oil added to the matte layer is retained on the surface layer, which may hinder the adhesion of the topcoat layer formed thereon. Therefore, it is necessary to improve the glass transition point of the resin for the matte layer, and to provide abrasion resistance together with the matte effect.
The surface of the matte layer is subject to direct frictional force, which may change the surface shape and increase gloss and gloss. However, the external force is mainly retained by the convex surface of the topcoat layer and blended. The reactive silicone oil that is used exhibits good slipperiness improving effect, so that it is not damaged.

Below, the preferable manufacturing method of the decorative sheet of this invention is demonstrated.
Each layer of the decorative sheet of the present invention having the above-mentioned each layer structure on the glass woven fabric of the substrate having a layer made of glass woven fabric as a surface layer is a layer that can be formed by any lamination of a resin film or a coating film. And a layer (first smoothing layer) to be formed only by laminating resin films. In the case where the layer to be laminated is a resin film, it is laminated and formed by an adhesive process or a thermocompression process of the resin film using an adhesive as necessary.
The decorative sheet of the present invention comprises a glass woven fabric or a glass woven fabric laminated with a resin film as a first smoothing layer on the glass woven fabric side surface of a glass woven fabric to which an auxiliary layer has been bonded in advance. After confirming that the surface of the resin film whose unevenness is the first smoothing layer on the opposite side of the glass woven fabric has been smoothed, construct a decorative layer such as a printing layer by gravure printing in order. It can be manufactured by laminating other layers. The auxiliary layer may be laminated on the opposite side of the glass woven fabric at the same time as the first smoothing layer is laminated.
As the other decorative layer, a printing layer, a matte layer, and a topcoat layer are sequentially applied on the first smoothing layer or the second smoothing layer, and dried, and each layer or how many layers. These can be collectively formed by applying a coating forming process such as curing and aging.
In particular, during heating in the coating film curing process, after heating, the shape stability of the glass woven fabric that is the substrate is good, so in the curing process of various coating films, the elongation of the resin film laminated on the glass woven fabric or There is no wrinkle.
A colored layer serving as a background color may be formed before the printed layer is formed, and the colored layer may be given a function as a second smoothing layer. On the printed layer, a topcoat layer may be formed for improving the rigidity of the decorative layer surface side and for improving the scratch resistance of the decorative layer surface. It is preferable to further improve the design of the decorative layer by adding a layer.
That is, a second resin layer for embossing may be formed on a printed layer by gravure printing, and a concavo-convex pattern may be formed on the resin layer, or a transparent resin layer may be formed after forming a matte layer. It may be formed in synchronism with the pattern of the printing layer to form a glossy printing layer. In addition, when performing gloss printing, in order to maintain a clear gloss pattern, a protective layer with uniform gloss is not further laminated on it, but only the top coat layer, which is a gloss printing layer, is scratch resistant. Is preferably maintained.

Further, the decorative sheet of the present invention includes a glass woven fabric in which each layer formed on a printing layer by gravure printing is laminated in reverse order on a temporary support, and then a glass woven fabric on which a first smoothing layer is laminated. It may be laminated on the surface of the first smoothing layer of the body by a transfer process.
Alternatively, the first smoothing layer and all the layers formed thereon can be thermocompression-bonded with the glass woven fabric as one decorative layer. The auxiliary layer may be bonded to the glass woven fabric in advance, but can be thermocompression bonded simultaneously with the one decorative layer and the glass woven fabric interposed therebetween.
Thus, the first of the decorative layer having a printed layer formed by gravure printing on the first smoothing layer on the surface of the substrate having the glass woven fabric layer as the surface layer on the glass woven fabric side. The method for producing a decorative sheet is characterized in that the first smoothing layer is a resin film, and the surface on the smoothing layer side is opposed to the first smoothing layer. In addition, since the gravure printing is performed, the printing layer by the gravure printing is more preferable because there is no possibility of being affected by the unevenness of the glass woven fabric. In addition, by laminating the printing layer and other layers on the first or second smoothing layer, the rigidity of the printing layer side on the first or first and second smoothing layers and the surface hardness are improved. Then, since all the layers formed on the first smoothing layer or the first and second smoothing layers are laminated on the glass woven fabric at once, the texture of the glass woven fabric is more decorative. It is preferable that it is difficult to be visually recognized from the layer surface. At this time, it is preferable that a layer for covering the printed layer is formed before thermocompression bonding. The layer covering the printing layer may be a protective layer or a matte layer, but it is preferable that these layers have a curing step. By using such a manufacturing method, the decorative layer as a whole can be formed such that rigidity and surface hardness gradually increase from the first smoothing layer toward the printing layer.
Therefore, even when printing by a high-design doubling method or printing by a gloss matting method, all the layers including the printing layer laminated on the first smoothing layer or the second smoothing layer are included. It is preferable to perform thermocompression bonding to the surface of the substrate having the surface layer of the glass woven fabric layer on the surface of the glass woven fabric side.

  As described above, the first smoothing layer is laminated on the glass woven fabric by forming another layer constituting the decorative layer on the first smoothing layer, preferably the second smoothing layer or the protective layer. Can be done after. Such a method for producing a decorative sheet is preferable because the pattern forming step by gravure printing can be performed on a smoothing layer which is not at all affected by the glass woven fabric. If there are irregularities on the surface of the gravure printing, the irregularities will be amplified as uneven printing on the pattern, so it will be much larger than if the irregularities will occur later on the surface of the pre-formed pattern. This is because damage is given to a fine pattern.

Example 1
A first smoothing layer (colored) was adhered on a glass woven fabric, and a decorative sheet having a printed layer by gravure printing thereon was produced (see FIG. 1). As the glass fiber, about 250 monofilament-based glass filaments bundled into a glass yarn were used which were plain woven at a density of 32 warps / 25 mm and 32 wefts / 25 mm. As the first smoothing layer, a white-colored vinyl chloride resin sheet (Tatsuno Chemical Co., Ltd., thickness 120 μm, plasticizer blending amount 11 parts by mass with respect to 100 parts by mass of resin) was prepared.
A vinyl chloride adhesive was applied onto a vinyl chloride resin sheet, and the glass woven fabric was thermocompression bonded to the coated surface.
The coating amount of the acrylic resin-containing ink (manufactured by DIC) as a printing layer on the side opposite to the side in contact with the glass woven fabric of the vinyl chloride resin sheet thermocompression bonded with the glass woven fabric is 1 The wood-grained conduit portion was printed so as to be 5 g / m ² . Next, acrylic matte coating agent (containing 100 parts of acrylic polyol manufactured by DIC, containing amorphous silica as a matting agent, and 20 parts of polyisocyanate as a curing agent is used as a matting layer. , A matting paint having a glass transition point of 100 ° C. at the time of curing) was printed so that the coating amount at the time of drying was 6.0 g / m ² .
Next, an acrylic coating agent (coating agent used by mixing 20 parts of polyisocyanate as a curing agent with 100 parts of acrylic polyol manufactured by DIC) as a topcoat layer, and an amino-modified reactive silicone as an additive The top coat layer paint containing 6 parts of reactive silicone oil (made by DIC) containing oil as the main component is tuned to the part other than the pattern pattern so that the coating amount when dried is 5.0 g / m ^2. Printed. Thereafter, aging was carried out for 72 hours in an environment of 40 ° C. to obtain a decorative sheet 1 on which a wood grain conduit pattern was printed by a gloss mat technique on a vinyl chloride resin substrate sheet. As a result, a decorative sheet was produced in which the topcoat layer was glossy printed, and the wood grain conduit pattern portion was visually recognized in a concave state.

(Example 2)
Before forming the printing layer on the vinyl chloride resin sheet (first smoothing layer) thermocompression-bonded with the glass woven fabric, the color of the vinyl chloride resin sheet is used as a solid colored layer by gravure printing. The same white acrylic resin-containing ink (manufactured by DIC) was applied so that the coating amount when dried was 2.0 g / m ^2, and a colored layer (second smoothing layer) was printed. Thereafter, a decorative sheet 2 was obtained in the same manner as in Example 1 (see FIG. 2).

(Example 3)
On a glass woven fabric, a vinyl chloride resin having a film thickness of 85 μm that is identical to the other side except the film thickness on the side opposite to the thermocompression bonding side of the 120 μm vinyl chloride resin sheet (first smoothing layer). A decorative sheet 3 was produced in the same manner as in Example 1 except that the sheet (auxiliary layer) was previously thermocompression bonded (see FIG. 3).

Example 4
The printed layer, matte layer, and top produced in Example 1 were bonded to the vinyl chloride resin sheet (first smoothing layer) having a thickness of 120 μm and the glass woven fabric on the vinyl chloride resin sheet. A decorative sheet 4 was produced in the same manner as in Example 1 except that the coating layer was formed in this order in advance.

(Example 5)
On the glass woven fabric, on the opposite side to the thermocompression-bonding side of the 120 μm-thick vinyl chloride resin sheet (first smoothing layer), the 85 μm-thick vinyl chloride resin sheet (identical except for the film thickness) A decorative sheet 5 was produced in the same manner as in Example 4 except that the auxiliary layer) was thermocompression bonded simultaneously.

(Example 6)
After forming the colored layer (second smoothing layer) used in Example 3 on the vinyl chloride resin sheet (first smoothing layer) having a thickness of 120 μm, a printed layer, a matte layer, and a top coat A decorative sheet 6 was produced in the same manner as in Example 5 except that the layers were formed in this order.

(Example 7)
After forming the printing layer produced in Example 1 on the vinyl chloride resin sheet (first smoothing layer) having a thickness of 120 μm, the side opposite to the side on which the printing layer is formed is a glass woven fabric. Thermocompression bonding was performed. Thereafter, the same matte layer and topcoat layer as those prepared in Example 1 were formed in this order on the printed layer, and a decorative sheet 7 was prepared.

(Comparative Example 1)
A vinyl chloride vinyl acetate paint containing a pigment capable of forming a coating film having a white hue similar to that of the vinyl chloride resin sheet used in Example 1 is used on a glass woven fabric. / M ² was applied by a roll coater to form a vinyl chloride vinyl acetate resin colored layer (first smoothing layer). A glossy printed layer as a printed layer, a matte layer, and a topcoat layer was formed thereon in the same manner as in Example 1 to prepare a decorative sheet 8.

(Comparative Example 2)
Before forming a printing layer on the vinyl chloride vinyl acetate resin layer (first smoothing layer), a solid colored layer (second smoothing layer) is formed in the same manner as in Example 2 by a gravure printing method. After that, a printed layer, a matte layer, and a topcoat layer were formed in the same manner as in Example 2 to prepare a decorative sheet 9.

(Comparative Example 3)
On the glass woven fabric, on the side opposite to the side on which the vinyl chloride vinyl acetate resin layer (first smoothing layer) is formed, an 85 μm vinyl chloride resin sheet (auxiliary layer) having the same properties except the film thickness is provided. A decorative sheet 10 was produced in the same manner as in Comparative Example 2 except that the thermocompression bonding was performed in advance.

(Comparative Example 4)
A silicone release agent is applied onto the polyester carrier, and the same vinyl chloride vinyl acetate resin layer (first smoothing layer) as prepared in Comparative Example 1 is applied to the silicone release agent application surface of the polyester film; A printing layer was formed in the order of a printing layer and a vinyl chloride vinyl acetate resin layer, and a vinyl chloride vinyl acetate adhesive layer having a dry film thickness of 20 μm was formed thereon to form a transfer decorative layer.
On the other hand, a vinyl chloride resin sheet was thermocompression bonded to one surface of the glass woven fabric in the same manner as in Example 2, and the adhesive layer of the transfer decorative layer was in contact with the other surface of the glass woven fabric. The polyester carrier was peeled off by thermocompression bonding, and a first smoothing layer and a printing layer were formed on the glass woven fabric through an adhesive layer. Thereafter, in the same manner as in Example 1, a matte layer and a topcoat layer were formed, and a decorative sheet 11 was produced.

(Comparative Example 5)
A transparent vinyl chloride sol was applied onto the polyester carrier film and dried to form a transparent vinyl chloride resin film having a thickness of 80 μm. A printed layer by gravure printing was formed on the surface of the transparent vinyl chloride film in the same manner as in Example 1, and a colored layer similar to that in Example 2 was formed thereon by gravure printing. At this time, as the ink used for forming the colored layer, 70% of a titanium pigment is blended for improving the concealing property of the coating film, and the dry coating thickness is 10 g / m ² as the maximum coating amount considering the cohesive force of the ink layer. did. A solution containing a vinyl chloride / vinyl acetate copolymer is applied onto the printed layer and dried to form an adhesive layer having a dry film thickness of 20 g / m ^2, and the carrier film is peeled off. A vinyl chloride film having an adhesive layer formed on the other surface was produced. And the decorative sheet 12 was obtained by heat laminating the obtained vinyl chloride film with the glass woven fabric through the adhesive layer.

  About the decorative sheets 1-12 produced in the said Examples 1-7 and Comparative Examples 1-5, the decorative sheet for evaluation of 10 cm x 10 cm was used, and the external appearance was evaluated on the following references | standards. Appearance evaluation was performed for both the pattern formation before the mat layer was formed after the printing layer was formed and the appearance of the final decorative sheet. The evaluation method, evaluation criteria and evaluation results are described below.

A. [Printing status during printing layer formation]
The printing situation before forming the matte layer at the time of printing layer formation was observed and evaluated according to the following criteria.
1. Influence by uneven pattern of glass woven fabric The uneven pattern of glass woven fabric was visually observed and evaluated according to the following evaluation criteria.
◎ ・ ・ ・ ・ ・ From any angle with respect to the incident direction of the irradiation light perpendicular to the sample
Unevenness is not visible even when observed.
○ …… It is not visible from the front, but it is slanted at an angle of 45 degrees or more
Can be visually recognized by observation from the position of △ .. Can be visually recognized by slight observation from the front direction.

2. Missing print
The state of printing omission was observed visually, and evaluation was performed according to the following evaluation criteria.
◎ …… Cannot detect missing prints even with a magnifying glass (3x) ○ …… Cannot see missing prints only with a magnifying glass (3x) loupe △ ・ ・ ・ ・・ Easy to see missing prints × …… The outline of the grain pattern is disturbed by missing prints

3. Concealing property White art paper and black art paper are laid on the back of the decorative sheet for evaluation, and the decorative sheet is placed on the boundary, resulting in a change in hue across the boundary and a lattice pattern along the pattern of the glass woven fabric The state of color difference was visually observed and evaluated according to the following evaluation criteria.
◎ ・ ・ ・ ・ ・ Changes in hue across the border and occur along the pattern of glass fabric
The grid-like color difference is not visible.
○ …… A change in hue across the boundary, or a lattice-like color difference generated along the pattern of the glass woven fabric can be visually recognized. However, if a distance of 50 cm is placed from the sample, it is difficult to see both.
Δ: Change in hue across the boundary, or lattice-like color difference that occurs along the pattern of the glass woven fabric can be visually recognized even at a distance of 50 cm, but both at a distance of 1 M Cannot be seen.
X: Changes in hue across the boundary, or lattice-like color difference that occurs along the pattern of the glass woven fabric can be visually recognized even from a distance of 1M.

B, [Appearance after formation of top coat layer]
The appearance of the decorative sheet after the topcoat layer was formed was evaluated according to the following evaluation criteria.
1. Appearance of decorative sheet after formation of topcoat layer The visual appearance of the decorative sheet is comprehensively evaluated.
... Uniform background color printing and fine pattern printing are formed.
Even if a magnifying glass (3x) is used, there is no disorder in printing.
○ …… When observed with a magnifier (3x), the presence of the woven fabric pattern is confirmed.
It is almost impossible to distinguish visually.
△ ・ ・ ・ ・ ・ Glass fabric pattern is slightly visible in the background color, and the outline of the pattern
Lacks smoothness × …… There is uneven printing due to the woven cloth pattern of glass woven cloth in the background color, and the pattern
The pattern is missing.

As can be seen from Table 1, in the decorative sheets 1 to 5 prepared in Examples 1 to 7, the texture pattern of the glass woven fabric is almost visually recognized at the stage where the top coat layer is formed and the decorative sheet is prepared. It was possible to form a print with a good pattern without any problem. When forming the printing layer before applying the matte layer, it is easy to observe the influence of the uneven pattern of the glass woven fabric, and it can be seen that the influence becomes smaller by the addition of the second smoothing layer and the auxiliary layer. In addition, the decorative sheet 4 prepared in Examples 4, 5, and 6, in which a decorative layer is formed in advance without interposing a glass woven fabric, and finally the glass woven fabric and the decorative layer are bonded as a thermocompression bonding step, In the cases of Nos. 5 and 6, the texture pattern of the glass woven fabric became less visible, and further, no printing omission occurred, so that a finer pattern print could be obtained. Further, since the first smoothing layer has a sufficient film thickness and is a uniform resin sheet, the concealment resulted in no problem. On the other hand, Example 7 in which a printing layer was formed on the first smoothing layer and thermocompression-bonded to the glass woven fabric was very small in the printing layer, and there was no essential problem in design, but the glass woven The effect of deformation from the unevenness of the fabric was observed.
On the other hand, for Comparative Examples 1 to 3 in which the resin film is not used as the first smoothing layer,
It was difficult to close the texture of the glass woven fabric by applying a fluid paint, and the uneven pattern of the glass woven fabric was easily visually recognized. In addition, printing failure occurs due to the effect that the paint could not close the concave portion of the glass woven fabric, and as a result, sufficient concealment cannot be obtained, and it occurs in a lattice pattern from the top of the pattern to the pattern of the glass woven fabric. The state of color difference was easily visible.
In Comparative Example 4, since the vinyl chloride / vinyl acetate adhesive layer is pressure-bonded to the warp and weft of the glass fiber in the glass woven fabric at the time of transfer, the film thickness variation and printing omission due to uneven transfer are likely to occur. Moreover, the state of the color difference generated in a lattice shape along the concavo-convex pattern of the glass woven fabric or the pattern of the glass woven fabric was easily visually recognized. In Comparative Example 5, since the thickness of the vinyl chloride vinyl acetate copolymer adhesive layer is thin, the surface of the colored layer and the printing layer is affected by the unevenness of the glass woven fabric, and the pattern is passed through the transparent vinyl chloride film layer. It was visible. Furthermore, since the colored layer formed by gravure printing and the thickness of the printed layer are thin, sufficient concealability cannot be obtained, and the state of the color difference that occurs in a lattice shape from the top of the pattern along the pattern of the glass woven fabric. It was easily visible. However, no printing omission occurred because printing was performed before bonding to the glass woven fabric.
In Comparative Examples 1 to 5, the difference in image quality from the examples was clear even when the top coat was formed.

  The decorative sheet of the present invention is a decorative sheet having both high designability and good nonflammability, and can be used for interior decoration of buildings by covering the ceiling, floor, wall surface, etc. It can be used for coating of compartments and the like, and can improve nonflammability and flameproofness. Further, the decorative sheet itself can be used as a suspended ceiling sheet, a membrane ceiling sheet, a blind or the like having excellent incombustibility.

DESCRIPTION OF SYMBOLS 1 Glass woven fabric 2 1st smoothing layer 3 Printing layer 4 2nd smoothing layer 5 Auxiliary layer 6 Matting layer 7 Resin film layer 8 Protective layer 9 After embossing recessed part 10 Topcoat layer (gloss difference printing layer)
11 decorative layer 12 sheet-like substrate

Claims (11)

On the surface of the substrate having a layer made of glass woven fabric as a surface layer, the surface of the glass woven fabric side has a printed layer formed by gravure printing via a first smoothing layer, and the first smoothing layer is A decorative sheet, which is a colored vinyl chloride resin film, and has an auxiliary layer made of a vinyl chloride resin film on a surface opposite to the first smoothing layer across the glass woven fabric .   The decorative sheet according to claim 1, further comprising a second smoothing layer between the first smoothing layer and the printing layer.   The decorative sheet according to claim 2, wherein the second smoothing layer is a resin layer formed through a coating process and a curing process. The decorative sheet according to any one of claims 1 to 3 , wherein the base body and the first smoothing layer are laminated on a base body having glass fibers by a laminating step. The decorative layer has a matte layer and a topcoat layer in this order on the printed layer formed on the smoothing layer, and the topcoat layer is formed in synchronization with the pattern of the printed layer, The decorative sheet according to any one of claims 1 to 4 , wherein the decorative sheet has higher gloss than the matte layer. The decorative sheet according to any one of claims 1 to 5, which is used for an interior of a building. A building interior material using the decorative sheet according to any one of claims 1 to 7. Opposite to the printed layer of a decorative layer having a printed layer formed by gravure printing on the first smoothed layer on the surface of the substrate having a layer of glass woven fabric as a surface layer on the glass woven fabric side The first smoothing layer is a resin film, and the matte layer and the top coat layer are formed on the printed layer formed on the first smoothing layer. In this order, the top coat layer is formed in synchronism with the pattern of the print layer, and has a gloss higher than that of the matte layer . When the decorative layer is thermocompression bonded to a substrate having a layer made of the glass woven fabric as a surface layer, an auxiliary layer made of a vinyl chloride resin film is thermocompression bonded to the surface opposite to the surface to which the decorative layer is thermocompression bonded. The manufacturing method of the decorative sheet of Claim 8. A first smoothing layer made of a resin film is thermocompression-bonded to the surface of the substrate having a layer made of glass woven fabric on the surface side of the glass woven fabric, and formed by gravure printing on the first smoothing layer. A mat layer and a top coat layer are formed in this order on the print layer formed on the first smoothing layer, and the top coat layer has a pattern of the print layer. A method for producing a decorative sheet, wherein the decorative sheet is formed synchronously and has a higher gloss than the matte layer. The substrate having a layer made of the glass woven fabric as a surface layer is a substrate having an auxiliary layer made of a vinyl chloride resin film on the other side of the surface to which the first smoothing layer made of the resin film is thermocompression bonded. The method for producing a decorative sheet according to claim 10.

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