JP5205707B2 - Resin decorative board - Google Patents

Description

  The present invention relates to a resin decorative board.

With the recent trend toward consumer luxury goods, high-quality feeling has been demanded for furniture, desks, housing equipment such as various counters and doors, and interior materials. What has the appearance which gives a feeling is desired. As a decorative board, generally, a resin decorative board obtained by shaping a synthetic resin material, such as a polyester decorative board, is widely used.
Such a resin decorative board has the uneven pattern by applying a resin composition such as an unsaturated polyester resin on a substrate and then overlaying a forming sheet having an uneven pattern to cure the resin composition. There is known a method for producing a decorative board having an uneven surface by peeling a shaping sheet. And, as a shaping sheet used for producing a resin decorative board having an uneven surface by such a method, the surface has a grainy uneven pattern on the surface, and is obtained by curing the entire surface with a silicone resin. Have been proposed (for example, Patent Document 1). However, there is a problem that the uneven shape sufficiently imparted to the decorative board is not sufficiently delicate, and the strength of the surface is not sufficient, so that repeated use is difficult.

Further, a polyester decorative board having a high design has been proposed in which the color pattern of the grain pattern and the uneven pattern are well matched (for example, Patent Document 2). However, since the room temperature curing agent resin is used, the pattern size changes due to the shrinkage of the sheet, so that there is a problem that correction work for the printing original plate is necessary.
JP-A-7-144398 JP-A-8-267687

  An object of this invention is to provide the resin decorative board which has a delicate uneven | corrugated shape and has a high-class feeling in such a condition.

  As a result of intensive studies to achieve the above object, the present inventors have found that the above problem can be solved by using a specific shaping sheet in the production of a resin decorative board. The present invention has been completed based on such findings.

That is, the present invention
(1) An adhesive layer and a decorative sheet layer are sequentially laminated on the upper surface of the substrate, a resin composition is applied on the decorative sheet layer, and then the shaping sheet is brought into contact with and integrally cured, A resin decorative board having a resin layer formed by peeling a molding sheet, wherein the molding sheet is present on an ink layer at least partially or entirely on a substrate, and on the ink layer. A decorative sheet having a surface-forming layer that is in contact with the surface and covering the entire surface, wherein the surface-forming layer is obtained by crosslinking and curing an ionizing radiation-curable resin composition,
(2) An adhesive layer and a decorative sheet layer are sequentially laminated on the upper surface of the substrate, a resin composition is applied on the decorative sheet layer, and then the shaping sheet is brought into contact with and integrally cured, A resin decorative board having a resin layer formed by peeling a molding sheet, wherein the molding sheet has a transparent or translucent matte containing a release agent provided at least on the entire surface of the substrate. Crosslinking of an ionizing radiation curable resin composition comprising a coating layer and a surface shaping layer partially provided on the undercoat layer, wherein the surface shaping layer contains a release agent Resin decorative board that is cured,
(3) The resin decorative board according to (2) above, wherein the surface shaping layer is obtained by crosslinking and curing a curable resin composition further containing a matting agent,
(4) An adhesive layer and a decorative sheet layer are sequentially laminated on the upper surface of the substrate, a resin composition is applied on the decorative sheet layer, and then the shaping sheet is brought into contact with and integrally cured, A resin decorative board having a resin layer formed by peeling a shaping sheet, wherein the shaping sheet comprises (i) a liquid repellent ink containing a binder having liquid repellency per se, ( B) A liquid repellent ink in which a liquid repellent substance is added to a binder that does not itself have liquid repellent properties, and (c) a liquid repellent additive is further added to the binder that has liquid repellent properties per se. A pattern layer is formed with an ink selected from the group consisting of a liquid repellent ink, and a coating layer is formed on the pattern layer by applying an ionizing radiation curable resin composition containing a release agent, The pattern layer by a liquid repellent action between the liquid repellent pattern layer and the coating layer A concave portion is formed in the coating layer formed on the upper portion, and further, the coating layer on which the unevenness synchronized with the pattern layer is formed by irradiating the coating layer with ionizing radiation is cured. Resin decorative board,
(5) An adhesive layer and a decorative sheet layer are sequentially laminated on the upper surface of the substrate, a resin composition is applied on the decorative sheet layer, and then the shaping sheet is brought into contact with and integrally cured, A resin decorative board having a resin layer formed by peeling a shaping sheet, wherein the shaping sheet contains (b) a binder having liquid repellency on the entire surface of the substrate. (B) a liquid-repellent ink in which a liquid-repellent substance is added to a binder that is not liquid-repellent per se; and (c) a liquid-repellent additive that is added to the liquid-repellent binder itself. An ink layer is formed with an ink selected from the group consisting of added liquid repellent ink, and a coating layer is formed on the ink layer by applying a curable resin composition containing a release agent, The coating is performed by a liquid repellent action between the ink layer and the coating layer. Layer forms a convex portion at the top of the ink layer, further resin decorative plate is obtained by curing the coating layer to form a convex portion formed in this manner,
(6) An adhesive layer and a decorative sheet layer are sequentially laminated on the upper surface of the substrate, a resin composition is applied onto the decorative sheet layer, and then the shaping sheet is brought into contact with and integrally cured, A resin decorative board having a resin layer formed by peeling a molding sheet, wherein the molding sheet has a substrate and a surface molding layer obtained by crosslinking and curing an ionizing radiation curable resin composition, A decorative material in which at least an ink layer and an interaction preventing layer are laminated in this order from the base material side between the material and the surface shaping layer, wherein the ink layer is a portion that develops an interaction region or A resin decorative board formed over the entire surface of the base material and having the shape in which the interaction preventing layer is cut out from the portion that expresses the interaction region,
(7) In the above-mentioned shaping sheet, the base material comprises a polyester film, and the base material has a weight loss of 1.0% by mass or less after being immersed in xylene at 140 ° C. for 24 hours. ), And (8) the resin decorative board according to any one of (1) to (7), wherein the resin in the resin composition is an unsaturated polyester resin or a silicone resin,
Is to provide.

  ADVANTAGE OF THE INVENTION According to this invention, it can have a delicate uneven | corrugated shape and can obtain the high-quality resin decorative board.

The resin decorative board of the present invention is obtained by laminating an adhesive layer and a decorative sheet layer in this order on the upper surface of a substrate, applying a resin composition on the decorative sheet layer, and then contacting the shaping sheet to cure integrally. Then, the shaping sheet is peeled to form a resin layer.
The resin decorative board of the present invention will be described with reference to FIG.

The substrate 2 of the resin decorative board of the present invention is not particularly limited, and a plastic sheet, a metal plate, a wooden board such as wood, a ceramic material, or the like can be appropriately selected depending on the application. When these substrates, particularly plastic sheets, are used as substrates, physical or chemical surface treatment such as oxidation or unevenness is applied to one or both sides as desired in order to improve adhesion to the decorative material. Can be applied.
Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment method, and examples of the unevenness method include a sand blast method and a solvent treatment method. These surface treatments are appropriately selected according to the type of the substrate, but in general, the corona discharge treatment method is preferably used from the viewpoints of effects and operability.

  As a plastic sheet, what consists of various synthetic resins is mentioned. Synthetic resins include polyethylene resin, polypropylene resin, polymethylpentene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, vinyl chloride-vinyl acetate copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl. Representative examples include alcohol copolymer resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate-isophthalate copolymer resin, polymethyl methacrylate resin, polyethyl methacrylate resin, polybutyl acrylate resin, nylon 6 or nylon 66 And polyamide resin, cellulose triacetate resin, cellophane, polystyrene resin, polycarbonate resin, polyarylate resin, polyimide resin, and the like.

As a metal plate, what consists of aluminum, iron, stainless steel, or copper can be used, for example, and what gave these metals by plating etc. can also be used.
Examples of wood-based boards include veneer of various materials such as cedar, firewood, firewood, pine, lawan, teak and melapie, and wood materials such as wood veneer, wood plywood, particle board, and medium density fiber board (MDF). . These can be used alone or in a laminated manner. The wooden board includes not only a wooden board but also a plastic board containing paper powder and reinforced paper having strength.
Examples of the ceramic material include ceramic building materials such as a gypsum plate, a calcium silicate plate, and a wood piece cement plate, ceramics, glass, firewood, fired tiles, plates made mainly of volcanic ash, and the like.
In addition to these, composites of various materials such as a fiber reinforced plastic (FRP) plate, a paper honeycomb on which both sides of an iron plate are attached, and a polyethylene resin sandwiched between two aluminum plates can be used as the substrate.

The adhesive layer 3 is a layer provided to adhere the substrate 2 and the decorative sheet layer 4.
The adhesive used for the adhesive layer 3 is applied using a coating device such as a spray, a spreader, or a bar coater. As this adhesive, urea-based, vinyl acetate resin-based, urea resin-based, melamine resin-based, phenolic resin-based, isocyanate-based adhesives, etc. can be used, either alone or as a mixed adhesive that is arbitrarily mixed. . As needed, talc, calcium carbonate, clay, titanium white and other inorganic powders, wheat flour, wood flour, plastic powder, coloring agents, insect repellents, fungicides and the like can be added and mixed in the adhesive. . In general, the adhesive is applied to the substrate surface with a solid content of 35 to 80% by mass and an application amount of 50 to 300 g / m ² .

  Adhesion of the decorative sheet layer 4 on the substrate 2 is usually performed by forming the adhesive layer 3 on the back surface of the decorative sheet layer 4 of the present invention and attaching the substrate 2 or applying an adhesive on the substrate 2. And by a method such as attaching the decorative sheet layer 4. For the sticking, a sticking apparatus such as a cold press, hot press, roll press, laminator, wrapping, edge sticking machine, vacuum press or the like can be used.

The decorative sheet layer 4 gives decorativeness to the resin decorative board of the present invention, and a solid print layer 42 and a pattern layer 43 provided in order on the sheet layer 41 are provided in this order.
The sheet layer 41 is not particularly limited as long as it is normally used as a base material for a decorative sheet, and various papers, plastic films, plastic sheets, and the like can be appropriately selected depending on the application. Each of these materials may be used alone, but may be a laminate of any combination such as a composite of paper or a composite of paper and a plastic film.
When using these substrates, particularly plastic films or plastic sheets, as a substrate, an oxidation method or a concavo-convex method may be applied to one or both sides as desired in order to improve the adhesion to the layer provided thereon. Physical or chemical surface treatment can be applied.
Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment method, and examples of the unevenness method include a sand blast method and a solvent treatment method. These surface treatments are appropriately selected depending on the type of substrate, but generally, a corona discharge treatment method is preferably used from the viewpoints of effects and operability.
Further, the substrate may be subjected to a treatment such as forming a primer layer, or a coating for adjusting the color or a pattern from a design viewpoint may be formed in advance.

As various papers used as the sheet layer 41, thin paper, kraft paper, titanium paper and the like can be used. These paper base materials are used to reinforce the interlaminar strength between the fibers of the paper base material or between the other layers and the paper base material, and to prevent the occurrence of scuffing, in addition to these paper base materials, acrylic resin, styrene butadiene rubber, A resin such as a melamine resin or a urethane resin may be added (resin impregnation after paper making or embedded during paper making). For example, inter-paper reinforced paper, resin-impregnated paper, and the like.
In addition to these, various papers often used in the field of building materials such as linter paper, paperboard, base paper for gypsum board, or a vinyl wallpaper raw material in which a vinyl chloride resin layer is provided on the surface of the paper can be mentioned. Furthermore, coated paper, art paper, sulfate paper, glassine paper, parchment paper, paraffin paper, Japanese paper, or the like used in the office field or normal printing and packaging can also be used. Moreover, although distinguished from these papers, woven fabrics and non-woven fabrics of various fibers having an appearance and properties similar to paper can be used as the base material. Examples of various fibers include inorganic fibers such as glass fibers, asbestos fibers, potassium titanate fibers, alumina fibers, silica fibers, and carbon fibers, or synthetic resin fibers such as polyester fibers, acrylic fibers, and vinylon fibers.

  As a plastic film or a plastic sheet, what consists of various synthetic resins is mentioned. Synthetic resins include polyethylene resin, polypropylene resin, polymethylpentene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, vinyl chloride-vinyl acetate copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl. Representative examples include alcohol copolymer resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate-isophthalate copolymer resin, polymethyl methacrylate resin, polyethyl methacrylate resin, polybutyl acrylate resin, nylon 6 or nylon 66 And polyamide resin, cellulose triacetate resin, cellophane, polystyrene resin, polycarbonate resin, polyarylate resin, polyimide resin, and the like.

Although there is no restriction | limiting in particular about the thickness of the sheet layer 41, When using the sheet | seat which uses a plastic as a raw material, thickness is about 20-150 micrometers normally, Preferably it is the range of 30-100 micrometers, and a paper base material is used. When used, the basis weight is usually about ²⁰ to 150 g / m ² , preferably 30 to 100 g / m ² .

The solid printing layer 42 provided on the sheet layer 41 is also referred to as a concealing layer provided as desired in order to enhance the design of the resin decorative plate of the present invention. The solid printing layer 42 is formed when the surface of the sheet layer 41 is adjusted so that the sheet layer 41 itself is colored or uneven in color, and gives the intended color to the surface of the sheet layer 41. Is. Usually, it is formed with an opaque color, but it may be formed with a colored transparent color to make use of the pattern of the base. When taking advantage of the fact that the sheet layer 41 is white, or when the sheet layer 41 itself is appropriately colored, it is not necessary to form the solid print layer 42.
As the ink used for forming the solid print layer 42, an ink in which a binder, a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, or a curing agent is appropriately mixed is used. The binder is not particularly limited, and examples thereof include polyurethane resins, vinyl chloride / vinyl acetate copolymer resins, vinyl chloride / vinyl acetate / acrylic copolymer resins, chlorinated polypropylene resins, acrylic resins, and polyesters. Arbitrary resins, polyamide resins, butyral resins, polystyrene resins, nitrocellulose resins, cellulose acetate resins and the like may be used alone or in combination of two or more.
Colorants include carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine, cobalt blue and other inorganic pigments, quinacridone red, isoindolinone yellow, phthalocyanine Organic pigments or dyes such as blue, metallic pigments composed of scaly foil pieces such as aluminum and brass, pearlescent pigments composed of scaly foil pieces such as titanium dioxide-coated mica and basic lead carbonate, and the like are used.
The colored layer 6 is preferably a so-called solid print layer having a thickness of about 1 to 20 μm.

The pattern layer 43 gives decorativeness to the sheet layer 41 and is formed by printing various patterns on the sheet layer 41 or the solid print layer 42 using ink and a printing machine. . As patterns, there are stone patterns imitating the surface of rocks such as wood grain patterns, marble patterns (for example, travertine marble patterns), fabric patterns imitating cloth and cloth patterns, tiled patterns, brickwork patterns, etc. There are also patterns such as marquetry and patchwork that combine these. These patterns are formed by multicolor printing with the usual yellow, red, blue and black process colors, as well as by multicolor printing with special colors prepared by preparing the individual color plates that make up the pattern. Is done.
As the pattern ink used for the pattern layer 43, the same ink as that used for the solid print layer 42 can be used.

The resin layer 5 is a layer formed by applying the resin composition on the decorative sheet layer 4 and then bringing the shaping sheet into contact therewith and curing it, and then peeling the shaping sheet. the thickness of the resin layer 5 is preferably from 100 to 500 g / m ^2, more preferably 100~350g / m ^2, more preferably 150 to 250 g / m ^2.
The resin composition is a composition comprising a resin and a polymerization initiator, a polymerization accelerator, a polymerization inhibitor, and other additives that are added as necessary.
The resin in the resin composition used in the present invention is not particularly limited as long as it is cured at room temperature or by heating, for example, silicone resin, unsaturated polyester resin, saturated polyester resin, melamine resin, phenol Resin, polyamide, ketone resin, epoxy resin, urethane resin, urea resin, acrylic resin, vinyl resin, alkyd resin, amino alkyd resin, hydrocarbon resin (aromatic and aliphatic), rubber resin, fluorine resin, etc. Can be mentioned. Of these, silicone resins and unsaturated polyester resins are preferred.

A polymerization initiator, a polymerization accelerator, and a polymerization inhibitor are added to adjust the curing rate of the resin composition.
As the polymerization initiator, for example, a peroxide such as methyl ethyl ketone peroxide, benzoyl peroxide, and hydroperoxide, and a radical initiator such as azobisisobutyronitrile are appropriately selected and used. 0.5-3 mass% is preferable and, as for the addition amount in the resin composition of a polymerization initiator, 0.5-2.0 mass% is more preferable. As the polymerization accelerator, for example, a cobalt compound such as cobalt naphthenate, a metal compound such as a vanadium compound or a manganese compound, an amine compound such as dimethylnitrile, or the like is preferably 0.1 to 2.0 mass with respect to the resin composition. %, More preferably 0.3 to 1.0% by mass. As the polymerization inhibitor, for example, hydroquinone, trihydroquinone, benzoquinone, trihydrobenzene and the like can be used. As other additives, for example, in order to adjust the coating viscosity and to crosslink the resin, a compound having a vinyl group such as a styrene monomer can be preferably mentioned, and the addition amount in the resin composition is 10 to 40 mass. % Is preferable, and 15 to 30% by mass is more preferable.
These curing rate modifiers and other additives can be used alone or in combination.

  The shaping sheet 71 used in the present invention is an ink layer in which the shaping sheet is provided at least over the entire surface or partially on the substrate, and is present on and in contact with the ink layer. A surface-forming layer covering the surface-forming layer, the surface-forming layer is obtained by crosslinking and curing the ionizing radiation curable resin composition, and the surface of the surface-forming layer has an uneven shape. is there.

The structure of the shaping sheet 71 used by this invention is demonstrated using FIG. 3, FIG. 3 and 4 are schematic views showing a cross section of the shaped sheet 71 of the present invention. In the example shown in FIG. 3, a uniform and uniform penetration preventing layer 76 covering the entire surface of the substrate 72, an ink layer 73, and a surface shaping layer 75 obtained by crosslinking and curing an ionizing radiation curable resin composition are laminated in this order. It is a thing. The ink layer 73 exists partially, and an interaction region 74 is formed in the surface shaping layer immediately above and in the vicinity thereof. The interaction area 74 is represented by a set of points in the figure.
The upper part of the interaction region 74 on the outermost surface of the surface shaping layer 75 is raised with the formation of the ink layer 73 and has a convex shape 77. When the surface of the surface shaping layer 75 has such a convex shape, a shaping sheet having a concavo-convex shape as a whole is formed. In addition, about the height of this convex shape, although it does not specifically limit in the range with the effect of this invention, Usually, it is the range of 1-3 micrometers.

  The extent of the expansion of the interaction region 74 formed in the surface shaping layer 75 is not particularly limited as long as it is within the range where the effects of the present invention can be achieved. As shown in FIG. It may stay in the middle of the shaping layer 75 in the thickness direction, or may reach the outermost surface of the surface shaping layer 75 as shown in FIG.

Moreover, the ink layer may exist over the entire surface. The shaping sheet when the ink layer is present over the entire surface will be described with reference to FIGS.
In the example shown in FIG. 9, a uniform and uniform penetration preventing layer 86 covering the entire surface of the substrate 82, an ink layer 83, and a surface shaping layer 85 in which a curable resin composition is crosslinked and cured are laminated in this order. The surface shaping layer 85 has a fine irregular surface 813 on the surface. The ink layer 83 exists over the entire surface, and an interaction region 84 is formed in the surface shaping layer immediately above the ink layer 83. The interaction area 84 is represented by a set of points in the figure.
The upper part of the interaction region 84 on the outermost surface of the surface shaping layer 85 has a fine uneven surface 813 as the ink layer 83 is formed. Since the surface of the surface shaping layer 85 has such a fine uneven surface, a shaped sheet having a delicate uneven shape can be obtained.
Further, in the example of FIG. 11, by changing the thickness of the ink layer 83, the raised shape 87 is expressed on the surface of the surface shaping layer 85 according to the thickness of the ink layer 83, thereby indicating that the ink layer 83 has an uneven shape. Is.

The extent of the expansion of the interaction region 84 formed in the surface shaping layer 85 is not particularly limited as long as it is within the range where the effects of the present invention are achieved, and the surface of the ink layer 83 as shown in FIGS. May remain in the middle of the thickness direction of the surface shaping layer 85, or may reach the outermost surface of the surface shaping layer 85.
Further, the fine ridge shape 812 caused by the fine particles and the calcined kaolin particles gives the ridge shape 87 and the fine concavo-convex surface 813 which are expressed over the entire surface of the surface shaping layer 85 to a partially fine ridge shape. .
The effect of the fine uneven surface due to the interaction region 84 in the surface shaping layer 85, the effect of cueing of fine particles on the surface with the surface shaping layer 85, and the raised shape formed according to the thickness of the ink layer 83 Due to the effect, it is possible to obtain a shaped sheet that has a delicate uneven shape and enables high-quality and precise shaping.

  The base materials 72 and 82 of the shaping sheets 71 and 81 used in the present invention are not particularly limited as long as they are normally used as the base material of the shaping sheet. Specifically, in addition to the various papers, plastic films, and plastic sheets used in the sheet layer 41, a metal foil, a metal sheet, a metal plate, a ceramic material, and the like can be appropriately selected depending on the application. . Each of these materials may be used alone, but may be a laminate of any combination such as a composite of paper or a composite of paper and a plastic film.

As metal foil, a metal sheet, or a metal plate, what consists of aluminum, iron, stainless steel, or copper, for example can be used, and what gave these metals by plating etc. can also be used. Examples of the ceramic material include ceramic building materials such as gypsum board, calcium silicate board, and wood cement board, ceramics, glass, firewood, and fired tile. In addition to these, composites of various materials, such as fiber reinforced plastic (FRP) plates, paper honeycombs with iron plates pasted on both sides, and two aluminum plates sandwiched with polyethylene resin can also be used as the base material. .
Among these, as the base material, a material excellent in heat resistance and dimensional stability is preferable, and among them, a polyester film such as a polyethylene terephthalate film is particularly preferable.

Although there is no restriction | limiting in particular about the thickness of a base material, When using the sheet | seat which uses a plastic as a raw material, thickness is about 20-150 micrometers normally, Preferably it is the range of 30-100 micrometers, and uses a paper base material. In some cases, the basis weight is usually in the range of about ²⁰ to 150 g / m ² , preferably 30 to 100 g / m ² .

  The permeation preventive layers 76 and 86 of the shaping sheets 71 and 81 are layers provided as desired, and the ink composition constituting the ink layer described later and the ionizing radiation curable resin constituting the surface shaping layer are based on It has a function of suppressing penetration into the material, and is particularly effective when the substrate is a permeable substrate such as paper or nonwoven fabric. Therefore, the penetration preventing layer may be positioned between the base material and the ink layer. Usually, a uniform and uniform layer obtained by crosslinking and curing an ionizing radiation curable resin constituting the surface shaping layer and an adhesive curable resin is formed between the substrate and the ink layer as shown in FIGS. Provide. This also serves to enhance the adhesion between the substrate, the ink layer, and the surface shaping layer.

The ink layers 73 and 83 of the shaping sheets 71 and 81 are provided partially or entirely on the permeation prevention layer or the like provided as necessary as shown in FIGS. It is a layer which produces the uneven | corrugated shape of the surface of a layer.
Although the mechanism of the uneven shape generation in the shaping sheets 71 and 81 has not been fully elucidated, the ionization for forming the surface shaping layer on the surface of the ink layer is based on the results of various experiments, observations and measurements. When an uncured product of radiation curable resin is applied, the resin component of the ink layer and the surface shaping layer may be partially eluted, dispersed, mixed, etc. This is presumably due to the interaction. At this time, each resin component in the ink composition of the ink layer and the uncured product of the ionizing radiation curable resin becomes a suspended state without being completely compatible in a short time, and immediately above the ink layer. And the part which exists in the vicinity and became this suspension state makes an interaction area | region, and it is thought that a convex shape is expressed. When this state is fixed by crosslinking and curing the surface shaping layer while maintaining this suspended state, as shown in FIGS. 3 and 4, the interaction region is partially formed in the surface shaping layer. It is estimated that the convex shape 7 is formed. Moreover, when an ink layer is provided over the whole surface, as shown in FIGS. 9-11, the interaction area | region 84 is formed over the whole surface in a surface shaping layer, and it is estimated that the fine uneven surface 813 is made.

The ink composition forming the ink layer of the shaping sheets 71 and 81 has a property capable of expressing an interaction such as elution, dispersion, and mixing with the ionizing radiation curable resin composition forming the surface shaping layer. And is appropriately selected in relation to the ionizing radiation curable resin composition (uncured product). Specifically, an ink composition having a non-crosslinkable resin as a binder resin is preferable. For example, a thermoplastic (non-crosslinked) urethane resin is preferable. Here, the content of the urethane resin is 50% by mass or more from the viewpoint of further strengthening the interaction with the ionizing radiation curable resin composition forming the surface shaping layer and obtaining a feeling of unevenness of the further pattern. More preferably it is.
As the urethane resin, a non-cross-linked type, that is, a three-dimensionally crosslinked thermoplastic resin having a linear molecular structure is selected instead of a network-like three-dimensional molecular structure. It is preferable to do. Examples of such non-crosslinked urethane resins include polyol components such as acrylic polyols, polyester polyols and polyether polyols, and isocyanate components such as tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate and other aromatic isocyanates, and isophorone diisocyanate. And a urethane resin obtained by reacting an isocyanate such as an aliphatic or alicyclic isocyanate such as hexamethylene diisocyanate and hydrogenated tolylene diisocyanate. Usually, the number of hydroxyl groups in one molecule of polyol and the number of isocyanate groups in one molecule of isocyanate are two on average. The average molecular weight of the urethane resin is about 10,000 to 50,000, and the glass transition temperature (Tg) is preferably about −70 to −40 ° C. for the expression of the interaction region.

  The ink composition may contain a saturated or unsaturated polyester resin, an acrylic resin, or a vinyl chloride-vinyl acetate copolymer, etc., as necessary, in order to adjust the degree of expression of the interaction region. it can. Of these, polyester resins are preferable, and unsaturated polyester resins are particularly preferable. The addition amount of the unsaturated polyester resin is preferably in the range of 10 to 50% by mass with respect to the total amount of the binder resin in the ink composition. Within this range, a sufficient enhancement effect of expression of the interaction region can be obtained. The unsaturated polyester resin is not particularly limited as long as it is a reaction product of an unsaturated dicarboxylic acid and a glycol. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, and the like. Examples include ethylene glycol, diethylene glycol, propylene glycol, and butylene glycol.

An extender is preferably contained in the ink composition forming the ink layer. By containing the extender, thixotropy can be imparted to the ink composition, and the shape of the ink composition is maintained when the ink layer is printed using a plate. As a result, the sharpness of the concavo-convex shape at the end portion that transitions from the convex portion to the concave portion can be emphasized, and a sharp design expression is possible.
The extender is not particularly limited, and is suitably selected from, for example, silica, talc, clay, barium sulfate, barium carbonate, calcium sulfate, calcium carbonate, magnesium carbonate and the like. Of these, silica, which is a material having a high degree of freedom in material design such as oil absorption, particle size, pore volume, etc., and excellent in designability, whiteness, and coating stability as an ink composition, is preferred. Of these, silica is preferred. As a particle size of a silica, the range of 0.1-5 micrometers is preferable. When the thickness is 0.1 μm or more, the thixotropy of the ink does not become extremely high when added to the ink composition, and the viscosity of the ink does not increase so much that the printing can be easily controlled. In other words, it becomes easier to control the uneven shape. In addition, when trying to express a conduit pattern part in the production of a wood grain pattern, the ink head thickness of the conduit pattern part is usually 5 μm or less, and if the silica particle size is smaller than the application thickness, the particle heads are compared. Since the state of the interaction region becomes natural because the target is not conspicuously pressed, the uneven shape is unlikely to occur, and the natural finish is obtained.
The content of these extender pigments in the ink composition is preferably in the range of 5 to 15% by mass. When the content is 5% by mass or more, sufficient thixotropy can be imparted to the ink composition, and when it is 15% by mass or less, the effect of imparting the convex shape is not deteriorated at all.

About the application quantity of the ink composition which forms an ink layer, it is preferable that it is the range of 1-50 g / m < ² >. When the amount is 1 g / m ² or more, the above-described ink composition and ionizing radiation curable resin composition interact with each other, and a sufficient interaction area is obtained, so that a sufficient uneven shape is obtained on the surface of the shaping sheet. . On the other hand, when it is 50 g / m ² or less, there is no mechanical restriction when printing the ink composition, and it is economically advantageous. From the above viewpoint, the coating amount of the ink composition is preferably further range of 1 to 10 g / m ^2, is preferably in the range especially of 1 to 7 g / m ^2.

Further, by changing the coating amount of the ink composition, the thickness of the ink composition constituting the ink layer can be made non-uniform, and the degree of the height difference of the convex portion expressed thereby is stepwise or As a result, the pattern of the shaping sheet can be a gradation pattern in which the uneven shape changes stepwise or a continuous pattern in which the unevenness changes continuously.
This is because the interaction between the ink layer and the surface shaping layer is relatively increased as the coating amount of the ink layer is relatively increased, and the degree of suspension is higher. This is thought to be because the undulation of the shape becomes larger.

The shaping sheet | seat 71 in which an ink layer is provided partially is demonstrated in detail below using FIGS. In FIG. 5, the ink compositions 73-a, 73-b and 73-c constituting the ink layer 73 have different thicknesses. That is, the film thickness is gradually reduced in the order of 73-a, 73-b, and 73-c. By doing so, the interaction regions 74-a, 74-b, and 74-c can be changed in stages, and the resulting concavo-convex raised shapes 77-c, 77-b, and 77-a are in this order. The bulging part rises more gradually. This is because the thickness of the ink composition constituting the ink layer 73 is not uniform, and is applied so that the thickness of the ink composition decreases in the order of 73-a, 73-b, 73-c. It is considered that the ridge-shaped undulation becomes more remarkable in the thick portion of the ink composition, and the ridge-shaped undulation changes in gradation in the order of 73-a, 73-b, and 73-c. By changing the thickness of the ink composition more finely, the uneven shape can be continuously changed.
With the shaped sheet having such a structure, it becomes possible to give a more diverse and delicate texture. The method of changing the thickness of the ink composition constituting the ink layer 73 can usually be easily performed by changing the coating amount of the ink composition, and the coating amount of the ink composition is continuously changed. By doing so, the stepwise change can be continuously changed steplessly.

Next, in the example shown in FIG. 6, the ink layer 73 on the base material 72 is continuously changed in thickness in a plane parallel to the base material surface (the central part is thicker and the side part is closer to the side part). A surface shaping layer 75 in which the ionizing radiation curable resin composition is cross-linked and cured is laminated thereon (to be thin). In the same manner as shown in FIG. 5, the surface shaping layer immediately above the ink layer and in the vicinity thereof forms an interaction region. In the example of FIG. 6, the interaction layers 74-c, 74-b, and 74-a correspond to the thickness of the ink layer increasing in the order of 73-c, 73-b, and 73-a. The undulations of the convex shape increase successively. As a result, in the surface shaping layer 75, convex-shaped undulations continuously increase in this order.
The extent of the expansion of the interaction region 74 formed in the surface shaping layer 75 is not particularly limited as long as it is within the range where the effects of the present invention can be achieved. As shown in FIG. The surface shaping layer 75 may remain in the middle of the thickness direction, or may reach the outermost surface of the surface shaping layer 75 as shown in FIGS. A convex shape may be formed on the outermost surface of the layer 75.

The shaping sheet 81 on which the ink layer is provided over the entire surface will be described in detail below with reference to FIG. In FIG. 11, the ink compositions 83-a, 83-b, and 83-c constituting the ink layer 83 have different thicknesses. That is, the film thickness is gradually reduced in the order of 83-a, 83-b, and 83-c. By doing so, the interaction regions 84-a, 84-b, and 84-c can be changed stepwise, and the resulting convex and concave shapes 87-c, 87-b, and 87-a are obtained in this order. The convex part rises more gradually. This is because the thickness of the ink composition constituting the ink layer 83 is not uniform, and is applied so that the thickness of the ink composition decreases in the order of 83-a, 83-b, 83-c. It is considered that the convex portion of the thick portion of the ink composition has a more pronounced undulation and changes so that the undulation of the convex shape becomes smaller in gradation in the order of 83-a, 83-b, and 83-c. By changing the thickness of the ink composition more finely, the uneven shape can be continuously changed.
With the shaped sheet having such a structure, it becomes possible to give a more diverse and delicate texture. The method of changing the thickness of the ink composition that constitutes the ink layer 83 can usually be easily performed by changing the coating amount of the ink composition, and the coating amount of the ink composition is continuously changed. By doing so, the stepwise change can be continuously changed steplessly.

  The extent of the expansion of the interaction region 84 formed in the surface shaping layer 85 is not particularly limited as long as it is within the range where the effects of the present invention can be achieved, and from the surface of the ink layer 83 as shown in FIG. The surface shaping layer 85 may remain in the middle of the thickness direction, or may reach the outermost surface of the surface shaping layer 85 as shown in FIG. A fine ridge shape may be formed on the outermost surface.

The surface shaping layers of the shaping sheets 71 and 81 are composed of a cross-linked and cured ionizing radiation curable resin composition as described above. Here, the ionizing radiation curable resin composition is one having an energy quantum capable of crosslinking and polymerizing molecules in an electromagnetic wave or a charged particle beam, that is, crosslinking or curing by irradiating ultraviolet rays or electron beams. Refers to a resin composition. Specifically, the ionizing radiation curable resin in the ionizing radiation curable resin composition is appropriately selected from polymerizable monomers and polymerizable oligomers or prepolymers conventionally used as ionizing radiation curable resin compositions. Can be used.
Typically, as the polymerizable monomer, a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is suitable, and by including the (meth) acrylate monomer, Interaction occurs, and the uneven shape difference is suitably formed. The content of the (meth) acrylate monomer is more preferably 50% by mass or more from the viewpoint of further strengthening the interaction with the ink and obtaining a further uneven shape.

  As the (meth) acrylate monomer, a polyfunctional (meth) acrylate is preferable. Here, “(meth) acrylate” means “acrylate or methacrylate”. The polyfunctional (meth) acrylate is not particularly limited as long as it is a (meth) acrylate having two or more ethylenically unsaturated bonds in the molecule. Specifically, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide-modified phosphate di ( (Meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylo Propane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris ( Acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. Is mentioned. These polyfunctional (meth) acrylates may be used singly or in combination of two or more.

  In the present invention, a monofunctional (meth) acrylate can be used in combination with the polyfunctional (meth) acrylate as long as the object of the present invention is not impaired, for the purpose of lowering the viscosity. Examples of monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl ( Examples include meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isobornyl (meth) acrylate. These monofunctional (meth) acrylates may be used alone or in combination of two or more.

  Next, as the polymerizable oligomer, an oligomer having a radical polymerizable unsaturated group in the molecule, for example, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate System oligomers and the like. Here, the epoxy (meth) acrylate oligomer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. . Further, a carboxyl-modified epoxy (meth) acrylate oligomer obtained by partially modifying this epoxy (meth) acrylate oligomer with a dibasic carboxylic acid anhydride can also be used. The urethane (meth) acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. Examples of polyester (meth) acrylate oligomers include esterification of hydroxyl groups of polyester oligomers having hydroxyl groups at both ends obtained by condensation of polycarboxylic acid and polyhydric alcohol with (meth) acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a carboxylic acid with (meth) acrylic acid. The polyether (meth) acrylate oligomer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.

Furthermore, other polymerizable oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity that have (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicone (meth) acrylate oligomers that have polysiloxane bonds in the main chain. In a molecule such as an aminoplast resin (meth) acrylate oligomer modified with an aminoplast resin having many reactive groups in a small molecule, or a novolak epoxy resin, bisphenol epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. There are oligomers having a cationic polymerizable functional group.
In the shaping sheets 71 and 81 used in the present invention, the interaction between the ink constituting the ink layer and the ionizing radiation curable resin composition constituting the surface shaping layer as described above is important, and from this viewpoint An appropriate ink and ionizing radiation curable resin composition are selected, but the ionizing radiation curable resin composition preferably contains a polyfunctional (meth) acrylate monomer.

When an ultraviolet curable resin composition is used as the ionizing radiation curable resin composition, it is desirable to add about 0.1 to 5 parts by mass of the photopolymerization initiator with respect to 100 parts by mass of the resin composition. The initiator for photopolymerization can be appropriately selected from those conventionally used and is not particularly limited. For example, for a polymerizable monomer or polymerizable oligomer having a radically polymerizable unsaturated group in the molecule. Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2 -Phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1 - 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4′-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2 -Tertiary butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal It is done.
Examples of the polymerizable oligomer having a cationic polymerizable functional group in the molecule include aromatic sulfonium salts, aromatic diazonium salts, aromatic iodonium salts, metallocene compounds, and benzoin sulfonic acid esters.
Moreover, as a photosensitizer, p-dimethylbenzoic acid ester, tertiary amines, a thiol type sensitizer, etc. can be used, for example.
In the shaping sheets 71 and 81 used in the present invention, it is preferable to use an electron beam curable resin as the ionizing radiation curable resin. This is because the electron beam curable resin can be made solvent-free, is more preferable from the viewpoint of environment and health, and does not require a photopolymerization initiator, and can provide stable curing characteristics.

  Moreover, it is preferable that the surface shaping | molding layer of the shaping sheets 71 and 81 contains a baked kaolin particle | grains as another component. By including calcined kaolin particles in the surface shaping layer, the uneven shape on the surface of the shaping sheet becomes more delicate, and marring resistance is improved. Here, the term “marling” means that small scratches are generated when the sheet surface is rubbed, and “excellent marring resistance” means that scratches are difficult to be made. By imparting such performance to the shaping sheet, it is possible to strengthen the surface shaping layer, obtain a shaping sheet that can withstand longer use, and reduce the manufacturing cost of the decorative board Become.

The calcined kaolin particles used for imparting a finer uneven shape and marling resistance to the surfaces of the shaping sheets 71 and 81 are kaolin particles obtained by calcining general (hydrous) kaolin particles. By adding calcined kaolin particles as a filler, improvement in marling resistance that cannot be achieved with silica particles or hydrous kaolin particles before firing is realized. The particle size of the calcined kaolin particles may be appropriately selected according to the application, required physical properties, etc. For example, those having an average particle size of about 0.5 to 2 μm are used. Further, the amount of calcined kaolin particles may be appropriately selected depending on the application, required physical properties, etc., for example, ionizing radiation curable resin (however, when the surface shaping layer contains other resin, The total of ionizing radiation curable resin and other resin) is about 5 to 50 parts by mass with respect to 100 parts by mass.
The calcined kaolin particles are superior in paint stability to the hydrous kaolin particles.

  As the calcined kaolin particles, those whose surfaces are further treated may be used. By using the surface-treated calcined kaolin particles, the effect of improving marring resistance can be further increased. As the surface treatment, there is a surface treatment with a silane coupling agent. Examples of the silane coupling agent include known silane coupling agents having an alkoxy group, amino group, vinyl group, epoxy group, mercapto group, chloro group and the like. For example, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyldimethylmethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxy Propyldimethylethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyldimethylmethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropylmethyldiethoxysilane , Γ-acryloxypropyldimethylethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysila Etc.

The ionizing radiation curable resin composition forming the surface shaping layer of the shaping sheets 71 and 81 preferably contains reactive silicone as the other component. This is because by including reactive silicone in the surface shaping layer, releasability is improved and resistance to repeated continuous use is improved.
Here, the reactive silicone means a modified silicone oil in which an organic group is introduced into the side chain or terminal and has reactivity depending on the nature of the introduced organic group. The reactive silicone is specifically modified silicone oil side chain type, modified silicone oil both end type, modified silicone oil one end type, modified silicone oil side chain both end type, etc. Examples thereof include epoxy modification, mercapto modification, carboxyl modification, carbinol modification, phenol modification, methacryl modification, and different functional group modification.
The reactive silicone reacts with and binds to the resin during curing with ionizing radiation. Therefore, when the decorative board of the present invention is molded by hot pressing, it does not bleed out (does not bleed out) on the surface of the decorative board, so that the adhesion between the shaped sheet of the present invention and the decorative board is significantly improved. Thus, it becomes possible to mold a delicate design having a fine uneven shape into a decorative material.
The amount of the reactive silicone used is in the range of about 0.1 to 50 parts by mass, preferably in the range of about 0.5 to 10 parts by mass, per 100 parts by mass of the ionizing radiation curable resin. When the amount of the reactive silicone used is 0.1 parts by mass or more, the decorative plate and the surface of the shaping sheet are sufficiently peeled off, the uneven shape of the surface of the shaping sheet is maintained, and it can withstand long-term use. sell. On the other hand, if the amount of the reactive silicone used is 50 parts by mass or less, no repelling occurs when the ionizing radiation curable resin composition is applied to the base material, so the surface of the coating film is not roughened and the paint stability is improved. Will improve.

Moreover, it is preferable that the ionizing radiation curable resin composition which forms the surface shaping layer of the shaping sheets 71 and 81 further contains fine particles as other components. As the fine particles, those having an average particle diameter that is a value close to the plus side of the maximum thickness of the surface shaping layer positioned immediately above the ink layer are used. The shaping sheets 71 and 81 used in the present invention in which fine particles are blended will be described in detail with reference to FIGS. 8 and 11, the ionizing radiation curable resin composition used for the surface shaping layer contains fine particles.
The fine particles 78 (78-a, 78-b) and 88 blended in the surface shaping layer have an average particle diameter d _A of the surface shaping layers 75 and 85 located immediately above the ink layers 73 and 83. From the surface of the surface shaping layers 75 and 85 located just above the ink layers 73 and 83, the value near the plus side of the maximum thickness t _M , that is, d _A is slightly larger than t _M , the fine particles 78-a, 88 cueing occurs. Since the portion where the cueing has occurred forms a convex shape, a fine unevenness can be formed. At the same time, in the surface shaping layer 75, the ink layers 73 and 83 are caused by the interaction between the ink in the ink layers 73 and 83 and the ionizing radiation curable resin composition constituting the surface shaping layers 75 and 85. Interaction regions 74 and 84 that express a convex shape are formed immediately above and in the vicinity thereof.
On the other hand, the fine particles 78-b located in a portion that is not directly above the ink layer 73 do not cue and contribute to the expression of the convex shape, but the position of the fine particles in the surface shaping layer in this way. There are various effects on the expression of the convex shape.
Therefore, the interaction regions 74 and 84 in the surface shaping layers 75 and 85, the effect of cueing the fine particles on the surface of the surface shaping layers 75 and 85, and the formation of the ink layers 73 and 83 described above. Due to the effect of the formed convex shape, the concave / convex shape is fine and further enhanced.
Note that the maximum thickness t _M of the surface shaping layers 75 and 85 positioned immediately above the ink layers 73 and 83 is the surface thickness when the convex shape associated with the formation of the ink layers 73 and 83 is not formed. It is the thickness of the mold layers 75 and 85, and when the convex shape is formed, the thickness includes that portion.

As the particle size distribution is closer to monodisperse, it is easier to set the amount of use, and the above effect is favorably exhibited with a small amount of use.
In the shaped sheets 71 and 81 used in the present invention, the coefficient of variation CV value [(standard deviation of particle size / average particle size) × 100] of the particle size distribution of the fine particles is preferably 30% or less. When the CV value is 30% or less, the fine particles have a practical particle size distribution and can sufficiently exhibit the above effects with an appropriate amount of use. This CV value is more preferably 20% or less, still more preferably 15% or less.

Further, the average particle diameter of the fine particles is d _A , the maximum thickness of the surface shaping layer located immediately above the ink layer is t _M , and the thickness of the surface shaping layer in the region where no ink layer is present is t _G. Formula (I)
1.05 × t _M ≦ d _A ≦ t _G (I)
It is preferable to satisfy the relationship. If the average particle diameter d _{A of the} fine particles is 1.05 × t _M or more, even if the fine particles sink into the ink layer, the surface of the surface shaping layer located immediately above the ink layer In this case, the fine particles are cueed, and the above effect is sufficiently exhibited. Further, when the d _A is equal to or less than t _G , cueing of the fine particles is suppressed in the surface shaping layer in the region where the ink layer does not exist.
The shape of the fine particles is not particularly limited, and fine particles such as spherical, ellipsoidal, and polyhedral shapes can be used, but spherical fine particles are preferable. In the present invention, the particle diameter of the fine particles having a shape other than the spherical shape is a value indicated by the diameter of the circumscribed sphere.

  The content of the fine particles in the surface shaping layer is usually selected in the range of 2 to 20% by mass, although it depends on the average particle size of the fine particles and the coefficient of variation CV of the particle size distribution. When the content is 2% by mass or more, the effect of containing the fine particles is exhibited, and when the content is 20% by mass or less, the unevenness of the uneven shape formed on the surface of the shaped sheet is good. The preferable content of the fine particles is 4 to 16% by mass, and more preferably 4 to 13% by mass.

The fine particles may be either inorganic fine particles or organic fine particles. Examples of the fine particles include inorganic particles such as silica, alumina, aluminosilicate, kaolinite, calcium carbonate, barium sulfate, and glass, and organic fine particles include acrylic resin, polycarbonate resin, and urethane type. Examples thereof include particles such as resin, urea resin, benzoguanamine resin, and benzoguanamine-melamine-formaldehyde condensate.
These fine particles may be used alone or in combination of two or more. From the viewpoint of the effect of the present invention, silica particles are preferred.
The fine particles may be used in combination with the calcined kaolin particles having the same effect.

Moreover, various additives can be mix | blended with an ionizing radiation curable resin composition according to the desired physical property of the cured resin layer obtained. Examples of the additive include a weather resistance improver, an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, an adhesion improver, an antioxidant, a leveling agent, a thixotropic agent, Examples include coupling agents, plasticizers, antifoaming agents, fillers, and solvents.
Here, as the weather resistance improving agent, an ultraviolet absorber or a light stabilizer can be used. It is added for long-term use of the shaped sheet. The ultraviolet absorber may be either inorganic or organic, and as the inorganic ultraviolet absorber, titanium dioxide, cerium oxide, zinc oxide or the like having an average particle diameter of about 5 to 120 nm can be preferably used. Examples of the organic ultraviolet absorber include benzotriazole-based compounds, specifically 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-). Amylphenyl) benzotriazole, 3- [3- (benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] propionic acid ester of polyethylene glycol, and the like. On the other hand, examples of the light stabilizer include hindered amines, specifically 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2′-n-butylmalonate bis (1,2,2). , 6,6-pentamethyl-4-piperidyl), bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl)- 1,2,3,4-butanetetracarboxylate and the like. Further, as the ultraviolet absorber or light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth) acryloyl group in the molecule can be used.

Examples of the wear resistance improver include, for inorganic substances, spherical particles such as α-alumina, silica, kaolinite, iron oxide, diamond, and silicon carbide. Examples of the particle shape include a sphere, an ellipsoid, a polyhedron, a scale shape, and the like. Although there is no particular limitation, a spherical shape is preferable. Organic materials include synthetic resin beads such as cross-linked acrylic resin and polycarbonate resin. The particle size is usually about 30 to 200% of the film thickness. Among these, spherical α-alumina is particularly preferable because it has high hardness and a large effect on improving wear resistance, and it is relatively easy to obtain spherical particles.
Examples of the polymerization inhibitor include hydroquinone, p-benzoquinone, hydroquinone monomethyl ether, pyrogallol, and t-butylcatechol. Examples of the crosslinking agent include a polyisocyanate compound, an epoxy compound, a metal chelate compound, an aziridine compound, and an oxazoline compound. Used.
As the filler, for example, barium sulfate, talc, clay, calcium carbonate, aluminum hydroxide and the like are used.
As the infrared absorber, for example, a dithiol metal complex, a phthalocyanine compound, a diimmonium compound, or the like is used.

The surface shaping layer of the shaping sheets 71 and 81 can be formed as follows, for example. First, the ionizing radiation curable resin, other components blended as necessary, and various additives are homogeneously mixed at predetermined ratios to prepare a coating liquid composed of an ionizing radiation curable resin composition. . The viscosity of the coating solution is not particularly limited as long as it is a viscosity capable of forming an uncured resin layer on the surface of the substrate by a coating method described later.
Gravure coating, bar coating, roll coating, reverse roll coating, comma coating, etc., so that the coating liquid prepared in this manner is applied to the surface of the substrate so that the thickness after curing is 1 to 20 μm. This method is preferably applied by gravure coating to form an uncured resin layer.

When the uncured resin layer thus formed is irradiated with ionizing radiation such as an electron beam and ultraviolet rays to cure the uncured resin layer, the desired function is obtained when the thickness after curing is 1 μm or more. A cured resin layer is obtained. The thickness of the surface shaping layer after curing is preferably about 2 to 20 μm.
Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the resin used and the thickness of the layer, but the uncured resin layer is usually cured at an acceleration voltage of about 70 to 300 kV. preferable.
In electron beam irradiation, the transmission capability increases as the acceleration voltage increases. Therefore, when using a base material that deteriorates due to the electron beam as the base material, the transmission depth of the electron beam and the thickness of the resin layer are substantially equal. By selecting the accelerating voltage so as to be equal to each other, it is possible to suppress the irradiation of the electron beam to the base material, and to minimize the deterioration of the base material due to the excessive electron beam.
The irradiation dose is preferably such that the crosslink density of the resin layer is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).
Further, the electron beam source is not particularly limited. For example, various electron beam accelerators such as a cockroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type. Can be used.
When ultraviolet rays are used as the ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted. There is no restriction | limiting in particular as an ultraviolet-ray source, For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, etc. are used.
The cured resin layer thus formed has various functions by adding various additives, for example, a so-called hard coat function, anti-fogging coat function, and anti-fouling coat having high hardness and scratch resistance. A function, an antiglare coating function, an antireflection coating function, an ultraviolet shielding coating function, an infrared shielding coating function, and the like can be provided.

The shaping sheet 91 used in the present invention is provided at least partially on a transparent or translucent matte undercoat layer containing a release agent provided on the entire surface of the base material, and on the undercoat layer. A shaped sheet having a surface-shaped layer, which is obtained by crosslinking and curing an ionizing radiation-curable resin composition containing a release agent.
The structure of the shaping sheet 91 will be described with reference to FIG. FIG. 12 is a schematic view showing a cross section of the shaping sheet 91 of the present invention. In the example shown in FIG. 12, a uniform and uniform penetration preventing layer 95 covering the entire surface of the base material 92, a matte undercoat layer 93, and a surface shaping layer 94 obtained by crosslinking and curing an ionizing radiation curable resin composition are provided. They are stacked in this order.
The surface shaping layer 94 is partially provided to form a shaping sheet having an uneven shape as a whole. In addition, although it does not specifically limit in the range with the effect of this invention about the height of this convex shape, Usually, it is the range of 1-5 micrometers.

The shaping sheet 91 is characterized by having a transparent or translucent matte undercoat layer 93 containing a release agent provided on the entire surface.
The matte undercoat layer 93 is made of a colorless or colored transparent ink containing a matting agent. Specifically, as a vehicle component, two liquids in which polyisocyanate is added as a curing agent to a resin having a functional group such as a hydroxyl group, a carboxyl group, or an amino group in an acrylic, polyester, acrylic urethane, or urethane resin. A curable resin is desirable.
Silica is preferable as the matting agent, and the particle size is preferably in the range of 1 to 10 μm, more preferably in the range of 2 to 5 μm. The gloss of the matte undercoat layer is set so that the grain size and amount of the matting agent are set so that the gloss is lower than the portion where the surface shaping layer is laminated, thereby improving the design.

The matte undercoat layer 93 preferably contains a release agent. The matte undercoat layer 93 is a direct molding portion and is in contact with the substrate at a portion where there is no surface molding layer immediately above, and therefore it is necessary to impart releasability. As the mold release agent contained in the matte undercoat layer 93, reactive silicone is preferable, and among these, silicone (meth) acrylate is preferably used. It is because a mold release property improves by making the coating layer 5 contain a mold release agent, and the tolerance with respect to repeated continuous use improves.
Here, the reactive silicone means a modified silicone oil in which an organic group is introduced into the side chain or terminal and has reactivity depending on the nature of the introduced organic group. The reactive silicone is specifically modified silicone oil side chain type, modified silicone oil both end type, modified silicone oil one end type, modified silicone oil side chain both end type, etc. Examples thereof include epoxy modification, mercapto modification, carboxyl modification, carbinol modification, phenol modification, methacryl modification, and different functional group modification.
The reactive silicone reacts with and binds to the resin during curing with ionizing radiation. Therefore, when the decorative board of the present invention is molded by hot pressing, it does not bleed out (does not bleed out) on the surface of the decorative board, so that the adhesion between the shaped sheet of the present invention and the decorative board is significantly improved. Thus, it becomes possible to mold a delicate design having a fine uneven shape into a decorative material.
The amount to be added is appropriately selected according to the type of silicone to be used and the like, but is usually preferably in the range of 0.1 to 10 parts by mass per 100 parts by mass of the ink solid content. Within this range, silicone is not transferred to the surface shaping layer 4 during gravure printing of the surface shaping layer 4, and adhesion after crosslinking is not hindered.
Further, among the reactive silicones as described above, silicone (meth) acrylate is preferably used. Silicone (meth) acrylate is obtained by introducing (meth) acrylate having an ethylenically unsaturated double bond at the side chain and terminal of silicone, reacting with resin at the time of curing with ionizing radiation, and combining and integrating. Is. In addition, the usage-amount of this silicone (meth) acrylate is the same as that of the said reactive silicone.

It is preferable to add a polymerization monomer or polymerizable oligomer which is an ionizing radiation curable resin to the matte undercoat layer 93. As the ionizing radiation curable resin, an ionizing radiation curable resin used in the surface shaping layer 74 of the shaping sheet 71 can be used. The heat resistance of the matte undercoat layer 3 can be improved, and the adhesion with the surface shaping layer 94 can be improved.
In addition, various additives such as extender pigments, leveling agents, and antifoaming agents can be appropriately used for the matte undercoat layer 93.

The ionizing radiation curable resin in the ionizing radiation curable resin composition used for the surface shaping layer 94 of the shaping sheet 91 is the same as that used for the shaping sheet 71 and further includes a release agent. It takes a thing. As the release agent, silicone (meth) acrylate which is preferably used also in the matte undercoat layer 93 is preferable. By including silicone (meth) acrylate in the surface shaping layer 94, the releasability is improved and the resistance to repeated continuous use is improved.
The amount of the silicone (meth) acrylate used is preferably in the range of 0.1 to 10 parts by mass, more preferably in the range of 0.5 to 5 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin. It is. When the amount of the silicone (meth) acrylate used is 0.1 parts by mass or more, peeling between the decorative plate and the surface of the shaping sheet is sufficient, the uneven shape on the surface of the shaping sheet is maintained, and a longer period of time is maintained. Can withstand use. On the other hand, when the amount of the silicone (meth) acrylate used is 10 parts by mass or less, no repelling occurs when the ionizing radiation curable resin composition is applied to the substrate, and the coating surface is not roughened. Stability is improved.

Further, it is preferable to further add a matting agent to the ionizing radiation curable resin composition used for the surface shaping layer 94. A matting agent adjusts a particle size and the addition amount suitably considering the designability when shape | molding.
The matting agent may be either inorganic fine particles or organic fine particles. Examples of the fine particles include inorganic particles such as silica, alumina, aluminosilicate, kaolinite, calcium carbonate, barium sulfate, and glass, and organic fine particles include acrylic resin, polycarbonate resin, and urethane type. Examples thereof include particles such as resin, urea resin, benzoguanamine resin, and benzoguanamine-melamine-formaldehyde condensate. Of these, silica particles are preferred from the viewpoint of the effects of the present invention.
Moreover, these fine particles may be used individually by 1 type, and may be used in combination of 2 or more type.

  The base material 92 used for the shaping sheet 91 is the same as that used for the shaping sheet 71 described above. The permeation preventive layer 95 is the same as the permeation preventive layer 76 of the shaping sheet 71 described above. In addition, the composition of the ionizing radiation curable resin composition used for the surface shaping layer 94 is a release agent as described above, if necessary, as compared with that used for the surface shaping layer 74 of the shaping sheet 71. Although different in that it contains a matting agent, other points such as ionizing radiation curable resin, various additives, formation of a surface shaping layer, and the like are the same as those of the shaping sheet 71.

The moldable sheet 101 used in the present invention comprises (i) a liquid repellent ink containing a binder having liquid repellency per se, and (b) a liquid repellency in a binder having no liquid repellency per se. A pattern made of an ink selected from the group consisting of a liquid-repellent ink to which a substance having a property is added, and (c) a liquid-repellent ink in which an additive having a liquid-repellent property is further added to the binder having the liquid-repellent property itself. Forming a coating layer on the pattern layer by coating an ionizing radiation curable resin composition containing a release agent, and the liquid repellent pattern layer thus formed; A concave portion is formed in the coating layer formed on the upper part of the pattern layer by a liquid repellent action between the coating layer, and ionizing radiation is irradiated to the coating layer thus formed. , Cure the coating layer with the irregularities in sync with the pattern layer It is intended.
The structure of the shaping sheet 101 used by this invention is demonstrated using FIG. FIG. 13 is a schematic diagram showing a cross section of the shaping sheet 101. In the example shown in FIG. 13, there is a permeation preventing layer 104 covering the entire surface of the base material 102, a pattern layer 103 having liquid repellency, and a coating layer 105 in which an ionizing radiation curable resin composition is crosslinked and cured. is there. The pattern layer 103 having liquid repellency is partially present, and the ionizing radiation curable resin composition is coated on the pattern layer 103, and the pattern layer 103 having liquid repellency thus formed and the ionizing radiation. A concave shape 106 was formed in the coating layer 105 formed on the top of the pattern layer 103 by a liquid repellent action with the coating layer 105 made of the curable resin composition, and thus formed in this manner. The shaping sheet 101 can be obtained by irradiating the coating layer with ionizing radiation to crosslink and cure the coating layer in which the uneven shape synchronized with the pattern layer 103 is formed.

The pattern layer 103 of the shaping sheet 101 used in the present invention is laminated on the penetration preventing layer 104 or the like provided as necessary as shown in FIG. It is a layer having liquid repellency that generates a shape, and is formed by creating gravure plates having various patterns and printing by gravure printing. In order to obtain good liquid repellency, the coating amount of the liquid repellent ink is preferably set to a plate depth (coating thickness) of 30 to 60 μm.
The uneven shape of the shaping sheet according to the present invention is such that the upper part of the pattern layer 103 is applied by a liquid repellent action between the pattern layer 103 having liquid repellency and the coating layer 105 made of an ionizing radiation curable resin composition. It is obtained by forming a concave shape 106 on the work layer 105.

  As described above, the ink having liquid repellency for forming the pattern layer 103 is a liquid repellent ink containing a binder having liquid repellency per se, and (b) liquid repellency in a binder having no liquid repellency per se. Ink selected from the group consisting of a liquid-repellent ink to which a substance having a property is added and (c) a liquid-repellent ink in which an additive having a liquid-repellent property is further added to a binder having a liquid-repellent property. .

[Liquid repellent ink b)]
The resin used for the binder of the liquid repellent ink in (a) is not particularly limited as long as it satisfies the [critical surface tension of the binder <surface tension of the ionizing radiation curable resin composition (liquid state)]. However, for example, fluorine resins such as polyvinylidene fluoride and polyvinyl fluoride, silicone resins such as polysiloxane and silicone (meth) acrylate, copolymer resins of fluorine and silicone resins and acrylic resins, and the like.

The liquid repellent ink (a) preferably contains an extender pigment in order to improve the transferability of the ink. By containing the extender, thixotropy can be imparted to the ink, and the shape of the pattern layer 103 is maintained when the pattern layer 103 is printed using a plate. As a result, the sharpness of the concavo-convex shape at the end portion that transitions from the convex portion to the concave portion can be emphasized, and a sharp design expression is possible.
The extender is not particularly limited, and is suitably selected from, for example, silica, talc, clay, barium sulfate, barium carbonate, calcium sulfate, calcium carbonate, magnesium carbonate and the like.
In addition, a matting agent can be added to the liquid repellent ink in order to obtain a delicate design. As the matting agent, silica is preferable because it has a high degree of freedom in material design and is excellent in coating stability. As a particle size, the range of 2-5 micrometers is preferable, and as the addition amount, the range of 1-5 mass% is preferable.
The shaped sheet of the present invention may or may not be colored, but is preferably colored for confirmation of the uneven shape. Examples of the pigment added to the liquid repellent ink for the purpose of coloring the forming sheet include known coloring pigments such as quinacridone red, 磯 indolinone yellow, phthalocyanine blue, phthalocyanine green, titanium oxide, and carbon black. Is used.

[Liquid repellent ink]
Examples of the liquid-repellent substance (b) include silicone resins and fluororesins that are resins used for the binder (a) above, polyolefin resins such as polyethylene and polypropylene, and waxes. Moreover, as a binder which does not itself have liquid repellency, amino alkyd resin, acrylic resin, polyester resin, urethane resin and the like that are generally commercially available as melamine alkyd resin, urea alkyd resin, and the like are preferably used.
In addition, extender pigments and matting agents can be added to the liquid repellent ink b) in the same manner as the liquid repellent ink b). Specifically, those mentioned in the liquid repellent ink of the above a) are used.

[Liquid repellent ink]
As the binder having the liquid repellency of c), the resins listed in the above a) are preferably used, but ionizing radiation curable resins can also be preferably used. The ionizing radiation curable resin is the same as the ionizing radiation curable resin used in the surface shaping layer 74 of the shaping sheet 71. In addition, extender pigments and matting agents that are mentioned in the liquid repellent ink of the above a) are used.
The additive having liquid repellency is added in order to obtain sufficient liquid repellency of the liquid repellent ink of c) and sufficient releasability of the shaping sheet. And fluorine-based resins.

The ionizing radiation curable resin composition used for the coating layer 105 of the shaping sheet 101 used in the present invention is the same as that used for the shaping sheet 71, but further contains a release agent. In short, a matting agent is preferably included.
As the mold release agent, reactive silicone is preferable, and among these, silicone (meth) acrylate is preferably used. It is because a mold release property improves by making the coating layer 5 contain a mold release agent, and the tolerance with respect to repeated continuous use improves. The release agent is the same as the release agent used in the matte undercoat layer 93 of the shaping sheet 91. The usage-amount of a mold release agent is the range of 0.1-50 mass parts with respect to 100 mass parts of ionizing radiation curable resin, Preferably it is the range of 0.5-10 mass parts. When the amount of the reactive silicone used is 0.1 parts by mass or more, the decorative plate and the surface of the shaping sheet are sufficiently peeled off, the uneven shape of the surface of the shaping sheet is maintained, and it can withstand long-term use. sell. On the other hand, if the amount of the reactive silicone used is 50 parts by mass or less, no repelling occurs when the ionizing radiation curable resin composition is applied to the base material, so the surface of the coating film is not roughened and the paint stability is improved. Will improve.
The matting agent is the same as that used for the surface shaping layer 94 of the shaping sheet 91.

  The base material 102 is the same as that used in the shaping sheet 71. The penetration preventing layer 104 is the same as the penetration preventing layer 76 of the shaping sheet 71. In addition, the composition of the ionizing radiation curable resin composition used for the coating layer 105 includes a release agent and a matting agent as compared with that used for the surface shaping layer 74 of the shaping sheet 71. Although different, other points, for example, the ionizing radiation curable resin, various additives, the method of forming the surface shaping layer, and the like are the same as those of the shaping sheet 71.

The moldable sheet 111 used in the present invention has a liquid repellent ink containing (b) a liquid repellent binder on the entire surface of the substrate, and (b) a liquid repellent ink itself. An ink selected from the group consisting of a liquid repellent ink to which a substance having liquid repellency is added, and (c) a liquid repellant ink in which an additive having liquid repellency is further added to a binder having liquid repellency. An ink layer is formed by coating a curable resin composition containing a release agent on the ink layer to form a coating layer, and the ink layer thus formed and the coating The coating layer is formed by forming a convex portion on the top of the ink layer by a liquid repellent action between the layers, and further curing the coating layer forming the convex portion thus formed.
The structure of the shaping sheet 111 of this invention is demonstrated using FIG. FIG. 14 is a schematic view showing a cross section of the shaping sheet 111 of the present invention. In the example shown in FIG. 14, there are a permeation preventing layer 114 covering the entire surface of the substrate 112, an ink layer 113 having liquid repellency, and a coating layer 115 in which a curable resin composition is crosslinked and cured. The ink layer 113 having liquid repellency exists over the entire surface, and a curable resin composition is applied on the ink layer 113, and the ink layer 113 having liquid repellency formed in this manner and the curable resin composition. Due to the liquid repellency between the coating layer 115 and the coating layer 115, the coating layer 115 forms a convex shape 117 made of a curable resin composition formed on the ink layer 113, and in this way. By crosslinking and curing the coating layer forming the formed convex shape, the shaped sheet 111 having the concave and convex shape can be obtained as a result.

  The base material 112, the permeation prevention layer 114, and the coating layer 115 are the same as the equipment 102, the permeation prevention layer 104, and the coating layer 105 used in the shaping sheet 101, respectively. The ink layer 113 is provided over the entire surface of the substrate, while the pattern layer 103 is partially provided, but other points such as the ink used, the coating thickness, and the like are the same as those of the pattern layer 103. .

The shaping sheet 121 used in the present invention has a substrate and a surface shaping layer obtained by crosslinking and curing the ionizing radiation curable resin composition, and the substrate side is interposed between the substrate and the surface shaping layer. From the above, it is a decorative material in which at least an ink layer and an interaction prevention layer are laminated in this order, and the ink layer is formed over the entire surface of the part or the base material that develops the interaction region, It is formed to have a shape in which a portion for expressing the interaction region is cut out.
The structure of the shaping sheet 121 used by this invention is demonstrated using FIG.15 and FIG.16. In short, the shaping sheet 121 includes a base material 122, an ink layer 125, an interaction preventing layer 126, a surface shaping layer 127, a permeation preventing layer 129, and the like.

The surface shaping layer 127 is obtained by crosslinking and curing the ionizing radiation curable resin composition, and is coated on the outermost surface of the decorative material 121. The ink layer 125 is made of a material that is permeable to the uncured ionizing radiation curable resin composition that forms the surface shaping layer 127, and is formed to have a desired uneven shape. On the other hand, the interaction preventing layer 126 is made of a material that is not permeable to the uncured ionizing radiation curable resin composition forming the surface shaping layer 127, and the device 122 or the penetration preventing provided as necessary. On the layer 129, it is laminated in contact with the surface shaping layer 127. Further, the interaction region preventing layer 126 has a shape having a cutout portion 126a obtained by cutting out a portion that expresses the interaction region. Therefore, the ink layer 125 exists in the cutout portion 126a, and the uncured ionizing radiation curable resin composition forming the surface shaping layer 127 is in contact with the ink layer 125 in the cutout portion 126a. Are stacked.
The interaction preventing layer 126 is laminated thicker than the ink layer 125. Therefore, the uncured ionizing radiation curable resin composition, which is a raw material of the surface shaping layer 127 laminated on the interaction preventing layer 126 including the cutout portion 126a, is in contact with the ink layer 125 in the cutout portion 126a. It is laminated in a state.

The ink layer 125 is directly laminated on the base material 122, or is laminated on the permeation prevention layer 129 provided as necessary, and may be partially provided as shown in FIG. Alternatively, it may be provided over the entire surface as shown in FIG.
The ink layer 125 is a layer that produces a convex shape on the surface of the surface shaping layer. With respect to the lamination range of the ink layer 125, it is not necessary to select and form only the region where the uneven shape is to be formed, and the ink layer 125 may be laminated on the entire surface of the base material 122 (so-called solid printing). Therefore, even if the portion where the convex shape is to be formed is a delicate pattern having a width of about 100 μm, it can be easily manufactured.
The ink composition forming the ink layer 125 has a property capable of expressing an interaction such as elution, dispersion, and mixing with the ionizing radiation curable resin composition forming the surface shaping layer 127. The ionizing radiation curable resin composition (uncured product) is appropriately selected.
The mechanism for generating the uneven shape on the surface shaping layer 127 of the shaping sheet 121 is such that the interaction preventing layer 126 has a shape obtained by cutting out a portion that expresses the interaction region, and is laminated on the ink layer 125. Further, when an uncured product of ionizing radiation curable resin is applied to form the surface shaping layer 127, the ink layer 125 is formed in or near the cutout portion 126a of the interaction preventing layer 126. It is assumed that the resin component is partly eluted, dispersed, mixed, or penetrated into the surface protective layer. At this time, the respective resin components in the ink composition of the ink layer 125 and the uncured product of the ionizing radiation curable resin are not completely compatible in a short time, but are in a suspended state, and the ink layer 125 It is considered that the portion immediately in the vicinity and in the vicinity thereof, that is, in the cut-out portion of the interaction preventing layer 126, and the suspended portion forms the interaction region 128. When this state is fixed by crosslinking and curing the surface shaping layer while maintaining this suspended state, an interaction region 128 is formed in the surface shaping layer, and the portion expresses a convex shape. Presumed to be.
Further, the shape of the interaction region 128 is mainly formed in the cutout portion 126a of the interaction preventing layer 126, and therefore does not exist beyond the width of the cutout portion 126a. A convex shape with a precise (sharp) pattern is formed.
On the other hand, in the upper part of the interaction preventing layer 126, since the interaction region 128 does not appear as described above, it does not form a convex shape, and as a result, on the surface of the shaping sheet 121 depending on the presence or absence of the interaction preventing layer 126. Has an uneven shape.

  Specifically, the ink composition forming the ink layer 125 preferably has a non-crosslinkable resin as a binder resin, and for example, a thermoplastic (non-crosslinked) urethane resin is preferable. If necessary, an unsaturated polyester resin, an acrylic resin, a vinyl chloride-vinyl acetate copolymer, or the like can be mixed in order to adjust the degree of expression of the interaction region 128.

About the application quantity of the ink composition which forms the ink layer 125, it is preferable that it is the range of 1-30 g / m < ² >. When it is 1 g / m ² or more, the above-described ink composition has sufficient interaction with the ionizing radiation curable resin composition, and a sufficient uneven shape on the surface of the decorative material can be obtained. On the other hand, when it is 30 g / m ² or less, there is no mechanical restriction when printing the ink composition, and it is economically advantageous. From the above viewpoint, the coating amount of the ink composition is preferably in the range of ² to 10 g / m ² .

  The interaction preventing layer 126 is laminated on the ink layer 125, and is further laminated by being sandwiched between the surface shaping layer 127 and the ink layer 125 laminated thereon. The shape of the interaction preventing layer 126 is a shape having a cutout portion 126a in which a portion for expressing the interaction region is cut out as described above. For example, in the case of expressing a wood grain pattern, the shape is a shape obtained by cutting out the conduit portion of the wood grain, and in the case of expressing a tile pasting pattern, the shape is obtained by cutting out the joint groove portion of the tile pasting. Since the interaction preventing layer 126 has such a shape, the ionizing radiation curable resin composition that is a raw material of the surface shaping layer 127 that has penetrated into the cutout portion 126a and the ink layer 125 are in contact with each other. This portion is blocked by the interaction preventing layer 126. Therefore, the interaction preventing layer 126 is a layer that forms the interaction region 128 in the cut-out portion and prevents the interaction region from appearing in other portions.

  The interaction preventing ink composition for forming the interaction preventing layer 126 does not exhibit an interaction such as elution, dispersion, and mixing with the ionizing radiation curable resin composition for forming the surface shaping layer 127 described later. And is appropriately selected in relation to the ionizing radiation curable resin composition (uncured product). Specifically, an ink composition having a crosslinkable resin composition having a shielding property as a binder resin is preferable, and for example, polyester polyol, acrylic polyol, polyvinyl butyral, and the like are preferable.

About the application quantity of the interaction prevention ink composition which forms the interaction prevention layer 126, it is preferable that it is the range of 1-30 g / m < ² >. When it is 1 g / m ² or more, it is possible to shield the interaction between the ink composition forming the ink layer 126 and the ionizing radiation curable resin composition, and to give a sufficient uneven shape to the surface of the decorative material. Can do. On the other hand, if it is 30 g / m ² or less, there is no mechanical restriction when printing the interaction preventing ink composition, and it is economically advantageous. From the above viewpoint, the coating amount of the interaction preventing ink composition is preferably in the range of ² to 10 g / m ² .
However, when the interaction preventing layer 126 is thicker than the ink layer 125 as in the decorative material 121 shown in FIGS. 15 and 16, the application amount of the interaction preventing ink composition is 1 to 30 g / m. ² and further in the range of ^{2 to} 10 g / m ^2, and the coating amount of the ink composition forming the ink layer 125 is preferably in the range of 1 to ²⁰ g / m ² , more preferably ^{2 to 5} g / m ^2. . In this case, the thickness of the coating film is 1 to 30 μm for the interaction preventing ink composition, further 2 to 10 μm, 1 to 20 μm for the ink composition forming the ink layer 125, and further 2 to 5 μm. Preferably there is.

The base material 122 used for the shaping sheet 121 is the same as the base material 72 used for the shaping sheet 71, and the penetration preventing layer 129 constituting the shaping sheet 121 is a penetration preventing layer constituting the shaping sheet 71. This is the same as 76.
The ionizing radiation curable resin in the ionizing radiation curable resin composition constituting the surface shaping layer 127 used for the shaping sheet 121 is ionizing radiation curable used in the surface shaping layer 75 of the shaping sheet 71. It is the same as the resin, and other additives, the method of forming the surface shaping layer, and the like are the same as those of the surface shaping layer 75 of the shaping sheet 71.

Moreover, a polyester-type film can be preferably used as a base material used for said shaping sheets 71, 81, 91, 101, 111, and 121. As the polyester film, for example, a resin such as polyethylene terephthalate (hereinafter referred to as “PET”), polybutylene terephthalate, polyethylene-2,6-naphthalate, poly-1,4-cyclohexanedimethylene terephthalate is formed into a film. Things can be mentioned. Of these, polyethylene terephthalate is particularly preferable because it is inexpensive. In addition, these resins may be a homopolymer or a copolymer. Further, a mixture of these resins may be used.
Although there is no restriction | limiting in particular about the thickness of a base material, Usually, about 20-150 micrometers, Preferably it is the range of 30-100 micrometers.

Moreover, when using a polyester-type film for a base material, the weight loss measured by immersing the base material in xylene at 140 ° C. for 24 hours and then drying is required to be 1.0% by mass or less. By using such a base material, even when the shaped sheet is repeatedly used, there is little precipitation of impurities from the base material, and the surface of the shaped sheet is not soiled. There is no inconvenience that the uneven pattern cannot be formed.
From the above points, it is preferable that the base material has a weight reduction by 0.65% by mass or less due to immersion in xylene. The lower limit of the weight reduction is not particularly limited, and the lowering of the weight reduction is preferable for the contamination of the surface of the shaping sheet. However, excessively suppressing the decrease in weight results in excessive processing in the method for suppressing the decrease in weight as described in detail below, and may lower other physical properties of the substrate. . From such a viewpoint, the weight reduction is particularly preferably in the range of 0.30 to 0.65% by mass.
The impurities referred to here are considered to be oligomer components such as ethylene terephthalate cyclic trimer in the case of PET, for example.

Examples of a method for reducing the amount of weight reduction by immersion in xylene include surface treatments such as cleaning treatment, corona discharge treatment, plasma treatment, and flame treatment.
The washing treatment is usually performed by passing the polyester film through a washing tank filled with a solvent. As a solvent used here, water, alcohol, etc. are mentioned suitably, and especially ethanol is preferable. Moreover, it is preferable to apply ultrasonic vibration continuously during the cleaning process. By ultrasonic vibration, the oligomer on the surface of the polyester film can be washed away more completely. After the washing treatment, it is preferable that the reattached oligomer is further washed with a shower-like washing liquid (solvent) and dried.

Corona discharge treatment is a process in which a material to be treated is sandwiched between a pair of electrodes under atmospheric pressure, an alternating high voltage is applied between both electrodes to excite corona discharge, and the surface of the material to be treated is exposed to corona discharge. It is. Examples of corona-generated gas include helium, argon, nitrogen, carbon monoxide, carbon dioxide, oxygen, and the like, and a mixed gas thereof can also be used.
Corona discharge treatment also has the effect of improving interlayer adhesion between the substrate and the layer above it. Therefore, the conditions for the corona discharge treatment must be determined in consideration of the suppression of the volatilization of impurities in the substrate and the control of the interlayer adhesion strength. Specifically, it is preferable to control the surface tension and interlayer adhesion strength by controlling the discharge time.

In the plasma treatment, active species higher than the corona discharge can be generated under a low pressure of about 0.001 to 0.01 Torr by glow discharge, and the surface treatment of the substrate 2 can be efficiently performed. . However, since plasma processing is performed in a vacuum system, continuous processing is difficult, productivity may be inferior, and equipment itself becomes large.
Corona discharge treatment and plasma treatment have the advantage that only oligomers on the surface of the polyester substrate are decomposed and removed, no harmful substances remain, and the temperature rise is extremely low.

  Also in the flame treatment (flame treatment), only the deposits on the polyester film surface can be removed as in the surface treatment. As the frame processing method, a surface treatment method using a clean burner is preferably used.

  In addition, these base materials can be subjected to chromium oxidation treatment, hot air treatment, ozone / ultraviolet treatment, or the like as desired for the purpose of improving interlayer adhesion. Furthermore, a treatment such as forming a primer layer may be applied to enhance interlayer adhesion.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this example.
(Evaluation method)
The resin decorative board obtained in each Example and the used shaping sheet were evaluated by the following methods.
(1) Measurement of surface roughness The sample to be evaluated is 400 mm long by 400 mm wide, and the surface shape and surface roughness (arithmetic) are measured using a three-dimensional non-contact surface shape measurement system (Micromap manufactured by Ryoka System Co., Ltd.). The average surface roughness), the effect of formability, and the molding reproducibility when repeatedly used were confirmed.
(2) Peelability The peel strength of the shaped sheet was measured using a tensile / compression tester (Orientec Co., Ltd. RTC-1250A). The sample to be evaluated was 25 mm wide × 50 mm long, and the test was performed at a peeling speed of 300 mm / min, a peeling direction of 180 ° (vertical direction), a load cell load of 10 N, and a measurement environment temperature of 23 ° C. (room temperature).
(3) Suitability for continuous molding The molding was carried out 10 times with the same shaped sheet, the peel strength for each molding was measured, and the peel stability when the shaped sheet was repeatedly used was measured.

Example 1: Production of a shaping sheet Primer ink (manufactured by Showa Ink Industry Co., Ltd.) was formed on the entire surface of an easily adhesive-treated polyester film ("A4100 (50 μm)" manufactured by Toyobo Co., Ltd.) that had already been easily adhered An acrylic ink “EBF tuning primer”) was gravure-printed to form a permeation prevention layer (primer layer).
Next, ink (urethane-based conduit ink “conduit MINI (A)” manufactured by The Inktec Co., Ltd.) was printed on the wood-patterned conduit portion by a pattern plate to form an ink layer. Further, an electron beam curable resin obtained by adding 5% by mass of calcined kaolin particles and 2% by mass of reactive silicone methacrylate to an electron beam curable resin ("REB-GE" manufactured by Dainichi Seika Kogyo Co., Ltd.) on these ink layers. The composition was applied at a coating amount of 4 g / m ² by a gravure offset coater method. After coating, an electron beam with an acceleration voltage of 175 kV and an irradiation dose of 30 kGy (3 Mrad) was irradiated to cure the electron beam curable resin composition to form the surface shaping layer 5 to obtain a shaping sheet. The shaping sheet has a convex shape in which the surface of the surface shaping layer located immediately above and near the ink layer is raised by 1 to 3 μm, and has a high-class feeling and a delicate wood grain expression. Met.

Example 2
As the base material, a reinforced paper with a weight of 30 g / m ² of rice is used, and on one side, acrylic resin and nitrified cotton are used as a binder, and titanium white, petal, and yellow lead are used as colorants. A solid printing layer having a work amount of 5 g / m ² was applied by gravure printing. On top of this, a woodgrain pattern layer was formed by gravure printing using an ink containing a nitrified cotton as a binder and a colorant mainly composed of a dial, and a decorative sheet layer was obtained. Subsequently, after roll-coating the urea-vinyl acetate adhesive on the MFD of the substrate, the obtained decorative sheet layer was bonded. Thereafter, a polyester resin composition obtained by mixing unsaturated polyester and peroxide was applied to the entire upper surface of the decorative sheet layer at a coating amount of 200 g / m ^2. The shaped sheet was covered and contacted while aligning with the registration mark, and using a rubber roll, rolled and defoamed 5 times at 10 kgf / 930 m / m, so that the position did not shift, The polyester resin was cured at room temperature by heating at 40 ° C. for 2 hours. After curing, the molded sheet was peeled off to obtain a polyester decorative board having a delicate uneven surface.

  The polyester decorative board obtained in Example 2 was excellent in molding reproducibility, and the surface roughness was approximately the same as 4.2 μm after the 10th molding, compared with 4.5 μm at the first time. Also, the peel strength at the first molding is good at 100 gr / inch or less, and the peel strength at the tenth molding is 100 gr / inch or less, almost the same as the first peel strength, good Results were obtained.

  ADVANTAGE OF THE INVENTION According to this invention, it can have a delicate uneven | corrugated shape and can obtain the high-quality resin decorative board.

It is a schematic diagram which shows the cross section of the resin decorative board of this invention. It is a schematic diagram which shows the peeling process of the shaping sheet used by this invention. It is a schematic diagram which shows the cross section of the shaping sheet used by this invention. It is a schematic diagram which shows the cross section of the shaping sheet used by this invention. It is a schematic diagram which shows the cross section of the shaping sheet used by this invention. It is a schematic diagram which shows the cross section of the shaping sheet used by this invention. It is a schematic diagram which shows the cross section of the shaping sheet used by this invention. It is a schematic diagram which shows the cross section of the shaping sheet used by this invention. It is a schematic diagram which shows the cross section of the shaping sheet used by this invention. It is a schematic diagram which shows the cross section of the shaping sheet used by this invention. It is a schematic diagram which shows the cross section of the shaping sheet used by this invention. It is a schematic diagram which shows the cross section of the shaping sheet used by this invention. It is a schematic diagram which shows the cross section of the shaping sheet used by this invention. It is a schematic diagram which shows the cross section of the shaping sheet used by this invention. It is a schematic diagram which shows the cross section of the shaping sheet used by this invention. It is a schematic diagram which shows the cross section of the shaping sheet used by this invention.

Explanation of symbols

1. Resin decorative board Substrate 3. Adhesive layer 4. Cosmetic sheet layer 41. Sheet layer 42. Solid print layer 43. Pattern layer 5. Resin layer 6. Shaping sheet 71. Molding sheet 72. Base material 73. Ink layer 73-a. Ink composition 73-b. Ink composition 73-c. Ink composition 74. Interaction region 74-a. Interaction region 74-b. Interaction region 74-c. Interaction region 75. Surface shaping layer 76. Infiltration prevention layer 77. Convex shape 77-a. Convex shape 77-b. Convex shape 77-c. Convex shape 78. Fine particles or calcined kaolin particles 78-a. Fine particles or calcined kaolin particles 78-b. Fine particles or calcined kaolin particles 81. Molding sheet 82. Base material 83. Ink layer 83-a. Ink composition 83-b. Ink composition 83-c. Ink composition 84. Interaction region 84-a. Interaction region 84-b. Interaction region 84-c. Interaction region 85. Surface shaping layer 86. Penetration preventing layer 87. Raised shape 87-a. Raised shape 87-b. Raised shape 87-c. Raised shape 88. Fine particles or calcined kaolin particles 812. Fine bump shape 813. Fine irregular surface 814. Concave shape 814-a. Concave shape 814-b. Concave shape 814-c. Concave shape 91. Shaping sheet 92. Base material 93. Matte undercoat layer 94. Surface shaping layer 95. Penetration preventing layer 96. Convex shape 101. Molding sheet 102. Base material 103. Pattern layer 104. Infiltration prevention layer 105. Coating layer 106. Concave shape 107. Convex shape 111. Molding sheet 112. Base material 113. Ink layer 114. Infiltration prevention layer 115. Coating layer 116. Concave shape 117. Convex shape 121. Molding sheet 122. Substrate 125. Ink layer 126. Matting prevention layer 127. Surface shaping layer 128. Interaction region 129. Penetration prevention layer

Claims (7)

An adhesive layer and a decorative sheet layer are sequentially laminated on the upper surface of the substrate, a resin composition is applied onto the decorative sheet layer, and then the molded sheet is brought into contact with and integrally cured, and then the molded sheet A resin decorative board manufacturing method in which a resin layer is formed by peeling off an ink layer provided on the substrate, at least partially or over the entire surface, and the shaped sheet is present on the ink layer. with contact therewith Te has a surface embossing layer that covers the entire surface state, and are not surface shaping layer was crosslinked and cured ionizing radiation-curable resin composition, uncrosslinked said ink layer as a binder resin method for producing a resin veneer ing from the ink composition comprising rESIN.   An adhesive layer and a decorative sheet layer are sequentially laminated on the upper surface of the substrate, a resin composition is applied onto the decorative sheet layer, and then the molded sheet is brought into contact with and integrally cured, and then the molded sheet A method for producing a resin decorative board in which a resin layer is formed by peeling off a transparent or translucent matte sheet containing a release agent provided on at least the entire surface of the mold sheet. It has a coating layer and a surface shaping layer partially provided on the undercoat layer, and the surface shaping layer is obtained by crosslinking and curing an ionizing radiation curable resin composition containing a release agent. Manufacturing method of resin decorative board.   The method for producing a decorative resin board according to claim 2, wherein the surface shaping layer is obtained by crosslinking and curing a curable resin composition further containing a matting agent. The method for producing a resin decorative board according to claim 1 , wherein the ionizing radiation curable resin composition contains calcined kaolin particles and / or fine particles. The method for producing a resin decorative board according to claim 1 or 4 , wherein the ionizing radiation curable resin composition contains reactive silicone. The shaping sheet made substrate is a polyester film, the substrate according to any of claims 1 to 5 weight loss after 24 hours immersion at 140 ° C. in xylene is less than 1.0 wt% Manufacturing method of resin decorative board. The method for producing a resin decorative board according to claim 1 , wherein the resin in the resin composition is an unsaturated polyester resin or a silicone resin.

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