JP2007098630A - Shaping sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a shaping sheet capable of being subjected to dense shaping having a fine uneven shape and a high grade feeling, also excellent in mold releasability and prevented from the surface staining caused by impurities precipitated from a base material or the like, and a decorative sheet shaped from the shaping sheet. <P>SOLUTION: The shaping sheet is constituted of the ink layer at least partially provided on a base material comprising a polyester film and the surface shaping layer present on the ink layer in a contact state to cover the whole surface, which includes the ink layer formed region and ink layer non-formed region, of the base material. The surface shaping layer is formed by crosslinking and curing an ionizing radiation curable resin composition and the base material is characterized in that its weight reduction after the base material is immersed in xylene for 24 hr at 140°C is 1.0 mass% or below. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a shaped sheet having a delicate uneven shape, capable of high-quality dense molding, and excellent in releasability, and a decorative board molded by the shaping sheet.

As building materials used as furniture, desk top plates, various types of housing equipment such as counters and doors, and interior materials, generally, decorative boards formed with synthetic resin materials, such as melamine resin decorative boards, are widely used.
Conventionally, there are two types of thermosetting resin decorative plates having a concavo-convex shape on the surface, one having a concavo-convex shape formed by an embossing die or a resin concavo-convex sheet, and one having a concavo-convex shape formed by a shaping sheet. However, when an embossing mold having a concavo-convex shape is used, it is necessary to subject the die to surface treatment such as blasting or etching, which limits the concavo-convex shape and the fineness of the pattern. Furthermore, when manufacturing a thermosetting resin decorative board, an expensive template and a spare template are required, which increases the labor and cost of preparing the decorative board, greatly increasing the manufacturing cost and making the product expensive. . Also, in the case of a resin uneven sheet, it is necessary to sandwich an aluminum foil, a polypropylene film, etc. between the mold plate and the thermosetting resin decorative board because it becomes difficult to peel off after the resin is cured. It is very difficult to form a sharp.

By the way, due to the recent trend toward consumer luxury goods, furniture, desks, interior materials, etc. have been required to have a high-class feeling, and the decorative panels used for these have a high-quality appearance. Is desired. For this reason, it is also important to impart a texture, and various methods for imparting a delicate uneven shape to a decorative board have been proposed.
For example, it is a moldable sheet provided with an uneven shape with ionizing radiation curable resin on the surface of the base sheet, and is desired by having a crosslinking density such that the uneven shape is not broken when the formed sheet is peeled off. A shaping sheet has been proposed that faithfully reproduces the pattern shape to be used and can be used repeatedly (see Patent Document 1 and Claims). However, since the step of peeling from the roll intaglio is made when producing the shaping sheet, there is a limit to the expression of the concavo-convex shape when the concave portion is thin.
In addition, this method has a problem that unevenness does not appear cleanly when the concave portion is thin. On the other hand, when there is a concave portion with a certain thickness, an uneven pattern is obtained on the surface of the substrate, but the height of the raised portion is high. For example, in the case of a wood grain pattern, there is a problem that there is no real feeling and the appearance and the touch feeling are not good.

  In addition, when the molded sheet using a polyester film as a base material is used repeatedly, impurities are precipitated from the base material, and the surface of the molded sheet is stained, and the fine uneven pattern caused by the dirt In some cases, it was difficult to form a sharp shape.

JP 7-164519 A

  Under such circumstances, the present invention has a delicate uneven shape, can be given a high-quality and precise shaping, is excellent in releasability, and can be used repeatedly, even if it is used repeatedly. An object of the present invention is to provide a shaped sheet in which the surface of the shaped sheet is not soiled by impurities deposited from the surface, and a decorative board shaped by the shaped sheet.

  As a result of intensive studies to achieve the above object, the present inventors have found that an ink layer provided at least partially on a base material made of a polyester film and the ink layer is present on the ink layer. A surface-forming layer that covers the entire surface including a region where the ink layer is formed and a region where the ink layer is not formed, the surface-forming layer being ionized 1. A weight reduction (hereinafter, simply referred to as “weight reduction”) after the radiation-curable resin composition is crosslinked and cured and the substrate is immersed in xylene at 140 ° C. for 24 hours. It has been found that the above problem can be solved by setting the content to 0% by mass or less. The present invention has been completed based on such findings.

That is, the present invention
(1) An ink layer provided at least partially on a base material made of a polyester film, an area on the ink layer that is in contact with the ink layer, and an area where the ink layer is formed, and the ink layer A surface-forming layer that covers the entire surface including the region where no ion is formed, wherein the surface-forming layer is obtained by crosslinking and curing the ionizing radiation-curable resin composition, and A shaped sheet, wherein the weight loss after the material is immersed in xylene at 140 ° C. for 24 hours is 1.0% by mass or less,
(2) The shaped sheet according to (1), wherein the substrate is surface-treated,
(3) The shaping sheet according to (2), wherein the surface treatment is at least one selected from cleaning treatment, corona discharge treatment, plasma treatment and flame treatment,
(4) The shaping sheet according to any one of (1) to (3), wherein the surface of the surface shaping layer located immediately above the ink layer and the upper portion in the vicinity thereof has a convex shape,
(5) The above (1) to (1), wherein the ink constituting the ink layer contains a non-crosslinked urethane resin as a binder, and the ionizing radiation curable resin composition contains a (meth) acrylate monomer. (4) the shaping sheet according to any one of
(6) The shaping sheet according to (5), wherein the ink constituting the ink layer contains a non-crosslinked urethane resin and an unsaturated polyester resin as a binder,
(7) The shaping sheet according to any one of (4) to (6) above, wherein the thickness of the ink constituting the ink layer is not uniform,
(8) The ink layer is composed of a thick film region having a relatively large film thickness and a thin film region having a relatively thin film thickness, and the surface layer located immediately above the thick film region and in the vicinity thereof. The convex shape on the surface of the mold layer is relatively high, and the convex shape on the surface of the surface shaping layer located immediately above the thin film region and in the vicinity thereof is relatively low. Sheet,
(9) The shaping sheet according to any one of (4) to (8), wherein the height of the convex shape is 1 to 3 μm,
(10) The shaping sheet according to any one of (1) to (9), wherein the surface shaping layer contains reactive silicone.
(11) The surface shaping layer contains fine particles, and the average particle size of the fine particles is a value close to the plus side of the maximum thickness of the surface shaping layer located immediately above the ink layer. The shaped sheet according to any one of (4) to (10),
(12) The shaped sheet according to (11), wherein 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 30% or less,
(13) The average particle size 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)
The molding sheet according to (11) or (12), which satisfies the relationship:
(14) The shaping sheet according to any one of (11) to (13), wherein the content of fine particles in the surface shaping layer is 2 to 20% by mass,
(15) The shaping sheet according to any one of (1) to (14), wherein the surface shaping layer contains calcined kaolin particles,
(16) The forming sheet according to any one of (1) to (15), wherein the ink constituting the ink layer contains an extender pigment,
(17) The moldable sheet according to any one of (1) to (16), wherein the ionizing radiation curable resin composition is an electron beam curable resin composition,
(18) A decorative board formed by shaping the shaping sheet according to any one of (1) to (17) on a substrate,
(19) A makeup characterized by being molded by inserting the shaping sheet according to any one of (1) to (17) above between a substrate and a pressure plate that are molded by pressing between heated pressure plates. Board,
(20) The decorative board according to (18) or (19) above, wherein the substrate is a melamine resin decorative board, and (21) The above (18) or (19), wherein the substrate is a diallyl phthalate (DAP) resin decorative board. The decorative board,
Is to provide.

  According to the present invention, it has a delicate uneven shape, can be densely shaped with a high-class feeling, is excellent in releasability, and impurities that precipitate from the substrate even after repeated use Thus, it is possible to obtain a shaped sheet that does not contaminate the surface of the shaped sheet.

  The moldable sheet of the present invention has an ink layer at least partially provided on a substrate made of a polyester film, and is present on and in contact with the ink layer, and the ink layer is formed. It is a shaping sheet having a surface shaping layer that covers the entire surface including the area and the area where the ink layer is not formed, and the surface shaping layer is obtained by crosslinking and curing the ionizing radiation curable resin composition. is there. In particular, when the ink layer is partially provided, the surface of the surface shaping layer located immediately above the ink layer and the upper portion in the vicinity thereof has a convex shape.

The structure of the shaping sheet of this invention is demonstrated using FIG. 1, FIG. 1 and 2 are schematic views showing a cross section of the shaped sheet 1 of the present invention. In the example shown in FIG. 1, a uniform uniform permeation preventive layer 6 covering the entire surface, an ink layer 3, and a surface shaping layer 5 obtained by crosslinking and curing an ionizing radiation curable resin composition are laminated in this order on the substrate 2. It is a thing. The ink layer 3 exists partially, and an interaction region 4 is formed in the surface shaping layer immediately above and near the ink layer 3. The interaction area 4 is represented by a set of points in the figure.
The upper part of the interaction region 4 on the outermost surface of the surface shaping layer 5 is raised with the formation of the ink layer 3 and has a convex shape 7. When the surface of the surface shaping layer 5 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.
On the other hand, when the ink layer 3 is applied to the entire surface in a solid shape, the convex shape 7 does not appear, but the outermost surface of the surface shaping layer 5 has finer irregularities than the convex shape 7. When this is used as a shaping sheet, a matte design can be shaped on the surface of the decorative board to be shaped.

  The extent of the expansion of the interaction region 4 formed in the surface shaping layer 5 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 remain in the middle of the shaping layer 5 in the thickness direction, or may reach the outermost surface of the surface shaping layer 5 as shown in FIG.

Hereinafter, the structure of a base material and each layer is demonstrated in detail using FIGS.
The substrate 2 used in the present invention is composed of a polyester film. 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 the base material 2, Usually, about 20-150 micrometers, Preferably it is the range of 30-100 micrometers.

In the present invention, the weight loss measured by immersing the substrate 2 in xylene at 140 ° C. for 24 hours and then drying it is 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 2 has a weight loss of 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.
The corona discharge treatment also has an effect of improving interlayer adhesion between the base material 2 and the layer thereon. 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.

  The permeation prevention layer 6 shown in FIG. 1 is a layer provided as desired, and an ink constituting the ink layer 3 described later and an ionizing radiation curable resin constituting the surface shaping layer 5 are contained in the substrate 2. It has a function of suppressing permeation and is located between the substrate 2 and the ink layer 3. Usually, a uniform and uniform layer obtained by crosslinking and curing an ionizing radiation curable resin and an adhesive curable resin constituting the surface shaping layer 5 is formed between the base material 2 and the ink layer 3 as shown in FIG. Provided. This also fulfills the function of enhancing the adhesion between the base material 2, the ink layer 3 and the surface shaping layer 5.

The ink layer 3 in the decorative material of the present invention is laminated on the permeation preventive layer 6 or the like provided as necessary as shown in FIG. It is a layer to be made.
Although the mechanism of the uneven shape generation in the present invention has not been fully elucidated, ionizing radiation curing for forming the surface shaping layer 5 on the surface of the ink layer 3 from the results of various experiments, observations and measurements. When an uncured resin is applied, the resin component of the ink layer 3 and the surface shaping layer may partially dissolve, disperse, mix, etc., depending on the combination of materials and appropriate selection of coating conditions. It is presumed to be due to manifesting the action. At this time, the respective resin components in the ink of the ink layer 3 and the uncured product of the ionizing radiation curable resin are not completely compatible and suspended in a short time, and are directly above the ink layer 3. And the part which exists in the vicinity and became this suspension state is considered to form the interaction area | region, and to express the convex shape 7. FIG. When this state is fixed by crosslinking and curing the surface shaping layer with this suspended state, the interaction region 4 is partially formed in the surface shaping layer as shown in FIGS. It is presumed that it is formed like a convex shape 7.

The ink that forms the ink layer 3 has a property capable of expressing an interaction such as elution, dispersion, and mixing with the ionizing radiation curable resin composition that forms the surface shaping layer 5, and the ionizing radiation. It is appropriately selected in relation to the curable resin composition (uncured product). Specifically, an ink having a non-crosslinkable resin as the binder resin is preferable, and for example, a thermoplastic (non-crosslinked type) 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 5 and obtaining a feeling of unevenness of the further pattern. More preferably.
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.

  If necessary, a saturated or unsaturated polyester resin, an acrylic resin, or a vinyl chloride-vinyl acetate copolymer is mixed to adjust the degree of expression of the interaction region, that is, the degree of undulation of the convex shape. can do. 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 of the ink. 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 for forming the ink layer 3. 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 3 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 pigment used in the present invention 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, is preferred. Is preferred. As a particle size of a silica, the range of 0.1-5 micrometers is preferable. When it is 0.1 μm or more, the thixotropy of the ink does not become extremely high when it is added to the ink, and the viscosity of the ink does not increase too much, so that printing can be controlled easily. 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 which forms the ink layer 3, 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 and the 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 30 g / m ² or less, there is no mechanical restriction in printing the ink, and it is economically advantageous. From the above viewpoint, the coating amount of the ink 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 constituting the ink layer 3 can be made non-uniform, and the degree of the height difference of the convex portions developed thereby is stepwise or continuous. 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, as the coating amount of the ink layer 3 is relatively increased, the interaction between the ink layer 3 and the surface shaping layer 5 is relatively increased, and the degree of the suspended state is further increased. This is because the undulations of the convex shape are higher.
This will be described in detail below with reference to FIGS. In FIG. 3, the thicknesses of the inks 3-a, 3-b and 3-c constituting the ink layer 3 are made different. That is, the film thickness is gradually reduced in the order of 3-a, 3-b, and 3-c. By doing so, the interaction regions 4-a, 4-b, and 4-c can be changed stepwise, and the resulting convex and concave shapes 7-c, 7-b, and 7-a are obtained in this order. The convex part rises more gradually. This is because the thickness of the ink constituting the ink layer 3 is not uniform and is applied so that the thickness of the ink decreases in the order of 3-a, 3-b, 3-c. It is considered that the undulation of the convex shape becomes more remarkable in the large portion and changes so that the undulation of the convex shape becomes smaller in gradation in the order of 3-a, 3-b, and 3-c. By changing the thickness of the ink more finely, the concavo-convex 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 constituting the ink layer 3 can usually be easily performed by changing the amount of ink applied, and by changing the amount of ink applied continuously, the above steps It is also possible to continuously change the change continuously.

Next, in the example shown in FIG. 4, the thickness of the ink layer 3 on the base material 2 is continuously changed in a plane parallel to the surface of the base material (the thicker the central part, the more toward the side part). The surface shaping layer 5 in which the ionizing radiation curable resin composition is crosslinked and cured is laminated thereon (to be thin). As shown in FIG. 3, the surface shaping layer immediately above and near the ink layer forms an interaction region. In the example of FIG. 4, the thickness of the ink layer increases in the order of 3-c, 3-b, 3-a, and the interaction regions 4-c, 4-b, 4-a The undulations of the convex shape increase successively. As a result, the surface shaping layer 5 has convex undulations continuously increasing in this order.
The extent of the expansion of the interaction region 4 formed in the surface shaping layer 5 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. 3, from the surface of the ink layer 3. The surface shaping layer 5 may remain in the middle of the thickness direction, or may reach the outermost surface of the surface shaping layer 5 as shown in FIGS. A convex shape may be formed on the outermost surface of the layer 5.

Next, the surface shaping layer 5 is composed of a material obtained by crosslinking and curing the 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, it can be appropriately selected from polymerizable monomers, polymerizable oligomers or prepolymers conventionally used as ionizing radiation curable resin compositions.
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 present invention, the interaction between the ink constituting the ink layer 3 and the ionizing radiation curable resin composition constituting the surface shaping layer 5 is important as described above. 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 present invention, it is preferable to use an electron beam curable resin composition as the ionizing radiation curable resin composition. This is because the electron beam curable resin composition 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.

  The surface shaping layer 5 preferably contains calcined kaolin particles. 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 to impart a more delicate uneven shape and marling resistance to the surface of the shaped sheet are kaolin particles obtained by calcining general (hydrous) kaolin particles, but as a filler By adding the calcined kaolin particles, the improvement in marling resistance, which could not be realized 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 shaped sheet of the present invention preferably contains a reactive silicone in the ionizing radiation curable resin composition. It is because the release property is improved and the resistance to repeated continuous use is improved by adding reactive silicone to the surface shaping layer 5.
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 fine particles are further mix | blended with the ionizing radiation-curable resin composition in the shaping sheet of this invention. 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 5 located immediately above the ink layer 3 are used. The shaped sheet of the present invention in which fine particles are blended will be described in detail with reference to FIG. The shaped sheet shown in FIG. 6 is obtained by blending fine particles with an ionizing radiation curable resin composition.
The fine particles 8 (8-a, 8-b) blended in the surface shaping layer have an average particle diameter d _A of the maximum thickness t _M of the surface shaping layer 5 located immediately above the ink layer 3. The value near the plus side, that is, d _A is slightly larger than t _M , and cueing of the fine particles 8-a occurs from the surface of the surface shaping layer 5 located immediately above the ink layer 3. Since the portion where the cueing has occurred forms a convex shape, a fine unevenness can be formed. At the same time, inside the surface shaping layer 5, the ink layer 3 and the ionizing radiation curable resin composition constituting the surface shaping layer 5 interact with each other immediately above and near the ink layer 3. The interaction area | region 4 which makes a part express convex shape is formed.
On the other hand, the fine particles 8-b located in a portion that is not directly above the ink layer 3 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, due to the interaction region 4 in the surface shaping layer 5, the effect of cueing the fine particles on the surface of the surface shaping layer 5, and the effect of the convex shape formed with the formation of the ink layer 3 described above. The concavo-convex shape is fine and further emphasized.
The maximum thickness t _M of the surface shaping layer 5 located immediately above the ink layer 3 is the thickness of the surface shaping layer 5 when the convex shape associated with the formation of the ink layer 3 is not formed. When the convex shape is formed, the thickness includes the 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 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 the ionizing radiation-curable resin composition in this invention 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. Moreover, as an organic type ultraviolet absorber, benzotriazole type, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-) is specifically mentioned. 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.

In the present invention, a polymerizable monomer, a polymerizable oligomer and various additives, which are the ionizing radiation curable components, are uniformly mixed at predetermined ratios to prepare a coating liquid composed of an ionizing radiation curable resin composition. To do. 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.
In the present invention, the coating liquid prepared in this way is applied to the surface of the substrate so that the thickness after curing is 1 to 20 μm, gravure coating, bar coating, roll coating, reverse roll coating, Coating is performed by a known method such as comma coating, preferably gravure coating, to form an uncured resin layer. When the thickness after curing is 1 μm or more, a cured resin layer having a desired function is obtained. The thickness of the surface shaping layer after curing is preferably about 2 to 20 μm.

In the present invention, 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. 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 also be imparted.

Next, the decorative board of the present invention is a decorative board formed by molding the above-mentioned shaping sheet on a base material. In particular, it is preferable that the decorative plate has a fine uneven shape on the surface by inserting and molding the shaped sheet between a molded product molded by pressing between the heated pressure plates and the pressure plate. Specifically, as shown in FIG. 7, the decorative sheet 11 having a certain shape is obtained by peeling the molded sheet 1 from the decorative sheet 11 after hot pressing.
The decorative board 11 of the present invention is not particularly limited as long as it is a decorative board produced using the shaped sheet of the present invention, but the surface is hard, heat resistance and stain resistance are excellent, and design properties Because of its rich color pattern, melamine resin decorative boards, diallyl phthalate (DAP) resin decorative boards, polycarbonate resin decorative boards, especially melamine resin decorative boards and diallyl phthalate (DAP) resin decorative boards are suitable. is there. There are no particular limitations on the production of these decorative plates as long as they are publicly known and generally used, and for example, they can be obtained by the following production methods.
The melamine resin decorative board is made by laminating a melamine resin-impregnated sheet on about 4 phenol resin-impregnated core papers, and an overlay paper impregnated with melamine resin, and sandwiching it between two specular metal plates. For example, the mold sheet is inserted, heat-pressed at 0.98 MPa and 160 ° C. for 20 minutes, allowed to cool to room temperature, and then peeled off from the mold sheet.
Further, diallyl phthalate (DAP) resin decorative board is obtained by sequentially stacking diallyl phthalate resin-impregnated paper on a plate-like base material, and in the same manner as the production method of melamine resin decorative board, It is obtained by using and pressing at 140 to 150 ° C., 0.98 MPa for about 10 minutes, allowing to cool to room temperature, and then peeling the shaped sheet. In any case, the decorative board has a delicate uneven shape.

The decorative board 11 of the present invention can be used by being attached to various substrates. Specifically, as shown in FIG. 8, a decorative board 11 is attached to the substrate 10 via an adhesive layer 9.
The board | substrate used as a to-be-adhered body is not specifically limited, A plastic board, a metal board, woody board | plates, such as a timber, a ceramic material, etc. can be selected suitably according to a use. 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, for example can be used, 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.

  In this way, the substrate 10 on which the decorative plate 11 is placed every leaf or continuously through the adhesive layer 9 is cold-pressed, hot-pressed, roll-pressed, laminator, lapping, edge pasting machine, vacuum press. The decorative plate 11 is bonded to the surface of the substrate 10 by pressing with a sticking device such as the above.

The adhesive is applied using an application device such as a spray, spreader, or bar coater. As the adhesive, vinyl acetate resin-based, urea resin-based, melamine resin-based, phenol resin-based, isocyanate-based adhesives, etc., are used alone or as a mixed adhesive obtained by arbitrarily mixing them. 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 plate 11 on the substrate 10 is usually performed by forming the adhesive layer 9 on the back surface of the decorative plate 11 of the present invention and applying the adhesive on the substrate 10. For example, the decorative plate 11 is attached.

  The building materials manufactured as described above are optionally cut into the building materials and subjected to arbitrary decorations such as grooving and chamfering using a cutting machine such as a router or a cutter on the surface or the end of the wood. Can do. And various uses, for example, interior or exterior materials of buildings such as walls, ceilings, floors, window frames, doors, handrails, skirting boards, margins, surface decorative boards for fittings such as malls, kitchens, furniture or light electrical appliances, It can be used for surface decorative boards of cabinets such as OA equipment, interiors and exteriors of vehicles.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this example.
(Evaluation methods)
The shaping sheet and decorative board obtained in each example were evaluated by the following methods.
(1) Observation of surface shape Using electron microscope ("S-2400 scanning electron microscope" manufactured by Hitachi High-Tech Co., Ltd.), surface shape (surface unevenness, uneven pitch), confirmation of effect of shaped sheet, repeated use The molding reproducibility was observed.
(2) 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
A primer ink (acrylic ink “EBF tuning” manufactured by Showa Ink Industry Co., Ltd.) is applied to the entire treated surface of a PET film (“Lumirror (thickness: 50 μm, weight reduction: 0.65 mass%)” manufactured by Toray Industries, Inc.). The primer “) was gravure-printed to form a penetration preventing layer 6 (primer layer).
Next, ink (urethane-based conduit ink “conduit MINI (A)” manufactured by The Inktec Co., Ltd.) was printed on the conduit portion of the wood grain pattern with the pattern plate to form the ink layer 3. Further, an electron beam curable resin obtained by adding 5% by weight of calcined kaolin particles and 2% by weight of reactive silicone methacrylate to an electron beam curable resin (“REB-GE” manufactured by Dainichi Seika Kogyo Co., Ltd.) on these ink layers. It was coated by gravure offset coater method in coating weight 4g / m ² of composition. 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 5 located immediately above and near the ink layer 3 is raised by 1 to 3 μm, and has a high-class feeling and a delicate wood grain expression. Film.

Example 2
A sheet of melamine resin impregnated on about 4 sheets of phenol resin-impregnated core paper, and further, a laminate of approximately 35 g / m ² of impregnated melamine resin is laminated on it and sandwiched between two mirror metal plates. The shaping sheet produced in Example 1 having an uneven shape formed thereon was inserted, and heated and pressed at 0.98 MPa and 160 ° C. for 20 minutes.
After allowing to cool to room temperature, the shaped sheet was peeled off to obtain a melamine resin decorative board having a delicate uneven surface.

Comparative Example 1
Urethane acrylate UV curable resin (Daisen Seika Kogyo Co., Ltd.) on the easy-adhesion surface of a commercially available PET film (weight reduction; 1.5% by mass) that has already been subjected to easy-adhesion treatment, using a drum printing film (hereinafter “DPS”) method. Convex pattern layer by XD-808 manufactured by Co., Ltd. was formed.
On the intaglio surface of the roll, an uneven pattern having a grain pattern (depth: 70 μm, width of convex part and width of concave part is 35 μm each) was provided by an etching method. Note that the line speed of the DPS method was 10 m / min, and ozone high pressure mercury lamp (manufactured by Nippon Batteries Co., Ltd.) 160 W and two lamps were used for ultraviolet irradiation.
The shaped sheet thus obtained had an uneven shape. Using the shaped sheet thus obtained, the same operation as in Example 2 was performed to produce a melamine resin decorative board.

The decorative board obtained in Example 2 was very delicate in the concavo-convex shape, and a high-quality design expression was possible. Moreover, the shaping sheet obtained by Example 1 was rich in durability, and even if molding was repeated 10 times, the surface shape and the releasability after shaping (ease of peeling) were not changed at all. In addition, even if molding is repeated 10 times, the surface of the molded decorative board has a convex portion (a portion where the concave shape 13 of the shaping sheet is shaped) and a concave portion (the convex shape 7 of the shaping sheet). The shaped part) was sharply shaped and had a fine uneven shape in the concave part of the decorative board, and no change was observed. Further, even when used repeatedly, the surface of the shaping sheet was not soiled by impurities precipitated from the base material.
The decorative board according to Comparative Example 1 was not able to express a delicate uneven shape although the expression of dynamic unevenness was good. In addition, the film needs to use a thick and thick sheet due to manufacturing problems, and the manufacturing cost has increased. The durability and peelability were the same as in Example 2.

  According to the present invention, it has a delicate concavo-convex shape, can be high-quality dense molding, is excellent in releasability, and has an excellent separability from the substrate, etc. A shaped sheet whose surface is not soiled is obtained. Moreover, the decorative board which has the delicate uneven | corrugated shape shape | molded by this shaping sheet can be obtained. In particular, when used for delicate patterns such as wood grain patterns, the unevenness of the conduit part can be expressed realistically, and the molded decorative material can obtain the same texture as the material using actual wood .

It is a schematic diagram which shows the cross section of the shaping sheet of this invention. It is a schematic diagram which shows the cross section of the shaping sheet of this invention. It is a schematic diagram which shows the cross section of the shaping sheet of this invention. It is a schematic diagram which shows the cross section of the shaping sheet of this invention. It is a schematic diagram which shows the cross section of the shaping sheet of this invention. It is a schematic diagram which shows the cross section of the shaping sheet of this invention. It is a schematic diagram which shows the peeling process of the shaping sheet of this invention. It is a schematic diagram which shows the cross section of building materials.

Explanation of symbols

1. Molding sheet 2. Base material 3. Ink layer 3-a. Ink 3-b. Ink 3-c. Ink 4. Interaction region 4-a. Interaction region 4-b. Interaction region 4-c. 4. Interaction region 5. Surface shaping layer 6. Penetration prevention layer Convex shape 7-a. Convex shape 7-b. Convex shape 7-c. Convex shape Fine particles or calcined kaolin particles 8-a. Fine particles or calcined kaolin particles 8-b. 8. Fine particles or calcined kaolin particles Adhesive layer 10. Substrate 11. Decorative plate 12. Fine uneven surface

Claims (21)

An ink layer provided at least partially on a substrate made of a polyester film, and an area on which the ink layer is formed and the ink layer are formed while being present on and in contact with the ink layer. A surface-forming layer that covers the entire surface including the unexposed region, wherein the surface-forming layer is obtained by crosslinking and curing the ionizing radiation-curable resin composition, and the base material is xylene A shaped sheet characterized in that the weight loss after immersion for 24 hours at 140 ° C. is 1.0% by mass or less. The shaping sheet according to claim 1, wherein the substrate is surface-treated. The shaped sheet according to claim 2, wherein the surface treatment is at least one selected from cleaning treatment, corona discharge treatment, plasma treatment and flame treatment. The shaping sheet according to any one of claims 1 to 3, wherein a surface of the surface shaping layer located immediately above the ink layer and an upper portion in the vicinity thereof has a convex shape. The ink constituting the ink layer contains a non-crosslinked urethane resin as a binder, and the ionizing radiation curable resin composition contains a (meth) acrylate monomer. The shaping sheet as described in 1. The shaping sheet according to claim 5, wherein the ink constituting the ink layer contains a non-crosslinked urethane resin and an unsaturated polyester resin as binders. The shaping sheet according to any one of claims 4 to 6, wherein the thickness of the ink constituting the ink layer is not uniform. The ink layer comprises a thick film region having a relatively large thickness and a thin film region having a relatively small film thickness, and a surface shaping layer positioned immediately above the thick film region and an upper portion in the vicinity thereof. The shaping sheet according to claim 7, wherein the convex shape of the surface is relatively high, and the convex shape of the surface of the surface shaping layer located immediately above the thin film region and in the vicinity thereof is relatively low. The shaped sheet according to any one of claims 4 to 8, wherein the height of the convex shape is 1 to 3 µm. The shaping sheet according to any one of claims 1 to 9, comprising reactive silicone in the surface shaping layer. The fine particle is included in the surface shaping layer, and the average particle size of the fine particle is a value close to the plus side of the maximum thickness of the surface shaping layer located immediately above the ink layer. Item 10. The shaped sheet according to any one of Items 4 to 10. 12. The shaped sheet according to claim 11, wherein 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 30% or less. When 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)
The shaping sheet according to claim 11 or 12, satisfying the relationship: The moldable sheet according to any one of claims 11 to 13, wherein the content of fine particles in the surface moldable layer is 2 to 20% by mass. The shaping sheet according to any one of claims 1 to 14, wherein the surface shaping layer contains calcined kaolin particles. The shaped sheet according to any one of claims 1 to 15, wherein the ink constituting the ink layer contains an extender pigment. The shaped sheet according to any one of claims 1 to 16, wherein the ionizing radiation curable resin composition is an electron beam curable resin composition. The decorative board formed by shape | molding the shaping | molding sheet in any one of Claims 1-17 on a board | substrate. A decorative board, which is molded by inserting the shaping sheet according to any one of claims 1 to 17 between a pressure plate and a substrate to be molded by pressing between the heated pressure plates. The decorative board according to claim 18 or 19, wherein the substrate is a melamine resin decorative board. The decorative board according to claim 18 or 19, wherein the substrate is a diallyl phthalate (DAP) resin decorative board.

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