JPH0427943B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for manufacturing a decorative board having a concave pattern that matches a pattern. Several methods are known for forming recesses, particularly recesses that match a printed pattern, in a thermosetting resin decorative board, such as a melamine decorative board or a diallyl phthalate decorative board. In particular, the method using a printing method is extremely easy because the location where the concave portion is to be provided and the other pattern are matched in the printing process, and moreover, it has a surface shape that matches the other methods, especially the printed pattern. Compared to a method using a mold or the like, this method is industrially superior because most of the normal steps after printing can be used as they are. As a method using such a printing method, a research group to which the present inventor belongs has already developed a method for manufacturing a decorative board with symmetrical embossed projections and recesses (Japanese Patent Application Laid-Open No. 111554/1983). In this method, a normal printing layer with a desired pattern is formed on decorative base paper using normal printing ink, and then a foamed printing layer with a desired pattern is formed using heat-foamable printing ink.
Next, the decorative base paper on which the two types of printing layers have been formed is impregnated with a thermosetting resin and dried to form an impregnated paper,
This impregnated paper is combined with a base material and then subjected to heating and pressure molding treatment. During heating and pressure molding, the foamable printing layer foams, and the thermosetting resin around the foamed portions causes poor curing. For this reason, when peeling off the mirror plate used during heating and pressing, the poorly cured parts adhere to the mirror plate and are removed.
A concave portion that matches the printed pattern is formed. However, the above method has several problems. First, the recessed portions formed by the above method are formed by cohesive failure due to a decrease in cohesive force in the poorly cured resin and the resin foamed portion. However, such cohesive failure is accompanied by chance, and it is not always the case that clear recesses are formed corresponding to the foamed printing layer, and sometimes only matte portions are formed. In addition, uncured resin adheres to the mirrored plate, so if the same mirrored plate is used repeatedly for heat and pressure molding without being removed, unevenness may occur on the surface of the finished decorative plate. In order to solve the problems of the above method, the inventors
In the same manner as the above method, however, the laminate is integrated by curing the thermosetting resin during heating and pressure molding, and the foamable printing layer is foamed to form a foam printing layer, and then the laminate is A method has also been developed in which the entire surface of the decorative sheet is coated with a solvent and polished to remove the foamed printing layer swollen by the solvent (Japanese Patent Application Laid-open No. 136446/1983). According to this method, the problems in the above-mentioned Japanese Patent Application Laid-open No. 54-111554 are solved and clear recesses are formed,
Since there is no deposit on the mirrored board, a decorative board with no unevenness can be obtained. However, in this method, the foaming agent is relatively easy to remove when removing the foamed printing layer, but some of the coloring agent consisting of dyes and/or pigments in the foaming printing layer is removed from the decorative base paper, normal printing Because it becomes integrated with the layer or thermosetting resin, it is not completely removed, and the proportion of the remaining material in the decorative board without being removed is not constant, which may cause color unevenness in the recesses that are formed. The present invention provides a method for manufacturing a thermosetting resin decorative board having concave portions that are clear and uniform in color and consistent with a printed pattern, while eliminating the above-mentioned problems of the conventional method for manufacturing a thermosetting resin decorative board. With the goal. The above-mentioned purpose is the same as the method in JP-A-58-136446, except that the heat-foamable printing layer is formed using a heat-foamable printing ink containing no colorant consisting of dyes and/or pigments. It was discovered that what could be achieved. That is, the method for producing a tone embossed decorative board of the present invention is to form a decorative sheet in which a normal printed layer with a desired pattern and a heat-foamable uncolored printed layer with a desired pattern are sequentially formed on a decorative base paper. The impregnated decorative sheet obtained by impregnating with resin liquid and drying is laminated on a base material, and the laminate is sandwiched between a pair of hot plates and molded under heat and pressure to form a laminate by curing the thermosetting resin. At the same time, the above-mentioned foamable uncolored printed layer is foamed to form a foamed uncolored printed layer, and then a solvent is applied to the entire surface of the decorative sheet of the laminate and polished, and the foamed printed layer swollen by the solvent is removed. It is characterized by: Hereinafter, the method for manufacturing a thermosetting resin decorative board of the present invention will be explained in more detail with reference to the drawings. In the following description, "%" and "part" are based on weight unless otherwise specified. FIG. 1 is a partial sectional view showing the conceptual structure of a decorative sheet A used in the method of the present invention. This decorative sheet A is made by forming a normal printing layer 2 with a desired pattern on a decorative base paper 1 using normal printing ink, and then forming a foamable non-colored printing layer 2 with a desired pattern using heat-foamable non-colored printing ink. Obtained by forming 3. The decorative base paper 1 may be paper used for ordinary melamine decorative boards or diallyl phthalate decorative boards, such as paper commonly called titanium paper, which uses purified pulp and incorporates a large amount of titanium oxide, etc. You can use any of them. As a normal printing ink, one prepared using an appropriate vehicle can be used, but it is preferable to use one that has good impregnability with the thermosetting resin liquid described below. Preferred examples include ethyl cellulose and ethyl hydroxyethyl cellulose. , cellulose derivatives such as cellulose acetate propionate, nitrocellulose, and cellulose acetate, and butyral resin. To form the normal printing layer 2 with a desired pattern using normal printing ink, gravure printing, gravure offset printing, planar offset printing, die-line printing, intaglio printing, jet printing, silk screen printing, electrostatic printing, etc. This can be done by any known printing method. In particular, in order to form a normal printed layer with a wood grain pattern, gravure printing using a gravure printing plate capable of continuously (endlessly) making a wood grain pattern, gravure offset printing, rotary screen printing, etc. are preferable. This is not the case. 100 parts of printing ink (as resin content) using an appropriate vehicle as heat-foamable uncolored printing ink
A foam obtained by adding 10 to 50 parts of a known blowing agent to the foam can be used. Suitable vehicles include, in addition to the resins mentioned above as examples of vehicles for ordinary printing inks, styrene resins such as polystyrene, poly-α-methylstyrene, styrene copolymer resins, polymethyl methacrylate, polyethyl methacrylate, Single or copolymer resins of acrylic or methacrylic resins such as polyethyl acrylate and polybutyl acrylate, rosin, rosin-modified maleic acid resin, rosin-modified phenolic resin, rosin ester resin such as polymerized rosin, polyvinyl acetate resin, coumaron One or more of resins, vinyl toluene resins, vinyl chloride resins, polyester resins, polyurethane resins, polyamide resins, vinyl chloride-vinyl acetate copolymer resins, etc. can be used. As the blowing agent, inorganic blowing agents such as sodium bicarbonate, ammonium carbonate, sodium boron hydride, silicon oxyhydride, etc., which are known blowing agents, azodicarbonamide, azobisisobutyronitrile, dinitrosopentamethylenetetramine, para Organic blowing agents such as toluenesulfonylhydrazide and 4,4'-oxybisbenzenesulfonylhydrazide, as well as microballoons (or microspheres) containing gas or low-boiling point organic solvents in synthetic resin capsules, etc. Select and use them according to the softening temperature of the vehicle, processing conditions of the decorative paper, etc. In addition to the vehicles and blowing agents mentioned above, plasticizers, stabilizers, surfactants,
Wax/grease, a desiccant, an auxiliary desiccant, a curing agent, an emulsifier, a thickener, a filler, a dispersant, a solvent, and a diluent are added as appropriate, and the mixture is kneaded and used. In the present invention, it is important to use a heat-foamable printing ink that does not contain a coloring agent consisting of a dye and/or a pigment as described above.
Therefore, it is desirable to use colorless additives other than the colorant. However, additives other than colorants are generally colorless or light-colored, and even if they are colored, the degree of coloration is sufficiently low compared to the degree of coloration of dyes and pigments, so additives are generally not used. In many cases, there is no need to give special consideration to In addition, the degree of non-coloring in the present invention is sufficient as long as the foam printing layer remaining in the concave portions of the decorative board finally obtained is not colored noticeably differently compared to other parts, and is not completely colored. In addition to being colorless, there is no problem as long as it is light colored. In particular, when printing using colorless or white ink, it is difficult to check the print finish during printing, so in this sense it is better to have some coloring, and dyes and/or
Alternatively, a coloring agent consisting of a pigment may be added in an amount of, for example, about 1/100 or less of the amount of a normal colored ink. As a method for forming the foamable non-colored printed layer 3 with a desired pattern using the heat-foamable non-colored ink as described above, there may be mentioned a known printing method similar to the method for forming the normal printed layer 2 described above. However, a method using a printing method in which a relatively large amount of ink is transferred during printing is preferable because the pattern is raised due to foaming, and the recesses formed become deeper by that amount. In that sense, gravure printing, gravure offset printing, intaglio printing, or silk screen printing is preferable. In addition, when forming a wood grain pattern as a normal printed layer, printing a wood grain conduit groove pattern as a foamable uncolored printed layer, and creating recesses in the conduit groove pattern portion in a post-process, the wood grain pattern and foaming, which are the normally printed patterns, are printed. It is preferable that the wood grain conduit pattern, which is a transparent printing layer, be formed by the same printing method because it can be formed using the same printing machine, and it is easy to match both patterns. In addition to the above-mentioned wood grain conduit groove pattern, the foamable printed layer 3 can also be patterned in areas where depressions are desired to be formed within the pattern of the printed layer, such as tile joints, wood peeling grooves, and stone cracks. Alternatively, it is preferable to use a printing plate made by removing a desired portion of a material having a three-dimensional surface texture such as leather or cloth and making a plate. The coating amount of the foamable uncolored printed layer 3 (on a dry basis; the same applies to this layer below) varies depending on the pattern to be formed, but for example, when forming a conduit pattern, it is 1 to 10 g/m Approximately ² is appropriate. By impregnating the thus obtained decorative sheet A with a thermosetting resin liquid 4 and drying it, an impregnated decorative sheet B as shown in FIG. 2 is obtained. As the thermosetting resin liquid, there are thermosetting resins used in manufacturing known decorative boards, such as melamine resin, phenol resin, diallyl phthalate resin,
Benzoguanamine resin, epoxy resin, thermosetting modified vinyl chloride resin, etc. can be used, and if necessary, these resins are dissolved in an appropriate solvent or monomer, and a catalyst etc. are added to form a resin liquid, and the above-mentioned Coat and impregnate decorative paper using a known coating method. The coating method can be gravure coating, roll coating, dip coating, or the like. Drying is performed below the curing temperature of the thermosetting resin 4.
Specifically, it varies depending on the resin used, but for example, in the case of melamine resin, the temperature is 1 to 1 at 90 to 140℃
Drying for about 10 minutes is appropriate. At this time, the heat-foamable printed layer 3 may partially foam. Next, the thus obtained impregnated decorative sheet B
As shown in FIG. 3, the material 5 is stacked on top of the material 5, and heated and pressed by being sandwiched between a pair of hot plates (mirror plates) 6a and 6b. Examples of the base material 5 include core paper, which is a stack of several sheets of paper with a basis weight of 140 to 180 g/m ² impregnated with 30 to 60% phenol resin, or a wood base material such as wood, plywood, particle board, etc. In addition, gypsum base materials such as gypsum board and gypsum slag board, fiber cement board such as pulp cement board, asbestos cement board, wood chip cement board, GRC and concrete,
Metal foils or sheets of iron, aluminum, copper, etc., as well as composites of the above base materials, etc. can be used. In particular, when applying the method of the present invention to high-pressure melamine laminated decorative laminates, the structure used when manufacturing ordinary melamine decorative laminates, for example, core paper (basis weight 140
g/ ^m2 to 180g/ ^m2 ) with 30 to 60 g/m2 of phenolic resin.
It is preferable to use a base material having a structure in which several sheets of melamine resin impregnated with 60% of melamine resin are stacked according to the required thickness, and a layer of balance paper (basis weight: 80 g/m ³ ) impregnated with 60% of melamine resin is further layered underneath. In the present invention, it is preferable not to use an overlay paper, which is used in general melamine decorative boards, on the impregnated sheet B, since this prevents the formation of recesses. The heating and pressure molding conditions vary depending on the thermosetting resin used, but for example, in the case of melamine resin.
Appropriate conditions are 130 to 140°C, 80 to 120 Kg/cm ² , and 10 to 30 minutes. In the above heating and pressure molding, the foamable uncolored printed layer 3 is foamed and the thermosetting resin 4 is cured. Then, when the hot plates 6a and 6b are opened, the fourth
As shown in the figure, a foamed printing layer 3a is formed,
An integral cured laminate c is obtained in which the thermosetting resin layer 4a is cured while being pushed away by the foamed uncolored printed layer 3a. Next, when a solvent is applied to the entire surface of this laminate, the foamed non-colored printed layer 3a absorbs the solvent and the fifth layer is formed.
It swells as shown as 3b in the figure. The solvent to be used is a solvent that dissolves or swells the foam layer 3a, and more specifically, when using a vehicle for heat-foamable ink constituting the foamable print layer 3 or a microcapsule-type foaming agent, it is a solvent that dissolves or swells the foam layer 3a. Solvents that dissolve or swell can be appropriately selected and used, such as aromatic hydrocarbons such as toluene and xylene, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and n-butyl acetate, methanol, and ethanol. , alcohols such as isopropanol, and halogenated hydrocarbons such as trichlorethylene and perchlorethylene. These solvents may be applied to the decorative board by any application method such as roll coating, spray coating, pour coating, flow coating, or spraying. No. 5 obtained by applying the solvent as described above.
When the surface of the laminate in the state shown in the figure is polished using an appropriate means such as a buff roller or a brush, most of the swollen or dissolved foam layer 3b is removed, leaving a layer 3c made of foamable ink only at the bottom. A recess 7 corresponding to (therefore corresponding to the foamable printed layer 3) is formed. Furthermore, in order to remove polishing slag if necessary, it is preferable to use a malt roller whose surface is made of woven fabric or the like. In the present invention, the layer 3c remaining at the bottom of the recess 7
Since it is constructed using an uncolored heat-foamable ink, it is possible to provide a substantially constant appearance regardless of the remaining proportion of the layer 3c. Further, according to the present invention, it is possible to form a recessed portion with a low degree of coloring, and in some cases, the recessed portion has the same color as the surrounding area. Depending on the decorative board, it may be necessary for the bottom of the recess to be clearly colored, so in such cases, the printed pattern made with a regular ink composition synchronized with the foamable uncolored printed layer is mixed with the foamed non-colored printed layer. It is preferable to provide it between the non-colored printed layers. Applying the present invention to wood grain,
When it is desired to obtain a decorative board with the conduit portions colored in a dark color or other suitable color, a wood grain pattern is formed using a conventional ink composition, and then a wood grain conduit pattern is formed using a conventional ink composition. Furthermore, by forming the wood grain conduit pattern using a foaming non-colored printing ink in synchronization with the wood grain conduit pattern described above, even if the upper foam printing layer is removed after hot-pressure molding, the lower layer normal ink will remain intact. Since the wood grain conduit pattern created by the composition remains in sync with the recesses, coloring of the recesses is ensured. Thereafter, post-treatments such as heating or radiation treatment for complete drying or curing are performed as necessary. In the above, the most basic aspect of the method for producing a decorative material of the present invention has been explained. However, the method of the present invention can be implemented with various modifications as described below, and corresponding improvements can be obtained thereby. Modification 1 By carrying out the method of the present invention according to the basic embodiment described above, a tuned embossed decorative board having clear recesses can be obtained. However, the above-mentioned Japanese Patent Application Publication No. 54
- Mirror plate 6a, 6b transitioning from FIG. 3 to FIG. 4 as in the method described in Publication No. 111554
Since the foamed layer 3a or the thermosetting resin around its periphery adheres to the mirror plate 6a during the opening stage, repeated use of the mirror plate 6a may cause unevenness on the surface of the product decorative board. In order to solve this problem, in this embodiment, as shown in FIG.
It has heat resistance and is commonly known as “release paper”.
In addition, a disposable sheet 8 with a smooth surface is attached to a mirror plate 6.
A method is adopted in which a foamed resin or an uncured resin is applied by inserting the material between the material and the impregnated decorative sheet. As the release paper, polyethylene terephthalate film, polypropylene film, aluminum foil, parchment paper, or a composite thereof can be used. Modification 2 Modification 1 described above can solve the problem of stains on the specular board and the resulting unevenness of the product decorative board. However, this method requires the use of a disposable sheet 8, which is uneconomical, and has drawbacks such as complicated sheet insertion. Therefore, in this embodiment, a condition is provided in which the foamed resin or the like does not adhere to the mirror plate even without intervening the disposable sheet as described above. According to the present inventor, it has been found that such conditions can be solved by using a foaming agent whose foaming temperature is close to the heating and pressure molding temperature for curing the thermosetting resin. Ta. Here, "near the heat molding temperature" means the center temperature of the molding temperature of the thermosetting resin used (for example, in the case of melamine resin, the center 135 °C of its molding temperature range of 130 to 140 °C) ±15 °C. do. Especially the center temperature of the molding -15℃~-
A range of 5°C (ie 120°C to 130°C) is preferred. Further, the foaming temperature of a foaming agent is determined as the temperature at which substantial foaming starts, and in the case of a microcapsule type foaming agent, it is generally close to the softening temperature of the capsule-constituting resin. When a foaming agent having a foaming temperature range in the molding temperature range is used in this way, the above-mentioned resin can be prevented from adhering to the mirror plate. The reason for this is not necessarily clear, but one reason is that foaming during molding is suppressed compared to when a foaming agent with a lower foaming temperature is used, and as shown in Figure 4, the subsequent solvent Thermosetting resin 4a to the extent that it does not impede impregnation.
This is thought to be due to the formation of an appropriate foamed portion 3a that does not protrude and adhere to the mirror plate. The foaming agent is optional as long as it has the above foaming temperature range. However, the most preferred foaming agent is a microcapsule type foaming agent, since the foaming temperature range can be easily controlled. The foaming temperature of this microcapsule-type foaming agent can be adjusted depending on the resin constituting the capsule wall and the type of vaporizable substance to be encapsulated. The capsule wall-constituting resin preferably has a softening point within the range of -20°C to -10°C, which is the center of the thermosetting resin molding temperature.For melamine resin, polyacrylonitrile resin, vinylidene chloride-acrylonitrile-methyl methacrylate, etc. Copolymers (softening point: 120 to 130°C) are preferably used. It is preferable to use a resin with relatively high heat resistance as the capsule wall material in order to prevent the resin from adhering to the end plate wall. Further, as the evaporative substance to be encapsulated, it is preferable to use a liquid whose boiling point falls within a temperature range whose upper limit is the center of the molding temperature of the thermosetting resin and whose lower limit is 20° C. lower than that. Specifically, when the thermosetting resin is a melamine resin, hydrocarbons such as isobutane, chlorofluorocarbon gas, chloroform, halogen, tetramethyl silicone, petroleum ether, etc. are preferably used. In addition, as a microcapsule, the outer diameter is 5~
A wall thickness of 20 μm and a wall thickness of 2 to 4 μm is preferred. More specifically, in terms of foaming ratio, it is preferable to have a large outer diameter, thin wall thickness, and a large amount of liquid filled inside, but when forming a heat-foamable printed layer by ordinary printing means, ink formation, The above range is preferable in terms of the storage stability of the ink and the transfer from the printing plate to the printing material when using the gravure printing method. In manufacturing, making the capsule larger makes the wall thicker and makes it difficult to foam, and making the capsule smaller makes the wall thinner and the gas barrier properties deteriorate. The solvent is preferably one that does not dissolve or swell the walls of the microcapsule-type foaming agent, and in this sense, for example, in the case of the above-mentioned vinylidene chloride-acrylonitrile-methyl methacrylate copolymer, esters and ketones are not preferred, and alcohols, Water is preferred. Modification 3 As mentioned above, in the method of the present invention, it is preferable not to use an overlay paper as in ordinary melamine decorative boards in order to form clear recesses. Therefore, the decorative board obtained according to the basic embodiment inevitably suffers from a decrease in surface properties such as abrasion resistance. In order to solve this problem and provide decorative laminates with excellent surface properties, the following method, which has been developed for flat thermosetting resin decorative laminates, is known per se. Can be applied to law. b) A method using a suspension of cellulose heated in nitric acid as a thermosetting resin liquid (see Japanese Patent Publication No. 43-21986), b) A synthetic resin layer containing cellulose microcrystals is placed on an impregnated decorative sheet. After forming, a method of carrying out heating and pressure molding as shown in FIG. (See Japanese Patent Publication No. 47-33297), d) A method using a thermosetting resin liquid to which microcrystalline cellulose powder, glass fiber or microcrystalline asbestos powder, and Erosil (colloidal silica) are added (see Japanese Patent Publication No. 47-30635) ), e) A method of using a thermosetting resin liquid mixed with abrasive grains such as alumina, silicon carbide, etc. or a mixture of these and microcrystalline cellulose (Japanese Unexamined Patent Application Publication No. 1977-49-
14587 and JP-A-49-96089), f) Instead of overlay paper, a method of using decorative base paper in which a resin layer containing abrasion-resistant mineral fine particles is formed on a printed pattern layer (JP-A-53 −92875 publication,
(Refer to each publication No. 55-67459). Each of the above-mentioned publications is included in the present specification as a reference. As mentioned above, these methods for improving surface properties were developed simply as a method for manufacturing planar thermosetting resin decorative laminates, but it is the present invention that they can be combined without contradiction with the method for manufacturing tone embossed decorative laminates of the present invention. This was discovered by the inventor. Among the above-mentioned methods, method f) provides a decorative board with particularly excellent surface properties and is therefore most preferably used in the method of the present invention. Therefore, the case where the above method (f) is applied will be explained in some detail below. In this embodiment, instead of the decorative base paper A described in FIG. 1, a decorative base paper AA on which a resin layer 9 containing wear-resistant mineral fine particles is further formed as shown in FIG. 8 is used, and as shown in FIG. By performing the same operations as in the basic embodiment described above with reference to FIG. 6, a decorative board as shown in FIG. 9 corresponding to FIG. 6 can be obtained. In FIG. 9, 10 is a composite cured resin layer obtained by infiltrating and hardening a thermosetting resin into a wear-resistant mineral particle-containing resin layer. As wear-resistant mineral fine particles, the particle size is 10 to 50 μm.
Alumina, silica, silicon carbide, zirconium oxide, cerium oxide, etc. are preferably used, but
Alumina, which has both hardness and economic efficiency, is particularly preferred. The mineral fine particle-containing resin layer 4 contains 100 parts of such mineral particles, microcrystalline cellulose, acrylic resin,
A paint obtained by mixing and kneading 25 to 50 parts of a binder resin such as carboxymethyl cellulose, methyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, etc., and water, a solvent or a dispersion medium,
It is obtained by coating by gravure coating, roll coating, air knife coating, etc. and drying. If necessary, a bonding promoter such as a silane coupling agent may be added to the coating material to improve the bonding properties between the mineral fine particles and the thermosetting resin. The coating amount is 3 to 10 g/m ² , especially 3.5 to 5.0
About g/m ² is preferable. If the amount applied is too small, the effect of improving surface properties such as wear resistance will be poor, and if it is excessive, formation of recesses will be inhibited. As can be seen from FIG. 9, in the recess 7, the composite cured resin layer 10 containing wear-resistant mineral fine particles is removed. Therefore, deterioration of surface properties in this portion is unavoidable. However, in thermosetting resin decorative boards, such partial loss of the surface protective layer often causes almost no problem. For example, the most attractive pattern to add to a thermosetting resin decorative board is a wood grain pattern, and it is often desirable to form recesses that match the conduit pattern, especially as is the case with natural wood boards. . In this case, since the conduit pattern is in the form of fine lines, the loss of the protective layer in that part will hardly cause a decrease in surface properties, especially wear resistance, which is usually the most required property. . Furthermore, since such a mineral fine particle-containing resin layer is removed, the visual contrast between the recessed portion and the surrounding area is increased, which has the advantage of giving a clearer three-dimensional effect at first glance. As described above, according to the present invention, in the conventional manufacturing method of thermosetting resin decorative board, by improving the printing method for forming the decorative base paper, a concave pattern that is synchronized with the printed pattern is formed and It is possible to form deeper and clearer recesses than the method described in the developed Japanese Patent Application Laid-Open No. 111554/1983. Moreover,
By making modifications as necessary, a decorative board with uniform surface gloss can be obtained without complicating the process, and it is also possible to produce a thermosetting resin decorative board with excellent surface properties. Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 A wood grain pattern was gravure printed on the surface of a colored base paper for decorative boards with a basis weight of 80 g/m ² using a conventional gravure ink having the following composition. Normal gravure ink Cellulose acetate 5-6% Color pigment 15-35% Dibutyl phthalate (plasticizer) 2-3% Solvent 56-78% Methanol 15 parts Ethyl acetate 60 parts Xylene 15 parts Cyclohexane 10 parts A conduit portion perfectly aligned with the wood grain pattern was gravure printed using a heat-foaming ink with the following formulation. Heat-foaming ink Butyl methacrylate resin 25% Diphenyl octyl phosphate (plasticizer) 1% Solvent 49% Toluene 35 parts N-hexane 45 parts Isopropyl alcohol 20 parts Foaming agent 25% (manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd., Microcapsule-type foaming agent F-60) Next, a thermosetting resin liquid consisting of 50 parts of melamine formaldehyde resin, 45 parts of water, and 5 parts of isopropyl alcohol was added to this decorative sheet, and a thermosetting resin solution of 50 parts of melamine formaldehyde resin, 45 parts of water, and 5 parts of isopropyl alcohol was added to the decorative sheet. Using an impregnating device, melamine resin is 90g/
m ² (dry) and dried to obtain an impregnated decorative sheet. This impregnated decorative sheet was laminated on four sheets of core paper, the laminate was sandwiched between two mirrored plates, and heated and pressed using a heat press at a pressure of 100 kg/cm ² at 135°C for 20 minutes. When molding was carried out, a melamine decorative board intermediate was obtained in which the conduit pattern was in sync with the normally printed wood grain pattern and faded compared to the surrounding area. Furthermore, when ethyl acetate was applied to the entire surface of the obtained decorative board intermediate at a rate of about 10 g/m ² and polished with a buff roller, and the residue from the polishing was removed using a Motorun roller, a three-dimensional structure with concave conduit portions was formed. A decorative board with a nice feel was obtained. Furthermore, even if the above ethyl acetate coating and buffing were repeated, there was almost no change in the color of the conduit.
Furthermore, even when different samples were coated with ethyl acetate and buffed, there was almost no difference in the color of the recesses between the samples. Example 2 After forming a wood grain pattern in the same manner as in Example 1,
A conduit portion matching the wood grain pattern was formed using regular gravure ink (dark brown), and then a heat-foaming ink was used to overprint the conduit portion. Thereafter, the same procedure as in Example 1 was carried out to obtain a decorative board in which the concave portions were colored dark brown. Example 3 On the decorative sheet obtained by applying the heat-foamable non-colored ink of Example 1, a resin liquid containing alumina fine particles of the following composition was applied by air knife coating for 3.5 minutes.
g/m ² (dry) and at a temperature of 100°C.
A dry decorative sheet was obtained. Resin liquid containing alumina fine particles Water 89.0% Alumina (average particle size 30μ) 7% Microcrystalline cellulose 1.8% Silane coupling agent 0.4% (Nippon Unicar Co., Ltd., A-1100) Carboxymethyl cellulose 0.8% Using the obtained decorative sheet, Thereafter, in the same manner as in Example 1, impregnation with thermosetting resin liquid, lamination with core paper, heating and pressure molding, polishing with a buff roller, and removal of residue with a Molton roller were carried out to form a three-dimensional structure in the same manner as in Example 1. A decorative board with a nice feel was obtained. The surface abrasion resistance of the thus obtained decorative board was evaluated by a JIS thermosetting resin decorative board abrasion test. The evaluation results are shown in the table below along with the evaluation results for the high-pressure melamine decorative board produced using the overlay sheet using a conventional method.

[Table] Looking at the results, it can be seen that the melamine decorative board formed with the resin layer containing fine mineral particles of this example not only has a wood grain-like synchronized embossed pattern with excellent three-dimensional effect, but also has only a general planar pattern. It can be seen that it has better abrasion resistance than the high-pressure melamine decorative board with an overlay sheet. Example 3 After obtaining a decorative sheet in the same manner as in Example 1, this decorative sheet was impregnated with a resin liquid prepared using quick-drying melamine resin (Sunstop M-700, manufactured by Nissan Chemical Industries, Ltd.) during drying. It was impregnated at a rate of 108 g/m ³ and dried to obtain an impregnated sheet. This impregnated decorative sheet was layered on particle board with a thickness of 15 mm, and heat and pressure molded under the conditions of a pressure of 20 kg/cm ² and 150°C for 3 minutes, followed by solvent coating, polishing, and residual coating in the same manner as in Example 1. was removed.
As a result, the conduit pattern is in sync with the normal printed layer,
A synchronized embossed low-pressure melamine decorative board with a three-dimensional effect that is smoother than the surrounding area and has unevenness was obtained. Example 4 A decorative sheet similar to Example 1 was produced. However, as a foaming agent, Micropearl manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.
RQ-507 was used. The resulting decorative sheet was coated with a thermosetting resin liquid of the following composition to a dry impregnation amount of 120%.
g/m ² and dried in a hot air dryer having drying zones each having a temperature of 60°C to 100°C to prepare an impregnated decorative sheet. Thermosetting resin liquid Diaryl phthalate prepolymer 100 parts Benzoyl peroxide 3 parts Internal mold release agent 0.5 parts Polymerization inhibitor (hydroquinone) 0.01 parts Methylated silica (diameter 16 mμ) 3 parts Acetone 150 parts This impregnated decorative sheet was made into a 15 mm thick sheet. This decorative board is layered on particle board and heated and pressure molded using mirror-finished duralumin boards at a pressure of 20 kg/cm ² at 130°C for 15 minutes, resulting in a conduit pattern that is slightly matte than the surrounding area. An intermediate was obtained. Furthermore, 10 g/m ² of ethyl acetate was applied to the above intermediate using a roll coater, the surface was polished with a buff roller, and the residue was removed using a Molton roller, resulting in a three-dimensional effect with concave conduit pattern parts. A matching embossed diallyl phthalate decorative board was obtained.

[Brief explanation of drawings]

Figures 1 to 9 are cross-sectional views of the decorative laminate viewed from the thickness direction for explaining the decorative laminate manufacturing method of the present invention. Figure 1 is the decorative sheet used, and Figure 2 is the impregnated decorative sheet. , Figure 3 shows the heating and pressure molding process, Figure 4
The figure shows a laminated board after hot-pressing molding, Figure 5 shows a decorative board after solvent coating, Figure 6 shows a decorative board after polishing, Figure 7 shows another example of the hot-pressing molding process, and Figure 8 shows a decorative sheet. Another Example, FIG. 9 shows another example of the decorative board obtained. A, AA... Decorative sheet, B... Impregnated decorative sheet, C... Laminated board after heating and pressing, 1... Decorative base paper, 2... Ordinary printing layer, 3... Foaming non-colored printing layer, 3a ...After foaming, 3b...Solvent swollen state, 3
c... After polishing, 4... Thermosetting resin liquid, 5... Base material, 6a, 6b... Hot plate (mirror plate), 7... Recessed part,
8...Disposable sheet, 9...Abrasion-resistant mineral fine particle-containing resin layer, 10...Mineral fine particle-containing composite cured resin layer.

Claims (1)

[Scope of Claims] 1. A decorative sheet formed by sequentially forming a normal printed layer with a desired pattern and a heat-foamable non-colored printed layer with a desired pattern on a decorative base paper is impregnated with a thermosetting resin liquid. After drying, the obtained impregnated decorative sheet is laminated on a base material, the laminate is sandwiched between a pair of hot plates and molded under heat and pressure, and the laminate is integrated by curing the thermosetting resin. It is characterized by foaming the foamable uncolored printed layer to form a foamed uncolored printed layer, and then applying a solvent to the entire surface of the decorative sheet of the laminate and polishing it to remove the foamed printed layer swollen by the solvent. Manufacturing method of matching embossed decorative board. 2. The foaming agent contained in the heat-foamable printed layer has a foaming temperature range near the heat-pressing molding temperature.
Section method. 3. The method of item 1 or 2 above, which comprises microcapsules in which a thermoplastic resin capsule is encapsulated with a liquid in which the foaming agent contained in the heat-foamable printed layer can be vaporized by heating. 4. The first foamed printing layer is pre-foamed when the decorative sheet impregnated with the thermosetting resin liquid is dried.
Any method from Section 3 to Section 3. 5. The method according to any one of items 1 to 4 above, wherein a resin layer containing wear-resistant mineral fine particles is formed on the heat-foamable printed layer of the decorative sheet. 6. The method according to any one of items 1 to 5 above, wherein the wear-resistant mineral fine particles are alumina with a particle size of 10 to 50 μm. 7. The method according to any one of the above items 1 to 6, wherein the pattern of the foam printing layer is a wood conduit pattern. 8. The method according to item 7 above, characterized in that a conduit pattern is formed between the normal printing layer and the foam printing layer using a normal ink composition that is synchronized with the foam printing layer.