JP2826729B2 - Method for forming irregularities and transfer sheet used in the method - Google Patents

Description

The present invention relates to a method for forming a concavo-convex pattern and a transfer sheet used in the method. [Problems to be Solved by Conventional Techniques and the Invention] Conventionally, in order to give a three-dimensional effect to a pattern provided on a smooth surface, it is performed to give the pattern itself a thickness. In addition to this, a special printing method is required in order to provide a sharp pattern, and it is difficult to form a sharp bulge, and there is a problem that a beautiful three-dimensional pattern cannot be easily formed. [Means for Solving the Problems] The present invention has been made in order to solve the above-mentioned drawbacks of the prior art, and a method for forming a concavo-convex pattern capable of easily forming a sharp three-dimensional pattern and a method for using the method. It is an object to provide a transfer sheet to be formed. That is, the present invention provides: (1) a method for forming a concavo-convex pattern, which comprises sequentially performing the following steps (a) to (f). (A) An ionizing radiation-transmissive release substrate and a substrate for forming a concavo-convex pattern having releasability from an ionizing radiation-curable resin having a cured surface are prepared, and either the front or back surface of the ionizing radiation-transmissive release substrate is prepared. Alternatively, a step of providing an ionizing radiation shielding pattern using an ink containing a substance that absorbs ionizing radiation on the surface of the substrate for forming an uneven pattern. (B) The surface on which the peeling substrate and the substrate for forming a concavo-convex pattern facing each other are provided with the above-mentioned pattern pattern. Coating the entire surface with an ionizing radiation-curable resin layer. (C) a step of laminating the substrate for forming a concavo-convex pattern and the release substrate via an ionizing radiation-curable resin layer. (D) a step of irradiating ionizing radiation from the side of the peeling substrate or the side of the substrate for forming a concavo-convex pattern to cure the ionizing radiation-curable resin layer corresponding to a portion having no pattern. (E) a step of peeling off the release base material and attaching a part of the uncured resin of the ionizing radiation-curable resin layer to the release base material or the pattern to remove the resin together with the release base material; (F) A step of applying a solvent onto the uneven surface of the transfer-receiving substrate, and then performing buff polishing using a brush or a cotton buffing roller to remove the remaining uncured ionizing radiation-curable resin layer. . (2) A method for forming a concavo-convex pattern, wherein the following steps (a) to (f) are sequentially performed. (A) An ultraviolet-transmissive release substrate and a substrate for forming a concavo-convex pattern having a releasability from an ultraviolet-curable resin having a cured surface are prepared, and either the front or back surface or the concavo-convex pattern of the ultraviolet-transmissive release substrate is prepared. The surface of the forming substrate contains a substance that absorbs ultraviolet light selected from benzophenol-based, salicylate-based, benzotriazole-based or acrylonitrile-based ultraviolet absorbers, and metal complex salt-based or hindered amine-based quencher. A step of providing a pattern using ink. (B) The surface on which the peeling substrate and the substrate for forming a concavo-convex pattern facing each other are provided with the above-mentioned pattern pattern. Coating the entire surface with an ultraviolet curable resin layer. (C) a step of laminating the substrate for forming a concavo-convex pattern and the release substrate via an ultraviolet-curable resin layer. (D) a step of irradiating ultraviolet rays from the side of the peeling substrate or the side of the substrate for forming a concavo-convex pattern to cure the ultraviolet-curable resin layer corresponding to a portion having no pattern. (E) a step of peeling off the release base material and attaching a part of the uncured resin of the ultraviolet-curable resin layer to the release base material or the pattern to remove the resin together with the release base material; (3) The method for forming an uneven pattern according to claim 2, wherein after the release substrate is released, the uncured ultraviolet-curable resin remaining on the transfer substrate is cured by further irradiating ionizing radiation. . (4) The method of forming an uneven pattern according to claim 2 or 3, wherein a surface protective layer is formed on the uneven surface as necessary. (5) A benzophenol-based, salicylate-based, benzotriazole-based or acrylonitrile-based ultraviolet absorber, a metal complex salt-based or a hindered amine-based quencher is provided on either one of the front and back surfaces of the ultraviolet-transmissive release substrate having a peelable surface. The transfer sheet used in the method of forming a concavo-convex pattern in the following step, characterized by providing a pattern that is not transferred, formed using an ink containing a substance that absorbs ultraviolet light selected from any of . A method for forming a concavo-convex pattern, which comprises sequentially performing the following steps (a) to (e). (A) An ultraviolet-transmissive release substrate and a substrate for forming a concavo-convex pattern having a releasability from an ultraviolet-curable resin having a cured surface are prepared, and either the front or back surface or the concavo-convex pattern of the ultraviolet-transmissive release substrate is prepared. The surface of the forming substrate contains a substance that absorbs ultraviolet light selected from benzophenol-based, salicylate-based, benzotriazole-based or acrylonitrile-based ultraviolet absorbers, and metal complex salt-based or hindered amine-based quencher. A step of providing a pattern using ink. (B) The surface on which the peeling substrate and the substrate for forming a concavo-convex pattern facing each other are provided with the above-mentioned pattern pattern. Coating the entire surface with an ultraviolet curable resin layer. (C) a step of laminating the substrate for forming a concavo-convex pattern and the release substrate via an ultraviolet-curable resin layer. (D) a step of irradiating ultraviolet rays from the side of the peeling substrate or the side of the substrate for forming a concavo-convex pattern to cure the ultraviolet-curable resin corresponding to a portion having no pattern. (E) a step of peeling off the release base material and attaching a part of the uncured resin of the ultraviolet-curable resin layer to the release base material or the pattern to remove the resin together with the release base material; It is the gist. [Function] According to the present invention, in a portion having a pattern formed using an ink containing a substance that absorbs ultraviolet light, the ionizing radiation-curable resin on the transfer-receiving substrate is not cured and the release substrate is not cured. The ionizing radiation-curable resin is hardened and left in portions where there is no pattern, and as a result, a sharp uneven pattern is formed on the uneven pattern forming substrate. Embodiment An embodiment of the present invention will be described below with reference to the drawings. FIG. 1 shows an embodiment of the transfer sheet 1 of the present invention used in the method of the present invention. The transfer sheet 1 has a pattern 3 provided on the surface thereof. The release substrate 2 is made of a sheet or a film having an ionizing radiation transmitting property, such as a sheet or a film of polyester, polyamide (eg, nylon), polypropylene, or a fluororesin. Are preferred. When the ionizing radiation is an electron beam, there is no particular limitation because the electron beam has high transparency, and the above-mentioned sheet or film can be used in principle, and paper and the like can be used. At least the surface of the release substrate 2 on the side in contact with the ionizing radiation-curable resin layer needs to be releasable, and if the material itself does not have releasability, it is necessary to apply a releasable resin or composition. And used as a surface peeling property. Release substrate 2
Has a thickness of preferably 5 to 200 μm, particularly preferably 25 to 100 μm. The pattern 3 is used to shield ionizing radiation when irradiating ionizing radiation from the upper surface of the release substrate, and the pattern 3 is provided at the lower surface of the release substrate 2 as shown in FIG. Although not particularly shown, it may be on the upper surface side of the release substrate 2, and if another layer is provided on the release substrate 2 as needed, it may be provided on a layer provided on the release substrate 2. Good. As a material for forming the pattern 3, a quencher (for example, a benzophenol-based, salicylate-based, benzotriazole-based, acrylonitrile-based, or other ultraviolet absorber, a light-absorbing pigment, carbon black, or an inorganic substance) may be used. And a metal complex salt-based or hindered amine-based ink. It is preferable that the ink forming the pattern 3 contains 1 to 20% by weight of the above substance that absorbs ultraviolet rays. If the content of the substance is less than 1% by weight, absorption of ionizing radiation cannot be performed satisfactorily, and the resulting sharp pattern may not have the intended sharpness. There is a possibility that the adhesive force to the adhesive may be weakened. The pattern 3 can be formed by a normal printing method using these inks. As shown in FIG. 2, the transfer sheet 1 is overlaid and adhered to the side of the ionizing radiation-curable resin layer 4 of the base material 5 for forming a concavo-convex pattern provided by applying the ionizing radiation-curable resin layer 4 separately prepared as shown in FIG. (FIG. 3), it is preferable to use the release substrate 2 stretched over a frame, because the release substrate 2 can be used repeatedly. The ionizing radiation-curable resin layer 4 is formed by being applied to the opposite surface between the release substrate 2 and the substrate 5 for forming an uneven pattern. The coating may be provided on the side of the material 2 or may be provided on both the substrate 5 for forming an uneven pattern and the release substrate 2. As the uneven pattern forming base material 5, any material may be used, for example, a metal plate or molded product such as stainless steel, steel, aluminum, or copper, glass, marble, ceramic, gypsum board, asbestos cement plate, Calcium silicate plate, inorganic plate or molded product such as GRC (glass fiber reinforced cement), organic polymer plate or molded product such as polyester, melamine, polyvinyl chloride, diallyl phthalate, or sheet, film, wood or plywood of these , A wooden board or a molded product such as a particle board, and the like. The base material 5 for forming a concavo-convex pattern may be subjected to a base treatment such as a filling treatment or a primer treatment, a treatment for improving adhesiveness, or the like. A colored pattern layer 6 can be provided on the uneven pattern forming substrate 5 as necessary. The pattern of the colored pattern 6 may be provided in a pattern synchronized with the pattern of the pattern 3,
It is not always necessary to form them so that they are synchronized. The colored pattern layer 6 can be formed by a known printing method using ordinary ink, paint, or the like. Alternatively, the colored pattern layer 6 may be formed by transferring the colored pattern itself or attaching a sheet provided with the colored pattern. it can. The colored pattern layer 6 is usually provided on the side (upper surface side) of the substrate 5 for forming an uneven pattern, on which the ionizing radiation-curable resin layer 4 is provided.
When the base material 5 for forming an uneven pattern is made of a transparent material,
It can also be provided on the lower surface side of the substrate 5. Coloring pattern layer 6
May be provided as needed, and is not necessarily provided. A solid colored layer may be provided instead of the colored pattern layer 6, and the ionizing radiation-curable resin layer 4 itself may be colored. When coloring the ionizing radiation-curable resin layer 4, it is preferable to use a coloring agent that does not hinder the transmission of ionizing radiation. When a solid colored layer is provided or the ionizing radiation-curable resin layer 4 itself is colored, the formation of a concavo-convex pattern facilitates the expression of a shade pattern of a color synchronized with the pattern. The ionizing radiation-curable resin layer 4 is mainly composed of a polymer, an oligomer, a monomer, or the like having a radical polymerizable double bond in the structure, and includes a photopolymerization initiator, a sensitizer, and other non-reactive Various grades containing polymers, organic solvents, waxes and other additives are readily available from the market and can be used in the method of the present invention. The ionizing radiation-curable resin layer 4 can be formed by a known method such as gravure coating, roll coating, flow coating or spray coating. The thickness of the ionizing radiation curable resin layer 4 is preferably 3 μm to 1 mm, particularly preferably 30 μm to 200 μm. After the peeling substrate 2 and the uneven pattern forming substrate 5 are overlapped with each other via the ionizing radiation-curable resin layer 4 to bring them into close contact with each other, ionizing radiation 7 is irradiated from the peeling substrate 2 side. Typical examples of the ionizing radiation 7 are ultraviolet rays and electron beams, but other types can be used. Due to the irradiation of the ionizing radiation 7, the ionizing radiation-curable resin layer 4 is cured in a portion where the pattern 3 is not provided, and the ionizing radiation-curable resin layer 4 is left uncured in a portion where the pattern 3 is present. When the release substrate 2 is peeled off after irradiation with the ionizing radiation 7, the uncured ionizing radiation-curable resin adheres to the release substrate 2 at the uncured portion of the ionizing radiation-curable resin layer 4 and adheres together with the peeling of the substrate. As a result, a concave portion 8 in which a small amount of uncured ionizing radiation-curable resin remains and a convex portion 9 made of cured ionizing radiation-curable resin are formed. After the release substrate 2 is peeled off, the uncured ionizing radiation-curable resin remaining in the recesses 8 may be cured by further irradiating ionizing radiation, but as shown in FIG. A concave portion from which the ionizing radiation-curable resin is removed may be formed. There are various physical removal methods and chemical removal methods for removing the uncured ionizing radiation-curable resin remaining in the concave portion 8, but the fact that the remaining uncured portion has high solubility in an organic solvent is used. It is preferable to employ a chemical removal method for dissolving and removing the uncured ionizing radiation-curable resin using an appropriate solvent. Ethyl acetate, acetic acid-
Esters such as n-butyl, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone,
There are alcohols such as ethanol, isopropanol and n-butanol, etc., which are selected and used according to the type of ionizing radiation-curable resin used. Dissolution removal with these solvents can be performed only by pouring or immersion,
As a more preferable method, there is a method in which a solvent is applied on the formed uneven surface and buffing is performed using a brush or a cotton buffing roller. In this way, a concavo-convex pattern is formed by the method of the present invention, and a protective layer may be further provided for protecting the surface of the concavo-convex pattern. The protective layer can be formed of the same ionizing radiation curable resin as described above, or may be formed of a thermosetting resin. In the above embodiment, the case where the ionizing radiation is irradiated from the release substrate side by providing the ionizing radiation shielding pattern on the release substrate side, but the method of the present invention is not limited to this, and as shown in FIG. The pattern 3 can also be provided on the side of the substrate 5 for forming an uneven pattern. In such a case, the release substrate 2 is brought into close contact with the surface of the ionizing radiation-curable resin layer 4 as shown in FIG.
When the release substrate 2 is peeled off by irradiation with the ionizing radiation 7, the ionizing radiation-curable resin layer 4 may be peeled off from the pattern 3. Such a method has an advantage that an uncured ionizing radiation-curable resin is less likely to remain and an excellent uneven shape can be obtained without performing post-treatment. When the substrate for forming a concavo-convex pattern has ionizing radiation transparency, ionizing radiation can be applied from the substrate side. Hereinafter, the present invention will be described in more detail with reference to specific examples. Example 1 The surface of a calcium silicate plate was treated with an alkali stopper sealer, and the treated surface was cured with an ultraviolet curable paint [Nippon Paint Co., Ltd.]
Was coated by flow coating to a thickness of 100 μm. Separately, a polyester film (manufactured by Toray Industries, Inc.) was used as a base sheet, and an abstract pattern was printed using a 60 μm deep gravure plate using a UV shielding ink containing a benzophenone-based UV absorber to form a transfer sheet. did. The transfer sheet obtained above was overlaid so that the printing surface was in contact with the flow coat surface, and 20 m / cm in an irradiation device provided with five ozoneless ultraviolet lamps having an output of 80 W / cm from the base sheet side of the transfer sheet. Irradiation was performed while passing at a speed of 1 minute. After the irradiation, the base sheet of the transfer sheet was peeled off. By peeling, most of the UV curable paint adheres to the substrate sheet and is removed in the portion corresponding to the pattern portion printed with the UV shielding ink on the transfer sheet, and the cured UV curable resin remains in other portions. An uneven pattern is formed,
A decorative calcium silicate plate having an excellent appearance corresponding to sharp irregularities was obtained. Thereafter, an ultraviolet curable paint was further applied to the uneven pattern surface by spray coating so as to have a thickness of 5 μm, and was cured by irradiation using the same ultraviolet irradiation device as described above. Example 2 The surface of a calcium silicate plate was treated with an alkali stopper sealer, and silk-printed with a silk ink containing 5% by weight of an ultraviolet absorber. Flow coating was performed. Separately, a polyester film (manufactured by Toray Industries, Inc.) is used as a base sheet, and a colored pearl ink (manufactured by Morohoshi Ink Co., Ltd.) is used, and the solid printed by gravure printing is transferred so that the thickness after drying becomes 3 μm. Sheet. The transfer sheet obtained above was overlaid so that the printing surface was in contact with the flow coat surface, and 20 m / cm in an irradiation device provided with five ozoneless ultraviolet lamps having an output of 80 W / cm from the base sheet side of the transfer sheet. Irradiation was performed while passing at a speed of 1 minute. After the irradiation, the base sheet of the transfer sheet was peeled off. By peeling, most of the UV-curable paint adheres to the base sheet and is removed at the part corresponding to the pattern part printed with silk ink on the base material, and the other part is accompanied by a layer printed with colored pearl ink The cured ultraviolet-curable resin remained to form a colored uneven pattern, and a decorative calcium silicate plate having an excellent appearance colored according to the unevenness was obtained. Thereafter, an ultraviolet curable paint was further applied to the uneven pattern surface by spray coating so as to have a thickness of 5 μm, and was cured by irradiation using the same ultraviolet irradiation device as described above. [Effects of the Invention] As described above, according to the method of the present invention, a beautiful three-dimensional pattern can be easily formed on various materials on which an uneven surface is to be formed. Further, the transfer sheet of the present invention can be used extremely conveniently in carrying out such a method of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The drawings show an embodiment of the method of the present invention, and FIGS.
Fig. 5 is a longitudinal sectional view showing each step of the method of the present invention, Fig. 5 is a longitudinal sectional view showing an example of a sheet having an uneven pattern obtained by the method of the present invention, and Figs. It is a longitudinal cross-sectional view which shows each process of Example of this. DESCRIPTION OF SYMBOLS 1 ... Transfer sheet 2 ... Peeling base material 3 ... Pattern pattern 4 ... Ionizing radiation curable resin layer 5 ... Substrate 7 for forming a concavo-convex pattern ...... Ionizing radiation 8 ... Concave part 9 ... Convex part

   ────────────────────────────────────────────────── ─── Continuation of front page       (56) References JP-A-57-29420 (JP, A)                 JP-A-58-148766 (JP, A)                 JP-A-61-37499 (JP, A)                 Tokiko Sho 51-24287 (JP, B2)

Claims (1)

(57) [Claims] A method for forming a concavo-convex pattern, which comprises sequentially performing the following steps (a) to (f). (A) An ionizing radiation-transmissive release substrate and a substrate for forming a concavo-convex pattern having releasability from an ionizing radiation-curable resin having a cured surface are prepared, and either the front or back surface of the ionizing radiation-transmissive release substrate Alternatively, a step of providing an ionizing radiation shielding pattern using an ink containing a substance that absorbs ionizing radiation on the surface of the substrate for forming an uneven pattern. (B) The surface on which the peeling substrate and the substrate for forming a concavo-convex pattern facing each other are provided with the above-mentioned pattern pattern. Coating the entire surface with an ionizing radiation-curable resin layer. (C) a step of laminating the substrate for forming a concavo-convex pattern and the release substrate via an ionizing radiation-curable resin layer. (D) a step of irradiating ionizing radiation from the side of the peeling substrate or the side of the substrate for forming a concavo-convex pattern to cure the ionizing radiation-curable resin layer corresponding to a portion having no pattern. (E) a step of peeling off the release base material and attaching a part of the uncured resin of the ionizing radiation-curable resin layer to the release base material or the pattern to remove the resin together with the release base material; (F) A step of applying a solvent onto the uneven surface of the transfer-receiving substrate, and then performing buff polishing using a brush or a cotton buffing roller to remove the remaining uncured ionizing radiation-curable resin layer. . 2. A method for forming a concavo-convex pattern, which comprises sequentially performing the following steps (a) to (e). (A) An ultraviolet-transmissive release substrate and a substrate for forming a concavo-convex pattern having a releasability from an ultraviolet-curable resin having a cured surface are prepared, and either the front or back surface or the concavo-convex pattern of the ultraviolet-transmissive release substrate is prepared. The surface of the forming substrate contains a substance that absorbs ultraviolet light selected from benzophenol-based, salicylate-based, benzotriazole-based or acrylonitrile-based ultraviolet absorbers, and metal complex salt-based or hindered amine-based quencher. A step of providing a pattern using ink. (B) The surface on which the peeling substrate and the substrate for forming a concavo-convex pattern facing each other are provided with the above-mentioned pattern pattern. Coating the entire surface with an ultraviolet curable resin layer. (C) a step of laminating the substrate for forming a concavo-convex pattern and the release substrate via an ultraviolet-curable resin layer. (D) a step of irradiating ultraviolet rays from the side of the peeling substrate or the side of the substrate for forming a concavo-convex pattern to cure the ultraviolet-curable resin layer corresponding to a portion having no pattern. (E) a step of peeling off the release base material and attaching a part of the uncured resin of the ultraviolet-curable resin layer to the release base material or the pattern to remove the resin together with the release base material; 3. 3. The method according to claim 2, wherein the uncured ultraviolet-curable resin remaining on the transfer-receiving substrate is cured by further irradiating ionizing radiation after peeling the release-backing substrate. 4. 4. The method for forming an uneven pattern according to claim 2, wherein a surface protective layer is formed on the uneven surface as required. 5. Either a benzophenol-based, salicylate-based, benzotriazole-based or acrylonitrile-based ultraviolet absorber, a metal complex salt-based or a hindered amine-based quencher on one of the front and back surfaces of the ultraviolet-transmissive release substrate having a peelable surface. A transfer sheet for use in a method for forming a concavo-convex pattern in the following step, characterized by providing an untransferred pattern formed using an ink containing a substance that absorbs ultraviolet light selected from the group consisting of: A method for forming a concavo-convex pattern, which comprises sequentially performing the following steps (a) to (e). (A) An ultraviolet-transmissive release substrate and a substrate for forming a concavo-convex pattern having a releasability from an ultraviolet-curable resin having a cured surface are prepared, and either the front or back surface or the concavo-convex pattern of the ultraviolet-transmissive release substrate is prepared. The surface of the forming substrate contains a substance that absorbs ultraviolet light selected from benzophenol-based, salicylate-based, benzotriazole-based or acrylonitrile-based ultraviolet absorbers, and metal complex salt-based or hindered amine-based quencher. A step of providing a pattern using ink. (B) The surface on which the peeling substrate and the substrate for forming a concavo-convex pattern facing each other are provided with the above-mentioned pattern pattern. Coating the entire surface with an ultraviolet curable resin layer. (C) a step of laminating the substrate for forming a concavo-convex pattern and the release substrate via an ultraviolet-curable resin layer. (D) a step of irradiating ultraviolet rays from the side of the peeling substrate or the side of the substrate for forming a concavo-convex pattern to cure the ultraviolet-curable resin layer corresponding to a portion having no pattern. (E) a step of peeling off the release base material and attaching a part of the uncured resin of the ultraviolet-curable resin layer to the release base material or the pattern to remove the resin together with the release base material;