JP2014213247A - Decoration structure and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a decoration structure capable of improving adhesion with a base material of a projection part, capable of forming a pattern having a complicated and irregular three-dimensional feeling and capable of freely adjusting glossiness.SOLUTION: The manufacturing method of a decoration structure 1 includes (a) a process of forming a plurality of projection parts 3 having a height of 40 to 200 μm on at least one surface of a base material 2, that is, a process of forming the projection part 3 by curing activation energy ray curable projection part ink by activation energy ray irradiation and (b) a process of forming an overcoat layer 4 so as to cover the projection part 3, that is, a process of forming the overcoat layer 4 by coating and curing a coating material for the overcoat layer by an inkjet system ot a spray system and reducing a film thickness of the overcoat layer 4 more than a height of the projection part 3.

Description

  The present invention relates to a decorative structure including a base material, a convex portion, and an overcoat layer, and a method for producing the decorative structure, and in particular, the adhesion of the convex portion to the base material can be improved, and is complicated and irregular. The present invention relates to a method for manufacturing a decorative structure that can form a pattern with a three-dimensional effect and can freely adjust its gloss.

  At present, synthetic resin molded products and metal substrates that are lightweight and have excellent impact resistance are widely used for various members such as mobile phones, home appliances, OA equipment, and automobiles. In addition, these synthetic resin molded articles and metal base materials are required to be provided with weather resistance, wear resistance, and appropriate cosmetics depending on the application and the environment in which they are used.

  In recent years, these synthetic resin molded products and metal bases have a tendency to demand high-quality decoration and individual decoration, and have a design in which texture and color tone are emphasized by applying a three-dimensional pattern and a colored pattern. It is demanded.

  As a method of applying a high-grade design to the surface of a metal substrate, there are an etching process using chemicals and a sand blasting process, but the chemical process is troublesome in the etching process, and the load on the environment is great. Moreover, since sandblasting sprays sand and glass beads, these post-treatments are troublesome.

  On the other hand, as a method of giving a high-grade design to the surface of a synthetic resin molded product made of PP, ABS resin, etc., for example, a method of attaching a sheet or film that gives a high-class feeling to the surface, or a molded product of interior parts And a method of applying hydraulic pressure to a molded product of an interior part. These methods can also be applied to a metal substrate. Moreover, after decorating the surface of an interior part, a protective coating may be given or the outermost layer may be given a glossy finish.

  Although direct painting and transfer as described above can express a wide variety of patterns, there is a problem that it tends to be flat. As one method for solving such a problem, there is a method of combining a step of providing fine irregularities with a mold or the like and a step of transferring and applying a planar colored pattern. However, in this method, it is extremely difficult to mold the unevenness and the planar coloring pattern, and the expression of the unevenness is also very limited. As a result, a three-dimensional pattern corresponding to the colored pattern to be applied cannot be formed. The problem is that the design expression is greatly limited.

  As methods for solving the above problems, methods described in Japanese Patent Application Laid-Open No. 2008-264729 (Patent Document 1) and International Publication No. 2010/013667 (Patent Document 2) have been proposed. Patent Document 1 discloses a method of forming a hard convex pattern by forming a functional coating layer on a substrate and then ejecting an ultraviolet curable ink with an ink jet apparatus. Patent Document 2 discloses a decorative surface structure composed of a base coating portion and one or more convex bodies made of a cured product of ultraviolet curable ink on the surface of a synthetic resin molded product. Yes.

JP 2008-264729 A International Publication No. 2010/013667

  However, in the method described in Patent Document 1, since the hard convex pattern is exposed, the adhesion between the hard convex pattern layer and the functional coating layer decreases due to long-term exposure, and the hard convex pattern layer is detached. There are concerns.

  On the other hand, in paragraph 0046 of Patent Document 2, although there is a description that a top coat portion can be formed on the base coat portion and the convex body, there is no mention of a method for coating the top coat portion. Moreover, it may be difficult to obtain a desired glossiness by forming the film on the top coat portion.

  Therefore, the object of the present invention is to solve the above-mentioned problems of the prior art, to improve the adhesion of the convex part to the base material, to form a complex and irregular three-dimensional pattern, and to freely gloss It is providing the manufacturing method of the decorating structure which can be adjusted. Moreover, the other objective of this invention is to provide the decorating structure obtained by the said manufacturing method.

  As a result of intensive studies to achieve the above object, the present inventor can improve the adhesion of the convex portion to the base material by providing an overcoat layer that covers the convex portion. By limiting the film thickness of the overcoat layer to a specific range, it is possible to form a pattern with a complicated and irregular three-dimensional effect, and further, by forming the overcoat layer using a spray method or an inkjet method, The inventors have found that the gloss can be freely adjusted, and have completed the present invention.

That is, the method for manufacturing a decorative structure according to the present invention includes a base material, a plurality of convex portions arranged on at least one surface of the base material, and an overcoat layer covering at least the convex portions. A method for manufacturing a body,
(A) A step of forming a plurality of convex portions on at least one surface of the substrate, wherein the convex portions are formed by curing an active energy ray-curable convex portion ink by active energy ray irradiation. And the height of the convex part is 40 to 200 μm,
(B) a step of forming an overcoat layer so as to cover the convex portion, wherein the overcoat layer is formed by coating and curing an overcoat layer coating material by an ink jet method or a spray method, The overcoat layer and the convex portion have the following formula (1):
H1> H2 (1)
And H1 is a height (μm) of the convex portion, and H2 is a film thickness (μm) of the overcoat layer.

  In another preferred embodiment of the method for producing a decorative structure according to the present invention, the overcoat layer directly covers at least a part of the substrate surface.

  In another preferred embodiment of the method for producing a decorative structure according to the present invention, the occupied area of the convex portion in the decorative region of the base material surface on which the convex portion is arranged is 60% of the area of the decorative region. And within 90%.

  In another preferred embodiment of the method for producing a decorative structure according to the present invention, the overcoat layer coating material is an active energy ray-curable ink, and the active energy used for forming the convex portions and the overcoat layer. The line curable inks are the same or different.

  The decorative structure of the present invention is obtained by the above production method.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the decoration structure which can improve the adhesiveness with the base material of a convex part, can form a pattern with a complicated and irregular three-dimensional effect, and can adjust gloss freely is provided. can do. Moreover, a decoration structure can be provided by this manufacturing method.

It is sectional drawing of an example of the decorating structure of this invention. It is the schematic of the process (a) in an example of the manufacturing method of the decorating structure of this invention. It is a figure for demonstrating the decoration area | region in an example of the decorating structure of this invention. It is a figure which shows the relationship between the glossiness of the decorating structure of Examples 2-5, and the frequency | count of scanning of overcoat layer discharge conditions.

  Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 is a cross-sectional view of an example of the decorative structure of the present invention. The decorative structure 1 in the illustrated example includes a base material 2, a plurality of convex portions 3 disposed on the surface of the base material, and an overcoat layer 4 that covers the convex portions 3. In addition, in the decorative structure 1 of the example of illustration, although the convex part 3 is arrange | positioned only on one surface of the base material 2, as for the decorative structure of this invention, several convex part is at least 1 of a base material. The protrusions 3 may be disposed on a plurality of surfaces of the substrate 2 as long as they are disposed on one surface. Moreover, although the overcoat layer 4 has covered both the base material 2 and the convex part 3 in the decoration structure 1 of the example of illustration, the overcoat layer covers at least a convex part in the decoration structure of this invention. Therefore, the overcoat layer 4 may not cover the surface of the substrate 2.

  The decorative structure is a structure that can be decorated on a substrate with a plurality of convex portions, and is an exterior member for mobile phones, home appliances and OA equipment, an interior member for automobiles, tiles and bricks. It can be used for various members such as interior / exterior members of industrial machinery such as ceramic building materials, chemical machinery or construction machinery, interior / exterior members of elevators, and sashes.

  The decorative structure of the present invention requires that the height of the convex portion is 40 to 200 μm, and is preferably 50 to 150 μm. Since the height of the convex portion is in the range of 40 to 200 μm, it is possible to form a complicated and irregular pattern with a three-dimensional effect, for example, to form a leather-like pattern or a hairline on the substrate. Is possible.

  In this invention, the height of a convex part is an average value of the maximum height from a base material to a convex part vertex, and is calculated from the height of ten convex parts selected at random. Moreover, the maximum height of a convex part can be measured using a laser microscope.

In the decorative structure of the present invention, the overcoat layer and the convex portion have the following formula (1):
H1> H2 (1)
It is necessary to satisfy the relationship [where H1 is the height (μm) of the convex portion, and H2 is the film thickness (μm) of the overcoat layer], and further, the following formula (2):
0.7 × H1> H2 (2)
It is preferable that the relationship of [wherein H1 and H2 are synonymous with the definition of the formula (1)] is satisfied. When the film thickness of the overcoat layer covering the convex part is smaller than the height of the convex part, the stereoscopic effect on the surface of the decorative structure can be sufficiently maintained even when the overcoat layer is laminated.

  In the present invention, the film thickness of the overcoat layer is an average of film thicknesses at 10 locations randomly selected from the overcoat layer covering the convex portions. As a method for measuring the film thickness of the overcoat layer, for example, a cross-section of the decorative structure is cut out and the cut surface is polished so that the configuration of the decorative structure can be confirmed with a laser microscope. The method of measuring using a microscope is mentioned.

  In addition, it is preferable that the film thickness of the said overcoat layer is 1-150 micrometers.

  In the decorative structure of the present invention, the overcoat layer needs to cover at least the convex portion in order to improve adhesion between the base material and the convex portion and to prevent the convex portion from being separated. It is preferable that at least a part of the overcoat layer is directly covered, and the overcoat layer is preferably a continuous layer. When the overcoat layer covering the convex portion also covers a part of the surface of the base material, the adhesion between the base material and the convex portion can be further improved, and separation of the convex portion can be largely prevented. In addition, if the overcoat layer is a continuous layer, this effect can be more reliably exhibited.

  In the decorative structure of the present invention, the area occupied by the convex portions in the decorative region of the base material surface on which the convex portions are arranged exceeds 60% of the area of the decorative region and is within 90%. preferable. Here, a decoration area | region is an area | region where the decoration was given on the base material, and is comprised from the base-material surface 5 and the convex part 6, as FIG. 3 shows. FIG. 3 is a diagram for explaining a decoration region in an example of the decorative structure of the present invention. In the figure, reference numeral 2 denotes a base material, reference numeral 5 denotes a base material surface, and reference numeral 6 denotes a convex shape. The overcoat layer is not shown in the figure. If the area occupied by the protrusions is within the above specified range, it is possible to easily form a complicated and irregular pattern such as a leather pattern or a hairline. In the present invention, the occupying area of the convex portion is obtained by photographing the surface of the base material on which the convex portion is arranged with a digital camera or the like from above, analyzing the obtained image data with image analysis software, and decorating the base material. It can be obtained by calculating the ratio of the area where the convex portions are arranged on the substrate in the region.

  As described above, the decorative structure of the present invention includes a base material, a plurality of convex portions arranged on at least one surface of the base material, and an overcoat layer covering at least the convex portions. It can be manufactured by the method described in detail below.

  In the method for producing a decorative structure according to the present invention, (a) a step of forming a plurality of convex portions on at least one surface of a substrate, and (b) an overcoat layer is formed so as to cover the convex portions. And a process.

  In the above step (a), the base material is not particularly limited as long as it is a base material that requires decoration, but for example, a base material used for mobile phones, home appliances, OA equipment, automobiles, and the like. Is mentioned. The material of the substrate is not particularly limited, and examples thereof include paper, fabric, plastic, metal, rubber, glass, etc. Among these, plastic, metal, and glass are preferable as materials that are difficult for ink to penetrate, More preferred is plastic. Moreover, a base material is used with various forms according to a use, For example, the various molded products manufactured by a shaping | molding process etc. other than a film, a sheet | seat, a board are also contained.

  Examples of the plastic include acrylonitrile-butadiene-styrene (ABS), polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), polycarbonate (PC), polysulfone (PSF), and polyphenylene. In addition to plastic materials such as oxide (PPO) and polyphenylene sulfide (PPS), heat of polystyrene, polyolefin, polyvinyl chloride, polyurethane, polyester, polyamide, chlorinated polyethylene, 1,2-polybutadiene A plastic elastomer is also included, and a base material can be prepared by molding these by a known molding method such as an injection molding method, an extrusion molding method, or a blow molding method.

  About a plastic base material, it can use as it is and a primer may be apply | coated before formation of a convex part. By applying the primer in advance, the adhesion between the convex portion and the substrate can be further improved.

  Examples of the metal include zinc, iron, stainless steel, steel, and those whose surfaces have been subjected to galvanization treatment or aluminum plating treatment. Specific examples of the metal substrate include hot rolled steel plate, cold rolled steel plate, and the like. Examples of the metal plate include steel plates, galvanized steel plates, and aluminum plated steel plates.

  The metal substrate can be used as it is, but is preferably degreased in advance. Moreover, a primer may be apply | coated before formation of a convex part from an adhesive viewpoint.

  In the step (a), the convex portion has a height of 40 to 200 μm from the viewpoint of forming a complicated and irregular three-dimensional pattern as described above, and the convex portion is active. It is formed by curing energy ray curable convex ink by irradiation with active energy rays. Here, the active energy ray-curable ink means an ink that can be cured by irradiation with active energy rays such as visible light, ultraviolet rays, and electron beams, but it can be cured in a shorter time than other types of ink. Therefore, it is possible to easily form a complicated and irregular pattern with a three-dimensional effect.

  The active energy ray curable convex ink includes at least a photopolymerizable compound and a photopolymerization initiator, and, if necessary, a sensitizer or a dispersant for accelerating the initiation reaction of the photopolymerization initiator. Additives such as surface conditioners, heat stabilizers, antioxidants, preservatives, pH adjusters, antifoaming agents, penetrants, ultraviolet absorbers, and light stabilizers can be blended.

  Examples of the photopolymerizable compound include a radical photopolymerizable compound and a cationic photopolymerizable compound. Examples of the photoradical polymerizable compound include a radical polymerizable monofunctional monomer, a radical polymerizable bifunctional monomer, a radical polymerizable polyfunctional monomer having 3 or more functional groups, and a (meth) acrylate oligomer. The photopolymerizable compound may be selected in consideration of the viscosity of the active energy ray-curable ink, and may be used alone or in combination of two or more. Moreover, in this invention, a functional group refers to the functional group which shows photopolymerization property.

  Specific examples of the monofunctional monomer include stearyl acrylate, acryloylmorpholine, tridecyl acrylate, lauryl acrylate, N, N-dimethylacrylamide, decyl acrylate, isodecyl acrylate, isobornyl acrylate, dicyclopentanyl acrylate, dicyclo Pentenyl acrylate, isooctyl acrylate, octyl acrylate, dicyclopentenyloxyethyl acrylate, cyclohexyl acrylate, N-vinylcaprolactam, isoamyl acrylate, 2-ethylhexyl-diglycol acrylate, EO-modified 2-ethylhexyl acrylate, neopentyl glycol acrylic acid benzoic acid Ester, N-vinyl-2-pyrrolidone, N-vinylimidazole, tetrahydro Rufuryl acrylate, methoxydipropylene glycol acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate, cyclic trimethylolpropane formal acrylate, ethoxy-diethylene glycol acrylate, phenoxyethyl acrylate, EO Examples thereof include modified phenol acrylate, methylphenoxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, EO-modified nonylphenol acrylate, and PO-modified nonylphenol acrylate. Of these, isobornyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate and phenoxyethyl acrylate are preferred. In addition, these monofunctional monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  Specific examples of the bifunctional monomer include 1,10-decanediol diacrylate, 2-methyl-1,8-octanediol diacrylate, 2-butyl-2-ethyl-1,3-propanediol diacrylate, 1 , 9-nonanediol diacrylate, 1,8-octanediol diacrylate, 1,7-heptanediol diacrylate, polytetramethylene glycol diacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6- Hexanediol diacrylate, neopentyl glycol diacrylate, neopentyl glycol diacrylate hydroxypivalate, tripropylene glycol diacrylate, 1,4-butanediol diacrylate, dipropylene glycol diacrylate, 2- (2 Vinyloxy ethoxy) ethyl acrylate, EO-modified bisphenol A di acrylate, PO-modified bisphenol A diacrylate, EO-modified hydrogenated bisphenol A diacrylate, and EO-modified bisphenol F diacrylate, and the like. Among these, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and 2- (2-vinyloxyethoxy) ethyl acrylate are preferable. In addition, these bifunctional monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  Specific examples of the polyfunctional monomer include trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, ethoxylated glycerin triacrylate, tetramethylol methane triacrylate, penta Examples include erythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, EO-modified diglycerin tetraacrylate, ditrimethylolpropane tetraacrylate-modified acrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate. In addition, these polyfunctional monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  Specific examples of the acrylate oligomer include amino resin acrylate, polyurethane acrylate, polyepoxy acrylate, silicone acrylate, polyester acrylate, and polybutadiene acrylate. Among these, polyurethane acrylate is preferable from the viewpoint of weather resistance and adhesion.

  In the active energy ray curable convex ink, the content of the photopolymerizable compound is preferably 40 to 98% by mass, and more preferably 50 to 90% by mass.

  The said photoinitiator has the effect | action which starts superposition | polymerization of the photopolymerizable compound mentioned above by irradiating an active energy ray. In addition, the content of the photopolymerization initiator is preferably 1 to 25% by mass in the ink, and more preferably 1 to 10% by mass. If the content of the photopolymerization initiator is within the above specified range, the curability of the ink can be improved. Further, if the content of the photopolymerization initiator is less than 1% by mass, the printed matter may be poorly cured, and if it exceeds 25% by mass, precipitates are generated at low temperatures and ink ejection becomes unstable. There is. Furthermore, in order to accelerate the initiation reaction of the photopolymerization initiator, an auxiliary such as a photosensitizer can be used in combination.

  Examples of the photopolymerization initiator include benzophenone compounds, acetophenone compounds, thioxanthone compounds, phosphine oxide compounds, etc. From the viewpoint of curability, the wavelength of the active energy ray to be irradiated and the photopolymerization initiator It is preferable that the absorption wavelengths overlap as much as possible.

  Specific examples of the photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 2-hydroxy-2-methyl-1-phenylpropane. -1-one, benzophenone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-Hydroxy-2-methylpropionyl) -benzyl] -phenyl} -2-methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-di Tilamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 1,2-octanedione, 1- [4- (Phenylthio) -2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone and the like. Among these, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide is preferable from the viewpoint of the curability of the ink. In addition, these photoinitiators may be used individually by 1 type, and may be used in combination of 2 or more type.

  The active energy ray-curable convex portion ink may contain a color material in order to express a colorful design. When a color material is used, a colored three-dimensional pattern can be formed.

  As the color material, pigments, dyes and the like can be used. The pigment and the dye are not particularly limited, and known ones can be used, but it is preferable to use a pigment having excellent weather resistance and light resistance.

  Examples of the pigment include azo pigments (azo lake pigments, insoluble azo pigments, monoazo pigments, disazo pigments, condensed azo pigments, chelate azo pigments, azomethine pigments), polycyclic organic pigments (phthalocyanine pigments, anthraquinone pigments, perylene pigments, quinacridone pigments, Isoindoline pigment, benzimidazolone pigment, thioindigo pigment, dioxazine pigment, quinophthalone pigment, pyrrolopyrrole pigment), other organic pigments (nitro pigment, nitroso pigment, aniline black, fluorescent pigment, etc.), inorganic pigment (inorganic oxide pigment) , Hydroxide pigments, sulfide pigments, ferrocyanide pigments, chromate pigments, carbonate pigments, silicate pigments, phosphate pigments, carbon pigments, metal powders), metals Although complex pigments etc. are mentioned, it is not limited to these.

  Examples of the dye include oil-soluble dyes such as azos, anthraquinones, indigoids, phthalocyanines, carboniums, quinoneimines, methines, xanthenes, nitros, nitrosos, disperse dyes, acid dyes, reactive dyes, Cationic dyes, direct dyes and the like can be mentioned.

  In the active energy ray curable convex ink, the content of the coloring material is more than 0% by mass and not more than 20% by mass in consideration of ink dischargeability and storage stability. Is preferable, and it is still more preferable that it is 0.01-10 mass%.

  Further, when the active energy ray-curable convex portion ink includes a color material, it preferably includes a dispersant. Examples of the dispersant include an anionic compound, a cationic compound, a nonionic compound, an amphoteric compound, and a polymer compound, and these can be used alone or in combination. Among them, a polymer type having high dispersibility is preferable, and those having an acidic adsorbing group or a basic adsorbing group at the terminal group are more preferable. The content of the dispersing agent is appropriately determined depending on the type of the color material to be dispersed. However, in consideration of the dispersion effect and the ink discharge property, the content exceeds 0% by mass and 150% by mass. % Or less, and more preferably 10 to 60% by mass.

  The viscosity of the active energy ray curable convex portion ink may be adjusted depending on the coating method to be used. For example, in the case of an ink jet method, the supply system to the printer head portion (ink flow such as a tube and piping) In order to maintain fluidity in the road), the viscosity at 25 ° C. is preferably 100 mPa · s or less, more preferably 10 to 100 mPa · s or less. The viscosity at 45 ° C. is preferably 1 to 15 mPa · s. The viscosity can be measured using a generally known viscometer (for example, Ostwald viscometer, B-type viscometer, etc.).

  The active energy ray-curing convex ink may be adjusted in surface tension depending on the coating method and substrate used, but generally has a surface tension at 20 ° C. of 20 to 45 mN / m. Is preferable, and it is still more preferable that it is 25-40 mN / m. The surface tension at 20 ° C. is preferably 20 mN / m or more for the reason of suppressing wettability and facilitating the supply of ink to the coating machine. In addition, if the wettability is excessively lowered, the ink is repelled. To prevent this, the surface tension at 20 ° C. is preferably 45 mN / m or less. In the present invention, the surface tension is measured by a plate method.

  In the step (a), since a plurality of convex portions are formed on at least one surface of the substrate, the active energy ray-curable convex portion ink is preferably applied by an ink jet method. Here, the ink jet method is not particularly limited, and is a continuous discharge type such as a charge control method, an electromechanical conversion method (for example, a piezo method), an electrothermal conversion method (for example, a thermal ink jet method), An on-demand type such as an electrostatic suction method can be adopted.

  In addition, when the above-mentioned active energy ray-curable convex part ink is applied by an ink jet method, the region where the convex part is formed can be arbitrarily set by using image processing software, so that a variety of three-dimensional A pattern can be formed. In addition, the setting of the ink jet printer can freely control the coating conditions such as the amount of droplets and the amount of ink applied, the curing conditions, and the ink application location, so the shape and height of the protrusions can be determined from the size of the protrusions. In addition, the occupied area and the like can be arbitrarily set. This makes it possible to easily form a complicated and irregular pattern with a three-dimensional effect on the surface of the substrate.

  In addition, when the above active energy ray-curable convex ink is applied by an ink jet method, a heating device is provided on a head equipped in a normal ink jet printer, and the ink is heated to 25 to 150 ° C. It is preferable to discharge with a low viscosity. The heating temperature range is more preferably 25 to 70 ° C. The heating temperature is determined in consideration of the curability of the photopolymerizable compound to be used with respect to heat, and is preferably set to a temperature lower than the temperature at which curing starts.

In the step (a), the droplet amount of the active energy ray-curable convex portion ink ejected from the head is preferably 5 to 50 pL, and more preferably 7 to 40 pL. If it is less than 5 pL, since it is necessary to increase the number of times of printing in order to make the height of the convex portion 40 to 200 μm, the productivity is lowered. On the other hand, if it exceeds 50 pL, the amount of droplets becomes too large, the three-dimensional pattern tends to blur, and the three-dimensional effect is difficult to discriminate. Moreover, the coating amount of the active energy ray-curable convex portion ink is not particularly limited, but is usually 20 to 100 g / m ² .

  Further, when the coating method of the active energy ray curable convex portion ink is an ink jet method, printing is performed by scanning the same region x times (1 ≦ x) with the printer head with respect to the region where the convex portion is formed. One layer is formed. The number of scans (x) is not particularly limited, but needs to be determined in consideration of productivity, and is preferably 16 times or less. One printing layer is formed by one printing. Accordingly, the number of times of printing is repeated until a convex portion having a desired height is obtained. The number of times of printing is preferably 1 to 10 times. If the number of times of printing exceeds 10, the productivity will deteriorate. FIG. 2 is a schematic view of the step (a) in an example of the method for producing a decorative structure according to the present invention. The convex portion 3 is formed by forming a printed layer 3 ′ on the substrate 2 and then printing layer. It can be formed by coating 3 ″. Here, the print layer 3 ″ may be superimposed on the same part as the print layer 3 ′, or may be formed so as to partially overlap the print layer 3 ′. That is, the print layer 3 ′ and the print layer 3 ″ are not necessarily the same print image. Further, the coating conditions of the printing layer 3 ′ and the printing layer 3 ″ are not necessarily the same. In addition, the convex part 3 may be formed from the some printing layer, and may be formed by the single printing layer.

In the step (a), curing of the active energy ray-curable convex portion ink can be performed by irradiating with active energy rays (visible light, ultraviolet rays, electron beams or the like). Here, as the active energy ray source, an ultraviolet ray source such as a low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a xenon lamp, an excimer laser, a dye laser, and an LED lamp, and an electron beam accelerator can be used. The irradiation energy amount of the active energy ray is preferably 400 to 10,000 mJ / cm ² .

  In addition, as a three-dimensional pattern that can be formed by a plurality of convex portions, a geometric pattern, wood grain, leather-like pattern (for example, cowhide pattern, etc.), satin pattern, sandblasted pattern, hairline, silk screen-like pattern (for example, lattice pattern) Etc.), and leather-like patterns and hairlines are particularly suitable. Moreover, when coloring the said three-dimensional pattern, desired coloring can be achieved by using the ink set which combines the active energy ray hardening-type ink containing a different color material.

  In the said process (b), an overcoat layer is formed so that the convex part formed on the base material may be covered. Here, as described above, the overcoat layer needs to satisfy the relationship of the formula (1). In addition, as described above, the overcoat layer preferably directly covers at least a part of the substrate surface in addition to the convex portion, and further, the overcoat layer is preferably a continuous layer.

  In the step (b), the overcoat layer is formed by applying and curing an overcoat layer coating material by a spray method or an inkjet method. Here, by employing an ink jet method or a spray method, the coating material can be accurately applied, and the overcoat layer can be easily produced so as to cover the convex portion. Further, according to the ink jet method or spray method, the gloss can be freely adjusted. In particular, the ink jet method is preferable because gloss can be adjusted more freely and easily by appropriately setting the number of scans, the number of times of printing, and the amount of droplets during painting.

  In the case of the ink jet method, the overcoat layer coating material may be a known ink such as a water-based ink, a solvent-based ink, or an active energy ray-curable ink. Among these, an active energy ray-curable ink is preferable. When the active energy ray-curable ink is used, the curing conditions can be adjusted depending on the irradiation conditions of the active energy rays, so that a desired uneven shape can be formed and the glossiness can be easily adjusted. This active energy ray curable ink contains at least a photopolymerizable compound and a photopolymerization initiator, and, if necessary, a sensitizer for promoting the photopolymerization initiator initiation reaction, a coloring material, a dispersant, Additives such as surface conditioners, heat stabilizers, antioxidants, preservatives, pH adjusters, antifoaming agents, penetrants, UV absorbers, light stabilizers, etc. can be blended. The same active energy ray curable ink as the convex ink can be used. In the method for producing a decorative structure according to the present invention, the active energy ray-curable ink used for forming the overcoat layer may be the same as the active energy ray-curable ink used for forming the convex portion. And may be different.

  In the case of the spray method, the coating material for the overcoat layer is preferably a dry curable paint, a moisture absorption curable paint, a thermosetting paint, a two-component curable paint, or an active energy ray curable paint. These paints contain at least a resin and, if necessary, a curing agent for curing the coating film, a coloring material, a dispersion material, a surface conditioner, a heat stabilizer, an antioxidant, an antiseptic, a pH adjuster, a dissipator. Additives such as foaming agents, ultraviolet absorbers, and light stabilizers can be blended. In addition, these coating materials can use a well-known coating material without a restriction | limiting.

  The viscosity of the coating material for the overcoat layer may be adjusted depending on the coating method to be used. For example, in the case of an ink jet method, the flow in the supply system (ink flow path such as a tube or piping) to the printer head unit In order to maintain the properties, the viscosity at 25 ° C. is preferably 100 mPa · s or less, more preferably 10 to 100 mPa · s or less, and the viscosity at 45 ° C. is considered in consideration of ink jetting properties. Is preferably 1 to 15 mPa · s. On the other hand, in the case of a spray method, the viscosity of the paint used may be adjusted as appropriate. The viscosity can be measured using a generally known viscometer (for example, Ostwald viscometer, B-type viscometer, etc.).

  The coating material for the overcoat layer may be adjusted in surface tension depending on the coating method and substrate used, but generally the surface tension at 20 ° C. is preferably 20 to 45 mN / m, and preferably 25 to 25 mN / m. More preferably, it is 40 mN / m. The surface tension at 20 ° C. is preferably 20 mN / m or more for the reason of suppressing wettability and facilitating the supply of the coating material. In addition, if the wettability is excessively lowered, the ink is repelled. To prevent this, the surface tension at 20 ° C. is preferably 45 mN / m or less. In the present invention, the surface tension is measured by a plate method.

  In addition, when coating the coating material for the overcoat layer by the inkjet method, a heating device is installed on the head equipped in a normal inkjet printer, and the ink is heated to 25 to 150 ° C. to reduce the viscosity of the ink. Are preferably discharged. The heating temperature range is more preferably 25 to 70 ° C. The heating temperature is determined in consideration of the curability of the photopolymerizable compound to be used with respect to heat, and is preferably set to a temperature lower than the temperature at which curing starts.

Furthermore, when the coating method of the overcoat layer coating material is an inkjet method, the amount of droplets of the active energy ray-curable ink is preferably 5 to 50 pL, and more preferably 7 to 40 pL. The coating amount of the active energy ray-curable ink is not particularly limited as long as it can cover the convex portion, but is preferably ²⁰ to 100 g / m ² .

  Further, when the coating method of the overcoat layer coating material is an ink jet method, the print layer is formed by scanning the same region y times (preferably 8 ≦ y) with the printer head with respect to the region where the overcoat layer is formed. One layer is formed. The number of scans (y) is preferably 8 times or more, and more preferably 16 times or more, from the viewpoint of adjusting the gloss of the decorative structure. When the number of scans is small, the glossiness tends to increase, and when the number of scans is large, the glossiness tends to decrease. One printing layer is formed by one printing. Therefore, the number of times of printing is repeated until an overcoat layer having a desired thickness is obtained. The number of times of printing is preferably 1 to 10 times. If the number of times of printing exceeds 10, the productivity will deteriorate.

  When the coating method for the overcoat layer coating material is a spray method, the overcoat layer can be formed by air spray coating, airless spray coating, rotary atomization coating, or the like. When coating the overcoat layer coating material, it is preferable that the same region is coated with a spray gun 1 to 60 times with a spray gun in terms of forming a uniform film thickness. More preferably, 20 times. In the spray method, in order to adjust the gloss of the decorative structure, it is preferable to control the discharge rate from the spray gun within a range of 10 cc / min to 150 cc / min, and a more preferable range is 60 cc / min to 130 cc. / Min.

In the step (b), for the curing of the overcoat layer coating material, for example, a curing method such as drying curing, moisture absorption curing, thermal curing, two-component reaction curing, and active energy ray curing can be employed. Specifically, when the coating method for the overcoat layer coating material is an inkjet method, the curing of the overcoat layer coating material is caused by irradiation with active energy rays (visible light, ultraviolet rays, electron beams, etc.). It is preferable to carry out by reaction. Here, as the active energy ray source, an ultraviolet ray source such as a low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a xenon lamp, an excimer laser, a dye laser, and an LED lamp, and an electron beam accelerator can be used. The irradiation energy amount of the active energy ray is preferably 400 to 10,000 mJ / cm ² . On the other hand, when the coating method of the overcoat layer coating material is a spray method, the curing of the overcoat layer coating material may be performed in an appropriate curing mode (for example, dry curing, moisture absorption curing, thermal curing) according to the form of the paint. Two-component reaction curing, active energy ray curing, etc.) may be selected. In the case of dry curing, it is preferable to dry by heating to 20 to 150 ° C. For moisture absorption curing, polymerization curing, and two-component reaction curing, curing conditions may be set according to the form of the paint for spray coating, and for active energy ray curing, a method similar to the inkjet method may be employed. Good.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

1. Preparation example of active energy ray curable ink The raw materials according to the formulation shown in Table 1 and 200 parts by mass of glass beads (dispersion beads) were mixed, and the resulting mixture was kneaded in a bead mill for 4 hours. After kneading, filtration was performed to remove glass beads, and active energy ray-curable inks (Y-1, M-1, C-1, and K-1) were prepared.
Moreover, the active energy ray-curable ink (colorless-1) was prepared by mixing the raw materials according to the formulation shown in Table 1 and then sufficiently stirring.
Next, for each ink, the viscosity at 25 ° C. and 45 ° C. was measured with a B-type viscometer, and the surface tension at 20 ° C. was measured by a plate method. The results are shown in Table 1.

* 1 5GN-01 (Azomethine, Bayer)
* 2 SicoFast Red 3855 (Dimethylquinacridone, BASF)
* 3 Paligen Blue L7080 (phthalocyanine, BASF)
* 4 Raven 450 (carbon black, Columbian Carbon Japan)
* 5 Disper BYK-168 (Big Chemie Japan Co., Ltd.)

2. Preparation example of coating material for spray coating In accordance with the formulation shown in Table 2, the main agent and curing agent are prepared, the curing agent is added to the main agent, and the viscosity is adjusted for spray coating by adding thinner. The material was obtained.

* 6 ACRIDIC WAU-137 (acrylic polyol, manufactured by DIC)
* 7 Disparon LC-915 (Surface conditioner, manufactured by Enomoto Kasei Co., Ltd.)
* 8 CHISORB 292 (light stabilizer, manufactured by Double Honda Chemical Co., Ltd.)

3. Example of production of decorative structure <Example 1>
After setting the colorless-1 active energy ray curable ink to a piezo-type ink jet printer, the ink was applied to the upper surface of an ABS resin plate of 150 mm × 150 mm × thickness 1 mm under the discharge conditions shown in Table 3, A lattice pattern was produced by curing under the irradiation conditions shown in FIG. Next, the above-mentioned spray is applied so as to cover the entire silk screen-like pattern formed by the convex portions by a gravity air cup gun (paint nozzle diameter: 1.3 mm, air pressure: 4 MPa, discharge amount: 120 cc / min). The coating material for painting was painted by hand three times. Here, the gravity type air cup gun was separated from the base material by 20 to 25 cm, and the moving speed of the gun was 30 to 50 cm / s. Next, the coated coating material was heated to 60 ° C. and cured to form an overcoat layer (continuous layer), thereby producing a decorative structure.

<Examples 2 to 6>
After an ink set composed of four types of active energy ray curable inks Y-1, M-1, C-1, and K-1 is set in a piezo ink jet printer, an ABS resin of 150 mm × 150 mm × thickness 1 mm is used. On the upper surface of the plate, the ink was applied under the discharge conditions shown in Table 3, and cured under the irradiation conditions shown in Table 3, thereby producing a cowhide pattern (brown). Next, using the above ink set, coating is performed so as to cover the entire cowhide pattern formed by the convex portions under the discharge conditions shown in Table 3, and curing is performed under the irradiation conditions shown in Table 3 to obtain a brown overtone. A coat layer (continuous layer) was formed to produce a decorative structure.
The amount of irradiation energy was measured using an illuminometer (UVICURE® Plus II, sensor: UVA2; manufactured by Electronic Instrumentation and Technology).

<Example 7>
A decorative structure was produced in the same manner as in Example 3 except that the three-dimensional pattern formed by the convex portions was changed from a cowhide pattern to a hairline (brown).

<Comparative Example 1>
After an ink set composed of four types of active energy ray curable inks of Y-1, M-1, C-1, and K-1 is set in a piezo ink jet printer, an ABS resin of 150 mm × 150 mm × thickness 1 mm is used. By applying the ink on the top surface of the plate under the same conditions as the overcoat layer ejection conditions shown in Example 2, and curing the ink under the same conditions as the overcoat layer irradiation conditions shown in Example 3, an undercoat layer (continuous) Layer). Next, the ink was coated on the undercoat layer under the discharge conditions shown in Table 4, and cured under the irradiation conditions shown in Table 4, thereby producing a cowhide pattern (brown) and a decorative structure.

<Comparative Examples 2-3>
After an ink set composed of four types of active energy ray curable inks Y-1, M-1, C-1, and K-1 is set in a piezo ink jet printer, an ABS resin of 150 mm × 150 mm × thickness 1 mm is used. On the upper surface of the plate, the ink was applied under the discharge conditions shown in Table 4, and cured under the irradiation conditions shown in Table, thereby producing a cowhide pattern (brown). Next, using the above ink set, coating is performed so as to cover the entire cowhide pattern formed by the convex portions under the discharge conditions shown in Table 4, and curing is performed under the irradiation conditions shown in Table 4. A coat layer (continuous layer) was formed to produce a decorative structure.

<Comparative example 4>
After an ink set composed of four types of active energy ray curable inks Y-1, M-1, C-1, and K-1 is set in a piezo ink jet printer, an ABS resin of 150 mm × 150 mm × thickness 1 mm is used. The ink was painted on the upper surface of the plate under the discharge conditions shown in Table 4, and cured under the irradiation conditions shown in Table 4 to produce a cowhide pattern (brown). The overcoat layer was not prepared.

4). Measurement and Evaluation (1) Height measurement of convex portions Ten convex portions formed on the surface of the base material are selected at random, and the maximum height of each convex portion is measured using a laser microscope (VK-8510 manufactured by Keyence Corporation). The average value was measured. The results are shown in Tables 3-4.

(2) Measurement of film thickness of overcoat layer After cutting out the cross section of the decorative structure, the cut surface was polished, and then 10 spots were randomly selected from the overcoat layer covering the convex portion, and laser microscope The film thickness was measured by VK-8510 (Keyence Co., Ltd.), the average value of the film thickness at 10 locations was determined, and this was taken as the film thickness of the overcoat layer. The results are shown in Tables 3-4.

(3) Occupied area of convex part The decorative structure was photographed with a digital camera from above, and the ratio of the occupied area of the convex part on the upper surface of the substrate was calculated by analyzing the obtained image data with image analysis software . The results are shown in Tables 3-4.

(4) Appearance evaluation (visual three-dimensional evaluation)
Appearance evaluation was conducted by 15 employees of Dainippon Paint Co., Ltd. Specifically, according to the following evaluation criteria, a score was given to the pattern of the decorative structure, and a total score of 15 people was obtained. The results are shown in Tables 3-4.
(Evaluation criteria)
・ There is enough stereoscopic effect to express a given pattern ... 1 point ・ There is not enough stereoscopic effect to express a given pattern ... 0 point

(5) Tactile evaluation (Evaluation of unevenness)
Tactile evaluation was conducted by 15 employees of Dainippon Paint Co., Ltd. Specifically, according to the following evaluation criteria, a score was given to the pattern of the decorative structure, and a total score of 15 people was obtained. The results are shown in Tables 3-4.
(Evaluation criteria)
・ The pattern has a feeling of unevenness ・ 1 point ・ The pattern has no feeling of unevenness ・ 0 points

(6) Adhesion evaluation (cross-cut peel test)
Two straight cuts were put on the surface of the decorative structure until reaching the base material with a cutter knife at a cut angle of 60 °. Next, an adhesive tape (width 24 mm) was pressure-bonded to the cut portion so that no bubbles were generated in the cut portion, and then the adhesive tape was pulled rapidly. According to the following evaluation criteria, peeling of the decorative structure was evaluated. The results are shown in Tables 3-4.
(Evaluation criteria)
○: No peeling Δ: In the decorative region, the convex part was partially peeled.
X: The convex part peeled entirely in the decoration area | region.

(7) Glossiness Regarding the pattern of the decorative structure, specular gloss at 20 °, 60 ° and 85 ° was measured using a gloss meter (Micro-TRI-gloss manufactured by BYK Gardner). The results are shown in Tables 3 to 4 and FIG.
FIG. 4 is a diagram illustrating the relationship between the glossiness of the decorative structures of Examples 2 to 5 and the number of scans of overcoat layer discharge conditions. The decorative structures of Examples 2 to 5 were manufactured under the same conditions except for the number of scans among the overcoat layer discharge conditions, but by increasing the number of scans as shown in FIG. It can be seen that a decrease in glossiness can be confirmed and the gloss can be adjusted freely.

DESCRIPTION OF SYMBOLS 1 Decorating structure 2 Base material 3 Convex part 3 'Print layer 3''Print layer 4 Overcoat layer 5 Base material surface 6 Convex part

Claims (5)

A method for producing a decorative structure comprising a base material, a plurality of convex portions disposed on at least one surface of the base material, and an overcoat layer covering at least the convex portions,
(A) A step of forming a plurality of convex portions on at least one surface of the substrate, wherein the convex portions are formed by curing an active energy ray-curable convex portion ink by active energy ray irradiation. And the height of the convex part is 40 to 200 μm,
(B) a step of forming an overcoat layer so as to cover the convex portion, wherein the overcoat layer is formed by coating and curing an overcoat layer coating material by an ink jet method or a spray method, The overcoat layer and the convex portion have the following formula (1):
H1> H2 (1)
A process of satisfying the relationship: [wherein H1 is the height (μm) of the convex portion and H2 is the film thickness (μm) of the overcoat layer]. Manufacturing method.   The method for producing a decorative structure according to claim 1, wherein the overcoat layer directly covers at least a part of the surface of the base material.   The occupied area of the convex part in the decoration area | region of the base-material surface where the said convex part is arrange | positioned exceeds 60% of the area of this decoration area | region, and is less than 90%, It is characterized by the above-mentioned. The manufacturing method of the decorating structure of description.   The coating material for an overcoat layer is an active energy ray-curable ink, and the active energy ray-curable ink used for forming the convex portion and the overcoat layer is the same or different. The manufacturing method of the decorating structure of any one of claim | item 1-3.   The decorating structure obtained by the manufacturing method of any one of Claims 1-4.

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