JP7487496B2 - Method for manufacturing uneven surface objects - Google Patents

Description

The present invention relates to a method for manufacturing an object with a rough surface.

Flooring, wallpaper and other materials that have desired images printed on them and have been given a design by embossing or other methods are used for the floors, interior walls and ceilings of buildings. Attempts are also being made to improve the durability of flooring and wallpaper by coating them with ultraviolet (UV) curable materials or electron beam curable materials.

In recent years, attempts have been made to print desired images using an inkjet system and apply them to flooring materials, wallpaper, etc. In particular, printed matter that has an image and a textured surface has become widespread because it can provide a luxurious decorative effect with a three-dimensional appearance.
As a method for forming an uneven structure on a surface, for example, a manufacturing method for a decorative structure has been proposed in which the structure has a foam layer, an image forming layer, and a surface protective layer (overcoat layer), and the thickness of the overcoat layer is formed thinner than the height of the convex portions that form the overcoat layer (see, for example, Patent Document 1).

The present invention aims to provide a method for producing an uneven surface object that is highly productive and can produce an uneven surface object that has excellent design and robustness due to its uneven shape.

The method for manufacturing an uneven surface object of the present invention as a means for solving the above-mentioned problems includes a volume expansion agent-containing layer forming step of forming a volume expansion agent-containing layer containing a volume expansion agent on a substrate, an inhibitor application step of applying an inhibitor to the volume expansion agent-containing layer in a predetermined region to inhibit the expansion of the volume expansion agent, a volume expansion layer forming step of expanding the volume expansion agent in the volume expansion agent-containing layer to form a volume expansion layer in regions other than the predetermined region, and an overcoat layer forming step of forming an overcoat layer on the volume expansion agent-containing layer in the predetermined region and on the volume expansion layer in the other regions so that the average thickness in the predetermined region is thinner than the average thickness in the other regions.

The present invention makes it possible to obtain an object with a textured surface that has excellent design and robustness due to its textured shape, and to provide a method for manufacturing an object with a textured surface that is highly productive.

FIG. 1A is a schematic diagram showing an example of a product obtained after a volume expansion agent-containing layer forming step in the method for producing an article with a rough surface according to the present invention. FIG. 1B is a schematic diagram showing an example of a product after the inhibitor application step in the method for producing an article with a textured surface of the present invention. FIG. 1C is a schematic diagram showing an example of a product after the volume expansion layer forming step in the method for producing an article with a rough surface of the present invention. FIG. 2A is a cross-sectional view showing an example of an object with a textured surface manufactured using a conventional method for manufacturing an object with a textured surface. FIG. 2B is a cross-sectional view showing an example of an object with a textured surface produced using the method for producing an object with a textured surface of the present invention. FIG. 2C is a cross-sectional view showing another example of an object with a textured surface produced by the method for producing an object with a textured surface of the present invention. FIG. 3A is a cross-sectional view of an example of a textured surface article that does not have an overcoat layer. FIG. 3B is a cross-sectional view showing an example of an article with a textured surface on which an overcoat layer is formed using the method for producing an article with a textured surface of the present invention. FIG. 4 is a schematic diagram showing an example of an apparatus for producing an article with a rough surface according to the method for producing an article with a rough surface of the present invention. FIG. 5 is a diagram showing an example of a cross-sectional image of the uneven surface object according to the first embodiment.

(Method of manufacturing an object with a rough surface)
The method for producing an article with a rough surface of the present invention includes the steps of: forming a volume expansion agent-containing layer on a substrate; and
a suppressor application step of applying a suppressor that suppresses the expansion of the volume expansion agent on the volume expansion agent-containing layer in a predetermined region;
a volume expansion layer forming step of expanding the volume expansion agent in the volume expansion agent-containing layer to form a volume expansion layer in an area other than the predetermined area;
and an overcoat layer forming step of forming an overcoat layer on the volume expansion agent-containing layer in the specified region and on the volume expansion layer in the other regions so that the average thickness in the specified region is equal to or less than the average thickness in the other regions, and further including other steps as necessary.

Conventional technology uses a lamination method in which ultraviolet-curable resin is laminated multiple times using an inkjet method, so in order to impart a high level of design quality with an uneven surface, lamination and curing must be carried out multiple times, which can result in the problem that it is difficult to improve productivity.
Furthermore, in the conventional technology, when forming an overcoat layer, a fixed amount of a composition for forming an overcoat layer is applied to a surface with an uneven shape, and the composition for forming an overcoat layer flows into the recesses. As a result, the average thickness of the overcoat layer formed in the recesses is greater than the average thickness of the overcoat layer formed in the protrusions, which may reduce the design quality of the uneven surface formed.

As a result of intensive research, the inventors have found that it is possible to provide a method for producing an uneven surface article which improves robustness without reducing design due to reduced unevenness, and is also highly productive, by forming a volume expansion agent-containing layer on a substrate, applying an inhibitor to areas which are not to be volume-expanded, and then forming a volume expansion layer by volume expanding the volume expansion agent-containing layer, and forming an overcoat layer such that the average thickness of the surface of the volume expansion layer in areas where the inhibitor is not applied is thinner than the average thickness of the surface of the volume expansion layer in areas where the inhibitor is applied.
In the present invention, the "protruding portion" of the uneven surface object means at least one of an area that protrudes (projects) vertically upward from a reference plane and an area that does not protrude (depress) vertically downward from the reference plane. The reference plane is not particularly limited as long as it is a surface that includes the uneven surface object, and can be appropriately selected according to the purpose. For example, a surface that is parallel to a surface that includes a substrate and includes a volume expansion agent-containing layer to which an inhibitor is applied, or a surface that is parallel to a surface that includes a substrate and includes a volume expansion layer to which an inhibitor is not applied can be selected.
In addition, in the present invention, a "depression" of an uneven surface object means at least either an area that protrudes (is depressed) vertically downward relative to a reference surface, or an area that is not an area that protrudes (is protruding) vertically upward relative to the reference surface.
In the present invention, an object having an uneven surface means an object that includes an area that is not on the same plane as a reference surface, that is, an object that has the above-mentioned convex portions and concave portions.

<Volume expansion agent-containing layer forming step>
The volume expansion agent-containing layer forming step is a step of forming a volume expansion agent-containing layer containing a volume expansion agent on a substrate.
In the volume expansion agent-containing layer forming step, a volume expansion agent composition containing a volume expansion agent is applied onto a substrate to form the volume expansion agent-containing layer.

<Substrate>
The shape and structure of the substrate are not particularly limited and can be appropriately selected according to the purpose, and examples thereof include films, sheets, plates, etc. The film means a soft one having an average thickness of less than 200 μm. The sheet means a soft one having an average thickness of 200 μm or more, or a hard one having an average thickness of less than 500 μm.

The material of the substrate is not particularly limited and can be appropriately selected depending on the purpose. Examples include plastic, natural paper, synthetic paper made of synthetic fibers, nonwoven fabric, cloth, leather, wood, metal, glass, building materials, ceramics, and composite materials thereof. Among these, a durable substrate is preferred, and a building material is more preferred.

Examples of the plastic include polyester, polypropylene, polyethylene, nylon, vinylon, acrylic, and other plastics, and laminates of the above films.
The plastic is not particularly limited and can be appropriately selected depending on the purpose, but from the standpoint of strength, it is preferable that the plastic is uniaxially or biaxially oriented.

Examples of natural paper include Japanese paper, pulp paper, cotton paper, straw paper, and paperboard.

Examples of the synthetic paper include synthetic pulp paper, synthetic film paper, and synthetic plastic paperboard.

The nonwoven fabric is not particularly limited and can be appropriately selected depending on the purpose. For example, polyethylene fibers are dispersed in a sheet-like form and then heat-pressed to form a sheet.

Examples of the fabric include woven fabrics made of natural fibers, regenerated fibers, synthetic fibers, and combinations of these fibers.

Examples of the wood include composite materials such as MDF, HDF, particle board, and plywood, and decorative boards with a sheet attached to the surface. The average thickness of the wood is preferably 2 mm or more and 30 mm or less.

The metal is not particularly limited and can be appropriately selected depending on the purpose. Examples of the metal include alloys, aluminum, and aluminum composite materials. Examples of the alloy include Galvalume steel sheet (registered trademark). Examples of the aluminum composite materials include composite materials in which a thermoplastic resin or the like is sandwiched between aluminum sheets.

Examples of the glass include float glass, colored glass, tempered glass, wired glass, frosted glass, and mirror glass. The glass is preferably in the form of a glass plate. The average thickness of the glass plate is preferably 0.3 mm or more and 20 mm or less.

There are no particular limitations on the ceramics, and they can be selected appropriately depending on the purpose. For example, typical non-flammable building materials include gypsum board and calcium silicate board.

Examples of the building materials include thermosetting resins used in flooring, wallpaper, interior materials, wall panels, baseboards, ceiling materials, pillars, etc., fiberboards, particle boards, and materials in which the surfaces of these materials are provided with decorative panels made of thermosetting resins, olefins, polyesters, or PVC.

There are no particular limitations on the size of the substrate, and it can be selected appropriately depending on the purpose.

The method for forming a volume expansion agent-containing layer containing a volume expansion agent on the substrate is not particularly limited and can be appropriately selected depending on the purpose. For example, the volume expansion agent composition can be applied to the substrate by a coating method such as knife coating, nozzle coating, die coating, lip coating, comma coating, gravure coating, rotary screen coating, reverse roll coating, roll coating, spin coating, kneader coating, bar coating, blade coating, casting, dipping, curtain coating, or an inkjet method.

The average thickness of the volume expansion agent-containing layer is not particularly limited and may be appropriately selected depending on the purpose, but is preferably 25 μm or more, more preferably 100 μm or more, even more preferably 250 μm or more, and particularly preferably 300 μm or more and 500 μm or less.
When the average thickness of the volume expansion agent-containing layer is 25 μm or more, a volume expansion layer having unevenness can be formed, and excellent designability due to the uneven shape can be imparted.
The average thickness of the volume expansion layer after the volume expansion agent-containing layer is expanded is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 100 μm or more, more preferably 310 μm or more, even more preferably 400 μm or more, and particularly preferably 400 μm or more and 2,000 μm or less.
When the average thickness of the volume expansion layer is 100 μm or more, a volume expansion layer having unevenness due to the volume expansion inhibitor can be formed, and excellent designability due to the uneven shape can be imparted.
The average thickness may be an average value of thicknesses of the volume expansion agent-containing layer at 10 different points, or may be a value calculated from the amount of the volume expansion agent composition applied.

<<Volume Expansion Agent Composition>>
The volume expansion agent composition contains the volume expansion agent, and preferably contains a polymerizable compound, a polymerization initiator, and a surface tension modifier, and further contains other components as necessary.

-Volume expansion agent-
Examples of the volume expansion agent include thermally expandable microcapsules and thermally decomposable volume expansion agents. Among these, thermally expandable microcapsules are preferred because they have a high volume expansion ratio and can form uniform, small, independent bubbles. The volume expansion agent is also sometimes called a "foaming agent."

The thermally expandable microcapsules are particles with a core-shell structure in which the volume expansion agent is wrapped in a thermoplastic resin, and when the thermoplastic resin of the shell starts to soften by heating, the vapor pressure of the encapsulated volume expansion compound increases to a pressure sufficient to deform the particles, and the thermoplastic resin of the shell is stretched and expanded. Examples of the volume expansion compound include aliphatic hydrocarbons with low boiling points.
Examples of the low-boiling aliphatic hydrocarbons include ethane, ethylene, propane, propene, n-butane, isobutane, butene, isobutene, n-pentane, isopentane, neopentane, n-hexane, isohexane, n-heptane, cyclohexane, isooctane, and isododecane.

As the thermally expandable microcapsules, commercially available products can be used, such as the Advancell EM series manufactured by Sekisui Chemical Co., Ltd., the Expancell DU, WU, MB, SL, and FG series manufactured by AkzoNovel Inc. (sold in Japan by Nippon Phillite Co., Ltd.), the Matsumoto Microsphere F and FN series manufactured by Matsumoto Yushi Seiyaku Co., Ltd., and the Kureha Microsphere H750, H850, and H1100 manufactured by Kureha Corporation. These may be used alone or in combination of two or more types.

Examples of the thermally decomposable volume expansion agent include organic volume expansion agents and inorganic volume expansion agents.
Examples of the organic volume expansion agent include azodicarboxylic acid amide (ADCA), azobisisobutylnitrile (AIBN), p,p'-oxybisbenzenesulfonylhydrazide (OBSH), dinitrosopentamethylenetetramine (DPT), zinc naphthenate, etc. These may be used alone or in combination of two or more.

Examples of the inorganic volume expansion agent include bicarbonates such as sodium bicarbonate, carbonates, and combinations of bicarbonates and organic acid salts.

The content of the volume expansion agent is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1% by mass or more and 20% by mass or less, and more preferably 5% by mass or more and 15% by mass or less, based on the total amount of the volume expansion agent composition.

--Polymerizable compound--
The polymerizable compound is not particularly limited as long as it is a compound that can be polymerized by the application of energy, and can be appropriately selected depending on the purpose. Examples of the polymerizable compound include monofunctional monomers and polyfunctional monomers.

--Monofunctional monomer--
Examples of the monofunctional monomer include a monomer having one vinyl group, one acryloyl group, or one methacryloyl group in the molecular structure.
Examples of the monofunctional monomer include γ-butyrolactone (meth)acrylate, isobornyl (meth)acrylate, formalized trimethylolpropane mono(meth)acrylate, trimethylolpropane (meth)acrylic acid benzoate, (meth)acryloylmorpholine, 2-hydroxypropyl (meth)acrylamide, N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylformamide, cyclohexanedimethanol monovinyl ether, hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, dicyclopentadiene vinyl ether, tricyclodecane vinyl ether, benzyl vinyl ether, ethyloxetane methyl vinyl ether, hydroxybutyl vinyl ether, ethyl vinyl ether, ethoxy(4)nonylphenol (meth)acrylate, benzyl (meth)acrylate, and caprolactone (meth)acrylate. These may be used alone or in combination of two or more.
Among these, isobornyl (meth)acrylate is preferred because it has a high glass transition temperature (Tg) and good fastness.
The content of the monofunctional monomer is preferably from 80% by mass to 99.5% by mass, and more preferably from 90% by mass to 95% by mass, based on the total amount of the volume expansion agent composition.

--Polyfunctional monomer--
The polyfunctional monomer is a compound having two or more vinyl groups, acryloyl groups, or methacryloyl groups in the molecular structure.
Examples of the polyfunctional monomer include ethylene glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol dimethacrylate [CH ₂ ═CH-CO-(OC ₂ H ₄ )n-OCOCH=CH ₂ (n≈9), (n≈14), (n≈23)], dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol dimethacrylate [CH ₂ ═C(CH ₃ )-CO-(OC ₃ H ₆ ) _n -OCOC(CH ₃ )=CH ₂ (n≒7)], 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, propylene oxide modified bisphenol A di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, propylene oxide modified tetra(meth)acrylate, Lamethylolmethane tetra(meth)acrylate, dipentaerythritol hydroxypenta(meth)acrylate, caprolactone modified dipentaerythritol hydroxypenta(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, caprolactone Examples of the vinyl ether derivatives include ethylene glycol divinyl ether, ... These may be used alone or in combination of two or more.

The polyfunctional monomer preferably has a molecular weight/functional number of 250 or more, from the viewpoint of achieving both volume expansion properties and robustness.
The content of the polyfunctional monomer in the volume expansion agent composition is preferably 10% by mass or less, more preferably 1% by mass or less, based on the total amount of the polymerizable compound. The content of the polyfunctional monomer is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total amount of the polymerizable compound. When the content of the polyfunctional monomer is 10% by mass or less, based on the total amount of the polymerizable compound, there is an advantage that both design (volume expansion) and robustness can be achieved.

- Polymerization initiator -
Examples of the polymerization initiator include a thermal polymerization initiator, a photopolymerization initiator, etc. Among these, a photopolymerization initiator is more preferable from the viewpoints of designability due to the uneven shape and durability of image quality.
The photopolymerization initiator may be any one that can generate active species such as radicals and cations by the energy of active energy rays and initiate polymerization of a polymerizable compound. As such a polymerization initiator, known radical polymerization initiators, cationic polymerization initiators, base generators, etc. can be used alone or in combination of two or more kinds, and among these, it is preferable to use a radical polymerization initiator.
In order to obtain a sufficient curing rate, the content of the polymerization initiator is preferably from 1% by mass to 20% by mass, more preferably from 5% by mass to 15% by mass, based on the total amount of the volume expansion agent composition.
Examples of the radical polymerization initiator include aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (e.g., thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon-halogen bond, and alkylamine compounds.

In addition to the polymerization initiator, a polymerization accelerator (sensitizer) can also be used in combination.
The polymerization accelerator is not particularly limited and can be appropriately selected depending on the purpose. Examples of the accelerator include amine compounds such as trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, N,N-dimethylbenzylamine, and 4,4′-bis(diethylamino)benzophenone.
The content of the polymerization accelerator is not particularly limited, and may be appropriately set depending on the polymerization initiator used and its amount.

-Surface tension adjuster-
The surface tension adjuster is not particularly limited as long as it is capable of adjusting the surface tension and is non-reactive to energy, and can be appropriately selected depending on the purpose.
As the surface tension adjuster, commercially available products can be used, and examples thereof include BYK-UV3510 (manufactured by BYK-Chemie), BYK-3550 (manufactured by BYK-Chemie), BYK-3990 (manufactured by BYK-Chemie), and BYK35600 (manufactured by BYK-Chemie).

-Other ingredients-
The other components are not particularly limited and can be appropriately selected depending on the purpose. Examples of the other components include fillers, volume expansion promoters, dispersants, colorants, organic solvents, antiblocking agents, thickeners, preservatives, stabilizers, deodorizers, fluorescent agents, and ultraviolet blocking agents.

--filler--
Examples of the filler include aluminum hydroxide, magnesium hydroxide, barium hydroxide, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, ferrous hydroxide, basic zinc carbonate, basic lead carbonate, silica sand, clay, talc, silicas, titanium dioxide, magnesium silicate, etc. These may be used alone or in combination of two or more. Among these, calcium carbonate, magnesium carbonate, aluminum hydroxide, and magnesium hydroxide are preferred.

--Volume expansion promoter--
The volume expansion promoter is not particularly limited and can be appropriately selected depending on the purpose. Examples of the volume expansion promoter include zinc naphthenate, zinc acetate, zinc propionate, zinc 2-ethylpentanoate, zinc 2-ethyl-4-methylpentanoate, zinc 2-methylhexanoate, zinc 2-ethylhexanoate, zinc isooctanoate, zinc n-octanoate, zinc neodecanoate, zinc isodecanoate, zinc n-decanoate, zinc laurate, zinc myristate, zinc palmitate, zinc stearate, zinc isostearate, zinc 12-histearate, zinc ... Examples of the zinc hydroxystearate include zinc behenate, zinc oleate, zinc linoleate, zinc linoleate, zinc ricinoleate, zinc benzoate, zinc o-, m- or p-toluate, zinc p-t-butylbenzoate, zinc salicylate, zinc phthalate, zinc salts of monoalkyl (C4-18) phthalates, zinc dehydroacetate, zinc dibutyldithiocarbamate, zinc aminocrotonate, zinc salts of 2-mercaptobenzothiazole, zinc pyrithione, and zinc complexes of urea or diphenylurea. These may be used alone or in combination of two or more.

--Thickener--
Examples of the thickener include polycyanoacrylate, polylactic acid, polyglycolic acid, polycaprolactone, polyacrylic acid alkyl ester, and polymethacrylic acid alkyl ester.

--Preservative--
The preservatives include those which have been conventionally used and do not initiate polymerization of monomers, such as potassium sorbate, sodium benzoate, sorbic acid, and chlorocresol.

--Stabilizer--
The stabilizer serves the purpose of inhibiting polymerization of monomers during storage, and includes anionic stabilizers, free radical stabilizers, and the like.
Examples of the anionic stabilizer include metaphosphoric acid, maleic acid, maleic anhydride, alkylsulfonic acid, phosphorus pentoxide, iron(III) chloride, antimony oxide, 2,4,6-trinitrophenol, thiol, alkylsulfonyl, alkylsulfonic acid, alkyl sulfoxide, alkyl sulfite, sultone, sulfur dioxide, and sulfur trioxide.
The free radical stabilizer may, for example, be hydroquinone, catechol, or a derivative thereof.

-Preparation of volume expansion agent composition-
The method for preparing the volume expansion agent composition used in the present invention is not particularly limited, and it can be prepared using the various components described above, and the preparation means and conditions can be appropriately selected depending on the purpose.

<Suppressant application step>
The inhibitor application step is a step of applying an inhibitor that inhibits the expansion of the volume expansion agent on the volume expansion agent-containing layer in a predetermined region. The inhibitor may be not only the inhibitor itself but also an inhibitor-containing composition containing other components.
In the inhibitor application step, the inhibitor-containing composition is applied to a portion (area) of the volume expansion agent-containing layer where expansion of the volume expansion agent is to be inhibited in a volume expansion layer forming step described below.
The predetermined area means a desired area to which the inhibitor is to be applied.

<<Inhibitor-containing composition>>
The inhibitor-containing composition contains a polyfunctional monomer, and preferably contains a surface tension adjuster, and further contains other components as required.

- Multifunctional monomer -
The polyfunctional monomer may be the same as the polyfunctional monomer in the volume expansion agent composition, and examples thereof include 1,6-hexanediol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, etc. Also, a mixture of different polyfunctional monomers, a mixture of a polyfunctional monomer and a monofunctional monomer, a mixture of an oligomer having a polyfunctionality and a monofunctional monomer, or a mixture of a monofunctional monomer, a polyfunctional monomer, and an oligomer having a polyfunctionality may be used.
Since the inhibitor-containing composition contains the polyfunctional monomer, the polyfunctional monomer is three-dimensionally crosslinked by the application of energy, and the volume expansion agent-containing layer to which the inhibitor-containing composition is applied is cured more firmly than the volume expansion agent-containing layer to which the inhibitor-containing composition is not applied by the curing process described later, and the volume expansion of the volume expansion agent-containing layer to which the inhibitor-containing composition is applied can be suppressed. Therefore, by applying the inhibitor-containing composition to any location of the volume expansion agent-containing layer and forming a region in which the volume expansion agent-containing layer is expanded and a region in which the volume expansion agent-containing layer is not expanded, the region in which the volume expansion is expanded can be formed as a convex portion and the region in which the volume expansion is not expanded can be formed as a concave portion, and a designability due to an excellent uneven shape can be imparted.

-Surface tension adjuster-
The surface tension adjuster is not particularly limited as long as it can adjust the surface tension, and can be appropriately selected depending on the purpose. Examples of the surface tension adjuster include BYK-3550 (manufactured by BYK-Chemie), BYK-3990 (manufactured by BYK-Chemie), and BYK35600 (manufactured by BYK-Chemie).

The method for applying the inhibitor-containing composition is not particularly limited and can be appropriately selected depending on the purpose, but the inkjet method is preferred because it can flexibly accommodate various volume expansion patterns (volume expansion inhibition patterns).
As a means for applying the inhibitor-containing composition using the inkjet method, for example, a driving method for the ejection head can be used, such as an on-demand type head using a piezoelectric element actuator using PZT or the like, a method using thermal energy, or an actuator using electrostatic force, or a continuous ejection type charge control type head can be used.
The amount of the inhibitor-containing composition to be applied is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.014 μL/cm ² or more and 2.8 μL/cm ² or less relative to the surface area of the volume expansion agent-containing layer.

The active energy is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include ultraviolet light, electron beams, α-rays, β-rays, γ-rays, X-rays, and the like, which can provide the energy necessary to promote the polymerization reaction of the polymerizable components in the composition. In particular, when a high-energy light source is used, the polymerization reaction can be promoted without using a polymerization initiator. In addition, in the case of ultraviolet light irradiation, mercury-free devices are strongly desired from the viewpoint of environmental protection, and replacement with GaN-based semiconductor ultraviolet light-emitting devices is very useful both industrially and environmentally. Furthermore, ultraviolet light-emitting diodes (UV-LEDs) and ultraviolet laser diodes (UV-LDs) are small, have a long life, are highly efficient, and are low cost, making them preferable as ultraviolet light sources.

The curing conditions are not particularly limited and can be appropriately selected depending on the purpose. In the case of ultraviolet light, it is preferable to use an irradiation device capable of irradiating with an intensity of 6 W/ ^cm2 or more at an irradiation distance of 2 mm.
In the case of electron beams, the acceleration voltage is preferably such that a dose of 15 kGy or more is achieved when the object to be cured is placed at the farthest position from the electron beam irradiation device.

<Volume expansion layer forming process>
The volume expansion layer forming step is a step of expanding the volume expansion agent in the volume expansion agent-containing layer to form a volume expansion layer in areas other than the predetermined area.
The volume expansion layer forming means is not particularly limited as long as it is a means that can expand the volume of the volume expansion agent in the volume expansion agent-containing layer by heating, and can be appropriately selected depending on the purpose. For example, an infrared heater, a hot air heater, a heating roller, etc. can be mentioned.
The heating temperature is not particularly limited as long as the volume expansion agent causes volume expansion, and can be appropriately selected depending on the purpose, but is preferably 100° C. or more and 200° C. or less. The heating temperature here may be the set temperature of a heating device or the measured temperature of the base material.

<Overcoat Layer Forming Process>
The overcoat layer forming step is a step of forming an overcoat layer on the volume expansion agent-containing layer in the predetermined region and on the volume expansion layer in the other region such that the average thickness in the predetermined region is equal to or less than the average thickness in the other region, i.e., a step of forming an overcoat layer such that the average thickness _TA of the surface of the volume expansion agent-containing layer in the region where the inhibitor is applied is thinner than the average thickness _TB of the surface of the volume expansion layer in the region where the inhibitor is not applied.
For the sake of simplicity, the "predetermined region (region to which the inhibitor is applied)" may be referred to as a "recess" and the "other region (region to which the inhibitor is not applied)" as a "protrusion." The overcoat layer may be referred to as a protective layer.

The overcoat layer is formed by applying an overcoat layer-forming composition onto the volume expansion agent-containing layer in the predetermined region and onto the volume expansion layer in the other region, and then curing the composition.
The composition for forming an overcoat layer preferably contains a first polymerizable compound and a polymerization initiator. When the composition for forming an overcoat layer contains the first polymerizable compound, all layers can be cured using the same curing means.
As the first polymerizable compound, for example, the same polymerizable compound as in the volume expansion agent composition can be used, or a polymerizable compound different from the polymerizable compound in the volume expansion agent composition can be used.

The means for forming the overcoat layer is not particularly limited and can be appropriately selected depending on the purpose. For example, similar to the method for applying the inhibitor, the method can be a combination of a known material applying means (e.g., a coating means, a discharging means, etc.) and a known energy applying means (e.g., a thermal energy applying means, an active energy ray irradiating means, etc.) similar to that used in the curing step described later.
The material application means is preferably, for example, an inkjet method, a spray method, or the like. When the material application means is an inkjet method or a spray method, the overcoat layer can be formed without contacting the material application means with the volume expansion layer. Among these, it is preferable to use the inkjet method. When the material application means is an inkjet method, the overcoat layer can be formed at any position on the volume expansion layer.

Examples of the method for forming the overcoat layer such that the average thickness T _A in the recesses is thinner than the average thickness T _B in the protrusions include a method of reducing the amount of the overcoat layer-forming composition applied to the recesses relative to the amount applied to the protrusions. Examples of the method for reducing the amount of the overcoat layer-forming composition applied to the recesses relative to the amount applied to the protrusions include a method of controlling the amount of the overcoat layer-forming composition applied, a method of controlling the scanning (movement) speed of a material application means that applies the overcoat layer-forming composition, and a method of controlling the number of times the overcoat layer-forming composition is applied.
In addition, examples of a method for controlling the amount of the overcoat layer forming composition to be applied include a method for adjusting the amount of the overcoat layer forming composition to be applied by making the amount of the overcoat layer forming composition to be applied to the concave portions smaller than the amount to be applied to the convex portions.
In addition, examples of a method for controlling the scanning (movement) speed of the material application means that applies the overcoat layer forming composition include a method for adjusting the amount of application by speeding up the scanning of the overcoat layer forming composition, which is ejected in a constant amount at a desired timing, over the concave portions and slowing down the scanning over the convex portions.
Further, a method for controlling the number of times the overcoat layer forming composition is applied can be exemplified by adjusting the amount of application by reducing the number of times a certain amount of the overcoat layer forming composition is applied to the concave portions relative to the number of times it is applied to the convex portions.

The average thickness of the overcoat layer is not particularly limited as long as the average thickness _TA of the overcoat layer on the surface of the volume expansion agent-containing layer in the recessed portions is thinner than the average thickness _TB of the overcoat layer on the surface of the volume expansion agent-containing layer in the protruding portions, and can be appropriately selected depending on the purpose.
The average thickness _TA is preferably 10 μm or more and 80 μm or less, and more preferably 20 μm or more and 40 μm or less.
The average thickness _TB is preferably 10 μm or more and 100 μm or less, and more preferably 20 μm or more and 60 μm or less.
The average thicknesses T _A and T _B may be average values of thicknesses of the overcoat layer at 10 different points, or may be values calculated from the amount of the overcoat layer-forming composition applied.

Here, in order to provide a more detailed explanation of the overcoat layer, first, the method for producing an article with a textured surface of the present invention will be explained with reference to the drawings.
Fig. 1A is a schematic diagram showing an example of a product after a volume expansion agent-containing layer forming step in the method for producing an uneven surface product of the present invention. As shown in Fig. 1A, in the method for producing an uneven surface product of the present invention, a volume expansion agent-containing layer forming step is first carried out in which a volume expansion agent composition containing a volume expansion agent 22 is applied to a substrate 11 to form a volume expansion agent-containing layer 21.
Next, Fig. 1B is a schematic diagram showing an example of a product after the inhibitor application step in the method for producing an uneven surface product of the present invention. As shown in Fig. 1B, in the method for producing an uneven surface product of the present invention, an inhibitor application step is carried out in which an inhibitor 23 that inhibits the expansion of the volume expansion agent 22 is applied to the volume expansion agent-containing layer 21. In the inhibitor application step, the inhibitor 23 is applied to a portion (predetermined area) in the volume expansion agent-containing layer 21 where the expansion of the volume expansion agent 22 is to be inhibited in the volume expansion layer formation step described later, so that the area where the inhibitor 23 is applied in the volume expansion layer formation step can be formed as a recess, and the area where the inhibitor 23 is not applied can be formed as a protrusion.
FIG. 1C is a schematic diagram showing an example of a product after the volume expansion layer forming step in the manufacturing method of the uneven surface product of the present invention. FIG. 1C shows an example of a schematic diagram of a cross-sectional view of an uneven surface product having an uneven surface without an overcoat layer. As shown in FIG. 1C, the uneven surface product has a recess 23A having a volume expansion agent 22B in which the volume expansion in the volume expansion agent-containing layer 21 is suppressed, and a protrusion 24B having a volume expansion agent 22A in which the volume expansion is caused in the volume expansion layer 21' to which the suppressing agent is not applied, on a substrate 11. When there is no overcoat layer, the height difference _D1 of the unevenness in the uneven surface product reflects the difference between the surface of the recess 24A and the surface of the protrusion 24B, as shown in FIG. 1C.
However, in a conventional uneven surface object having an uneven surface, when an overcoat layer 31 is formed on a volume expansion layer 21', the average thickness _TA of the overcoat layer 31 on the recesses 24A may be larger than the average thickness _TB of the overcoat layer 31 on the protrusions 24B, as shown in Fig. 2A. As a result, the height difference _D2 of the unevenness in the uneven surface object, as shown in Fig. 2A, becomes smaller than the height difference _D1 in the case where there is no overcoat layer as shown in Fig. 1C, and the height difference _D1 cannot be reflected, and sufficient design properties may not be ensured.
In contrast, in the method for producing an article with a textured surface of the present invention, as shown in Fig. 2B, an overcoat layer is formed by applying a smaller amount of the composition for forming an overcoat layer to the recesses 24A _than to the protrusions 24B, so that the average thickness _TA of the overcoat layer in the recesses 24A is thinner than the average thickness TB of the overcoat layer in the protrusions 24B. This allows the height difference _D3 of the unevenness in the article with a textured surface to reflect the height difference _D1 without reducing the magnitude of the height difference _D1 in the case where there is no overcoat layer as shown in Fig. 1C, and allows robustness to be imparted while ensuring designability.

As shown in FIG. 3A, the volume expansion agent 22A expands in volume at the convex portions 24B of the textured surface object, which can cause the surface to become rough. However, in the textured surface object obtained by the method for producing a textured surface object of the present invention, as shown in FIG. 3B, a thick overcoat layer is formed at the volume-expanded convex portions, making it possible to smooth the surface of the roughened convex portions 24B.

<Other processes>
The other steps are not particularly limited and may be appropriately selected depending on the purpose. Examples of the other steps include a curing step, an image forming step, an embossing step, and a control step.
<<Curing process>>
The curing step is a step of curing at least one of the volume expansion agent-containing layer and the inhibitor.
The curing step may be performed after each layer is formed, or after each layer is semi-cured and all the steps are completed, curing the layers to completely react with each other, or may be performed once after the inhibitor application step, the overcoat layer formation step, and the image formation step.

The method for curing the volume expansion agent-containing layer to which the inhibitor has been applied is not particularly limited as long as it is possible to cure at least one of the volume expansion agent-containing layer and the inhibitor, and can be appropriately selected depending on the purpose. For example, a method of applying active energy rays can be mentioned.

The active energy is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include ultraviolet light, electron beams, α-rays, β-rays, γ-rays, X-rays, and the like, which can provide the energy necessary to promote the polymerization reaction of the polymerizable components in the composition. In particular, when a high-energy light source is used, the polymerization reaction can be promoted without using a polymerization initiator. In addition, in the case of ultraviolet light irradiation, mercury-free devices are strongly desired from the viewpoint of environmental protection, and replacement with GaN-based semiconductor ultraviolet light-emitting devices is very useful both industrially and environmentally. Furthermore, ultraviolet light-emitting diodes (UV-LEDs) and ultraviolet laser diodes (UV-LDs) are small, have a long life, are highly efficient, and are low cost, making them preferable as ultraviolet light sources.

The curing conditions are not particularly limited and can be appropriately selected depending on the purpose. In the case of ultraviolet light, it is preferable to use an irradiation device capable of irradiating with an intensity of 6 W/ ^cm2 or more at an irradiation distance of 2 mm.
In the case of electron beams, the acceleration voltage is preferably such that a dose of 15 kGy or more is achieved when the object to be cured is placed at the farthest position from the electron beam irradiation device.

<<Image forming process>>
The image forming step is a step of forming an image by applying ink onto the volume expansion layer.

<<Ink>>
The ink contains a coloring material, and from the viewpoints of the designability due to the uneven shape and the durability of the image quality, preferably contains a second polymerizable compound and a polymerization initiator, and further contains other components as necessary.

- Coloring materials -
As the coloring material, various pigments and dyes that impart glossy colors such as black, white, magenta, cyan, yellow, green, orange, gold, and silver can be used depending on the purpose and required properties of the coloring material composition of the present invention.
The content of the colorant may be appropriately determined in consideration of the desired color concentration, dispersibility in the composition, and the like, and is not particularly limited. However, the content is preferably 0.1% by mass or more and 20% by mass or less, and more preferably 1% by mass or more and 10% by mass or less, based on the total amount of the colorant composition.
As the pigment, an inorganic pigment or an organic pigment can be used, and one type may be used alone, or two or more types may be used in combination.
Examples of the inorganic pigment include carbon blacks (C.I. Pigment Black 7) such as furnace black, lamp black, acetylene black, and channel black, iron oxide, and titanium oxide.
Examples of the organic pigments include azo pigments such as insoluble azo pigments, condensed azo pigments, azo lakes, and chelate azo pigments; polycyclic pigments such as phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone pigments; dye chelates (e.g., basic dye chelates, acid dye chelates, etc.); dye lakes (e.g., basic dye lakes, acid dye lakes, etc.); nitro pigments, nitroso pigments, aniline black, and daylight fluorescent pigments.
In order to improve the dispersibility of the pigment, a dispersant may be further contained.
The dispersant is not particularly limited, but examples thereof include dispersants commonly used for preparing pigment dispersions, such as polymer dispersants.
As the dye, for example, acid dyes, direct dyes, reactive dyes, and basic dyes can be used, and one type may be used alone, or two or more types may be used in combination.

--Second polymerizable compound--
As the second polymerizable compound, for example, the same polymerizable compound as in the volume expansion agent composition can be used, or a polymerizable compound different from the polymerizable compound in the volume expansion agent composition can be used.

- Polymerization initiator -
As the polymerization initiator, the same polymerization initiator as that of the volume expansion agent composition in the volume expansion agent-containing layer can be used.

<Other ingredients>
The other components are not particularly limited and can be appropriately selected depending on the purpose. Examples of the other components include organic solvents, surfactants, polymerization inhibitors, leveling agents, defoamers, fluorescent brightening agents, penetration promoters, wetting agents (moisturizing agents), fixing agents, viscosity stabilizers, antifungal agents, preservatives, antioxidants, ultraviolet absorbers, chelating agents, pH adjusters, and thickeners.

--Organic solvent--
The ink used in the present invention may contain an organic solvent, but preferably does not contain an organic solvent if possible. If the composition does not contain an organic solvent, particularly a volatile organic solvent (VOC (Volatile Organic Compounds)-free), the safety of the place where the composition is handled is improved and it is possible to prevent environmental pollution. Note that the "organic solvent" means a general non-reactive organic solvent such as ether, ketone, xylene, ethyl acetate, cyclohexanone, toluene, etc., and should be distinguished from a reactive monomer. In addition, "not containing" an organic solvent means that the organic solvent is substantially not contained, and it is preferable that the organic solvent content is less than 0.1 mass %.

- Preparation of ink -
The ink used in the present invention can be prepared using the various components described above. There are no particular limitations on the preparation means or conditions. For example, the ink can be prepared by putting a pigment as a colorant, a dispersant, etc. into a dispersing machine such as a ball mill, a Kitty mill, a disk mill, a pin mill, or a Dyno mill, dispersing the pigment, preparing a pigment dispersion, and further mixing a polymerizable compound, a polymerization initiator, a polymerization inhibitor, a surfactant, etc. into the pigment dispersion.

<Viscosity>
The viscosity of the ink used in the present invention may be appropriately adjusted depending on the application and application means, and is not particularly limited. For example, when applying an ejection means for ejecting the composition from a nozzle, the viscosity in the range of 20°C to 65°C, desirably the viscosity at 25°C is preferably 3 mPa·s to 40 mPa·s, more preferably 5 mPa·s to 15 mPa·s, and particularly preferably 6 mPa·s to 12 mPa·s. It is particularly preferable that the viscosity range is satisfied without containing the organic solvent. The viscosity can be measured by using a cone-plate type rotational viscometer VISCOMETER TVE-22L manufactured by Toki Sangyo Co., Ltd., using a cone rotor (1°34'×R24), at a rotation speed of 50 rpm, and by appropriately setting the temperature of the constant temperature circulating water in the range of 20°C to 65°C. A VISCOMATE VM-150III can be used to adjust the temperature of the circulating water.

The method of applying the ink onto the volume expansion layer is not particularly limited and can be appropriately selected depending on the purpose. However, an inkjet method is preferred from the viewpoints of productivity and flexibility in handling small lots and a wide variety of products.
As the inkjet method, for example, as a driving method for the ejection head, an on-demand type head using a piezoelectric element actuator using PZT or the like, a method that uses thermal energy, an actuator that uses electrostatic force, or the like can be used, or a continuous ejection type charge control type head can be used.

<<Embossing process>>
The embossing step is a step of forming a concave-convex pattern on the volume expansion layer and the image, and is carried out by an embossing means.
The uneven pattern can be formed by selectively using a method such as embossing, chemical embossing, rotary screen processing, or raised printing, which is generally used for the purpose of imparting unevenness to wallpaper, decorative boards, and the like.
Examples of the embossing step include a method of providing projections and recesses by processing using an embossing plate, chemical embossing, rotary screen printing, or raised printing.

The embossing means may be either a means for embossing with a heated and then cooled roller, or a means for embossing all at once using a heated roller embosser.
The depth of the embossing by the embossing process is preferably 0.08 mm or more and 0.50 mm or less. When the embossing depth is 0.08 mm or more, a three-dimensional effect can be created, and when it is 0.50 mm or less, the abrasion resistance of the surface can be improved.
Examples of the shape of the uneven pattern formed by embossing include vascular grooves of a wood grain plate, unevenness on the surface of a stone slab, texture on the surface of a cloth, matte finish, sand grain, hairline, and linear grooves.

Here, the apparatus for producing an article with a textured surface of the present invention, which is used in the method for producing an article with a textured surface of the present invention, will be described in detail with reference to the drawings.
Fig. 4 is a schematic diagram showing an example of an apparatus for manufacturing an uneven surface object of the present invention. The apparatus for manufacturing an uneven surface object 100 in Fig. 4 includes a curtain coater 121 for applying a volume expansion agent composition onto a substrate 111, a head 130a for applying an inhibitor by an inkjet method downstream of the curtain coater, an active energy ray irradiation device 131a, a discharge head unit consisting of a black head 132a, a magenta head 132b, a cyan head 132c, and a yellow head 132d as heads for applying a plurality of inks by an inkjet method, a second active energy ray irradiation device 131b, a heating device 133, and an inkjet head 130b for forming an overcoat layer. In Fig. 4, 134 is a conveyor belt, 135a is a feed roller, and 135b is a take-up roller. The substrate 111 is conveyed in the direction of the arrow in Fig. 1.

First, a volume expansion agent composition is applied to the surface of the substrate 111 by a curtain coater 121 to form a volume expansion agent-containing layer.
Next, the substrate 111 on which the volume expansion agent-containing layer has been formed is conveyed at a predetermined speed, and the inhibitor is discharged from the inhibitor head 130a onto the area of the volume expansion agent-containing layer where the volume expansion is not to be performed.
Next, the volume expansion agent-containing layer and the inhibitor are irradiated with active energy rays under predetermined irradiation conditions using the active energy ray irradiation device 131a, and are cured.
Next, color material compositions for black, cyan, magenta, and yellow are ejected by inkjet printing from the heads for each color, namely the black head 132a, the magenta head 132b, the cyan head 132c, and the yellow head 132d, to form an image.
Next, the volume expansion agent-containing layer and the image are irradiated with active energy rays under predetermined irradiation conditions using the active energy ray irradiation device 131b, and are cured.
Next, the obtained cured product is heated by a heating device 133, and volume expansion occurs in the area of the volume expansion agent-containing layer to which the inhibitor is not applied, resulting in a volume expansion layer. However, volume expansion does not occur in the area to which the inhibitor is applied. In this way, an uneven surface object having an uneven surface can be obtained.
Next, a first active energy ray curable composition is applied onto the obtained uneven surface object using an inkjet head 130b for forming an overcoat layer such that the average thickness _TA of the surface of the volume expansion layer in the area where the inhibitor is applied is thinner than the average thickness _TB of the surface of the volume expansion layer in the area where the inhibitor is not applied, and an active energy ray irradiation device 131c is used to cure the first active energy ray curable composition to form an overcoat layer. This makes it possible to obtain an uneven surface object with excellent design while improving robustness.

The textured surface object produced by the method for producing a textured surface object of the present invention has excellent design and image quality due to the textured shape, and can maintain the excellent design and image quality due to the textured shape for a long period of time, making it suitable for applications such as flooring, wallpaper, interior materials, wall materials, baseboards, ceiling materials, and building materials such as pillars.

The following describes examples of the present invention, but the present invention is not limited to these examples.

Example 1
Using the following materials and the manufacturing apparatus for an object with a textured surface shown in FIG. 4, an object with a textured surface 1 was manufactured under the following forming conditions.
<Ingredients>
-Base material-
・Glass plate (manufactured by AS ONE Corporation)
--Volume expansion agent composition--
2-Acryloyloxypropyl phthalic acid (ACB-21, manufactured by Shin-Nakamura Kogyo Co., Ltd.)
: 50 parts by weight Isobornyl acrylate (SR506, manufactured by Arkema Co., Ltd.) : 50 parts by weight Microsphere (H750, manufactured by Kureha Co., Ltd.) : 15 parts by weight 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide (Omnirad TPO, manufactured by Irgacure) : 5 parts by weight 1,6-hexanediol acrylate (SR238, manufactured by Arkema Co., Ltd.) : 0.1 parts by weight -Inhibitor-
1,6-Hexanediol acrylate (SR238, manufactured by Arkema Co., Ltd.): 100 parts by mass 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide (Omnirad TPO, manufactured by Irgacure): 5 parts by mass - Overcoat layer forming composition -
1,6-Hexanediol acrylate (SR238, manufactured by Arkema Co., Ltd.): 100 parts by mass 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide (Omnirad TPO, manufactured by Irgacure): 5 parts by mass <Formation conditions>
-Volume expansion layer forming process-
- Curtain coater (laboratory flow coater, manufactured by Chefura)
Average thickness: 50 μm
- Inhibitor application process -
Inkjet head: GEN5 head (MH5420, 150 npi x 4 rows, manufactured by Ricoh Industry Co., Ltd.)
Pattern: Solid, 28pl/nozzle
Discharge speed: 7 m/sec
Frequency: 2.4KHz
- Hardening process -
・Irradiation device: Linear irradiation type UV-LED light source GJ-75 (Hamamatsu Photonics K.K.)
Irradiation intensity: 4 W/ ^cm2
Distance between substrate and irradiation device: 10 mm
Irradiation time: 1s
After the overcoat layer forming step described below, a curing step was carried out under the same conditions.
-Volume expansion layer forming process-
・Heating device: Lutex Blower G Series (manufactured by Hitachi Industrial Equipment Systems Co., Ltd.)
High-temperature hot air generating electric heater XS-2 (manufactured by Kansai Electric Heating Co., Ltd.)
High Blow Nozzle 50AL (Kansai Dennetsu Co., Ltd.)
Wind speed from nozzle tip: 30 m/s
Nozzle tip temperature: 200°C
Conveying speed: 100 mm/s
--Overcoat layer forming process--
The overcoat layer forming composition is not applied to the surface (concave portion) of the volume expansion layer to which the inhibitor is applied. The overcoat layer forming composition is applied only to the surface (convex portion) of the volume expansion layer to which the inhibitor is not applied under the following conditions. Inkjet method Head: Four GEN5 heads (MH5420, 150 dpi x 4 rows, manufactured by Ricoh Industry Co., Ltd.) Pattern: Solid Discharge amount: 18 pl/nozzle
Discharge speed: 7 m/sec
Frequency: 4.8KHz
Average thickness T _B : about 80 μm (1200 dpi × 2400 dpi × 18 pl / nozzle)

Example 2
An article with a textured surface 2 was produced in the same manner as in Example 1, except that an image forming step was carried out under the following conditions before the overcoat layer forming step.
<Formation conditions>
--Image forming process--
An image was formed on the surface (concave portion) of the volume expansion layer to which the inhibitor was applied, and on the surface (convex portion) of the volume expansion layer to which the inhibitor was not applied, using a magenta ink obtained by stirring materials having the following composition.
Magenta ink Phenoxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.): 25 parts by weight Acryloyl morpholine (manufactured by Tokyo Chemical Industry Co., Ltd.): 26 parts by weight Trimethylolpropane ethoxy triacrylate (manufactured by Daicel Allnex Co., Ltd.): 35 parts by weight Omnirad TPO (manufactured by IGM Resins): 5 parts by weight Solsperse 32000 (manufactured by Lubrizol): 2 parts by weight CINQUASIA MAGENTA RT-355-D (manufactured by BASF Japan): 7 parts by weight Inkjet method Head: GEN5 head (MH5420, 150 dpi x 4 rows, manufactured by Ricoh Industry Co., Ltd.)
Pattern: Solid Discharge amount: 14pl/nozzle
Discharge speed: 7 m/sec
Frequency: 2.4KHz
Immediately after the image was formed, the image was cured under the same curing conditions as those described above.

Example 3
An article with a textured surface 3 was produced in the same manner as in Example 1, except that the overcoat layer was formed under the following conditions.
<Formation conditions>
--Overcoat layer forming process--
The overcoat layer forming composition is applied to the surface (concave portion) of the volume expansion layer to which the inhibitor is applied, and the surface (convex portion) of the volume expansion layer to which the inhibitor is not applied, under the following conditions. Inkjet method Head: Four GEN5 heads (MH5420, 150 npi x 4 rows, manufactured by Ricoh Industry Co., Ltd.) Pattern: Solid Discharge amount: 9 pl
Discharge speed: 7 m/sec
Frequency: 2.4KHz
Average thickness T _A : Recessed portion approximately 20 μm (600 dpi × 2400 dpi × 9 pl/nozzle)
Average thickness T _B : Convex portion approx. 40 μm (1200 dpi × 2400 dpi × 9 pl/nozzle)

(Comparative Example 1)
An article with a textured surface 4 was produced in the same manner as in Example 1, except that the overcoat layer was formed under the following conditions.
<Formation conditions>
--Overcoat layer forming process--
The overcoat layer forming composition is applied to the surface (concave portion) of the volume expansion layer to which the inhibitor is applied, and the surface (convex portion) of the volume expansion layer to which the inhibitor is not applied, under the following conditions: Inkjet method Head: Four GEN5 heads (MH5420, 150 npi x 4 rows, manufactured by Ricoh Industry Co., Ltd.) Pattern: Solid Discharge amount: 18 pl/nozzle
Discharge speed: 7 m/sec
Frequency: 2.4KHz
Average thickness T _A : Recessed portion approximately 40 μm (600 dpi × 2400 dpi × 18 pl/nozzle)
Average thickness T _B : protrusion approx. 40 μm

Next, images were taken and the height difference D was measured for the concave and convex portions of the textured surface objects 1 to 4 produced in Examples 1 to 3 and Comparative Example 1 using a laser microscope (manufactured by Keyence Corporation). The measurement and analysis conditions are shown below. The results are shown in Table 1.
[Measurement and analysis conditions]
Equipment used: Laser microscope VK-X110 (manufactured by Keyence Corporation)
・Software used: VK-H1XA
・Objective lens magnification: 10x

In the measurement, as shown in Figures 2A and 2B, the cross sections of the uneven surface objects 1 to 4 were measured. If the intersection point Q is the perpendicular line drawn from point P1, which is closest to the substrate on the outermost surface of the convex portion 24B, to the substrate, and the line parallel to the substrate and including point P2, which is closest to the substrate on the outermost surface of the concave portion 24A, the distance between point P1 and point Q was measured as the height difference D. The measurement results of the uneven surface object 1 in Example 1 using a laser microscope are shown in Figure 5. The upper part of Figure 5 shows the laser microscope image, and the graph at the bottom shows the height (z) at the corresponding position on the x-axis shown in the image, with the outermost surface of the concave portion as the reference plane.

For example, aspects of the present invention are as follows.
<1> A volume expansion agent-containing layer forming step of forming a volume expansion agent-containing layer containing a volume expansion agent on a substrate;
a suppressor application step of applying a suppressor that suppresses the expansion of the volume expansion agent on the volume expansion agent-containing layer in a predetermined region;
a volume expansion layer forming step of expanding the volume expansion agent in the volume expansion agent-containing layer to form a volume expansion layer in an area other than the predetermined area;
and an overcoat layer forming step of forming an overcoat layer on the volume expansion agent-containing layer in the specified region and on the volume expansion layer in the other regions so that the average thickness in the specified region is equal to or less than the average thickness in the other regions.
<2> The method for producing an article with a textured surface according to <1>, wherein the overcoat layer forming step includes applying a first polymerizable compound.
<3> The method for producing an object with a textured surface according to <2>, wherein the first polymerizable compound is applied by ejecting the compound by an inkjet method.
<4> The method for producing an article with a textured surface according to any one of <1> to <3>, wherein an average thickness of the overcoat layer in the predetermined region is 20 μm or more and 40 μm or less.
<5> The method for producing an article with a textured surface according to any one of <1> to <4>, wherein an average thickness of the overcoat layer in the other region is 20 μm or more and 60 μm or less.
<6> The method for producing an article with a textured surface according to any one of <1> to <5>, further comprising an image forming step of applying ink onto the volume expansion layer to form an image.
<7> The method for producing an object with a textured surface according to <6>, wherein the ink contains a second polymerizable compound.
<8> The method for producing an article with a textured surface according to any one of <1> to <7>, further comprising a curing step of curing at least one of the volume expansion agent-containing layer and the inhibitor.
<9> A volume expansion agent-containing layer forming means for forming a volume expansion agent-containing layer containing a volume expansion agent on a substrate;
a suppressor applying means for applying a suppressor that suppresses the expansion of the volume expansion agent onto the volume expansion agent-containing layer in a predetermined region;
a volume expansion layer forming means for expanding the volume expansion agent in the volume expansion agent-containing layer to form a volume expansion layer in an area other than the predetermined area;
and an overcoat layer forming means for forming an overcoat layer on the volume expansion agent-containing layer in the specified region and on the volume expansion layer in the other regions so that the average thickness in the specified region is equal to or less than the average thickness in the other regions.

The method for manufacturing an object with a rough surface described in any one of <1> to <7> and the device for manufacturing an object with a rough surface described in <8> can solve the problems of the past and achieve the object of the present invention.

Reference Signs List 100: Apparatus for manufacturing an object having a convex and concave surface 11, 111: Substrate 21: Layer containing volume expansion agent 21': Volume expansion layer 22: Volume expansion agent 22A: Volume-expanded volume expansion agent 22B: Volume-unexpanded volume expansion agent 23: Inhibitor 24A: Concave portion 24B: Convex portion 31: Overcoat layer

Patent No. 6090744

Claims (8)

A volume expansion agent-containing layer forming step of forming a volume expansion agent-containing layer containing a volume expansion agent on a substrate;
a suppressor application step of applying a suppressor that suppresses the expansion of the volume expansion agent on the volume expansion agent-containing layer in a predetermined region;
a volume expansion layer forming step of expanding the volume expansion agent in the volume expansion agent-containing layer to form a volume expansion layer in an area other than the predetermined area;
and an overcoat layer forming step of forming an overcoat layer on the volume expansion agent-containing layer in the specified region and on the volume expansion layer in the other regions so that the average thickness in the specified region is thinner than the average thickness in the other regions. The method for manufacturing an article with a textured surface according to claim 1, wherein the overcoat layer forming step includes applying a first polymerizable compound to the volume expansion layer. The method for manufacturing an object with a rough surface according to claim 2, wherein the application of the first polymerizable compound is performed by ejecting the compound using an inkjet method. The method for manufacturing an uneven surface object according to any one of claims 1 to 3, wherein the average thickness of the overcoat layer in the specified region is 20 μm or more and 40 μm or less. The method for manufacturing an uneven surface object according to any one of claims 1 to 4, wherein the average thickness of the overcoat layer in the other region is 20 μm or more and 60 μm or less. The method for manufacturing an object with a textured surface according to any one of claims 1 to 5 further includes an image forming step of applying ink to the volume expansion layer to form an image. The method for producing an object with a textured surface according to claim 6, wherein the ink contains a second polymerizable compound. The method for manufacturing an uneven surface object according to any one of claims 1 to 7 further includes a curing step for curing at least one of the volume expansion agent-containing layer and the inhibitor.