Method for producing decorative objects and processing solution

Abstract

The objective is to provide a method for producing decorative materials with excellent abrasion resistance. [Solution] A method for producing a decorative object, comprising: a processing liquid application step of applying a processing liquid to the surface of a substrate having a three-dimensional shape; an ink composition application step of applying an ink composition containing a sublimable colorant to an intermediate recording medium by an inkjet method; and a colorant application step of pressing the intermediate recording medium onto the surface of the substrate to obtain a laminate, heating the laminate to sublimate the sublimable colorant and apply it to the surface of the substrate, wherein the surface of the substrate has hydroxyl groups, and the processing liquid contains a crosslinking agent, water, and a resin having aromatic rings and a glass transition temperature of 20°C or higher.

Description

Technical Field

[0001] The present invention relates to a method for producing a decorative article and a treatment liquid.

Background Art

[0002] Examples of recording media for recording images and the like include various types such as paper, fabric, and wood, and suitable printing methods differ depending on the type of recording medium. Therefore, various printing methods have been developed according to the type of recording medium. For example, Patent Document 1 discloses a method for dyeing a surface of a rush with a pattern using sublimation transfer printing in which a dye is sublimated and attached to a recording medium.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] Sublimation transfer printing can be carried out on various recording media with a low-cost and simple device. On the other hand, it has been found that there is room for improvement in the abrasion resistance and color development of the decorative article obtained by sublimation transfer printing.

Means for Solving the Problems

[0005] The present invention includes a treatment liquid application step of applying a treatment liquid to a surface having a three-dimensional shape of a base material, an ink composition adhesion step of adhering an ink composition containing a sublimable coloring material to an intermediate recording medium by an inkjet method, a step of obtaining a laminate by pressing the intermediate recording medium onto the surface of the base material, and heating the laminate to sublime the sublimable coloring material and attach it to the surface of the base material. The surface of the base material has a hydroxyl group, and the treatment liquid contains a crosslinking agent, water, and a resin having an aromatic ring and a glass transition temperature of 20°C or higher. It is a method for producing a decorative article.

[0006] The present invention relates to a treatment liquid to be applied to a surface having a three-dimensional shape of a substrate, and comprises a crosslinking agent, water, and a resin having an aromatic ring and a glass transition temperature of 20°C or higher. [Brief explanation of the drawing]

[0007] [Figure 1] This is a schematic diagram of the recording device used in this embodiment. [Figure 2] This table shows the results of the examples. [Modes for carrying out the invention]

[0008] The following describes in detail an embodiment of the present invention (hereinafter referred to as "this embodiment"), but the present invention is not limited thereto, and various modifications are possible without departing from its essence.

[0009] 1. Method for manufacturing decorative objects The method for manufacturing the decorative object of this embodiment comprises a processing liquid application step of applying a processing liquid to the three-dimensional surface of a substrate; an ink composition application step of applying an ink composition containing a sublimable colorant to an intermediate recording medium using an inkjet method; and a colorant application step of pressing the intermediate recording medium onto the surface of the substrate to obtain a laminate, heating the laminate to sublimate the sublimable colorant and attach it to the surface of the substrate, wherein the surface of the substrate has hydroxyl groups, and the processing liquid includes a crosslinking agent, water, and a resin having aromatic rings and a glass transition temperature of 20°C or higher.

[0010] In a recording method (hereinafter also referred to as the "sublimation transfer recording method") in which a sublimable colorant attached to an intermediate recording medium is sublimated to deposit the colorant onto a substrate, it is preferable that the substrate has a resin layer that accepts the colorant so that the sublimable colorant can adhere well to the substrate. For this reason, the surface of the substrate used in the sublimation transfer recording method generally has a resin layer provided by surface treatment or has a resin layer from the beginning. Furthermore, even when a substrate with a resin layer from the beginning is used, a new resin layer may be provided on the surface of the substrate by surface treatment in order to further improve the fixation of the sublimable colorant. On the other hand, if the surface of the substrate is not flat, such as when the surface of the substrate is uneven or greatly curved, that is, when the surface of the substrate has a three-dimensional shape, even if surface treatment is performed, it may be difficult to form a resin layer, or even if it is formed, the thickness of the layer may be uneven.

[0011] In this regard, the processing solution used in the processing solution application process of this embodiment contains a crosslinking agent and a resin, the resin having an aromatic ring and a glass transition temperature of 20°C or higher. Furthermore, the surface of the substrate in this embodiment has hydroxyl groups. As a result, even if the surface of the substrate has a three-dimensional shape, applying the processing solution of this embodiment to the surface tends to form a uniform resin layer. Consequently, the sublimable colorant adhering to the resin layer tends to be less likely to detach from the substrate. In other words, the abrasion resistance of the decorative object tends to improve.

[0012] Because the glass transition temperature of the resin is 20°C or higher, the thermal motion of the polymers in the resin is suppressed at room temperature (25°C), which is the typical operating temperature for decorative items. As a result, sublimable colorants attached to a resin layer containing such a resin are more easily retained within the resin layer. Furthermore, at room temperature, the resin layer containing the above resin tends to harden. In addition, because the treatment solution contains a crosslinking agent, the polymers in the resin crosslink with each other, further suppressing the movement of the resin, so that the sublimable colorants are more easily retained within the resin layer. Moreover, because the polymers in the resin interact with the hydroxyl groups on the surface of the substrate via the crosslinking agent, the resin layer containing the sublimable colorants tends to bond more firmly to the substrate. Therefore, it is presumed that the abrasion resistance of the decorative item will be improved.

[0013] Furthermore, because the glass transition temperature of the resin is 20°C or higher, the sublimable colorant is firmly held within the resin layer, which tends to improve the color development and resistance to discoloration of the decorated object. Additionally, because the treatment solution contains a crosslinking agent, the sublimable colorant is held even more firmly within the resin layer, and the resin layer containing the sublimable colorant is firmly bonded to the substrate, which tends to improve the color development and resistance to discoloration of the decorated object.

[0014] Furthermore, the presence of aromatic rings in the resin increases the interaction between the resin and the sublimable colorant, making it easier for the sublimable colorant to be retained in the resin layer, which tends to improve the scratch resistance, color development, and resistance to discoloration of the decorated object. When the sublimable colorant has aromatic rings, the aromatic rings of the sublimable colorant interact with the aromatic rings of the resin through π-π interactions, making it easier for the sublimable colorant to be retained in the resin, which tends to further improve the scratch resistance, color development, and resistance to discoloration of the decorated object.

[0015] The following describes in detail each step that may be involved in the manufacturing method of the decorative object according to this embodiment.

[0016] 1.1. Processing solution application process In the treatment liquid application step of this embodiment, a treatment liquid is applied to the surface having the three-dimensional shape of the base material. The application method is not particularly limited. For example, a method of injecting (jet application) or spraying (spray application) the treatment liquid toward the surface of the base material, a method of applying the treatment liquid to the surface of the base material using a brush or a blade, a method of rotating the base material while dropping the treatment liquid onto the surface of the base material and spreading the treatment liquid over the entire surface of the base material using the centrifugal force thereof (spin coating), a method of immersing the base material in a bath of the treatment liquid (dip coating), etc. may be mentioned.

[0017] After applying the treatment liquid, drying may be promoted by heating. The heating method is not particularly limited. For example, a heater may be used, or warm air may be used.

[0018] 1.1.1. Base material The surface of the base material has hydroxyl groups. The surface of the base material may originally have hydroxyl groups or may be given hydroxyl groups later. For example, wood, bamboo, and tatami originally have plant-derived hydroxyl groups on their surfaces. The method of imparting hydroxyl groups to the surface of the base material is not particularly limited. For example, a method of plasma-treating the surface of the base material may be mentioned.

[0019] The surface of the base material has a three-dimensional shape. Here, the three-dimensional shape means irregularities on the surface of tatami, irregularities derived from bamboo joints on the surface of bamboo, the surface shape of wood processed so that the surface is a curved surface, etc., and does not mean microscopic irregularities such as the surface of a non-woven fabric or ordinary paper. From this viewpoint, the maximum height Pz of the cross-sectional curve of the base material of this embodiment is 1 mm or more. The maximum height Pz of the cross-sectional curve is a value measured in accordance with JIS B0601:2013.

[0020] The base material of this embodiment is not particularly limited. For example, wood, bamboo, tatami, metal, stone, and concrete materials may be mentioned. Among these, as the base material, one or more selected from the group consisting of wood, bamboo, and tatami are preferable.

[0021] The thickness of the base material in this embodiment is preferably 0.5 cm or more, 1 cm or more, or 2 cm or more. Alternatively, the thickness of the base material in this embodiment is preferably 0.5 to 4.0 cm, 1.0 to 3.5 cm, or 2.0 to 3.0 cm.

[0022] Furthermore, it is preferable that the substrate in this embodiment has rigidity. Generally, when a decorative object is obtained by printing on a substrate using a sublimation transfer method, the texture of the decorative object tends to be harder than the texture of the substrate. In this respect, when a decorative object is obtained by printing on a soft substrate such as paper or cloth using a sublimation transfer method, it is sometimes necessary to print in a way that does not impair the soft texture of the substrate itself. On the other hand, when a decorative object is obtained by printing on a rigid substrate using a sublimation transfer method, the texture of the decorative object tends not to change significantly from the substrate before printing, because the substrate itself has rigidity and a hard texture.

[0023] In this regard, since the processing solution of this embodiment contains a resin with a glass transition temperature of 20°C or higher, the texture of the decorative object obtained using such a processing solution tends to become harder. However, because the substrate has rigidity, the influence of the processing solution on the texture tends to be reduced.

[0024] The rigid base material is not particularly limited, but examples include wood, bamboo, tatami mats, plastics, metals, stone, and concrete. Among these, wood, bamboo, and tatami mats are preferred as the base material.

[0025] The Young's modulus of a rigid substrate is not particularly limited, but is, for example, 5.0 GPa or higher. The Young's modulus is not particularly limited, but is measured, for example, with a TENSILON universal testing machine (product name: RTG-1250, manufactured by A&D Company, Limited).

[0026] In addition, it is preferable that the base material of this embodiment does not include fabrics such as cloth and nonwoven fabrics, or papers such as plain paper and glossy paper.

[0027] 1.1.2. Treatment solution The treatment solution of this embodiment is applied to the three-dimensional surface of a substrate and contains a crosslinking agent, water, and a resin having an aromatic ring and a glass transition temperature of 20°C or higher. The components that may be included in the treatment solution will be described in detail below.

[0028] 1.1.2.1. Crosslinking Agents Crosslinking agents include those that initiate the crosslinking reaction at room temperature and those that initiate the crosslinking reaction upon heating. Examples of crosslinking agents include self-crosslinking agents, compounds having multiple functional groups that react with unsaturated carboxylic acid components within the molecule, and metals having polyvalent coordination sites. Crosslinking agents may be used individually or in combination of two or more.

[0029] From the viewpoint of further improving the abrasion resistance, color development, and resistance to discoloration and fading of the decorative material, isocyanate compounds having an isocyanate group and oxazoline compounds having an oxazoline group are preferred as crosslinking agents.

[0030] Examples of isocyanate compounds include water-dispersible (blocked) polyisocyanates. (Blocked) polyisocyanate refers to polyisocyanate and / or blocked polyisocyanate.

[0031] Examples of water-dispersible polyisocyanates include those obtained by dispersing a polyisocyanate, which has been given hydrophilicity by polyethylene oxide chains, in water with an anionic or nonionic dispersant.

[0032] Examples of polyisocyanates include diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate; and derivatives (modified products) of these diisocyanates, such as trimethylolpropane adducts, biuret compounds, and isocyanurates.

[0033] Water-dispersible blocked polyisocyanates are obtained by blocking the isocyanate groups of water-dispersible polyisocyanates with a blocking agent. Examples of blocking agents include diethyl malonate, ethyl acetoacetate, ε-caprolactam, butanone oxime, cyclohexanone oxime, 1,2,4-triazole, dimethyl-1,2,4-triazole, 3,5-dimethylpyrazole, and imidazole.

[0034] Commercially available isocyanate compounds may be used as such. Examples of commercially available products include Fixer #100ECO, #104EA, #220, 70ECO, #70, #410, and #400 (all trade names, manufactured by Murayama Chemical Research Institute); and Elastron® BN-11, BN-27, BN-69, and BN-77 (all trade names, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

[0035] Examples of oxazoline compounds include compounds having two or more oxazoline groups in their molecule. Examples of such oxazoline group-containing compounds include 2,2'-bis(2-oxazoline), 2,2'-methylene-bis(2-oxazoline), 2,2'-ethylene-bis(2-oxazoline), 2,2'-trimethylene-bis(2-oxazoline), 2,2'-tetramethylene-bis(2-oxazoline), 2,2'-hexamethylene-bis(2-oxazoline), 2,2'-octamethylene-bis(2-oxazoline), Examples include 2,2'-ethylene-bis(4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylene-bis(2-oxazoline), 2,2'-m-phenylene-bis(2-oxazoline), 2,2'-m-phenylene-bis(4,4'-dimethyl-2-oxazoline), bis(2-oxazolinylcyclohexane) sulfide, bis(2-oxazolinylnorbornane) sulfide, and oxazoline ring-containing polymers.

[0036] Commercially available oxazoline compounds may be used. Examples of commercially available products include Epocross® K-2010, K-2020, K-2030, K-2035E, WS-300, WS-500, and WS-700 (all trade names, manufactured by Nippon Shokubai Co., Ltd.).

[0037] The crosslinking agent content is preferably 0.1 to 5.0% by mass, 0.5 to 4.5% by mass, and 1.0 to 3.0% by mass, relative to the total amount of the treatment solution. When the crosslinking agent content is within the above range, the abrasion resistance, color development, and resistance to discoloration and fading of the decorated material tend to be further improved.

[0038] 1.1.2.2. Resin The glass transition temperature of the resin in this embodiment is 20°C or higher. Preferably, the glass transition temperature of the resin is 40°C or higher, 60°C or higher, or 80°C or higher. Alternatively, preferably, the glass transition temperature of the resin is 20-190°C, 40-180°C, 60-170°C, or 80-160°C. When the glass transition temperature is within the above range, the scratch resistance, color development, and resistance to discoloration and fading of the decorated material tend to be further improved. Also, when the glass transition temperature is below the upper limit of the above range, the treatment solution tends to be easier to apply to the three-dimensional surface of the substrate.

[0039] The glass transition temperature of a resin can be adjusted, for example, by controlling the magnitude of the intermolecular interactions between polymers. For instance, increasing the intermolecular interactions between polymers tends to raise the glass transition temperature of the resin. There are no particular limitations on how to increase the intermolecular interactions between polymers, but examples include increasing the weight-average molecular weight of the polymers and introducing polar groups such as hydroxyl groups into the polymers to induce hydrogen bonding between them.

[0040] The weight-average molecular weight can be measured, for example, by gel permeation chromatography (GPC) using polystyrene equivalents. The glass transition temperature of the resin can be measured, for example, by differential scanning calorimeter (DSC).

[0041] Furthermore, the resin of this embodiment has an aromatic ring. The resin of this embodiment is preferably a polyester resin having an aromatic ring and a glass transition temperature of 20°C or higher, an acrylic-styrene resin having an aromatic ring and a glass transition temperature of 20°C or higher, and a urethane resin having an aromatic ring and a glass transition temperature of 20°C or higher, with a polyester resin having an aromatic ring and a glass transition temperature of 20°C or higher being more preferred. The resin may be used alone or two or more in combination.

[0042] Polyester resins are obtained by copolymerizing polycarboxylic acids and polyhydric alcohols. Polyester resins have constituent units derived from polycarboxylic acids and constituent units derived from polyhydric alcohols.

[0043] The polycarboxylic acids are not particularly limited, but examples include terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 4,4′-diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-potassium sulfoterephthalic acid, 5-sodium sulfisoisophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutaric acid, succinic acid, trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, phthalic anhydride, succinic anhydride, and p-hydroxybenzoic acid, as well as salts thereof. Examples of salts include potassium salts, sodium salts, calcium salts, and magnesium salts. The polycarboxylic acids may be used individually or in combination of two or more.

[0044] The polyhydric alcohol is not particularly limited, but examples include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propanediol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,5-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, p-xylylene glycol, bisphenol A-ethylene glycol adduct, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetramethylene oxide glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, sodium dimethylolethylsulfonate, potassium dimethylolethylsulfonate, and potassium dimethylolpropionate. The polyhydric alcohol may be used alone or in combination of two or more types.

[0045] Preferably, at least one of the polycarboxylic acid and the polyhydric alcohol has an aromatic ring.

[0046] As the polyester resin having an aromatic ring, one manufactured using a polycarboxylic acid and a polyhydric alcohol may be used, or a commercially available product may be used.

[0047] Acrylic-styrene resin is obtained by copolymerizing an acrylic acid ester monomer with a styrene compound, and has constituent units derived from the acrylic acid ester monomer and constituent units derived from the styrene compound.

[0048] The acrylic acid ester monomer is not particularly limited, but examples include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isopropyl (meth)acrylate, isobutyl (meth)acrylate, pentyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, and phenyl (meth)acrylate. In this embodiment, "(meth)acrylate" includes acrylate and methacrylate. The acrylic acid ester monomer may have an aromatic ring. The acrylic acid ester monomer may be used alone or in combination of two or more.

[0049] Examples of styrene compounds include styrene and modified styrene. Modified styrene is a compound in which the hydrogen atoms directly bonded to the carbon atoms constituting the benzene ring of styrene are replaced by other functional groups. Modified styrene is not particularly limited, but examples include chlorostyrene, fluorostyrene, phenylstyrene, methylstyrene, ethylstyrene, and carboxystyrene. Styrene compounds may be used individually or in combination of two or more.

[0050] As the acrylic-styrene resin having an aromatic ring, one manufactured using an acrylic acid ester monomer and a styrene compound may be used, or a commercially available product may be used.

[0051] Urethane resin is a resin having urethane bonds. Urethane resin is obtained, for example, by copolymerizing a polyhydric isocyanate and a polyhydric alcohol, and has constituent units derived from the polyhydric isocyanate and constituent units derived from the polyhydric alcohol.

[0052] The polyvalent isocyanates are not particularly limited, but examples include aliphatic polyvalent isocyanates and aromatic polyvalent isocyanates. The aliphatic polyvalent isocyanates are not particularly limited, but examples include chain-like polyvalent isocyanates such as tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, and 3-methylpentane-1,5-diisocyanate; and cyclic polyvalent isocyanates such as isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, and 1,3-bis(isocyanate-methyl)cyclohexane. The aliphatic polyvalent isocyanates may be used individually or in combination of two or more.

[0053] The aromatic polyvalent isocyanates are not particularly limited, but examples include tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyle diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, and α,α,α',α'-tetramethylxylylene diisocyanate. The aromatic polyvalent isocyanates may be used individually or in combination of two or more.

[0054] The polyhydric alcohol is not particularly limited, but examples include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propanediol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,5-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, p-xylylene glycol, bisphenol A-ethylene glycol adduct, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetramethylene oxide glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, sodium dimethylolethylsulfonate, potassium dimethylolethylsulfonate, and potassium dimethylolpropionate. The polyhydric alcohol may be used alone or in combination of two or more types.

[0055] It is preferable that at least one of the polyhydric isocyanate and the polyhydric alcohol has an aromatic ring.

[0056] As the urethane resin having an aromatic ring, one manufactured using a polyhydric isocyanate and a polyhydric alcohol may be used, or a commercially available product may be used.

[0057] The content of the resin having an aromatic ring and a glass transition temperature of 20°C or higher is preferably 1 to 20% by mass, 3 to 17% by mass, 5 to 15% by mass, and 7 to 13% by mass, relative to the total amount of the treatment solution. When the content of the resin having an aromatic ring is within the above range, the scratch resistance, color development, and resistance to discoloration and fading of the decorated material tend to be further improved.

[0058] The content of polyester resin having an aromatic ring and a glass transition temperature of 20°C or higher is preferably 1 to 20% by mass, 3 to 17% by mass, 5 to 15% by mass, and 7 to 13% by mass, relative to the total amount of the treatment solution. When the content of polyester resin having an aromatic ring is within the above range, the abrasion resistance, color development, and resistance to discoloration and fading of the decorated material tend to be further improved.

[0059] The content of polyester resin having an aromatic ring and a glass transition temperature of 20°C or higher is preferably 70-100% by mass, 80-100% by mass, or 90-100% by mass, relative to the total amount of resin having an aromatic ring and a glass transition temperature of 20°C or higher. When the content of polyester resin having an aromatic ring is within the above range, the abrasion resistance, color development, and resistance to discoloration and fading of the decorative material tend to be further improved.

[0060] The content of acrylic-styrene resin having an aromatic ring and a glass transition temperature of 20°C or higher is preferably 1 to 20% by mass, 3 to 17% by mass, 5 to 15% by mass, and 7 to 13% by mass, relative to the total amount of the treatment solution. When the content of acrylic-styrene resin having an aromatic ring is within the above range, the scratch resistance, color development, and resistance to discoloration and fading of the decorative material tend to be further improved.

[0061] The content of urethane resin having an aromatic ring and a glass transition temperature of 20°C or higher is preferably 1 to 20% by mass, 3 to 17% by mass, 5 to 15% by mass, and 7 to 13% by mass, relative to the total amount of the treatment solution. When the content of urethane resin having an aromatic ring is within the above range, the abrasion resistance, color development, and resistance to discoloration and fading of the decorative material tend to be further improved.

[0062] Crosslinking agent content W C Resin content W R The ratio (W R / W C The ratio (W) is preferably 2.0 to 10.0, 2.5 to 8.0, and 3.0 to 6.0. R / W C When the above range is present, the scratch resistance, color development, and resistance to discoloration and fading of the decorative material tend to be further improved.

[0063] 1.1.2.3.Water The dye composition of this embodiment contains water. The water is not particularly limited, but may be, for example, pure water or deionized water. The water content is preferably 60% by mass or more, 60-95% by mass, 65-90% by mass, or 70-90% by mass, relative to the total amount of the treatment solution. When the water content is within the above range, the abrasion resistance, color development, and resistance to discoloration and fading of the decorated material tend to be further improved.

[0064] 1.1.2.4. Other Additives The treatment solution of this embodiment may contain other additives in addition to the components described above. These other additives are not particularly limited, but examples include ultraviolet absorbers, surfactants, solubilizers, viscosity modifiers, humectants, pH adjusters, antioxidants, preservatives, fungicides, corrosion inhibitors, and chelating agents. The content of these other additives is not particularly limited, but is, for example, 0.1 to 5.0% by mass of the total amount of the treatment solution.

[0065] 1.1.3. Method for preparing the treatment solution The processing solution can be prepared by mixing the components in any order and removing impurities and foreign matter by filtration or other methods as needed. Methods for mixing the components include sequentially adding each component to a container equipped with a stirring device such as a mechanical stirrer or magnetic stirrer, and then stirring and mixing them. Filtration methods include centrifugal filtration and filter filtration.

[0066] 1.2. Ink composition application process In the ink composition coating process, an ink composition containing a sublimable colorant is coated onto an intermediate recording medium using an inkjet method.

[0067] In an inkjet system, the ink composition is ejected from the inkjet head. Examples of inkjet heads include piezo-type heads that use a piezoelectric element whose volume changes when voltage is applied, and thermal-type heads that generate bubbles in the ink by heating and eject the ink, but piezo-type heads are preferred.

[0068] Inkjet heads include line heads, which record using a line method, and serial heads, which record using a serial method.

[0069] In a line-type system using a line head, for example, an inkjet head with a width greater than or equal to the recording width of the intermediate recording medium is fixed to the recording device. The intermediate recording medium is then moved along the sub-scanning direction (the transport direction of the intermediate recording medium), and ink droplets are ejected from the nozzles of the inkjet head in conjunction with this movement, thereby recording an image on the intermediate recording medium.

[0070] In a serial method using a serial head, for example, an inkjet head is mounted on a carriage that can move in the width direction of the intermediate recording medium. The carriage is then moved along the main scanning direction (the width direction of the intermediate recording medium), and ink droplets are ejected from the nozzles of the inkjet head in conjunction with this movement, thereby recording an image on the intermediate recording medium.

[0071] 1.2.1. Ink Composition The ink composition applied to the intermediate recording medium by the inkjet method contains a sublimation colorant and may also contain a solvent and other additives. The components that may be included in the ink composition are described in detail below.

[0072] 1.2.1.1.Sublimable colorants The sublimable colorant of this embodiment is a colorant that sublimes upon heating, for example, a sublimable dye that sublimes upon heating. The sublimation temperature is not particularly limited, but for example, it is 120°C or higher, 140°C or higher, or 160°C or higher. The upper limit of the sublimation temperature is also not particularly limited, but for example, it is 220°C or lower, preferably 200°C or lower. The sublimable colorant preferably has an aromatic ring. The sublimation dyes are not particularly limited, but examples include CI Disperse Yellow 3, 7, 8, 23, 39, 51, 54, 60, 64, 71, 82, 86, 211, and 232; CI Disperse Orange 1, 1:1, 5, 20, 24, 25, 25:1, 33, 56, and 76; CI Disperse Brown 2 and 27; CI Disperse Red 11, 50, 53, 55, 55:1, 59, 60, 65, 70, 75, 93, 146, 158, 190, 1 Examples of disperse dyes include 90:1, 207, 239, 240, and 364; CI Disperse Violet 8, 17, 23, 27, 28, 29, 36, and 57; CI Disperse Blue 14, 19, 26, 26:1, 35, 55, 56, 58, 64, 64:1, 72, 72:1, 81, 81:1, 91, 95, 108, 131, 141, 145, 359, and 360; and solvent dyes such as CI Solvent Blue 36, 63, 94, 105, and 111. Disperse dyes are dyes that disperse in water using a dispersant. Solvent dyes are dyes that are soluble in organic solvents such as ethanol and acetone.

[0073] The amount of sublimation colorant is not particularly limited relative to the total amount of the ink composition, but is, for example, 0.5 to 20.0% by mass and 1.0 to 15.0% by mass.

[0074] 1.2.1.2. solvent The ink composition of this embodiment preferably contains a solvent. Examples of solvents include water; aprotic polar solvents such as pyrrolidones (e.g., 2-pyrrolidone), imidazolidinones, sulfoxides, lactones, amide ethers, and imidazoles; monoalcohols such as methanol and ethanol; alkyl polyols such as glycerin, ethylene glycol, diethylene glycol, triethylene glycol, and alkanediols; and alkyl ethers of polyhydric alcohols such as dialkyl ethers and monoalkyl ethers. Among these, water is preferred.

[0075] The solvent content is not particularly limited, but is, for example, 50 to 90% by mass relative to the total amount of the ink composition.

[0076] 1.2.1.3. Other Additives The ink composition of this embodiment may also contain other additives besides those described above. These other additives are not particularly limited, but examples include dispersants, surfactants, solubilizers, viscosity modifiers, humectants, pH adjusters, antioxidants, preservatives, fungicides, corrosion inhibitors, and chelating agents.

[0077] The content of other additives is not particularly limited in relation to the total amount of the ink composition, but is, for example, 0.1 to 10.0% by mass.

[0078] 1.2.2. Method for preparing ink compositions Ink compositions can be prepared by mixing each component in any order and removing impurities and foreign matter by filtration or other methods as needed. Methods for mixing the components include sequentially adding each component to a container equipped with a stirring device such as a mechanical stirrer or magnetic stirrer, and then stirring and mixing them. Filtration methods include centrifugal filtration and filter filtration.

[0079] 1.2.3. Intermediate recording media The intermediate recording medium to which the ink composition is applied is not particularly limited as long as it is a recording medium that can sublimate the sublimable colorant contained in the applied ink composition, for example, transfer paper. Specifically, examples of transfer paper include DS TRANSFER MULTI PURPOSE (manufactured by Seiko Epson Corporation).

[0080] 1.3. Coloring material adhesion process In the colorant adhesion process, an intermediate recording medium is pressed onto the surface of the substrate to obtain a laminate, and the laminate is heated to sublimate the sublimable colorant and adhere it to the surface of the substrate. The colorant adhesion process is performed after the processing solution application process, and the surface of the substrate to which the colorant adheres in the colorant adhesion process is the surface to which the processing solution has been applied. Preferably, a resin layer is formed on the surface of the substrate to which the colorant adheres in the colorant adhesion process.

[0081] The laminate may be heated after the laminate is obtained, or it may be heated simultaneously with the overlapping of the recording surface of the intermediate recording medium and the substrate. The heating temperature for the laminate is preferably 155 to 215°C, and more preferably 160 to 210°C.

[0082] When heating a laminate, pressure may be applied simultaneously with heating. For example, a heat press can be used to perform heating and pressure application at the same time. Alternatively, pressure may be applied to the laminate beforehand, and then the laminate may be heated. For example, the laminate may be wrapped in heat-resistant plastic wrap, pressure may be applied, and then the heat-wrapped laminate may be placed in an oven for heating.

[0083] 1.4.Protective layer formation process The manufacturing method of the decorative object according to this embodiment may include a protective layer formation step after the colorant application step, in which a protective layer is provided on the surface of the substrate to which the sublimable colorant has been applied. Providing a protective layer tends to further improve the abrasion resistance, color development, and resistance to discoloration and fading of the decorative object. The material of the protective layer is not particularly limited, but examples include urethane resin, acrylic resin, epoxy resin, silicone resin, and fluororesin.

[0084] On the other hand, decorative objects manufactured by the manufacturing method of this embodiment tend to have excellent scratch resistance, color development, and resistance to discoloration and fading even without a protective layer; therefore, the manufacturing method of this embodiment does not need to include a protective layer formation step.

[0085] 2. Inkjet recording device As an example of an inkjet device, Figure 1 shows a perspective view of a serial printer. As shown in Figure 1, the serial printer 20 comprises a transport unit 220 and a recording unit 230. The transport unit 220 transports the recording medium F fed into the serial printer to the recording unit 230 and discharges the recorded recording medium outside the serial printer. Specifically, the transport unit 220 has feed rollers and transports the fed recording medium F in the sub-scanning direction T2.

[0086] Furthermore, the recording unit 230 includes a carriage 234 on which an inkjet head 231 having nozzles for ejecting an ink composition onto the recording medium F sent from the transport unit 220 is mounted, and a carriage movement mechanism 235 for moving the carriage 234 in the main scanning directions S1 and S2 of the recording medium F.

[0087] In a serial printer, the inkjet head 231 is equipped with a head that is shorter than the width of the recording medium, and the head moves, performing recording in multiple passes (multipass). In a serial printer, the head 231 is mounted on a carriage 234 that moves in a predetermined direction, and as the carriage moves, the head moves, ejecting the ink composition onto the recording medium F. This allows for recording in two or more passes (multipass). A pass is also called a main scan. A sub-scan is performed between passes to transport the recording medium. In other words, main scans and sub-scans are performed alternately.

[0088] Furthermore, the inkjet device of this embodiment is not limited to the serial printer described above, but may also be a line printer as described above. A line printer is a printer that uses a line head, which is an inkjet head with a length greater than or equal to the recording width of the recording medium, to record on the recording medium in a single scan. [Examples]

[0089] The present invention will be described in more detail below using examples and comparative examples. The present invention is not limited in any way by the following examples. Unless otherwise specified, each operation in the examples was carried out at room temperature (25°C) and 1 atmosphere.

[0090] 1. Preparation of the treatment solution The components were placed in a stainless steel container, a mixing tank, to obtain the composition shown in Figure 2. The mixture was then mixed and stirred at room temperature, and filtration was performed as needed to remove impurities and foreign matter, thereby obtaining the treatment solution used in each example. Unless otherwise specified, the numerical values ​​for each component shown in the figure represent mass percentages. Furthermore, the mass percentage for resins represents the solid content concentration. The components shown in the figure are as follows: • Byronal MD-1480: Polyester resin containing aromatic rings, manufactured by Toyobo Co., Ltd. • Elitel KT-8803: A polyester resin containing aromatic rings, manufactured by Unitika Corporation. • Pluscoat Z-687: Polyester resin with aromatic rings, manufactured by Go-o Chemical Industry Co., Ltd. • Movinyl 6960: Acrylic-styrene resin, manufactured by Japan Coating Resin Co., Ltd. • Fixer #104EA: Crosslinking agent (isocyanate compound), manufactured by Murayama Chemical Research Institute Co., Ltd. • Epocross K-2035E: Crosslinking agent (oxazoline compound), manufactured by Nippon Shokubai Co., Ltd.

[0091] 2. Processing solution application process The treatment solution for each example was applied to a bamboo steamer mat using a sponge roller, and then dried in a 150°C oven for 3 minutes to obtain a substrate coated with the treatment solution.

[0092] 3. Ink composition application process Using a printer equipped with dye-sublimation ink (SC-F9450 (product name), manufactured by Seiko Epson), magenta ink (Epson, dye-sublimation ink SC20MP) was printed at 100% duty cycle on an intermediate recording medium (DS TRANSFER MULTI PURPOSE (product name), manufactured by Seiko Epson) at a resolution of 720 dpi horizontally and 720 dpi vertically.

[0093] Note that "duty" is a value calculated using the following formula, and 100% duty means that one drop of ink is applied to every pixel. Fuel efficiency (%) = Actual number of printed dots / (Vertical resolution × Horizontal resolution) × 100 (In the formula, "actual printable dot count" is the actual printable dot count per unit area, and "vertical resolution" and "horizontal resolution" are the resolutions per unit area, respectively.)

[0094] 4. Coloring material adhesion process A laminate was obtained by overlapping the surface of the substrate coated with the processing solution obtained in the processing solution coating step with the surface of the intermediate recording medium coated with ink obtained in the ink composition coating step. Then, using a heat press machine (AF-54TEN (product name), manufactured by Itsumi Co., Ltd.), the laminate was heated at 180°C for 60 seconds to sublimate the sublimable dye attached to the intermediate recording medium and transfer it to the surface of the substrate coated with the processing solution to obtain the decorated products of each example. In Comparative Example 3, the substrate did not undergo the processing solution coating step.

[0095] 5. Rating 5.1. Color development Using a spectrophotometer (FD-7 (product name), manufactured by Konica Minolta), D 65 Using a light source and under a viewing angle of 2 degrees, the optical density (OD value) of the printed surface of each example of the decorated material immediately after the colorant application process was measured and evaluated based on the following evaluation criteria. The evaluation results are shown in Figure 2. [Evaluation Criteria] AA: The OD value is 1.2 or higher. A: The OD value is 1.1 or higher and less than 1.2. B: The OD value is between 1.0 and 1.1. The C:OD value is less than 1.0.

[0096] 5.2. Resistance to discoloration and fading Each example of the decorated object was left for 3 days after the colorant application process. Then, using a spectrophotometer (FD-7 (product name), manufactured by Konica Minolta), D 65 Using a light source and under a viewing angle of 2 degrees, the OD value of the printed surface of each example of the decorative material was measured after being left for 3 days.

[0097] The decrease in the OD value of the printed surface of each decorative object after being left for 3 days was calculated compared to the OD value of the printed surface of each decorative object immediately after the colorant application process, and the results were evaluated based on the following evaluation criteria. The evaluation results are shown in Figure 2. [Evaluation Criteria] A: The rate of decrease in OD value ((OD value immediately after the colorant application process - OD value after 3 days of standing) / OD value immediately after the colorant application process × 100) is less than 2%. B: The decrease in OD value is between 2% and 5%. The decrease in C:OD value is 5% or more.

[0098] 5.3. Abrasion resistance (tape release properties) Immediately after the colorant application process, cellophane tape was applied to the printed surface of each example of the decorated material and left for 24 hours. Afterward, the tape was removed, and the presence or absence of colorant adhering to the removed tape was visually observed and evaluated based on the following evaluation criteria. The evaluation results are shown in Figure 2. A rating of B or higher indicates good abrasion resistance. [Evaluation Criteria] A: No colorant was found to be attached to the removed tape. B: A small amount of colorant can be seen adhering to the removed tape. C: Colorant residue was observed on the removed tape.

[0099] Furthermore, a similar evaluation was performed using a 100% by mass treatment solution obtained by adding 2% by mass of Fixer #104EA, a crosslinking agent, to the composition of Comparative Example 1, and reducing the mass of ion-exchanged water accordingly. The OD value immediately after the colorant application process was lower compared to the example. [Explanation of symbols]

[0100] 20...Serial printer, 220...Transport unit, 230...Recording unit, 231...Inkjet head, 234...Carriage, 235...Carriage movement mechanism, F...Recording medium, S1, S2...Main scanning direction, T2...Sub-scanning direction

Claims

1. A treatment solution application step in which a treatment solution is applied to the surface of a substrate having a three-dimensional shape, An ink composition application step in which an ink composition containing a sublimation colorant is applied to an intermediate recording medium using an inkjet method, The process includes a step of pressing the intermediate recording medium onto the surface of the substrate to obtain a laminate, and heating the laminate to sublimate the sublimable colorant and deposit it on the surface of the substrate, The surface of the substrate has hydroxyl groups, The aforementioned processing liquid comprises a crosslinking agent, water, and a resin having an aromatic ring and a glass transition temperature of 20°C or higher. Method for creating decorative objects.

2. The aforementioned base material includes one or more selected from the group consisting of wood, tatami mats, and bamboo. The manufacturing method according to claim 1.

3. The aforementioned resin includes one or more selected from the group consisting of polyester resin, acrylic-styrene resin, and urethane resin. The manufacturing method according to claim 1.

4. The glass transition temperature of the resin is 60°C or higher. The manufacturing method according to claim 1.

5. The resin content is 1 to 20% by mass relative to the total amount of the processing liquid. The manufacturing method according to claim 1.

6. The crosslinking agent comprises an isocyanate compound or an oxazoline compound. The manufacturing method according to claim 1.

7. The content of the crosslinking agent is 0.1 to 5.0% by mass relative to the total amount of the treatment liquid. The manufacturing method according to claim 1.

8. The water content is 60% by mass or more of the total amount of the treatment liquid. The manufacturing method according to claim 1.

9. The process does not include a protective layer formation step after the colorant application step, where a protective layer is provided on the surface of the substrate to which the sublimation colorant has been applied. The manufacturing method according to claim 1.

10. A treatment liquid applied to a surface having a three-dimensional shape, A crosslinking agent, water, and a resin having an aromatic ring and a glass transition temperature of 20°C or higher, Processing liquid.

11. The aforementioned resin includes one or more selected from the group consisting of polyester resin, acrylic-styrene resin, and urethane resin. The processing solution according to claim 10.

12. The glass transition temperature of the resin is 60°C or higher. The processing solution according to claim 10.

13. The resin content is 1 to 20% by mass relative to the total amount of the processing liquid. The processing solution according to claim 10.

14. The crosslinking agent comprises an isocyanate compound or an oxazoline compound. The processing solution according to claim 10.

15. The content of the crosslinking agent is 0.1 to 5.0% by mass relative to the total amount of the treatment liquid. The processing solution according to claim 10.

16. The water content is 60% by mass or more of the total amount of the treatment liquid. The processing solution according to claim 10.

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