A radiation curable ink composition, decal and high temperature decoration method thereof

Abstract

The present application relates to a kind of radiation-curable ink composition, paper and its high temperature decoration method.The composition includes by weight percentage: radiation-curable component 40%~90%, high temperature binder 5%~50%, inorganic mineral pigment 5%~50%, decomposition accelerator 1%~5% and auxiliary agent 0.5%~10%;And the particle size D50 of inorganic particle in composition is less than 3 μm.The radiation-curable component includes oligomer, active monomer and photoinitiator;Decomposition accelerator is used to reduce the thermal decomposition activation energy of the curing component in the range of 200 ℃~500 ℃;High temperature binder is configured to melt or transform to form inorganic bonding phase at ≥400 ℃.Paper is prepared by inkjet printing and photocuring using the composition, and is fired at ≥600 ℃ after being transferred to high temperature resistant substrate.The present application realizes the flexible regulation of film layer and the controllable decomposition of organic matter by component synergy, and finally forms a firm glaze decoration layer.

Description

Technical Field

[0001] This invention relates to the fields of special printing materials and fine chemical technology, and in particular to a radiation-curable ink composition, decals, and a high-temperature decoration method thereof. Background Technology

[0002] Traditionally, decal decoration on ceramics and glassware relies primarily on screen printing. This process boasts high color saturation, strong opacity, and low cost for mass production. However, its inherent limitations—long plate-making cycles, high registration accuracy requirements, and limited design freedom—make it difficult to adapt to the market demands for small-batch, personalized, and rapid-response products.

[0003] Digital inkjet printing technology eliminates the need for plate making, enabling direct printing of digital patterns onto substrates and enhancing production flexibility and design freedom. However, existing mainstream inkjet ink solutions face significant technical bottlenecks when applied to decal production, failing to meet the requirements of the complete decal production chain. First, for solvent-based or water-based inks, film formation depends on substrate adsorption and physical drying. To avoid ink droplet diffusion, transfer paper with a special ink-absorbing layer must be used, resulting in poor versatility. Furthermore, the mechanical strength and water resistance of the dried ink layer are usually insufficient, making it difficult to meet the requirements of subsequent transfer paper processes.

[0004] Secondly, UV-curable inks are cured in situ by UV irradiation, which can avoid ink droplet diffusion and achieve high-precision printing. However, existing UV-curable ink technologies face the following challenges when adapting to decal printing processes: (1) High-temperature color development failure: General-purpose UV inks usually use organic pigments, which decompose during subsequent high-temperature firing (usually above 600°C), making it impossible to achieve the final color development of ceramic glaze. (2) Mismatch in temporary film properties: Some UV inks developed for direct decoration (such as the technical solutions disclosed in EP4353787A1 and WO2017070236A1) have partially solved the high-temperature color development and adhesion problems by introducing inorganic pigments and glass powder, but the temporary protective film layer formed after curing is usually hard and brittle with poor flexibility. Since decals need to undergo stacking, curved surface transfer and other processes during production and use, there are specific requirements for the tensile flexibility of the temporary pattern layer, and existing film layers are prone to cracking or peeling. (3) Uncontrollable thermal decomposition behavior: The thermal decomposition behavior of the organic carrier in the above inks is usually an inherent property of its resin system and lacks effective control methods. This makes it difficult to match its decomposition temperature range with the temperature curve of the paper firing process, which easily leads to carbon residue caused by incomplete decomposition of organic matter (which in turn causes defects such as pinholes or black spots on the glaze), or causes cracking due to improper decomposition timing, thus affecting the final decorative quality.

[0005] Since decals are used as transfer carriers, the inkjet ink composition must simultaneously possess digital printing compatibility and curing capability. After curing, it must form a temporary protective film with certain tensile flexibility and water resistance. Furthermore, this temporary organic film layer must be able to fully degrade during the high-temperature firing stage to form a high-quality glaze layer. Existing technical solutions cannot systematically meet the above-mentioned composite performance requirements.

[0006] Therefore, there is an urgent need in this field for a new type of inkjet printing ink composition that can synergistically solve technical problems such as high-precision printing, flexibility of temporary film layers, and controllable high-temperature decomposition behavior of organic carriers, so as to meet the needs of large-scale application of digital inkjet printing technology for decals.

[0007] Furthermore, on the one hand, there are differences in understanding among those skilled in the art; on the other hand, the applicant studied a large number of documents and patents when making this invention, but due to space limitations, not all details and contents were listed in detail. However, this does not mean that the present invention does not possess the features of these prior art. On the contrary, the present invention already possesses all the features of the prior art, and the applicant reserves the right to add relevant prior art to the background art. Summary of the Invention

[0008] To address the shortcomings of existing technologies, this invention provides a radiation-curable ink composition, decals, and a high-temperature decoration method thereof, thereby solving problems in existing inkjet printing technologies for decals, such as precision dependence on substrate, high-temperature color development failure, lack of inorganic bonding, insufficient flexibility of temporary film layers, and uncontrollable high-temperature decomposition behavior of temporary film layers.

[0009] In a first aspect, the present invention discloses a radiation-curable ink composition suitable for inkjet printing on decal paper, comprising the following components by weight percentage: Radiation-curable components: 40%~90%; High-temperature adhesive: 5%~50%; Inorganic mineral pigments: 5%~50%; Decomposition accelerator: 1%~5%; Additives: 0.5%~10%; The radiation-curable components include oligomers, reactive monomers, and photoinitiators. The reactive functionality of the oligomers is less than or equal to 4. The reactive monomers include monofunctional monomers and polyfunctional monomers. By weight percentage, the total content of polyfunctional monomers does not exceed 20% of the total weight of the radiation-curable ink composition. The decomposition accelerator is selected from at least one of organic peroxides, organometallic salts, or high-temperature initiating plasticizers; The high-temperature binder is selected from at least one of nano-oxides or glass powders, and the high-temperature binder has the physicochemical properties of melting or transforming to form an inorganic binder phase at a temperature of 400°C or higher. The particle size D50 of the inorganic particles in the radiation-curable ink composition is less than 3 μm.

[0010] The radiation-curable ink composition provided by this invention solves the problems of poor film flexibility and uncontrollable thermal decomposition of organic carriers in existing decal inkjet processes by synergistically combining radiation-curable components, high-temperature binders, and decomposition accelerators. In existing UV-curable inks, the decomposition of the organic system during firing often mismatches with the decal firing process, easily resulting in carbon residue. This invention introduces a decomposition accelerator, which reduces the activation energy of thermal decomposition of the radiation-curable components, causing polymer molecular chain breakage within a specific temperature range, thereby reducing organic residue after high-temperature firing. Simultaneously, controlling the particle size parameters of inorganic particles in conjunction with the photocuring mechanism of the radiation-curable components restricts the lateral diffusion of ink droplets on the substrate surface. Combined with the liquid-phase wetting and encapsulation effect formed by the phase change of the high-temperature binder at high temperatures, this invention constructs a material phase change path from room-temperature photocuring to high-temperature sintering into a glaze, thereby forming an inorganic decorative layer on the substrate surface with a bonding strength meeting preset requirements.

[0011] According to a preferred embodiment, the oligomer is selected from at least one of aliphatic polyurethane acrylate and flexible polyester acrylate; By weight percentage, oligomers comprise 1% to 20% of the total weight of the radiation-curable ink composition.

[0012] This invention further improves the tensile properties of the cured film by limiting the molecular structure and reactivity of the oligomer. Existing temporary protective films generally suffer from brittleness due to excessively high crosslinking density. This invention selects oligomers containing aliphatic polyurethane acrylate or flexible polyester acrylate, utilizing the flexible segments in their main chain to provide intramolecular rotational freedom. Simultaneously, by limiting the reactivity to a lower level, the number of crosslinking nodes during photocuring is restricted from the network topology, reducing the volumetric shrinkage stress during film formation. This control of microscopic molecular structure and macroscopic network density enables the cured temporary film to possess the elongation at break and flexibility required for transferring curved surfaces of decals and for decal application, reducing the risk of stress-induced cracking during processing.

[0013] According to a preferred embodiment, the monofunctional monomer is selected from at least one of lauryl acrylate, tridecyl acrylate, lauryl methacrylate, isodecanyl acrylate, isooctyl acrylate / 2-ethylhexyl acrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl acrylate, tetrahydrofuran acrylate, cyclotrimethylolpropane methyl acetal acrylate, or phenoxyethyl acrylate. The multifunctional monomer is selected from at least one of tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, polypropylene glycol diacrylate, propoxylated bisphenol A diacrylate, or ethoxylated trimethylolpropane triacrylate.

[0014] This invention achieves the regulation of the liquid rheological properties and solid mechanical properties of inks by combining monofunctional and polyfunctional monomers and setting content thresholds. Monofunctional monomers, as reactive dilution systems, contain long-chain aliphatic or cyclic structures, which can reduce the initial viscosity of the composition to adapt to printhead characteristics. The linear polymeric segments they form also increase the free volume of the system and exert an internal plasticizing effect, thereby maintaining the flexibility of the film layer. The appropriate introduction of polyfunctional monomers is used to construct a crosslinked network system, providing the cohesive force required for the temporary film layer to withstand environmental friction. By limiting the total amount of polyfunctional monomers to a specific proportion, the rigidification of the polymer network caused by excessive crosslinking is effectively prevented, ensuring the water resistance of the temporary film layer while maintaining its tensile physical morphology to resist transferred stress.

[0015] According to a preferred embodiment, the photoinitiator is a free radical photoinitiator, and by weight percentage, the photoinitiator accounts for 1% to 15% of the total weight of the radiation-curable ink composition; The photoinitiator is selected from at least one of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-isopropylthioxanthone, macromolecular α-hydroxy ketone / acylphosphine oxide, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, methyl benzoylformate, isopropyl benzoylformate, or 2,2-dimethoxy-2-phenylacetophenone.

[0016] This invention selects a specific amount of free radical photoinitiator to provide reaction kinetics for the photocuring process of the ink composition. The absorption spectrum of the initiator can cover the emission band of commonly used ultraviolet light sources. After receiving radiation, the free radical photoinitiator undergoes decomposition, generating primary free radicals that can attack the unsaturated double bonds in oligomers and reactive monomers, thereby initiating a chain polymerization reaction. This reaction mechanism can promote gelation and even complete curing of the liquid phase system within a short illumination window, shortening the leveling time after ink droplets contact the substrate, limiting the lateral diffusion of pigments on the substrate surface, and thus ensuring the clarity of the physical boundaries of the printed pattern.

[0017] According to a preferred embodiment, the decomposition accelerator is selected from at least one of di-tert-butyl peroxide, zinc acetylacetonate, zinc octanoate, ammonium molybdate, polyester plasticizers, citrate plasticizers, or tributyl citrate.

[0018] The decomposition promoters specifically defined in this invention intervene in the pyrolysis kinetics of organic carriers through different catalytic pathways. If organic peroxides are used, the free radicals generated by their homolytic cracking upon heating can directly attack the polymer backbone, initiating the breakage and degradation of the main chain. If organometallic salts are used, their metal ions reduce the activation energy of polymer thermo-oxidative degradation through coordination or redox catalysis, accelerating the conversion of high molecules into low-molecular-weight gases. If high-temperature initiating plasticizers are used, they exert physical plasticizing effects at room temperature, but decompose at high temperatures to produce acidic substances, catalyzing the hydrolysis and breakage of weak bonds such as ester bonds in the polymer chain. All of the above decomposition promoters can guide the degradation and removal of the cured film layer within a specific temperature range during the firing process, reducing the probability of defects such as black spots or pores appearing on the glaze surface due to incomplete volatilization of organic residues.

[0019] According to a preferred embodiment, the melting temperature range of the glass powder is 400℃~1200℃, and the coefficient of thermal expansion is 4.0~8.0×10⁻⁶. -6 / ℃, and the glass powder is selected from at least one of bismuth-based glass powder, zinc-boron-silicon-based glass powder or lead-based glass powder; the nano oxide is selected from at least one of nano silicon dioxide, nano titanium dioxide, nano zirconium oxide or nano aluminum oxide.

[0020] Alternatively, the high-temperature adhesive may also include an organosilicon compound or nanosilicate with radiation curing activity.

[0021] The high-temperature binder parameters and categories defined in this invention improve the interfacial bonding state of pigments on the substrate surface. Selecting glass powder with a specific melting temperature range ensures that the glass powder preferentially transforms into a liquid phase and wets and encapsulates the inorganic mineral pigment particles before the substrate undergoes overall deformation. Matching the set range of thermal expansion coefficients reduces thermal stress caused by inconsistent thermal contraction between the decorative layer and the substrate interface during the cooling and curing stage, preventing glaze cracking or peeling. If nano-oxides are used, their high specific surface area and surface dangling bonds allow them to react with the substrate surface and pigment particles under high-temperature conditions, establishing silicon-oxygen or titanium-oxygen chemical bonds, thereby improving the anchoring strength of the inorganic mineral pigments in the decorative layer after firing.

[0022] According to a preferred embodiment, the inorganic mineral pigment is selected from at least one of the following types: Encapsulated pigments are selected from at least one of ZrSiO4 / Cd(S,Se) type encapsulated red, ZrSiO4 / praseodymium yellow, ZrSiO4 / vanadium zirconium blue, encapsulated orange, or encapsulated green. Non-encapsulated metal oxide and composite oxide pigments, wherein the non-encapsulated metal oxide and composite oxide pigments are selected from at least one of chrome tin red, iron red, yellow brown, red brown, cobalt blue, cobalt black or copper chrome black; Chalcogenide pigments, wherein the chalcogenide pigments are selected from at least one of cadmium red or cadmium yellow; Other stable oxide pigments are selected from at least one of rutile titanium yellow, praseodymium yellow, or copper red doped with Ni or Sb.

[0023] The inorganic mineral pigments specified in this invention ensure the color stability of the decorative layer during high-temperature firing. Unlike organic pigments, which are prone to carbonization and decomposition at high temperatures, the encapsulated pigments used in this invention utilize a chemically inert lattice to isolate and seal the color-producing ions, preventing chemical erosion of the color-producing core by the high-temperature melt and oxidizing atmosphere. Non-encapsulated metal oxide and chalcogenide pigments maintain their electronic transition characteristics based on their own stable lattice structure or solid solution morphology. These inorganic mineral pigments, as the main color-producing components in the system, maintain their spectral reflectance characteristics even after undergoing the physicochemical changes of organic carrier decomposition and high-temperature melting of the glass phase, ensuring the color stability of the final fired product.

[0024] According to a preferred embodiment, the additive is selected from at least one of dispersants, surfactants, leveling agents, or polymerization inhibitors; At a temperature of 25°C, the viscosity of the radiation-curable ink composition is 10~40 mPa·s, and the surface tension is 15~50 mN / m.

[0025] This invention ensures the hydrodynamic stability of the inkjet printing process by incorporating a specific additive system and limiting the physicochemical parameters of the ink. The dispersant, through steric hindrance and surface adsorption, inhibits the aggregation and gravitational sedimentation of inorganic particles in the organic phase, maintaining the homogeneity of the system. The surfactant and leveling agent synergistically regulate the surface tension of the liquid phase, enabling the system to adapt to the microfluidic requirements within the piezoelectric printhead, maintaining the continuity of droplet extrusion and breakup, and improving droplet wetting and spreading on the substrate. The polymerization inhibitor consumes trace free radicals within the system, suppressing prepolymerization. Combined with the defined viscosity and surface tension range at specific temperatures, this composition meets the rheological conditions for long-term operation of industrial piezoelectric printheads.

[0026] Secondly, the present invention discloses a decal, which includes a substrate and a decorative pattern disposed on the surface of the substrate. The decorative pattern is formed by inkjet printing of the above-mentioned radiation-curable ink composition and curing with ultraviolet light.

[0027] This invention provides a decal product in which a surface decorative pattern is constructed based on the aforementioned radiation-curable ink composition. Compared to decals prepared by traditional screen printing, this product is made using digital inkjet and photocuring processes, eliminating the plate-making process and reducing the overprinting requirements for pattern transfer. The cured pattern layer disposed on the substrate surface has a specific polymer cross-linking network inside, which endows the film layer with mechanical tensile properties, making it less prone to physical breakage when subjected to curved surface decals or physical transfers. At the same time, the water resistance of this pattern layer at room temperature allows it to adapt to the immersion environment of water transfer printing processes, providing a transition carrier that maintains structural integrity for subsequent high-temperature firing.

[0028] Thirdly, the present invention discloses a high-temperature decoration method for an article, which includes the following steps: S1. The above-mentioned radiation-curable ink composition is used to form a pattern on a decal substrate by inkjet printing; S2. The pattern is irradiated with ultraviolet light to cure the radiation-curable ink composition into a film to obtain decals with cured patterns; S3. Transfer the decal with the cured pattern to the surface of a high-temperature resistant substrate; S4. Under an oxidizing atmosphere, the ink composition is fired at a temperature of at least 600°C, which is higher than the melting temperature of the selected high-temperature binder, so that the organic components in the ink composition decompose and the high-temperature binder melts or transforms to form an inorganic binder phase, thereby bonding the inorganic mineral pigments in the ink composition to the surface of the high-temperature resistant substrate to form a glaze decorative layer.

[0029] This invention discloses a high-temperature decoration method that combines digital inkjet curing with the high-temperature sintering mechanism of inorganic materials. During the process, the liquid ink composition is cured in situ by ultraviolet radiation, fixing the spatial distribution of the pigments and obtaining a temporary organic pattern layer with transfer strength. In subsequent oxidizing atmospheres and firing steps at 600°C or higher, a pre-placed decomposition accelerator accelerates the chain breakage and vaporization of the organic cross-linked network, promoting the removal of the organic phase from the substrate surface. As the furnace temperature rises, the high-temperature binder undergoes a phase change and melts, bonding and coating the thermally stable inorganic mineral pigments onto the high-temperature resistant substrate surface. This method, through temperature gradient control, sequentially triggers the processes of photochemical curing, polymer thermo-oxidative degradation, and inorganic phase melting and sealing, ultimately forming a stable decorative layer on the substrate surface. Detailed Implementation

[0030] In some typical embodiments of the present invention, a radiation-curable ink composition is provided, which is suitable for inkjet printing on decals. The ink composition includes a radiation-curable component, a high-temperature binder component, and a decomposition accelerator; wherein, the radiation-curable component is subjected to radiation treatment after printing to form a cured shape; the high-temperature binder component binds inorganic pigments to the substrate surface in a subsequent high-temperature firing process; and the decomposition accelerator regulates the thermal decomposition behavior of the organic carrier during the firing stage to improve the decomposition rate and degree of the organic carrier.

[0031] Furthermore, in some embodiments of the present invention, the radiation-curable ink composition comprises, by weight percentage: 40% to 90% of radiation-curable components; 5% to 50% of high-temperature binder; 5% to 50% of inorganic mineral pigments; 1% to 5% of decomposition accelerators; and 0.5% to 10% of additives.

[0032] Furthermore, the radiation-curable components include UV-curable oligomers, reactive monomers, and photoinitiators. After radiation treatment, the radiation-curable components form a temporary film with tensile flexibility and water resistance, and the radiation-curable components and decomposition accelerators are used to synergistically regulate the thermal decomposition characteristics of the temporary film in subsequent high-temperature firing processes.

[0033] In some embodiments of the invention, the oligomer is selected from at least one of aliphatic polyurethane acrylate and flexible polyester acrylate, and the reactive power of the oligomer is less than or equal to 4. In an optional embodiment, the reactive power of the oligomer is less than or equal to 2. The oligomer forms the main structure for constructing the temporary film layer and provides tensile flexibility and water resistance suitable for resisting structural brittleness and moisture erosion during the transfer and lamination processes of the transfer paper. By weight percentage, the oligomer accounts for 1% to 20% of the total weight of the radiation-curable ink composition. In a more specific embodiment, the oligomer accounts for 1% to 10% of the total weight of the radiation-curable ink composition.

[0034] In some embodiments of the present invention, the active monomers include monofunctional monomers and polyfunctional monomers. The total content of polyfunctional monomers does not exceed 20% by weight of the total weight of the radiation-curable ink composition; in an optional embodiment, the total content of polyfunctional monomers does not exceed 10% by weight of the total weight of the radiation-curable ink composition.

[0035] In some specific embodiments, monofunctional monomers are monomers with long-chain aliphatic structures and water-resistant properties (such as lauryl acrylate, isobornyl acrylate, etc.). Monofunctional monomers can adjust the viscosity of the ink composition, participate in the radiation curing reaction, and provide tensile flexibility to the temporary film layer. Polyfunctional monomers (such as tripropylene glycol diacrylate (TPGDA), 1,6-hexanediol diacrylate (HDDA), etc.) can increase the crosslinking density of the temporary film layer and enhance its scratch resistance. By limiting the upper limit of the total content of polyfunctional monomers, film shrinkage or embrittlement due to excessive crosslinking is avoided, thereby maintaining the tensile properties of the temporary film layer.

[0036] Further, the active monomer is selected from one or more combinations of the following compounds: lauryl acrylate (LA), tridecyl acrylate (TDA), lauryl methacrylate (LMA), isodecyl acrylate (IDA), isooctyl acrylate / 2-ethylhexyl acrylate (EHA / 2-EHA), isobornyl acrylate (IBOA), isobornyl methacrylate (IBOMA), cyclohexyl acrylate (CHA), tetrahydrofuran acrylate (THFA), cyclotrimethylolpropane methyl acetal acrylate (CTFA), phenoxyethyl acrylate (PHEA), tripropylene glycol diacrylate (TPGDA), 1,6-hexanediol diacrylate (HDDA), polypropylene glycol diacrylate (PPGDA), propoxylated bisphenol A diacrylate (PO6-BPADA), and ethoxylated trimethylolpropane triacrylate (EO3-TMPTA).

[0037] In some embodiments of the present invention, the photoinitiator is a free radical photoinitiator. The effective initiation wavelength of the free radical photoinitiator covers the UV-A to UV-C range, and is used to initiate the curing reaction of the ink composition under ultraviolet light irradiation. By weight percentage, the photoinitiator accounts for 1% to 15% of the total weight of the radiation-curable ink composition; in a more specific embodiment, the photoinitiator accounts for 5% to 10% of the total weight of the radiation-curable ink composition.

[0038] Further, the photoinitiator is selected from one or more combinations of the following compounds: 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-isopropylthioxanthone, macromolecular α-hydroxy ketone / acylphosphine oxide, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, methyl benzoylformate, isopropyl benzoylformate, and 2,2-dimethoxy-2-phenylacetophenone.

[0039] In some embodiments of the present invention, the high-temperature binder is a substance that melts or transforms at a temperature of 400°C or higher to form an inorganic binder phase. In a high-temperature firing process at a temperature greater than 600°C, the high-temperature binder can encapsulate and bind inorganic mineral pigment particles, and promote the formation of a physical or chemical bond between the inorganic mineral pigments and the ceramic or glass substrate.

[0040] Furthermore, the high-temperature adhesive is selected from one or more combinations of the following compounds or materials: Organosilicon compounds with radiation curing activity: Organosilicon compounds can participate in polymerization reactions during the UV curing stage of the composition to form a temporary film and provide initial structural strength; furthermore, organosilicon compounds can undergo organic component decomposition during high-temperature sintering, and their residual siloxane (Si-O) network structure is further transformed into silicon dioxide (SiO2) or silicate structure, thereby forming chemical bonds with inorganic mineral pigments and substrates. Nano-oxides or nano-silicates: The nano-oxides are selected from at least one of nano-silica (SiO2), nano-titanium oxide (TiO2), nano-zirconium oxide (ZrO2), or nano-alumina (Al2O3). The nano-oxides or nano-silicates react with inorganic mineral pigment particles and the surface of ceramic or glass substrates under high-temperature conditions through dangling bonds (including at least one of Si-O- and Ti-O-) carried on their surface to form interfacial bonds. Glass powder (or frit): The glass powder is selected from at least one of bismuth-based glass powder, zinc-boron-silicon-based glass powder, or lead-based glass powder. The melting temperature range of the glass powder is 400℃~1200℃, and the coefficient of thermal expansion is 4.0~8.0×10⁻⁶. -6 / ℃. The glass powder can melt at the firing temperature to form a liquid phase that wets and encapsulates inorganic mineral pigment particles, and upon cooling, it transforms into a glassy phase to bond the inorganic mineral pigments to the substrate surface. In a more specific embodiment, the glass powder is selected from bismuth-based glass powder or lead-free zinc-boron-silicon-based glass powder with a melting temperature of 500℃~850℃.

[0041] In some embodiments of the present invention, the above-mentioned high-temperature binders can be used alone or in combination to adapt to different firing regimes, substrate types, and target physical and chemical properties (e.g., gloss and acid and alkali resistance). By weight percentage, the high-temperature binder accounts for 5% to 50% of the total weight of the radiation-curable ink composition, and it can maintain the printing performance of the ink composition and the mechanical properties of the temporary film while providing a predetermined bond strength.

[0042] Inorganic mineral pigments are inorganic compounds that maintain chemical stability within a high-temperature firing temperature range of 400℃ to 1200℃ and resist erosion by ceramic or glass substrate melts to maintain color stability. Inorganic mineral pigments are the main component for color development in ink compositions after high-temperature firing. By weight percentage, inorganic mineral pigments account for 5% to 50% of the total weight of radiation-curable ink compositions.

[0043] Furthermore, based on chemical and structural properties, inorganic mineral pigments are selected from at least one of the following types: Encapsulated pigments: Composite pigments formed by encapsulating chromogenic ions or compounds (such as cadmium selenide red, chrome tin red, etc.) with a high refractive index, chemically inert crystal structure (e.g., zirconium silicate, ZrSiO4). In one specific embodiment, the encapsulated pigment is selected from at least one of ZrSiO4 / Cd(S,Se) type encapsulated red, ZrSiO4 / praseodymium yellow (Pr-ZrSiO4), ZrSiO4 / vanadium zirconium blue (V-ZrSiO4), encapsulated orange, or encapsulated green.

[0044] Non-encapsulated metal oxide and composite oxide pigments: selected from chromium tin red (Cr dissolved in the SnO2 lattice) 3+ At least one of the following: iron oxide, iron oxide (Fe2O3), yellow-brown (Fe2O3·TiO2), red-brown (Fe2O3·Cr2O3), cobalt blue (CoAl2O4), cobalt black (CoFe2O4), or copper chromium black (CuCr2O4).

[0045] Other stable oxide pigments: selected from at least one of titanium yellow (rutile TiO2 doped with elements including Ni or Sb), praseodymium yellow (Pr-ZrSiO4) or copper red (Cu2O or its colloidal color system).

[0046] Chalcogenide pigments: selected from cadmium-based pigments. In one specific embodiment, the chalcogenide pigment is selected from cadmium red (CdS·CdSe) or cadmium yellow (CdS). Chalcogenide pigments can maintain structural stability under controlled glazing conditions.

[0047] In some embodiments of the present invention, the decomposition accelerator can reduce the thermal decomposition activation energy of the radiation-curable component within a temperature range of 200°C to 500°C. The decomposition accelerator can regulate the thermal decomposition behavior of the cured film layer, enabling it to decompose within the temperature window of the transfer paper firing process, thereby reducing the amount of organic residue. By weight percentage, the decomposition accelerator accounts for 1% to 5% of the total weight of the ink composition.

[0048] Furthermore, the decomposition accelerator is selected from one or more of organic peroxides, organometallic salts, or high-temperature initiating plasticizers.

[0049] Preferably, the organic peroxide is capable of decomposing at high temperatures to generate free radicals, thereby breaking polymer molecular chains and initiating chain degradation of the radiation-curable component. In one specific embodiment, the organic peroxide is, for example, di-tert-butyl peroxide.

[0050] Preferably, the organometallic salt can reduce the activation energy of polymer thermo-oxidative decomposition through the coordination of metal ions or redox catalysis. In one specific embodiment, the organometallic salt is selected from at least one of zinc acetylacetonate, zinc octanoate, or ammonium molybdate.

[0051] Preferably, the high-temperature initiating plasticizer can decompose under high-temperature conditions to produce organic acids, which can catalyze the hydrolysis of weak bonds such as ester bonds; and the high-temperature initiating plasticizer can act as an internal plasticizer to reduce intermolecular forces, thereby promoting the overall thermal decomposition process. In one specific embodiment, the high-temperature initiating plasticizer is selected from at least one of polyester plasticizers, citrate plasticizers, or tributyl citrate.

[0052] In some embodiments of the present invention, the additives are selected from at least one of dispersants, surfactants, leveling agents, or polymerization inhibitors. The additives can synergistically maintain the long-term storage stability of the ink composition, printing smoothness, pigment dispersion uniformity, and controllability of the curing process.

[0053] In some embodiments of the present invention, the dispersant prevents the aggregation or sedimentation of solid particles such as inorganic mineral pigments and high-temperature binders in the system, thereby maintaining the uniformity and stability of the ink composition. The dispersant is selected from one or more of polymer block copolymers, polymer graft copolymers, anionic dispersants, silane coupling agents, or titanate coupling agents. In one specific embodiment, the polymer block copolymer or polymer graft copolymer includes a polyurethane block copolymer or a polyacrylate copolymer.

[0054] Surfactants can modulate the surface tension of ink compositions to match printhead characteristics, maintain the stability of ink droplet formation and ejection, and improve substrate wettability. In one specific embodiment, the surfactant is selected from at least one of polyether-modified polysiloxanes, polyester-modified polysiloxanes, or fluorocarbon surfactants.

[0055] Leveling agents promote the flow and spread of ink film on the substrate after printing, reducing or eliminating defects such as orange peel or pinholes, thereby improving the smoothness of the cured film. Leveling agents are selected from at least one of modified polysiloxane polymers, fluorocarbon modified polymers, or acrylate polymers.

[0056] Polymerization inhibitors can suppress prepolymerization reactions of ink compositions caused by heat or impurities during storage or under non-light conditions, thereby maintaining storage stability. Polymerization inhibitors are selected from one or more of phenols and their derivatives, quinones, nitroxide radical inhibitors, phosphorus-based inhibitors, or metal chelating agents. In one specific embodiment, phenols and their derivatives include at least one of p-hydroxyanisole, BHT, or 4-methoxyphenol; nitroxide radical inhibitors include TEMPO; and metal chelating agents include disodium EDTA.

[0057] Furthermore, the aforementioned additives can be selected and compounded according to the preset performance requirements of the ink composition (including printhead type, substrate type, or storage conditions, etc.). By weight percentage, the total amount of additives accounts for 0.5% to 10% of the total weight of the radiation-curable ink composition.

[0058] In some embodiments of the present invention, to meet the requirements of digital inkjet printing, the inorganic particles (including inorganic mineral pigments and high-temperature binders) in the ink composition are subjected to ultrafine grinding, and their particle size D50 is less than 3 μm. In one specific embodiment, the particle size D50 of the inorganic particles is less than 1 μm; in a more specific embodiment, the particle size D50 of the inorganic particles is less than 0.5 μm.

[0059] Preferably, at a temperature of 25°C, the viscosity of the ink composition is 10~40 mPa·s; in one specific embodiment, the viscosity is 20~30 mPa·s. Furthermore, the surface tension of the ink composition is 15~50 mN / m; in one specific embodiment, the surface tension is 20~35 mN / m.

[0060] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to specific embodiments. It should be understood that the specific embodiments described herein are for illustrative purposes only and are not intended to limit the scope of protection of this invention. Furthermore, in the following embodiments and comparative examples, unless otherwise expressly stated, the raw materials, reagents, and equipment used can be conventionally obtained through commercial channels.

[0061] The main raw materials and their physicochemical parameters used in the embodiments and comparative examples of this invention are as follows: Oligomer A: Polyurethane acrylate with a reactive power of 2; for example, a commercially available product with the brand name FSP8310 (such as Runao Chemical) can be used.

[0062] Oligomer B: Rigid polyester acrylate with a reactive power of 6; for example, a commercially available product with the brand name 6311 (such as that produced by Baojun Chemical) can be used.

[0063] Monomer M1: Isobornyl acrylate (IBOA).

[0064] Monomer M2: Lauryl acrylate (LA).

[0065] Monomer M3: 1,6-hexanediol diacrylate (HDDA).

[0066] Photoinitiator PI: a mixture of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO) and 1-hydroxycyclohexylphenyl ketone (184) in a mass ratio of 1:1.

[0067] High-temperature binder G1: Bismuth-based low-melting-point glass powder with a particle size D50 of 1.5μm and a softening point of approximately 520℃.

[0068] High-temperature binder G2: Nano-silica with a particle size of approximately 20 nm.

[0069] Inorganic pigment P1: Encapsulated cadmium red (ZrSiO4 / Cd(S,Se)), with an unground original particle size D50 of 10~20μm.

[0070] Inorganic pigment P2: Cobalt blue (CoAl2O4), whose unground original particle size D50 is 10~15μm.

[0071] Decomposition promoter DP1: di-tert-butyl peroxide (DTBP).

[0072] Decomposition promoter DP2: Zinc acetylacetonate.

[0073] Decomposition promoter DP3: Tributyl citrate (TBC).

[0074] Dispersant D: High molecular weight block copolymer dispersant with an amine value of approximately 20 mg KOH / g; for example, a commercially available product with the brand name DISPERBYK®-111 can be used.

[0075] Leveling agent F: polyether-modified polysiloxane; for example, a commercially available product with the brand name BYK-358N can be used.

[0076] Polymerization inhibitor T: p-hydroxyanisole (MEHQ).

[0077] Based on the formulation parameters shown in Table 1 below (the values ​​of each component are in parts by weight), ink compositions of Examples 1 to 3 and Comparative Examples 1 to 3 were prepared and formulated respectively.

[0078] Table 1: Ink Composition Formulation (parts by weight)

[0079] The preparation method of the ink composition in the above embodiments and comparative examples can adopt a batch grinding process, specifically including the following steps: First, a portion of dispersant D is dissolved in a portion of monomers M1 and M2, and a high-temperature binder (high-temperature binder G1 or high-temperature binder G2) is slowly added under the action of a high-speed disperser at a speed of 1000~1500 rpm; after the material is evenly dispersed, it is transferred to a sand mill and ground until the fineness is less than or equal to 0.5 μm to obtain a binder slurry. Second, the remaining dispersant D is dissolved in another portion of monomers M1 and M2, and an inorganic pigment (inorganic pigment P1 or inorganic pigment P2) is slowly added under the action of a high-speed disperser at a speed of 1000~1500 rpm, and then transferred to a sand mill for dispersion and grinding, strictly controlling the pigment particle size D50 after grinding to be 1~2 μm to obtain a pigment slurry. The above grinding process is carried out under temperature-controlled conditions without photoinitiators and decomposition accelerators. Subsequently, the prepared binder slurry and pigment slurry were combined, and the remaining monomers, oligomers, photoinitiator PI, decomposition accelerator, and other additives were added to the system. The mixture was stirred at a medium speed of 500-800 rpm until homogeneous. Finally, the mixture was filtered using a filter bag with a pore size of 2 μm to obtain the target ink compositions.

[0080] Viscosity and surface tension of the radiation-curable ink compositions of the above-prepared embodiments and comparative examples were tested at a temperature of 25°C. The test results are summarized in Table 2 below.

[0081] Table 2: Test results of viscosity and surface tension of ink compositions

[0082] To verify the technical effects of the ink composition, systematic testing and characterization were conducted. For printing and curing performance testing, a Seiko 1536 piezoelectric printhead testing machine (the printhead heating temperature can be set, for example, to 40~45℃) was used to print the prepared ink onto a common transfer paper substrate as a standard test pattern. The pattern was then cured using an LED-UV light source with a wavelength of 395nm. The edge sharpness and degree of curing were subsequently observed and evaluated. For film-forming properties testing, tensile strength and water resistance were evaluated. For the tensile strength test, the cured ink film was peeled from the substrate and made into a standard dumbbell-shaped strip. The tensile strength of this strip was tested using a universal testing machine according to GB / T 1040.3 standard. For the water resistance test, the printed and cured transfer paper sample was completely immersed in deionized water at 25℃ for 24 hours. After removal, the pattern was observed for blurring, swelling, or peeling.

[0083] For thermal decomposition behavior testing, a suitable amount of cured ink film was taken using a thermogravimetric analyzer (TGA) and heated from room temperature to 600℃ at a heating rate of 10℃ / min under air atmosphere. During the test, the mass loss rate of the film in the temperature range of 300~450℃ and the mass residue rate at 600℃ were recorded to evaluate the completeness of organic component decomposition; a lower mass residue rate indicates more complete organic component decomposition. For firing performance testing, the printed and cured decal pattern was transferred to the surface of a ceramic plate, which was then placed in an electric kiln and heated at a heating rate of 5℃ / min under an oxidizing atmosphere. After holding at 450℃~500℃ for 20~30 minutes and venting, the temperature was further increased to 800℃ and held for 30 minutes. After natural cooling, the color development and gloss of the ceramic plate's glaze were observed. Simultaneously, adhesion testing was performed using the cross-cut adhesion test (100-grid method) according to GB / T 9286-1998 standard to evaluate the pigment binding degree.

[0084] In accordance with the aforementioned testing and characterization methods, the ink compositions, cured film layers, and fired decorative layers prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were systematically evaluated, and the test results are summarized in Table 3 below.

[0085] Table 3: Summary Table of Ink Performance Test Results

[0086] Based on the test results in Table 3, it can be seen that, in terms of printing and curing performance, the ink compositions of Examples 1 to 3 and Comparative Examples 1 to 3 all have printing clarity and instant curing capability, indicating that the ink composition system has physical adaptability and photocuring characteristics suitable for inkjet printing operations.

[0087] Regarding film-forming properties, the component of Example 1, which did not contain the multifunctional monomer M3, exhibited a cured film elongation at break of 10-15%, capable of withstanding bending stress during transfer of transfer paper. The component of Example 3 contained 10% oligomer A (flexible polyurethane acrylic resin) and 5% multifunctional monomer M3, resulting in a cured film elongation at break of 15-20%. The components of Examples 2 and Comparative Example 1 contained 10% multifunctional monomer M3; due to the increased crosslinking density, the elongation at break of the cured film decreased to 3-5%. The components of Comparative Examples 3 and 2, containing a rigid polyester acrylic resin with a reactive functionality of 6, exhibited increased structural brittleness in the cured film, with an elongation at break of less than 1% and fracture during tensile testing.

[0088] Experimental data show that by configuring flexible resins and adjusting the content ratio of monofunctional monomers (monomers M1 and M2) to polyfunctional monomers M3, the flexibility of the cured film can be controlled to meet the physical requirements of different transfer processes for the flexibility or toughness of the cured film. Furthermore, the test samples in all the above embodiments and comparative examples exhibit water resistance, meeting the water-based operating requirements of the transfer paper process.

[0089] Regarding thermal decomposition behavior, the components of Examples 1 and 2 contained decomposition accelerators (decomposition accelerator DP1 or decomposition accelerator DP3), exhibiting rapid thermal weight loss rates in the 300-450°C range, and a residual mass rate of 0.3% at 600°C. Test results indicate that the decomposition accelerators can lower the activation energy of thermal decomposition of the organic carrier, thus promoting its decomposition within the temperature window before glaze melting. The component of Comparative Example 3 contained a rigid polyester acrylic resin with a reactive functionality of 6. Due to the high degree of cross-linking in this high-functionality resin and the low content of decomposition accelerator DP3, its decomposition at high temperatures was limited, resulting in a relatively high residual mass rate (1.6%) at 600°C. The component of Example 3 contained decomposition accelerator DP2. Due to the coordination effect of metal ions and the catalytic effect of generating organic acid fragments, the decomposition of organic matter was promoted, and its residual mass rate at 600°C was 0.6%. The component of Comparative Example 1 did not contain a decomposition accelerator, exhibiting a slow thermal weight loss rate and a residual mass rate of 3.8% at 600°C. Since undecomposed organic residues can lead to defects in subsequent firing processes, the above data verifies that decomposition accelerators can promote the decomposition of organic carriers and reduce carbon residues, thereby preventing or reducing glaze contamination defects caused by incomplete decomposition of organic components.

[0090] Regarding firing performance, Examples 1 and 2, containing both decomposition accelerators and high-temperature binders, exhibited gloss and color development after firing, with pigment bonding reaching grade 0. This indicates that the high-temperature binder (high-temperature binder G1 or G2) melts during firing, bonding inorganic mineral pigments to the substrate surface to form a decorative glaze layer. Comparative Example 3, containing a high-temperature binder, achieved glaze bonding after firing, but its high organic residue due to the presence of hard resins and a high content of bifunctional monomers resulted in a darker color tone. The composition of Example 3, with its reduced inorganic mineral pigment content, was able to meet the requirements for light-colored decoration or translucency. The high-temperature binder G1 maintained a glaze bonding level of 0 after firing and provided a glossy finish. Comparative Example 1, containing a high-temperature binder but lacking a decomposition accelerator, exhibited a darker glaze tone after firing due to its 3.8% organic residue, and residual carbon interfered with the purity of the color development. Comparative Example 2 contained a decomposition accelerator but no high-temperature binder. Although its organic components decomposed (with a residual mass rate of 0.8%), the lack of a glassy phase substance that acts as a binder under high-temperature conditions prevented the pigment from bonding with the substrate, resulting in powdering and flaking (bonding degree test result was level 5), and thus no decorative layer was formed. Based on the above comparison results, it can be concluded that the high-temperature binder and the decomposition accelerator work synergistically in the system to jointly achieve the physical and chemical transformation from an organic temporary film layer to an inorganic glaze layer.

[0091] In summary, based on the test results of various embodiments and comparative examples, the radiation-curable ink composition of the present invention achieves the following technical effects through the synergistic configuration of the radiation-curable component system (e.g., by adjusting the monomer ratio to obtain the target flexibility in Example 1), the decomposition accelerator (e.g., decomposition accelerator DP1 or decomposition accelerator DP2), and the high-temperature binder (e.g., high-temperature binder G1 or high-temperature binder G2): First, it adapts to the decal substrate and meets the high-precision printing suitability requirements through a rapid UV curing mechanism; second, it forms a temporary film layer with adjustable tensile properties and adapts to the stress requirements of the decal processing process; finally, it controls the thermal decomposition behavior of the organic carrier and reduces the mass residue rate during the firing process to reduce or avoid glaze defects, thereby forming a glaze decorative layer on the substrate surface that has both a preset color state and bonding strength.

[0092] Furthermore, the comparative evaluation results show that without the addition of either a decomposition accelerator or a high-temperature binder to the ink composition, it is impossible to form a decorative layer with effective adhesion and color purity on the substrate surface. The above comparative data further verifies the necessity for the components of the present invention to work together to achieve the aforementioned technical effects and the physicochemical synergistic effect between the components.

[0093] It should be noted that the specific embodiments described above are exemplary. Those skilled in the art can devise various solutions inspired by the disclosure of this invention, and these solutions all fall within the scope of this invention and its protection. Those skilled in the art should understand that this specification is illustrative and does not constitute a limitation on the claims. The scope of protection of this invention is defined by the claims and their equivalents. This specification contains multiple inventive concepts; terms such as "preferredly," "according to a preferred embodiment," or "optionally" indicate that the corresponding paragraph discloses an independent concept. The applicant reserves the right to file divisional applications based on each inventive concept.

Claims

1. A radiation-curable ink composition suitable for inkjet printing on decal paper, characterized in that, By weight percentage, it includes the following components: Radiation-curable components: 40%~90%; High-temperature adhesive: 5%~50%; Inorganic mineral pigments: 5%~50%; Decomposition accelerator: 1%~5%; Additives: 0.5%~10%; The radiation-curable component includes oligomers, reactive monomers, and photoinitiators. The reactive functionality of the oligomers is less than or equal to 4. The reactive monomers include monofunctional monomers and polyfunctional monomers. By weight percentage, the total content of the polyfunctional monomers does not exceed 20% of the total weight of the radiation-curable ink composition. The decomposition accelerator is selected from at least one of organic peroxides, organometal salts, or high-temperature initiating plasticizers; The high-temperature binder is selected from at least one of nano-oxides or glass powders, and the high-temperature binder is configured to melt or transform into an inorganic binder phase at a temperature of 400°C or higher. The inorganic particles in the radiation-curable ink composition have a particle size D50 of less than 3 μm.

2. The ink composition according to claim 1, characterized in that, The oligomer is selected from at least one of aliphatic polyurethane acrylate and flexible polyester acrylate; The oligomer accounts for 1% to 20% of the total weight of the radiation-curable ink composition by weight percentage.

3. The ink composition according to claim 1 or 2, characterized in that, The monofunctional monomer is selected from at least one of lauryl acrylate, tridecyl acrylate, lauryl methacrylate, isodecanyl acrylate, isooctyl acrylate / 2-ethylhexyl acrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl acrylate, tetrahydrofuran acrylate, cyclotrimethylolpropane methyl acetal acrylate, or phenoxyethyl acrylate. The multifunctional monomer is selected from at least one of tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, polypropylene glycol diacrylate, propoxylated bisphenol A diacrylate, or ethoxylated trimethylolpropane triacrylate.

4. The ink composition according to any one of claims 1 to 3, characterized in that, The photoinitiator is a free radical photoinitiator, and by weight percentage, the photoinitiator accounts for 1% to 15% of the total weight of the radiation-curable ink composition; The photoinitiator is selected from at least one of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-isopropylthioxanthone, macromolecular α-hydroxy ketone / acylphosphine oxide, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, methyl benzoylformate, isopropyl benzoylformate, or 2,2-dimethoxy-2-phenylacetophenone.

5. The ink composition according to any one of claims 1 to 4, characterized in that, The decomposition accelerator is selected from at least one of di-tert-butyl peroxide, zinc acetylacetonate, zinc octanoate, ammonium molybdate, polyester plasticizers, citrate plasticizers, or tributyl citrate.

6. The ink composition according to any one of claims 1 to 5, characterized in that, The glass powder has a melting temperature range of 400℃ to 1200℃ and a coefficient of thermal expansion of 4.0 to 8.0 × 10⁻⁶. -6 / ℃, and the glass powder is selected from at least one of bismuth-based glass powder, zinc-boron-silicon-based glass powder, or lead-based glass powder; The nano-oxide is selected from at least one of nano-silica, nano-titanium oxide, nano-zirconium oxide, or nano-alumina. The high-temperature adhesive also includes organosilicon compounds or nano-silicates with radiation curing activity.

7. The ink composition according to any one of claims 1 to 6, characterized in that, The inorganic mineral pigment is selected from at least one of the following types: The encapsulated pigment is selected from at least one of ZrSiO4 / Cd(S,Se) type encapsulated red, ZrSiO4 / praseodymium yellow, ZrSiO4 / vanadium zirconium blue, encapsulated orange, or encapsulated green; Non-encapsulated metal oxide and composite oxide pigments, wherein the non-encapsulated metal oxide and composite oxide pigments are selected from at least one of chrome tin red, iron red, yellow brown, red brown, cobalt blue, cobalt black or copper chrome black; Chalcogenide pigments, wherein the chalcogenide pigments are selected from at least one of cadmium red or cadmium yellow; Other stable oxide pigments, wherein the other stable oxide pigments are selected from at least one of rutile titanium yellow, praseodymium yellow or copper red doped with Ni or Sb.

8. The ink composition according to any one of claims 1 to 7, characterized in that, The additive is selected from at least one of dispersants, surfactants, leveling agents, or polymerization inhibitors; At a temperature of 25°C, the viscosity of the radiation-curable ink composition is 10~40 mPa·s, and the surface tension is 15~50 mN / m.

9. A type of decal paper, characterized in that, The invention includes a substrate and a decorative pattern disposed on the surface of the substrate, the decorative pattern being formed by inkjet printing and ultraviolet curing of the radiation-curable ink composition according to any one of claims 1 to 8.

10. A high-temperature decoration method for an article, characterized in that, Includes the following steps: S1. Using the radiation-curable ink composition according to any one of claims 1 to 8, a pattern is formed on a decal substrate by inkjet printing; S2. The pattern is irradiated with ultraviolet light to cure the radiation-curable ink composition into a film to obtain decals with a cured pattern; S3. Transfer the decal with the cured pattern to the surface of a high-temperature resistant substrate; S4. Under an oxidizing atmosphere, the ink composition is fired at a temperature of at least 600°C, which is higher than the melting temperature of the selected high-temperature binder, so that the organic components in the ink composition decompose and the high-temperature binder melts or transforms to form an inorganic binder phase, thereby bonding the inorganic mineral pigments in the ink composition to the surface of the high-temperature resistant substrate to form a glaze decorative layer.

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