Photocurable inks and primers for automotive interior applications and glass articles comprising same

Abstract

To provide an alternative ink that satisfies requirements related to automotive interior display applications.SOLUTION: An ultraviolet curable ink composition includes from 25 wt% to 50 wt% of a pigment dispersion; from 10 wt% to 42 wt% of a reactive diluent; from 10 wt% to 20 wt% of a multifunctional monomer; and from 0 wt% to 25 wt% of a difunctional monomer. An ink primer includes from 2 wt% to 10 wt% of an adhesion promoter configured to bond to glass and from 90 wt% to 98 wt% of a solvent configured to promote bonding of the adhesion promoter to the glass. Another ink primer includes from 2 wt% to 10 wt% of an adhesion promoter configured to bond to glass, from greater than 0 wt% to 10 wt% of a photoinitiator package; and from 30 wt% to 45 wt% of a monofunctional monomer.SELECTED DRAWING: Figure 1

Description

Description of Related Applications

[0001] This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 601,925, filed November 22, 2023, and U.S. Provisional Patent Application No. 63 / 526,560, filed July 13, 2023, the contents of each of which are relied upon and incorporated herein by reference in their entireties. [Technical field]

[0002] This specification relates generally to glass articles for automotive interiors, and more particularly to photocurable inks and primers used to form opaque layers on display cover glass that have relatively high adhesion to glass and high optical density. [Background technology]

[0003] Automotive interiors may include displays with display cover glasses. A display module (e.g., a liquid crystal display ("LCD") module, an organic light emitting diode ("OLED") display module, or other suitable type of display module) may be laminated to or otherwise integrated with a cover glass such that the cover glass protects the display module and / or provides one or more performance enhancing attributes (e.g., anti-glare or anti-reflective properties) to the display module. Decorative inks may be applied to certain areas of the cover glass to hide various components of the display (e.g., electrical connections and mechanical bonds) and / or to give the display a uniform appearance when the display is turned off. Some existing inks used to decorate display cover glasses may have various deficiencies, such as low throughput, undesirable optical density, and inadequate adhesion, that make these inks unsuitable for automotive interior applications. Summary of the Invention [Problem to be solved by the invention]

[0004] Therefore, there is a need for alternative inks that meet the requirements associated with interior automotive display applications. [Means for solving the problem]

[0005] According to a first aspect A1, the UV curable ink composition comprises: greater than or equal to 25% and less than or equal to 50% by weight of a pigment dispersant, the pigment dispersant comprising at least 30% by weight of pigment and a reactive monomer, based on the total weight of the pigment dispersant; greater than 0% and less than or equal to 10% by weight of a photoinitiator package comprising a Type I photoinitiator, a Type II photoinitiator, and an amine synergist; greater than or equal to 10% and less than or equal to 42% by weight of a reactive diluent, the reactive diluent having a viscosity of less than 5 cP at 25° C.; greater than or equal to 5% and less than or equal to 20% by weight of a multifunctional monomer; and greater than or equal to 0% and less than or equal to 35% by weight of a difunctional monomer.

[0006] A second aspect A2 includes the UV-curable ink composition of the first aspect A1, in which the UV-curable ink composition includes 10% by weight or more and 35% by weight or less of a bifunctional monomer.

[0007] A third embodiment A3 includes the UV-curable ink composition of the second embodiment A2, in which the total amount of the reactive diluent, the polyfunctional monomer, and the difunctional monomer is 60% by weight or less.

[0008] A fourth aspect A4 includes the ultraviolet ray curable ink composition of any one of the first to third aspects A1 to A3, wherein the ultraviolet ray curable ink composition further includes more than 0 mass % and not more than 10 mass % of an adhesion promoter.

[0009] A fifth aspect A5 includes the ultraviolet ray curable ink composition of any one of the first to fourth aspects A1 to A4, in which the ultraviolet ray curable ink composition does not contain a resin and does not contain a TPO.

[0010] A sixth aspect A6 includes the ultraviolet ray curable ink composition of any one of the first to fifth aspects A1 to A5, in which the ultraviolet ray curable ink composition exhibits a viscosity of 8 cP or more and 13 cP or less over a temperature range of 30°C to 50°C.

[0011] A seventh aspect A7 includes the ultraviolet ray curable ink composition of any of the first to sixth aspects A1 to A6, in which the pigment dispersant contains 35% by mass or more of the pigment based on the total mass of the pigment dispersant, and the pigment is a carbon black pigment.

[0012] An eighth embodiment, A8, comprises the UV-curable ink composition of any of the first to seventh embodiments, A1-A7, wherein after being deposited on a glass substrate and cured using a UV source to form an opaque layer having a cured thickness of less than 15 μm, the opaque layer exhibits an optical density of greater than 5.

[0013] According to a ninth aspect A9, a glass article comprises a glass substrate having a first major surface and a second major surface opposite the first major surface; and an opaque layer disposed on the second major surface, the opaque layer made from a photocurable ink comprising at least 11% by weight pigment, the opaque layer being resin-free and TPO-free, the opaque layer having a thickness of 15 μm or less and an optical density of 5.0 or greater, the opaque layer, after being cured solely by exposure to ultraviolet ("UV") radiation, exhibiting a pencil hardness of 3H or greater, as measured according to ASTM 3363, and adhesion to the glass substrate of 4B or greater, as measured according to ASTM 3359, after being exposed to a temperature of 85° C. at 95% relative humidity for a period of at least 500 hours.

[0014] A tenth embodiment A10 comprises the glass article of the ninth embodiment A9, wherein the pigment has an average particle size of 200 nm or less.

[0015] In an eleventh embodiment, A11, the opaque layer has a refractive index of 36 dyne / cm (10 -3 The glass article of any of the ninth to tenth aspects A9 to A10 exhibits a post-cure surface tension of more than 1.0 N / m.

[0016] A twelfth embodiment, A12, has an opaque layer having a viscosity of 1×10 10 15 20 25 30 35 40 45 50 55 60 65 6 measured according to ASTM D-257 at 100 V DC. 9 The present invention includes the glass article according to any one of the ninth to eleventh aspects A9 to A11, which exhibits an electrical resistivity of Ω / □ or more.

[0017] The thirteenth aspect, A13, relates to a glass article having a CIELAB SCI L of 30 or less when illuminated at an angle of 10° by a D65 light source. * The present invention includes the glass article of any one of the ninth to twelfth aspects A9 to A12, which exhibits a value.

[0018] The fourteenth aspect, A14, relates to a glass article having a CIELAB SCI a value of -0.05 or more and 0.15 or less when illuminated at an angle of 10° by a D65 light source. * value, and CIELAB SCI b ≥ -0.3 and ≤ -0.1 * The present invention includes the glass article of any one of the ninth to thirteenth aspects A9 to A13, which exhibits a value.

[0019] A fifteenth aspect, A15, comprises the glass article of any of the ninth through fourteenth aspects, A9-A14, wherein the opaque layer exhibits adhesion to the glass substrate of 4B or greater when tested according to ASTM 3359 after being exposed to 500 one hour cycles of being held at a temperature of -40°C for 0.5 hours and at 95°C for 0.5 hours.

[0020] A sixteenth embodiment A16 includes the glass article of the fifteenth embodiment A15, wherein the glass article exhibits a maximum ΔE value (both SCI and SCE) of less than 2.0 when measured both before and after 500 one-hour cycles.

[0021] A seventeenth aspect A17 includes the glass article of any of the ninth to sixteenth aspects A9-A16, wherein the glass substrate is made from at least one of soda-lime glass, aluminosilicate glass, borosilicate glass, aluminoborosilicate glass, alkali-containing aluminosilicate glass, and alkali-containing borosilicate glass.

[0022] According to an eighteenth aspect A18, a method of manufacturing a glass article includes depositing a plurality of sublayers of a UV curable ink composition on a first major surface of a glass substrate using an inkjet printhead at a deposition temperature of 65° C. or less, wherein during the deposition, the UV curable ink composition has a viscosity of less than 13 cP, the UV curable ink composition comprising: greater than 25% and less than 50% by weight of a pigment dispersant, the pigment dispersant comprising at least 30% by weight of pigment and reactive monomer; greater than 0% and less than 10% by weight of a photoinitiator package; greater than 10% and less than 42% by weight of a reactive diluent, the reactive diluent having a viscosity of less than 5 cP at 25° C.; greater than 10% and less than 20% by weight of a multifunctional monomer; and greater than 0% and less than 35% by weight of a difunctional monomer; and, between deposition of adjacent layers of the plurality of sublayers, exposing the plurality of sublayers to UV light from a UV light source to at least partially cure the UV curable ink composition that constitutes the sublayer, thereby fixing each of the plurality of sublayers.

[0023] A nineteenth embodiment A19 includes the method of the eighteenth embodiment A18, wherein each of the plurality of sublayers has a thickness, after the fixing step, of not less than 2 μm and not more than 4 μm.

[0024] A twentieth embodiment A20 includes the method of the nineteenth embodiment A19, wherein the depositing and fixing steps are performed in three or more deposition and fixing stages, each of the deposition and fixing stages including an inkjet printhead for depositing one of the multiple sublayers and an ultraviolet light source for fixing the sublayer.

[0025] A twenty-first embodiment A21 includes the method of the twentieth embodiment A20, wherein during deposition and fixation, the glass substrate is moved relative to the deposition and fixation stage at a translation speed of 1 m / min or more and 5 m / min or less.

[0026] A twenty-second embodiment A22 includes the method of the twenty-first embodiment A21, wherein the glass substrate is moved over a plurality of rollers that contact a second major surface of the glass substrate opposite the first major surface.

[0027] A twenty-third embodiment A23 provides a method for producing a photothermographically-based ... 2 More than 10J / cm 2 The method of any of the twenty-first to twenty-second embodiments A21-22 is configured to apply a fixed dose of ultraviolet light to the sublayer as follows:

[0028] A twenty-fourth embodiment A24 includes the method of the twenty-third embodiment A23, wherein after the depositing and fixing steps with the deposition and fixing stage, the multiple sublayers form an opaque layer having a thickness less than 15 μm, an optical density greater than 5, and adhesion to a glass substrate of 4B or greater when tested according to ASTM 3359, without the application of any additional ultraviolet light outside the deposition and fixing stage.

[0029] A twenty-fifth embodiment, A25, further comprises exposing the sublayer to additional UV light in a final cure stage after the deposition and fixing stage, the final cure stage exposing the sublayer to at least 10 J / cm 2 More than 100 J / cm 2 The method of any of twenty-first to twenty-third aspects A21-A23, including a first ultraviolet light source configured to expose to a curing dosage of ultraviolet light of:

[0030] Twenty-sixth embodiment A26 includes the method of twenty-fifth embodiment A25, wherein after exposure to a curing dose, the plurality of sublayers form an opaque layer having a thickness less than 15 μm, exhibiting an optical density greater than 5, and adhesion to a glass substrate of 4B or greater when tested according to ASTM 3359.

[0031] A twenty-seventh embodiment A27 includes the method of the twenty-sixth embodiment A26, wherein the adhesion is exhibited without exposure to ultraviolet light from a side of a second major surface of the glass substrate opposite the first major surface.

[0032] Twenty-eighth embodiment A28 includes the method of twenty-sixth embodiment A26, wherein the final curing stage includes a second ultraviolet light source configured to expose the sublayer to ultraviolet light through the glass substrate from a side of a second major surface of the glass substrate opposite the first major surface.

[0033] According to a twenty-ninth aspect A29, the ink primer comprises, based on the total weight of the ink primer, 2% by weight or more and 10% by weight or less of an adhesion promoter designed to bond to glass, and 90% by weight or more and 98% by weight or less of a solvent designed to promote bonding of the adhesion promoter to the glass.

[0034] A thirtieth embodiment, A30, comprises the ink primer of the twenty-ninth embodiment, A29, wherein the adhesion promoter comprises an organofunctional silane.

[0035] A thirty-first embodiment A31 comprises the ink primer of the twenty-ninth embodiment A29 or the thirtieth embodiment A30, wherein the ink primer is an infrared curable ink primer.

[0036] A thirty-second embodiment, A32, comprises the ink primer of any of the twenty-ninth to thirty-first embodiments, A29-A31, wherein the solvent comprises 3-methoxy-3-methyl-1-butanol; butanol; ethylene glycol ether; 2-butoxyethanol; propylene glycol monomethyl ether acetate; propylene glycol; 2-butoxyethyl acetate; ethylene glycol; 1,4-butanediol; diethyl succinate; or a combination thereof.

[0037] A thirty-third embodiment A33 comprises the ink primer of any one of the twenty-ninth to thirty-second embodiments A29 to A32, in which the ink primer does not contain resin and does not contain TPO.

[0038] A thirty-fourth embodiment, A34, comprises the ink primer of any of the twenty-ninth to thirty-third embodiments, A29-A33, wherein the ink primer exhibits a viscosity of 8 cP or more and 13 cP or less over a temperature range of 30°C to 50°C.

[0039] According to a thirty-fifth aspect A35, the ink primer includes, based on the total weight of the ink primer, 2% by weight or more and 10% by weight or less of an adhesion promoter designed to bond to glass; greater than 0% by weight and 10% by weight or less of a photoinitiator package including a Type I photoinitiator, a Type II photoinitiator, and an amine synergist; and 30% by weight or more and 45% by weight or less of a monofunctional monomer.

[0040] A thirty-sixth embodiment, A36, comprises the ink primer of the thirty-fifth embodiment, A35, wherein the adhesion promoter comprises an organofunctional silane.

[0041] A thirty-seventh embodiment, A37, includes the ink primer of the thirty-fifth embodiment, A35 or the thirty-sixth embodiment, A36, wherein the ink primer is a UV-curable ink primer.

[0042] A thirty-eighth embodiment, A38, comprises the ink primer of any of the thirty-fifth to thirty-seventh embodiments, A35-A37, in which the ink primer comprises 4% or more and 10% or less by weight of an adhesion promoter.

[0043] A thirty-ninth embodiment A39 includes the ink primer of any of the thirty-fifth through thirty-eighth embodiments A35-A38, wherein the Type I photoinitiator comprises phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide; 1-hydroxycyclohexyl-phenyl ketone; (2,6-dimethoxybenzoyl)-2,4,4-trimethylphenylphosphine oxide; 2,2-dimethoxy-2-phenylacetophenone; (2,4,6-trimethylbenzoyl)diphenylphosphine oxide; ethoxy(2,4,6-trimethylbenzoyl)phenylphosphine oxide; or a combination thereof.

[0044] A fortieth embodiment, A40, includes the ink primer of any of the thirty-fifth through thirty-ninth embodiments, A35-A39, wherein the Type II photoinitiator comprises isopropylthioxanthone, benzophenone, 4-phenylbenzophenone, methyl-2-benzoyl benzoate, ketosulfone, or a combination thereof.

[0045] A forty-first embodiment, A41, includes the ink primer of any of the thirty-fifth through fortieth embodiments, A35-A40, wherein the amine synergist includes ethyl 4-(dimethylamino)benzoate; N,N-[2-(4-dimethylaminobenzoyl)oxyethylene-1-yl]methylamine; N-methyldiethanolamine; ethyl 4-dimethylaminobenzoate; 2-ethylhexyl 4-dimethylaminobenzoate; or a combination thereof.

[0046] A forty-second embodiment, A42, comprises an ink primer according to any one of the thirty-fifth through forty-first embodiments, A35-A41, in which the monofunctional monomer comprises isobornyl acrylate.

[0047] A forty-third embodiment, A43, includes the ink primer of any of the thirty-fifth to forty-second embodiments, A35 to A42, wherein the ink primer further comprises greater than 0% and not more than 30% by weight of a reactive diluent, the reactive diluent having a viscosity of less than 5 cP at 25°C.

[0048] A forty-fourth embodiment A44 includes the ink primer of the forty-third embodiment A43, wherein the reactive diluent comprises vinylmethyloxazolidinone; 5-methyl-3-vinyloxazolidin-2-one; an N-vinyl monomer; or a combination thereof.

[0049] A forty-fifth embodiment, A45, includes the ink primer of any of the thirty-fifth through forty-fourth embodiments, A35-A44, wherein the ink primer further includes greater than 0% and not greater than 35% by weight of a difunctional monomer.

[0050] A forty-sixth embodiment A46 includes the ink primer of the forty-fifth embodiment A45, wherein the difunctional monomer comprises 3-methyl-1,5-pentanediyl diacrylate; dipropylene glycol diacrylate; or a combination thereof.

[0051] A forty-seventh embodiment, A47, comprises the ink primer of any one of the thirty-fifth to forty-sixth embodiments, A35 to A46, in which the ink primer comprises 5% by mass or more and 10% by mass or less of a solvent.

[0052] A forty-eighth embodiment A48 includes the ink primer of the forty-seventh embodiment A47, wherein the solvent includes 3-methoxy-3-methyl-1-butanol; butanol; ethylene glycol ether; 2-butoxyethanol; propylene glycol monomethyl ether acetate; propylene glycol; 2-butoxyethyl acetate; ethylene glycol; 1,4-butanediol; diethyl succinate; or combinations thereof.

[0053] A forty-ninth embodiment, A49, comprises the ink primer of any one of the thirty-fifth to forty-eighth embodiments, A35 to A48, in which the ink primer contains no resin and no TPO.

[0054] A fiftieth embodiment, A50, comprises the ink primer of any of the thirty-fifth through forty-ninth embodiments, A35-A49, in which the ink primer exhibits a viscosity of 8 cP or more and 13 cP or less over a temperature range of 30°C to 50°C.

[0055] According to a fifty-first embodiment A51, a glass article comprises a glass substrate having a first major surface and a second major surface opposite the first major surface; and an opaque layer disposed on the second major surface, the opaque layer made from an ink composition comprising at least 11% by weight of a pigment and an adhesion promoter, the adhesion promoter being bonded to the glass substrate, the ink composition being polymerized with the adhesion promoter, the opaque layer having a thickness of 15 μm or less and an optical density of 5.0 or greater, the opaque layer exhibiting adhesion to the glass substrate of 4B or greater when tested in accordance with ASTM 3359 after being exposed to 500 1-hour cycles of being held at a temperature of −40° C. for 0.5 hours and at a temperature of 95° C. for 0.5 hours.

[0056] A fifty-second embodiment, A52, includes the glass article of the fifty-first embodiment, A51, wherein the adhesion promoter comprises an organofunctional silane.

[0057] A fifty-third embodiment A53 includes the glass article of the fifty-first embodiment A51 or the fifty-second embodiment A52, wherein the opaque layer is resin-free and TPO-free.

[0058] A fifty-fourth embodiment, A54, includes the glass article of any of the fifty-first to fifty-third embodiments, A51-A53, wherein the glass article exhibits a maximum ΔE value (both SCI and SCE) of less than 2.0 when measured both before and after 500 one-hour cycles.

[0059] A fifty-fifth embodiment, A55, includes the glass article of any of the fifty-first to fifty-fourth embodiments, A51-A54, wherein the glass substrate is made from at least one of soda-lime glass, aluminosilicate glass, borosilicate glass, aluminoborosilicate glass, alkali-containing aluminosilicate glass, and alkali-containing borosilicate glass.

[0060] According to a fifty-sixth aspect A56, a method of producing a glass article includes the steps of depositing an ink primer on a first major surface of a glass substrate using an inkjet printhead at a first deposition temperature of 65° C. or less, wherein during the depositing step, the ink primer has a viscosity of less than 13 cP, and the ink primer includes 2% by weight or more and 10% by weight or less of an adhesion promoter designed to bond to glass; exposing the ink primer to a first light source to at least partially cure the ink primer; depositing an ink composition on the ink primer using a second inkjet printhead at a second deposition temperature of 65° C. or less, wherein during the depositing step, the ink composition has a viscosity of less than 13 cP; and exposing the ink composition to a second light source to at least partially cure the ink composition.

[0061] A fifty-seventh embodiment A57 includes the method of the fifty-sixth embodiment A56, wherein the first light source is an infrared source.

[0062] A fifty-eighth embodiment A58 includes the method of the fifty-sixth embodiment A56, wherein the first light source is an ultraviolet light source.

[0063] A fifty-ninth embodiment A59 includes the method of fifty-sixth embodiment A56, wherein the ink primer further comprises greater than 0% and less than or equal to 10% by weight of a photoinitiator package including a Type I photoinitiator, a Type II photoinitiator, and an amine synergist; and greater than or equal to 30% and less than or equal to 45% by weight of a monofunctional monomer.

[0064] A sixtieth embodiment, A60, includes the method of any of the fifty-sixth to fifty-ninth embodiments, A56-A59, wherein the method further includes heating the ink primer at a first heating temperature of at least 25° C. and at most 150° C. for a period of at least 1 second and at most 1 hour prior to depositing the ink composition.

[0065] A sixty-first embodiment A61 includes the method of any of the fifty-sixth embodiment A56, the fifty-eighth embodiment A58, or the fifty-ninth embodiment A59, wherein the method further includes, after depositing the ink composition, heating the ink primer and the ink composition at a second heating temperature of at least 25° C. and at most 150° C. for a period of at least 1 second and at most 1 hour.

[0066] Additional features and advantages of the photocurable inks and primers described herein and glass articles incorporating same are set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description, or may be learned by practicing the embodiments described herein, including the following detailed description, claims, and accompanying drawings.

[0067] It should be understood that both the foregoing general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter. The accompanying drawings are included to provide a further understanding of the various embodiments, and are incorporated into and constitute a part of this specification. The drawings illustrate various embodiments described herein and, together with the description, serve to explain the principles and operation of the claimed subject matter. [Brief description of the drawings]

[0068] [Figure 1] FIG. 1 is a perspective view of a vehicle cabin with a vehicle cabin system having a display in accordance with one or more embodiments of the present disclosure. [Diagram 2] 2 is a cross-sectional view of a display of a cabin system taken through line 2-2 shown in FIG. 1 in accordance with one or more embodiments of the present disclosure. [Diagram 3] 1 is a flow diagram of a method of forming a glass article having an opaque layer according to one or more embodiments of the present disclosure. [Figure 4] FIG. 1 illustrates an apparatus for depositing an opaque layer on a glass substrate, in accordance with one or more embodiments of the present disclosure. [Diagram 5] 1 is a flow diagram of another method of forming a glass article having an opaque layer, according to one or more embodiments of the present disclosure. [Figure 6] 1 is a plot of measured optical density (y-axis) as a function of opaque layer thickness (x-axis, mm) for an example photocurable ink, according to one or more embodiments of the present disclosure. [Figure 7] Photographs of samples formed from exemplary photocurable inks after being subjected to a cross-hatch adhesion test, according to one or more embodiments of the present disclosure. [Figure 8] 1 is a plot of sample optical density (y-axis) as a function of thickness (x-axis, μm) of opaque layers formed from exemplary photocurable inks, according to one or more embodiments of the present disclosure. [Figure 9] Photographs of samples formed from exemplary photocurable inks after being subjected to a cross-hatch adhesion test, according to one or more embodiments of the present disclosure. [Figure 10] Photograph of the sample coated with the first commercial UV-curable ink after testing at elevated temperature and humidity. [Figure 11] Photograph of a sample coated with a second commercial UV-curable ink after testing at elevated temperature and humidity. [Figure 12] 1 is a plot of viscosity versus temperature for an example photocurable ink, according to one or more embodiments of the present disclosure; [Figure 13] Photograph of a sample having an exemplary ink composition deposited thereon after being subjected to a cross-hatch adhesion test, according to one or more embodiments of the present disclosure. [Figure 14] Photograph of a sample having an exemplary ink composition deposited thereon after being subjected to a cross-hatch adhesion test, according to one or more embodiments of the present disclosure. [Figure 15] 1 is a plot of optical density (y-axis) versus thickness (x-axis, μm) for opaque layers formed with example ink formulations, according to one or more embodiments of the present disclosure. [Figure 16] Photograph of a sample having an exemplary ink primer and an exemplary ink formulation deposited thereon after being subjected to a crosshatch adhesion test. [Figure 17] Photograph of a sample having an exemplary ink primer and an exemplary ink formulation deposited thereon after being subjected to a crosshatch adhesion test. [Figure 18] Photograph of a sample having an exemplary ink primer and an exemplary ink formulation deposited thereon after being subjected to a crosshatch adhesion test. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0069] Reference will now be made in detail to various embodiments of photocurable inks and ink primers used to form opaque layers on display cover glass having relatively high adhesion to glass and high optical density. In some embodiments, the UV curable ink composition comprises 25% to 50% by weight of a pigment dispersant, greater than 0% to 10% by weight of a photoinitiator package, 10% to 42% by weight of a reactive diluent, 10% to 20% by weight of a multifunctional monomer, and 0% to 35% by weight of a difunctional monomer, based on the total weight of the UV curable ink composition. The pigment dispersant comprises at least 30% by weight of pigment and reactive monomer, based on the total weight of the pigment dispersant. The photoinitiator package comprises a Type I photoinitiator, a Type II photoinitiator, and an amine synergist. The reactive diluent has a viscosity of less than 5 cP at 25° C.

[0070] In another embodiment, a glass article includes a glass substrate having a first major surface and a second major surface opposite the first major surface, and an opaque layer disposed on the second major surface. The opaque layer is disposed on the second major surface and includes a photocurable ink comprising at least 11% by weight pigment. The opaque layer is resin-free and TPO-free. The opaque layer has a thickness of 15 μm or less and an optical density of 5.0 or greater. The opaque layer, after being cured solely by exposure to ultraviolet ("UV") radiation, exhibits a pencil hardness of 3H or greater, as measured according to ASTM 3363, and adhesion to the glass substrate of 4B or greater, as measured according to ASTM 3359, after being exposed to a temperature of 85° C. at 95% relative humidity for a period of at least 500 hours.

[0071] In some embodiments, a method for manufacturing a glass article includes depositing a plurality of sublayers of a UV curable ink composition on a first major surface of a glass substrate using an inkjet printhead at a deposition temperature of 65° C. or less, and fixing each of the plurality of sublayers by exposing the plurality of sublayers to UV light from a UV light source between deposition of adjacent layers of the plurality of sublayers to at least partially cure the UV curable ink composition that constitutes the sublayer. During the deposition, the UV curable ink composition has a viscosity of less than 13 cP. The UV curable ink composition includes, by weight, 25% or more and 50% or less of a pigment dispersant, greater than 0% and 10% or less of a photoinitiator package, 10% or more and 42% or less of a reactive diluent, 10% or more and 20% or less of a multifunctional monomer, and 0% or more and 35% or less of a difunctional monomer, based on the total weight of the pigment dispersant. The pigment dispersant includes at least 30% by weight of the pigment and the reactive monomer, based on the total weight of the pigment dispersant. The reactive diluent has a viscosity of less than 5 cP at 25°C.

[0072] In other embodiments, the ink primer comprises from 2% to 10% by weight of an adhesion promoter designed to bond to glass, and from 90% to 98% by weight of a solvent designed to promote bonding of the adhesion promoter to the glass.

[0073] In some embodiments, the ink primer comprises 2% to 10% by weight of an adhesion promoter designed to bond to glass, greater than 0% to 10% by weight of a photoinitiator package, and 30% to 45% by weight of a monofunctional monomer, the photoinitiator package including a Type I photoinitiator, a Type II photoinitiator, and an amine synergist.

[0074] In another embodiment, a glass article includes a glass substrate having a first major surface and a second major surface opposite the first major surface, and an opaque layer disposed on the second major surface. The opaque layer includes an ink composition including at least 11% by weight of a pigment and an adhesion promoter. The adhesion promoter is bonded to the glass substrate, and the ink composition is polymerized with the adhesion promoter. The opaque layer has a thickness of 15 μm or less and an optical density of 5.0 or greater. The opaque layer exhibits adhesion to the glass substrate of 4B or greater after being exposed to 500 1-hour cycles of being held at a temperature of −40° C. for 0.5 hours and at a temperature of 95° C. for 0.5 hours.

[0075] In some embodiments, a method of manufacturing a glass article includes depositing an ink primer on a first major surface of a glass substrate using a first inkjet printhead at a first deposition temperature of 65° C. or less, exposing the ink primer to a first light source to at least partially cure the ink primer, depositing an ink composition on the ink primer using a second inkjet printhead at a second deposition temperature of 65° C. or less, and exposing the ink composition to a second light source to at least partially cure the ink composition. During the depositing step, the ink primer has a viscosity of less than 13 cP. The ink primer includes an adhesion promoter configured to bond to glass in an amount of 2% or more and 10% or less by weight. During the depositing step, the ink composition has a viscosity of less than 13 cP.

[0076] Various embodiments of photocurable inks and primers and glass articles incorporating same will now be described with particular reference to the accompanying drawings.

[0077] Ranges may be expressed herein as from "about" one particular value, and / or to "about" another particular value. When such a range is expressed, another embodiment includes from the one particular value and / or to the other particular value. Similarly, when values ​​are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms another embodiment. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.

[0078] As used herein, directional terms - e.g., up, down, right, left, front, back, upper and bottom - are used only with reference to the drawings as depicted and are not intended to imply absolute orientation.

[0079] Unless otherwise expressly stated, it is in no way intended that any method described herein be construed as requiring that its steps be performed in a particular order or as requiring a particular orientation for any apparatus. Thus, where a method claim does not actually recite an order in which its steps are to be followed, or an apparatus claim does not actually recite an order or orientation with respect to individual components, or where the claims or description do not recite the steps to be limited to a particular order or a particular order or orientation with respect to the apparatus components, no order or orientation is intended to be implied in any respect. This applies to any possible non-expressive criteria of interpretation, including sequence of steps, operational flow, order of components, or orientation of components; obvious meanings derived from grammatical construction or punctuation; and logical matters regarding the number or type of embodiments described in the specification.

[0080] As used herein, nouns include plural referents unless the context clearly indicates otherwise. Thus, for example, reference to an element includes aspects having two or more of such elements unless the context clearly indicates otherwise.

[0081] As used herein, "deposition temperature" refers to the temperature of the ink as it is ejected from the printhead.

[0082] As used herein, "optical density" refers to how well a material reduces the power of light transmitted through it per unit thickness as measured by a densitometer.

[0083] As used herein, "adhesion" refers to the ability of materials to adhere to each other after exposure to specified conditions when tested in accordance with ASTM 3359.

[0084] As used herein, "pencil hardness" is measured in accordance with ASTM 3363.

[0085] As used herein, "viscosity" is measured at a given temperature according to ASTM D445.

[0086] As used herein, the term "free," when used to describe the amount, concentration, or absence of a particular component in a composition or article, means that the component is not present in the composition or article.

[0087] Automotive interiors may include a display with a display cover glass. A display module (e.g., a liquid crystal display ("LCD") module, an organic light emitting diode ("OLED") display module, or other suitable type of display module) may be laminated to or otherwise integrated with the cover glass such that the cover glass protects the display module and / or provides one or more performance enhancing attributes (e.g., anti-glare or anti-reflective properties) to the display module. Decorative inks may be applied to certain areas of the cover glass to hide various components of the display (e.g., electrical connections and mechanical bonds) and / or to give the display a uniform appearance when the display is turned off.

[0088] Certain existing inks used to decorate display cover glass may have various deficiencies that make them unsuitable for automotive interior applications. For example, some existing inks may be applied by a screen printing process, which may require multiple layers to provide the desired optical density. Such inks may have a relatively low throughput in production. Other existing inks (e.g., UV-curable inks) may fail to provide adequate adhesion to the cover glass and / or fail to provide the desired optical density, either initially or after environmental testing associated with the variable environmental conditions (e.g., with respect to temperature and humidity) to which automotive interior components are exposed. Adequate adhesion may become more difficult to achieve as the amount of pigment in the ink increases.

[0089] Disclosed herein is an ink composition and an ink primer that alleviates the above-mentioned problems. In particular, the photocurable ink described herein may be used to form an opaque layer on a cover glass for a display by a high-throughput curing process. Once the photocurable ink is cured, the opaque layer may have relatively high adhesion to glass and high optical density. With regard to adhesion, the ink primer described herein with an adhesion promoter may be used to properly adhere an ink composition containing at least 11% by weight of pigment to a glass substrate without compromising the desired post-curing thickness (e.g., less than 15 μm) and optical density (e.g., greater than 5) of the resulting opaque layer.

[0090] Ink composition The ink compositions described herein may be used to form an opaque layer having a desired cured thickness (e.g., less than 15 μm) on a display cover glass by a high-throughput curing process. Once the photocurable ink is cured, the opaque layer may have relatively high adhesion to the glass (e.g., 4B or higher) and high optical density (e.g., greater than 5). The terms "photocurable ink," "ink composition," and "photocurable ink composition" are used interchangeably throughout.

[0091] The ink compositions described herein may be UV curable ink compositions, which may be generally described as including a pigment dispersant, a photoinitiator package, a reactive diluent, a multifunctional monomer, and optionally a difunctional monomer.

[0092] The pigment dispersant provides the desired optical density to the resulting opaque layer. The ink composition may include a minimum amount of pigment dispersant (e.g., 25% by weight or more) to ensure that the desired optical density (e.g., greater than 5) is achieved at the desired cured thickness (e.g., less than 15 μm). The amount of pigment dispersant in the ink composition may be limited (e.g., 50% by weight or less) to ensure that the ink composition is curable. Thus, in embodiments, the ink composition may include 25% by weight or more and 50% by weight or less of pigment dispersant, based on the total weight of the ink composition. In embodiments, the amount of pigment dispersant in the ink composition may be 25% by weight or more, 30% by weight or more, or even 35% by weight or more, based on the total weight of the ink composition. In embodiments, the amount of pigment dispersant in the ink composition may be 50% by weight or less, 45% by weight or less, or even 40% by weight or less, based on the total weight of the ink composition. In embodiments, the amount of pigment dispersant in the ink composition can be greater than or equal to 25% and less than or equal to 50% by weight, greater than or equal to 25% and less than or equal to 45% by weight, greater than or equal to 25% and less than or equal to 40% by weight, greater than or equal to 30% and less than or equal to 50% by weight, greater than or equal to 30% and less than or equal to 45% by weight, greater than or equal to 30% and less than or equal to 40% by weight, greater than or equal to 50% by weight, greater than or equal to 35% and less than or equal to 45% by weight, or even greater than or equal to 35% and less than or equal to 40% by weight, based on the total weight of the ink composition, or any and all subranges formed from any of these endpoints.

[0093] In embodiments, the pigment dispersant includes a pigment and a reactive monomer. In embodiments, the pigment may include carbon black, iron oxide, carbon nanotubes, graphene, carbon fiber, titanium dioxide (black), or a combination thereof. In embodiments, the pigment may include CI Pigment Black 6, 7, 12, 20, 31, and 32; PO71; PO38; carbon black, titanium black; aniline black; anthraquinone black pigment; or a combination thereof. The pigment dispersant may include a minimum amount of pigment (e.g., at least 30% by weight) to ensure that a desired optical density (e.g., greater than 5) is achieved at a desired cured thickness (e.g., less than 15 μm). The amount of pigment in the pigment dispersant may be limited (e.g., 40% by weight or less) to maintain UV curability and flexibility in composition space. Thus, in embodiments, the amount of pigment in the pigment dispersant may be 30% by weight or more, 33% by weight or more, or even 35% by weight or more based on the total weight of the pigment dispersant. In embodiments, the amount of pigment in the pigment dispersant can be 40% or less, or even 37% or less, by weight, based on the total weight of the pigment dispersant. In embodiments, the amount of pigment in the pigment dispersant can be greater than or equal to 30% and less than or equal to 40%, greater than or equal to 30% and less than or equal to 37%, greater than or equal to 33% and less than or equal to 40%, greater than or equal to 33% and less than or equal to 37%, greater than or equal to 35% and less than or equal to 40%, or even greater than or equal to 35% and less than or equal to 37%, by weight, based on the total weight of the pigment dispersant, or any and all subranges formed from any of these endpoints.

[0094] In embodiments, the ink composition may include at least 11% by weight of pigment, based on the total weight of the ink composition, to facilitate the formation therefrom of an opaque layer having a relatively high optical density (e.g., 5 or greater) at a relatively small thickness (e.g., 15 μm or less after curing). In embodiments, the amount of pigment in the ink composition may be 11% or more, 13% or more, 15% or more, 17% or more, or even 20% or more, by weight, based on the total weight of the ink composition.

[0095] In embodiments, the remainder of the pigment dispersant comprises reactive monomer. Thus, in embodiments, the amount of reactive monomer in the pigment dispersant can be greater than or equal to 60% and less than or equal to 70%, greater than or equal to 60% and less than or equal to 67%, greater than or equal to 60% and less than or equal to 65%, greater than or equal to 63% and less than or equal to 70%, greater than or equal to 63% and less than or equal to 67%, or even greater than or equal to 63% and less than or equal to 65%, by weight based on the total weight of the pigment dispersant, or any and all subranges formed from any of these endpoints.

[0096] In embodiments, the reactive monomer may include isobornyl acrylate, 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, triethylene glycol divinyl ether, ethylene glycol phenyl ether acrylate, propoxylated neopentyl glycol diacrylate, or combinations thereof.

[0097] The photoinitiator package of the ink composition promotes the curing of the ink composition, for example, using a UV LED. The ink composition may include a minimum amount of photoinitiator package (e.g., greater than 0% by weight) to ensure the curability of the ink composition. The amount of the photoinitiator package may be limited (e.g., 10% by weight or less) to provide favorable UV curing performance while maintaining flexibility in the composition space of the remaining components. Thus, in embodiments, the ink composition may include greater than 0% and less than or equal to 10% by weight of the photoinitiator package, based on the total weight of the ink composition. In embodiments, the amount of the photoinitiator package in the ink composition may be greater than 0%, 1% or more, 2% or more, 3% or more, or even 4% by weight or more, based on the total weight of the ink composition. In embodiments, the amount of the photoinitiator package in the ink composition may be 10% or less, or even 8% or less, based on the total weight of the ink composition. In embodiments, the amount of photoinitiator package in the ink composition can be greater than 0% and less than or equal to 10%, greater than 0% and less than or equal to 8%, greater than or equal to 1% and less than or equal to 10%, greater than or equal to 1% and less than or equal to 8%, greater than or equal to 2% and less than or equal to 10%, greater than or equal to 2% and less than or equal to 8%, greater than or equal to 3% and less than or equal to 10%, greater than or equal to 3% and less than or equal to 8%, greater than or equal to 4% and less than or equal to 10%, or even greater than or equal to 4% and less than or equal to 8%, based on the total weight of the ink composition, or any and all subranges formed from any of these endpoints.

[0098] The photoinitiator package in the ink composition may include a Type I photoinitiator, a Type II photoinitiator, and an amine synergist.

[0099] In embodiments, Type I photoinitiators may include phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (e.g., Irgacure 819 available from BASF); 1-hydroxycyclohexyl-phenyl ketone (e.g., Irgacure 184 available from BASF); (2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide (e.g., commercial blends Irgacure 1800, 1850, and 1700 available from BASF); 2,2-dimethoxy-2-phenylacetophenone (e.g., Irgacure 651 available from BASF); (2,4,6-trimethylbenzoyl)diphenylphosphine oxide (e.g., Lucirin TPO available from BASF, Munich, Germany); ethoxy(2,4,6-trimethylbenzoyl)phenylphosphine oxide (e.g., Lucirin TPO-L from BASF); or combinations thereof.

[0100] In embodiments, the amount of Type I photoinitiator in the ink composition can be greater than or equal to 2% and less than or equal to 8% by weight, greater than or equal to 2% and less than or equal to 6% by weight, greater than or equal to 4% and less than or equal to 8% by weight, or even greater than or equal to 4% and less than or equal to 6% by weight, based on the total weight of the ink composition, or any and all subranges formed from any of these endpoints.

[0101] In embodiments, Type II photoinitiators may include isopropylthioxanthone, benzophenone, 4-phenylbenzophenone, methyl-2-benzoyl benzoate, ketosulfone, or combinations thereof.

[0102] In embodiments, the amount of Type II photoinitiator in the ink composition can be greater than or equal to 1% and less than or equal to 4%, greater than or equal to 1% and less than or equal to 3%, greater than or equal to 2% and less than or equal to 4%, or even greater than or equal to 2% and less than or equal to 3%, by weight based on the total weight of the ink composition, or any and all subranges formed from any of these endpoints. In embodiments, the amount of Type I photoinitiator in the ink composition can be greater than the amount of Type II photoinitiator to facilitate photopolymerization.

[0103] In embodiments, the amine synergist may include ethyl 4-(dimethylamino)benzoate; N,N-[2-(4-dimethylaminobenzoyl)oxyethylene-1-yl]methylamine; N-methyldiethanolamine; ethyl 4-dimethylaminobenzoate; 2-ethylhexyl 4-dimethylaminobenzoate; or combinations thereof.

[0104] In embodiments, the amount of amine synergist in the ink composition can be greater than or equal to 1% and less than or equal to 4%, greater than or equal to 1% and less than or equal to 3%, greater than or equal to 2% and less than or equal to 4%, or even greater than or equal to 2% and less than or equal to 3%, by weight based on the total weight of the ink composition, or any and all subranges formed from any of these endpoints.

[0105] The reactive diluent in the ink composition provides a relatively low viscosity (e.g., less than 5 cP at 25° C.) to help provide an overall low viscosity while improving curing performance. In embodiments, the reactive diluent may include vinylmethyloxazolidinone; 5-methyl-3-vinyloxazolidin-2-one; other N-vinyl monomers such as N-vinylcarbazole, N-vinylindole derivatives, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinylacetamide derivatives, N-vinyl(na)phthalimide, N-vinylimidazolium salts, and N-vinyltriazole; or combinations thereof.

[0106] The ink composition may include a minimum amount of reactive diluent (e.g., 10% by weight or more) to ensure that the ink composition will cure. Thus, in embodiments, the ink composition may include 10% by weight or more and 42% by weight or less of reactive diluent, based on the total weight of the ink composition. In embodiments, the amount of reactive diluent in the ink composition may be 10% by weight or more, 15% by weight or more, 20% by weight or more, or even 25% by weight or more, based on the total weight of the ink composition. In embodiments, the amount of reactive diluent in the ink composition may be 42% by weight or less, 40% by weight or less, 35% by weight or less, 30% by weight or less, 25% by weight or less, or even 20% by weight or less, based on the total weight of the ink composition. In embodiments, the amount of reactive diluent in the ink composition is, based on the total weight of the ink composition, 10% by weight or more and 42% by weight or less, 10% by weight or more and 40% by weight or less, 10% by weight or more and 35% by weight or less, 10% by weight or more and 30% by weight or less, 10% by weight or more and 25% by weight or less, 10% by weight or more and 20% by weight or less, 15% by weight or more and 42% by weight or less, 15% by weight or more and 40% by weight or less, 15% by weight or more and 35% by weight or less, 15% by weight or more and 30% by weight or less, 15% by weight or more and 42% by weight or less, and 25% by weight or less, 15% or more and 20% or less, 20% or more and 42% or less, 20% or more and 40% or less, 20% or more and 35% or less, 20% or more and 30% or less, 20% or more and 25% or less, 25% or more and 42% or less, 25% or more and 40% or less, 25% or more and 35% or less, or even 25% or more and 30% or less, or any and all subranges formed from these endpoints.

[0107] The multifunctional monomer of the ink composition promotes curing through high cross-linking, thereby improving the mechanical properties of the resulting opaque layer. In embodiments, the multifunctional monomer may include dipentaerythritol hexaacrylate (e.g., M600 DPHA). Other suitable amide and acrylate compositions for use as reactive diluents and multifunctional monomers may be found in U.S. Patent No. 7,423,105 B2, entitled "Fast Curing Primary Optical Fiber Coatings," which is incorporated herein by reference in its entirety.

[0108] Examples of multifunctional acrylate monomers that may be included in the ink composition include hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, polyethylene glycol diacrylates (e.g., tetraethylene glycol diacrylate), dipropylene glycol diacrylate, tri(propylene glycol) triacrylate, neopentyl glycol diacrylate, bis(pentaerythritol)hexaacrylate, 3-methylpentanediol diacrylate, and acrylate esters of ethoxylated or propoxylated glycols and polyols, such as propoxylated neopentyl glycol diacrylate, ethoxylated trimethylolpropane triacrylate, and mixtures thereof.

[0109] In addition, suitable multifunctional methacrylate monomers can also include esters of methacrylic acid (i.e., methacrylates), such as hexanediol dimethacrylate, trimethylolpropane trimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, ethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, and mixtures thereof.

[0110] In embodiments, the multifunctional (meth)acrylate monomer may be selected from propoxylated neopentyl glycol diacrylate, ethoxylated trimethylolpropane triacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and mixtures thereof.

[0111] The ink composition may include a minimum amount of multifunctional monomer (e.g., 5% by weight or more) to ensure that the ink composition cures. The amount of multifunctional monomer may be limited (e.g., 20% by weight or less) to provide a relatively low viscosity and thereby preserve jettability. Thus, in embodiments, the ink composition may include 5% by weight or more and 20% by weight or less of multifunctional monomer, based on the total weight of the ink composition. In embodiments, the amount of multifunctional monomer in the ink composition may be 5% by weight or more, 7% by weight or more, or even 10% by weight or more, based on the total weight of the ink composition. In embodiments, the amount of multifunctional monomer in the ink composition may be 20% by weight or less, 16% by weight or less, or even 12% by weight or less, based on the total weight of the ink composition. In embodiments, the amount of multifunctional monomer in the ink composition can be greater than or equal to 5% and less than or equal to 20% by weight, greater than or equal to 5% and less than or equal to 16% by weight, greater than or equal to 5% and less than or equal to 12% by weight, greater than or equal to 7% and less than or equal to 20% by weight, greater than or equal to 7% and less than or equal to 16% by weight, greater than or equal to 7% and less than or equal to 12% by weight, greater than or equal to 10% and less than or equal to 20% by weight, greater than or equal to 10% and less than or equal to 16% by weight, or even greater than or equal to 10% and less than or equal to 12% by weight, based on the total weight of the ink composition, or any and all subranges formed from any of these endpoints.

[0112] The ink composition may further include a difunctional monomer that enhances mechanical properties while maintaining a low viscosity. In embodiments, the difunctional monomer may include difunctional acrylates and methacrylates, such as 3-methyl-1,5-pentanediyl diacrylate, dipropylene glycol diacrylate, or combinations thereof. In embodiments, the ink composition may include 0% or more and 35% or less by weight of the difunctional monomer, based on the total weight of the ink composition. In embodiments, the ink composition may include 10% or more and 35% or less by weight of the difunctional monomer, based on the total weight of the ink composition. In embodiments, the amount of the difunctional monomer in the ink composition may be 0% or more, 5% or more, 10% or more, or even 15% or more by weight, based on the total weight of the ink composition. In embodiments, the amount of the difunctional monomer in the ink composition may be 35% or less, 25% or less, or even 15% or less by weight, based on the total weight of the ink composition. In embodiments, the amount of difunctional monomer in the ink composition can be greater than or equal to 0% and less than or equal to 35% by weight, greater than or equal to 25% by weight, greater than or equal to 0% and less than or equal to 15% by weight, greater than or equal to 5% and less than or equal to 35% by weight, greater than or equal to 25% by weight, greater than or equal to 5% and less than or equal to 15% by weight, greater than or equal to 10% and less than or equal to 35% by weight, greater than or equal to 10% and less than or equal to 25% by weight, greater than or equal to 10% and less than or equal to 15% by weight, greater than or equal to 35% by weight, or even greater than or equal to 15% and less than or equal to 25% by weight, based on the total weight of the ink composition, or any and all subranges formed from any of these endpoints.

[0113] The relative amounts of reactive diluent, multifunctional monomer, and difunctional monomer may be adjusted based on the characteristics of the reactive monomers in the pigment dispersant, i.e., the amount of difunctional monomer relative to reactive diluent and the particular difunctional monomer used may be based on the viscosity and reactivity of the reactive monomers in the pigment dispersant, as illustrated in the Examples section below.

[0114] In embodiments, the total amount of reactive diluent, multifunctional monomer, and difunctional monomer may be 60% or less by weight to achieve a relatively low viscosity (e.g., less than 5 cP at 25° C.) while facilitating UV curability and providing sufficient compositional space for other components to achieve a desired optical density (e.g., greater than 5). In embodiments, the total amount of reactive diluent, multifunctional monomer, and difunctional monomer may be 60% or less by weight, 50% or less by weight, 40% or less by weight, or even 30% or less by weight.

[0115] The ink composition may further comprise an adhesion promoter to promote the ink to bond to the glass without the use of a primer. Suitable adhesion promoters include 3-(methacryloyloxy)propyltrimethoxysilane, 3-(acryloyloxy)propyltrimethoxysilane, (3-mercaptopropyl)trimethoxysilane, and allyltrimethoxysilane and any other acrylated silane. Other suitable adhesion promoters can be found in U.S. Patent Application No. 15 / 337459, filed October 28, 2016, which is incorporated herein by reference in its entirety. In an embodiment, the ink composition further comprises greater than 0% and less than or equal to 10% by weight of an adhesion promoter.

[0116] In embodiments, the ink compositions described herein are resin-free (which aids in maintaining a low viscosity suitable for inkjet printing) and TPO-free (which is a requirement of the REACH regulation).

[0117] The ink compositions described herein may also meet various environmental standards. For example, in embodiments, the ink compositions described herein may contain less than 10% by weight volatile organic compounds and therefore meet GB 35807-2020, entitled "Limits of Volatile Organic Compounds (VOCs) in Printing Ink," which is incorporated herein in its entirety by reference. Additionally, the ink compositions described herein may be free of halogenated hydrocarbons and free of solvents identified by CAS Registry Numbers in Table 1.

[0118] [Table 1]

[0119] Such solvents are known to have potentially harmful effects on the environment and / or human health. Some existing ink compositions include the solvents listed in Table 1 to provide UV curable inks with relatively high optical density compatible with inkjet printing. The ink compositions described herein provide such favorable attributes without such harmful solvents. The ink compositions of the present disclosure provide an uncured viscosity suitable for inkjet printing without the addition of harmful solvents, and therefore can be used at relatively high throughput (e.g., 20 m) with commercially available printheads. 2 / hour over 30m 2 / hour over 40m 2 / hour over 50m 2 The inkjet printing process is beneficially compatible with chemically strengthened cover glass, unlike certain other inks based on ceramic frits that require relatively high curing temperatures.

[0120] In embodiments, the ink composition may have a viscosity of 1 cP or more and 100 cP or less over a temperature range of 30° C. to 50° C. In embodiments, the ink compositions described herein may be compatible with commercial inkjet printing processes (e.g., have an uncured viscosity of less than 25 cP at temperatures up to 60° C., or at temperatures between 30° C. and 50° C.) to facilitate relatively low cost, high throughput manufacturing processes. In embodiments, the ink composition may have a viscosity of 8 cP or more and 13 cP or less over a temperature range of 30° C. to 50° C.

[0121] Ink primer As described herein, as the amount of pigment in the ink composition increases, it will become more difficult to achieve a suitable amount of adhesion of the ink composition to the glass substrate. The ink primer described herein includes an adhesion promoter to properly adhere an ink composition containing at least 11% by weight of pigment to a glass substrate without compromising the desired cured thickness (e.g., less than 15 μm) and optical density (e.g., greater than 5) of the resulting opaque layer. Although the ink primer described herein will be described with respect to the ink composition described herein, one skilled in the art will recognize that other suitable ink compositions may be used in combination with the disclosed ink composition.

[0122] In embodiments, the ink primers described herein are resin-free (which helps maintain a low viscosity suitable for inkjet printing) and TPO-free (which is a requirement of the REACH regulation).

[0123] In embodiments, the ink primer may have a viscosity of 1 cP or more and 100 cP or less over a temperature range of 30° C. to 50° C. In embodiments, the ink primer described herein may be compatible with commercial inkjet printing processes (e.g., having an uncured viscosity of less than 25 cP at temperatures up to 60° C., or at temperatures between 30° C. and 50° C.) to facilitate relatively low cost, high throughput manufacturing processes. In embodiments, the ink primer may have a viscosity of 8 cP or more and 13 cP or less over a temperature range of 30° C. to 50° C.

[0124] Infrared curable ink primer In some embodiments, an ink primer, such as an infrared curable ink primer, may be generally described as including an adhesion promoter and a solvent. The adhesion promoter may be designed to bond to the glass, and the solvent may be designed to promote the bonding of the adhesion promoter to the glass. For example, for proper bonding, hydrolysis and condensation of the silane molecules of the adhesion promoter should occur on the glass such that the silane molecules form a covalently bonded layer to the surface. Polymerization of the silane prior to deposition may affect the performance of the final ink primer. Therefore, the solvent should be selected so that the silane molecules do not hydrolyze and condense with adjacent silane molecules to form oligomeric aggregates.

[0125] The adhesion promoter may include an organofunctional silane. Suitable adhesion promoters can be found in U.S. Patent Application Serial No. 15 / 337,459, filed October 28, 2016. For example, in embodiments, the adhesion promoter can be represented by the general formula R n Six 4-n where R is a non-hydrolyzable organic group having functionality that allows the adhesion promoter to physically or chemically interact with organic resins and polymers; X is a hydrolyzable group such as alkoxy, acyloxy, amine, or a halogen such as chlorine; and n is an integer ranging from 0 to 4 or 1 to 3.

[0126] Representative organofunctional silane adhesion promoters include, but are not limited to, alkyltrialkoxysilanes, methyltriethoxysilane, methyltrimethoxysilane, octyltrimethoxysilane, octadecyltrimethoxysilane, polyalkoxysiloxane compounds, aminoalkyltrialkoxysilanes, gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, N-beta-(aminoethyl)-gamma-aminopropyltrimethoxysilane, gamma-ureidopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane. , 13-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, epoxypropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, mercaptoalkyltrialkoxysilane, gamma-mercaptopropyltrimethoxysilane, N-methylaminopropyl-trimethoxysilane, 3-azidopropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 1,4-bis(trimethoxysilylethyl)benzene.

[0127] The ink primer may have a minimum amount of adhesion promoter (e.g., 2% or more by weight) to ensure adequate adhesion. Thus, in embodiments, the ink primer may include 2% or more and 10% or less by weight of adhesion promoter, based on the total weight of the ink primer. In embodiments, the amount of adhesion promoter in the ink primer may be 2% or more, 4% or more, or even 6% or more by weight, based on the total weight of the ink primer. In embodiments, the amount of adhesion promoter in the ink primer may be 10% or less, or even 8% or less by weight, based on the total weight of the ink primer. In embodiments, the amount of adhesion promoter in the ink primer may be 2% or more and 10% or less, 2% or more and 8% or less, 4% or more and 10% or less, 4% or more and 8% or less, 6% or more and 10% or less, or even 6% or more and 8% or less by weight, based on the total weight of the ink primer, or any and all subranges formed from any of these endpoints.

[0128] In embodiments, the solvent may include 3-methoxy-3-methyl-1-butanol; butanol; ethylene glycol ethers (e.g., ethylene glycol monoethyl ether and diethylene glycol diethyl ether); 2-butoxyethanol; propylene glycol monomethyl ether acetate; propylene glycol; 2-butoxyethyl acetate; ethylene glycol; 1,4-butanediol; diethyl succinate; or combinations thereof.

[0129] In embodiments, the ink primer may include 90% or more and 98% or less by weight of solvent, based on the total weight of the ink primer. In embodiments, the amount of solvent in the ink primer may be 90% or more and even 92% or more by weight, based on the total weight of the ink primer. In embodiments, the amount of solvent in the ink primer may be 98% or less, 96% or less, or even 94% or less by weight, based on the total weight of the ink primer. In embodiments, the amount of solvent in the ink primer may be 90% or more and 98% or less, 90% or more and 96% or less, 90% or more and 94% or less by weight, based on the total weight of the ink primer, or any and all subranges formed from any of these endpoints.

[0130] UV-curable ink primer In other embodiments, the ink primer, such as a UV curable ink primer, may be generally described as including an adhesion promoter, a photoinitiator package, and a monofunctional monomer.

[0131] The type and / or amount of adhesion promoter in the UV curable ink primer may be the same as or similar to the type and / or amount of adhesion promoter described above for the IR curable ink primer. For example, in embodiments, the ink primer may include 2% or more and 10% or less by weight of adhesion promoter, based on the total weight of the ink primer. In embodiments, the adhesion promoter may include an organofunctional silane.

[0132] The photoinitiator package of the ink primer accelerates the curing of the ink primer, such as by using a UV LED. The ink primer may include a minimum amount of photoinitiator package (e.g., greater than 0% by weight) to ensure the curability of the ink primer. The amount of the photoinitiator package may be limited (e.g., 10% by weight or less) to provide favorable UV curing performance while still allowing flexibility in the composition space of the remaining components. Thus, in embodiments, the ink primer may include greater than 0% and less than or equal to 10% by weight of the photoinitiator package, based on the total weight of the ink primer. In embodiments, the amount of the photoinitiator package in the ink primer may be greater than 0%, 1% or more, 2% or more, 3% or more, or even 4% by weight or more, based on the total weight of the ink primer. In embodiments, the amount of the photoinitiator package in the ink primer may be 10% or less, or even 8% or less, based on the total weight of the ink primer. In embodiments, the amount of photoinitiator package in the ink primer can be greater than 0% and less than or equal to 10%, greater than 0% and less than or equal to 8%, greater than or equal to 1% and less than or equal to 10%, greater than or equal to 1% and less than or equal to 8%, greater than or equal to 2% and less than or equal to 10%, greater than or equal to 2% and less than or equal to 8%, greater than or equal to 3% and less than or equal to 10%, greater than or equal to 3% and less than or equal to 8%, greater than or equal to 4% and less than or equal to 10%, or even greater than or equal to 4% and less than or equal to 8%, based on the total weight of the ink primer, or any and all subranges formed from any of these endpoints.

[0133] The photoinitiator package of the ink primer may include a Type I photoinitiator, a Type II photoinitiator, and an amine synergist.

[0134] In embodiments, Type I photoinitiators may include phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (e.g., Irgacure 819 available from BASF); 1-hydroxycyclohexyl-phenyl ketone (e.g., Irgacure 184 available from BASF); (2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide (e.g., commercial blends Irgacure 1800, 1850, and 1700 available from BASF); 2,2-dimethoxy-2-phenylacetophenone (e.g., Irgacure 651 available from BASF); (2,4,6-trimethylbenzoyl)diphenylphosphine oxide (e.g., Lucirin TPO available from BASF, Munich, Germany); ethoxy(2,4,6-trimethylbenzoyl)phenylphosphine oxide (e.g., Lucirin TPO-L from BASF); or combinations thereof.

[0135] In embodiments, the amount of Type I photoinitiator in the ink primer can be greater than or equal to 2% and less than or equal to 8% by weight, greater than or equal to 2% and less than or equal to 6% by weight, greater than or equal to 4% and less than or equal to 8% by weight, or even greater than or equal to 4% and less than or equal to 6% by weight, based on the total weight of the ink primer, or any and all subranges formed from any of these endpoints.

[0136] In embodiments, Type II photoinitiators may include isopropylthioxanthone, benzophenone, 4-phenylbenzophenone, methyl-2-benzoyl benzoate, ketosulfone, or combinations thereof.

[0137] In embodiments, the amount of Type II photoinitiator in the ink primer can be greater than or equal to 1% and less than or equal to 4%, greater than or equal to 1% and less than or equal to 3%, greater than or equal to 2% and less than or equal to 4%, or even greater than or equal to 2% and less than or equal to 3%, by weight based on the total weight of the ink primer, or any and all subranges formed from any of these endpoints. In embodiments, the amount of Type I photoinitiator in the ink primer is greater than the amount of Type II photoinitiator to facilitate photopolymerization.

[0138] In embodiments, the amine synergist may include ethyl 4-(dimethylamino)benzoate; N,N-[2-(4-dimethylaminobenzoyl)oxyethylene-1-yl]methylamine; N-methyldiethanolamine; ethyl 4-dimethylaminobenzoate; 2-ethylhexyl 4-dimethylaminobenzoate; or combinations thereof.

[0139] In embodiments, the amount of amine synergist in the ink primer can be greater than or equal to 1% and less than or equal to 4%, greater than or equal to 1% and less than or equal to 3%, greater than or equal to 2% and less than or equal to 4%, or even greater than or equal to 2% and less than or equal to 3%, by weight based on the total weight of the ink primer, or any and all subranges formed from any of these endpoints.

[0140] The monofunctional monomers of the ink primer reduce cross-linking and reduce viscosity so that the acrylates of the ink primer can be copolymerized with subsequent ink layers, which differs from the ink compositions described herein, which may include multifunctional monomers to promote curing through higher cross-linking, thereby improving the mechanical properties of the resulting opaque layer.

[0141] In embodiments, the monofunctional monomer may include isobornyl acrylate. Other suitable monofunctional monomers can be found in U.S. Patent Application No. 15 / 337,459, filed October 28, 2016. For example, exemplary monofunctional monomers include, without limitation, hydroxyalkyl acrylates such as 2-hydroxyethyl-acrylate, 2-hydroxypropyl-acrylate, and 2-hydroxybutyl-acrylate; methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, amyl acrylate, isobutyl acrylate, t-butyl acrylate, pentyl acrylate, isoamyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, isooctyl acrylate (e.g., SR440 available from Sartomer Company, Inc., and Ageflex FA8 available from CPS Chemical Co.), 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, isodecyl acrylate (e.g., SR395 available from Sartomer Company, Inc., and Ageflex FA8 available from CPS Chemical Co.), and the like. long and short chain alkyl acrylates such as FA10), undecyl acrylate, dodecyl acrylate, tridecyl acrylate (e.g., SR489 available from Sartomer Company, Inc.), lauryl acrylate (e.g., SR335 available from Sartomer Company, Inc., Ageflex FA12 available from CPS Chemical Co., Old Bridge, NJ, Photomer 4812 available from IGM Resins), octadecyl acrylate, and stearyl acrylate (e.g., SR257 available from Sartomer Company, Inc.); aminoalkyl acrylates such as dimethylaminoethyl acrylate, diethylaminoethyl acrylate, and 7-amino-3,7-dimethyloctyl acrylate; butoxyethyl acrylate, phenoxyethyl acrylate (e.g., SR489 available from Sartomer Company, Inc.);alkoxyalkyl acrylates such as phenoxyglycidyl acrylate (e.g., CN131 available from Sartomer Company, Inc.), lauryloxyglycidyl acrylate (e.g., CN130 available from Sartomer Company, Inc.), and ethoxyethoxyethyl acrylate (e.g., SR256 available from Sartomer Company, Inc.); cyclohexyl acrylate, benzyl acrylate, dicyclopentadiene acrylate, dicyclopentanyl acrylate, tricyclodecanyl acrylate, bornyl acrylate, isobornyl acrylate (e.g., SR423 and SR506 available from Sartomer Company, Inc., and Ageflex IBOA available from CPS Chemical Co.), tetrahydrofurfuryl acrylate (e.g., SR423 and SR506 available from Sartomer Company, Inc., and Ageflex IBOA available from CPS Chemical Co.), and tetrahydrofurfuryl acrylate (e.g., SR423 and SR506 available from Sartomer Company, Inc.). monocyclic and polycyclic aromatic or nonaromatic acrylates such as acryloylmorpholine; polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, methoxyethylene glycol acrylate, methoxypolypropylene glycol acrylate, methoxypolyethylene glycol acrylate, ethoxydiethylene glycol acrylate, and ethoxylated (4) nonylphenol acrylates (e.g., Photomer 4003 available from IGM Resins, and Photomer 4004 available from Sartomer Company, Inc.); caprolactone acrylates (e.g., SR495 available from Sartomer Company, Inc., and Tone M100 available from Union Carbide Company, Danbury, Connecticut);alcohol-based acrylates such as various alkoxylated alkylphenol acrylates, such as propoxylated nonylphenol acrylate (e.g., Photomer 4960 available from IGM Resins); acrylamides such as diacetone acrylamide, isobutoxymethyl acrylamide, N,N'-dimethyl-aminopropyl acrylamide, N,N-dimethyl acrylamide, N,N-diethyl acrylamide, and t-octylacrylamide; vinyl compounds such as N-vinyl pyrrolidone and N-vinyl caprolactam (both available from Ashland Inc., Covington, Kentucky); and acid esters such as maleates and fumarates.

[0142] The ink primer may include a minimum amount of monofunctional monomer (e.g., 30% by weight or more) to achieve a relatively low viscosity and adhesion. The amount of monofunctional monomer may be limited (e.g., 45% by weight or less) so that the ink primer and the resulting opaque layer are not too soft and have the desired mechanical properties. Thus, in embodiments, the ink primer may include 30% by weight or more and 45% by weight or less of monofunctional monomer, based on the total weight of the ink primer. In embodiments, the amount of monofunctional monomer in the ink primer may be 30% by weight or more, or even 35% by weight or more, based on the total weight of the ink primer. In embodiments, the amount of monofunctional monomer in the ink primer may be 45% by weight or less, or even 40% by weight or less, based on the total weight of the ink primer. In embodiments, the amount of monofunctional monomer in the ink primer can be greater than or equal to 0% and less than or equal to 45% by weight, greater than or equal to 30% and less than or equal to 40% by weight, greater than or equal to 35% and less than or equal to 45% by weight, and even greater than or equal to 35% and less than or equal to 40% by weight, based on the total weight of the ink primer, or any and all subranges formed from any of these endpoints.

[0143] The ink primer may further include a reactive diluent to provide a relatively low viscosity (e.g., less than 5 cP at 25° C.) to improve curing performance while also helping to provide an overall low viscosity. In embodiments, the reactive diluent may include vinylmethyloxazolidinone; 5-methyl-3-vinyloxazolidin-2-one; other N-vinyl monomers such as N-vinylcarbazole, N-vinylindole derivatives, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinylacetamide derivatives, N-vinyl(na)phthalimide, N-vinylimidazolium salts, and N-vinyltriazole; or combinations thereof.

[0144] The ink primer may include a minimal amount of reactive diluent (e.g., greater than 0% by weight) to ensure that the ink composition cures. Thus, in embodiments, the ink primer may include greater than 0% and less than or equal to 30% by weight of reactive diluent, based on the total weight of the ink primer. In embodiments, the amount of reactive diluent in the ink primer may be 0% or more, 5% or more, 10% or more, or even 15% or more by weight, based on the total weight of the ink primer. In embodiments, the amount of reactive diluent in the ink primer may be 30% or less, or even 25% or less by weight, based on the total weight of the ink primer. In embodiments, the amount of reactive diluent in the ink primer can be, based on the total weight of the ink primer, greater than or equal to 0% and less than or equal to 30%, greater than or equal to 0% and less than or equal to 25%, greater than or equal to 5% and less than or equal to 30%, greater than or equal to 5% and less than or equal to 25%, greater than or equal to 10% and less than or equal to 30%, greater than or equal to 10% and less than or equal to 25%, greater than or equal to 15% and less than or equal to 30%, or even greater than or equal to 15% and less than or equal to 25%, or any and all subranges formed from any of these endpoints.

[0145] The ink primer may further include a difunctional monomer that enhances mechanical properties while maintaining a low viscosity. In embodiments, the difunctional monomer may include difunctional acrylates and methacrylates, such as 3-methyl-1,5-pentanediyl diacrylate, dipropylene glycol diacrylate, or combinations thereof. In embodiments, the ink primer may include 0% or more and 35% or less by weight of the difunctional monomer, based on the total weight of the ink primer. In embodiments, the amount of the difunctional monomer in the ink primer may be 0% or more, 5% or more, 10% or more, or even 15% or more by weight, based on the total weight of the ink primer. In embodiments, the amount of the difunctional monomer in the ink primer may be 35% or less, 25% or less, or even 15% or less by weight, based on the total weight of the ink primer. In embodiments, the amount of difunctional monomer in the ink primer can be greater than or equal to 0% and less than or equal to 35%, greater than or equal to 25%, greater than or equal to 0% and less than or equal to 15%, greater than or equal to 5% and less than or equal to 35%, greater than or equal to 25%, greater than or equal to 5% and less than or equal to 15%, greater than or equal to 10% and less than or equal to 35%, greater than or equal to 10% and less than or equal to 25%, greater than or equal to 10% and less than or equal to 15%, greater than or equal to 35% and less than or equal to 35%, or even greater than or equal to 15% and less than or equal to 25%, by weight based on the total weight of the ink primer, or any and all subranges formed from any of these endpoints.

[0146] The ink primer may further include a solvent. The type of solvent in the UV curable ink primer may be the same or similar to the types of solvents described above for the IR curable ink primer. For example, in embodiments, the ink primer may include 3-methoxy-3-methyl-1-butanol; butanol; ethylene glycol monoethyl ether; 2-butoxyethanol; propylene glycol monomethyl ether acetate; propylene glycol; 2-butoxyethyl acetate; diethylene glycol diethyl ether; ethylene glycol; 1,4-butanediol; diethyl succinate; ethylene glycol ether; or combinations thereof.

[0147] In embodiments, the ink primer may include greater than or equal to 5% and less than or equal to 10% by weight of a solvent, based on the total weight of the ink primer.

[0148] Glass articles Referring now to FIG. 1, a vehicle cabin 2000 is shown with three different vehicle cabin systems 100, 200, 300. The vehicle cabin system 100 includes a center console base 110 having a curved surface 120 that includes a display 130. The vehicle cabin system 200 includes a dashboard base 210 having a curved surface 220 that includes a display 230. The dashboard base 210 typically includes an instrument panel 215 that may also include a curved display. The vehicle cabin system 300 includes a dashboard handle base 310 having a curved surface 320 and a display 330. In an embodiment, the vehicle cabin system may include a base that is an armrest, a pillar, a seat back, a floor panel, a headrest, a door panel, or any part of the interior of a vehicle that includes a curved surface. In an embodiment, the display 130, 230, 330 is flat and includes a cover glass having a flat major surface. In embodiments, one or more of the displays 130, 230, 330 are curved, and the curved display may include a curved cover glass that may be hot or cold formed to have such a curvature. For example, such an embodiment may include an opaque layer formed from a photocurable ink composition described herein disposed on a cold-formed glass substrate.Such cold forming may include any of the techniques described in U.S. Patent Application Publication No. 2019 / 0329531 A1, entitled "Laminating thin strengthened glass to curved molded plastic surface for decorative and display cover application," U.S. Patent Application Publication No. 2019 / 0315648 A1, entitled "Cold-formed glass article and assembly process thereof," U.S. Patent Application Publication No. 2019 / 0012033 A1, entitled "Vehicle interior systems having a curved cover glass and a display or touch panel and methods for forming the same," and U.S. Patent Application No. 17 / 214124, entitled "Curved glass constructions and methods for forming same," all of which are incorporated herein by reference.

[0149] The glass article embodiments described herein may be used in any or all of the cabin systems 100, 200, and 300. Although FIG. 1 illustrates the interior of an automobile, the various embodiments of the cabin system may be incorporated into any type of vehicle, such as trains, automobiles (e.g., cars, trucks, buses, etc.), marine vehicles (boats, ships, submarines, etc.), and aircraft (e.g., drones, planes, jets, helicopters, etc.), including all human-operated, semi-autonomous, and fully autonomous vehicles. Additionally, while the description herein primarily relates to the use of glass articles in vehicle displays, it should be understood that the various embodiments described herein may be used in any type of display application.

[0150] Figure 2 illustrates a schematic cross-sectional view of display 230 through line 2-2 in Figure 1 according to an example embodiment in which display 230 is flat. While Figure 2 illustrates one example of display 230, it should be understood that displays 130, 330 described herein with respect to Figure 1 may have similar cross-sectional structures and similarly incorporate the photocurable inks described herein. While display 230 is flat in the embodiment illustrated in Figure 2, embodiments are also contemplated in which display 230 is curved and glass article 400 includes one or more curved surfaces (e.g., as a result of being cold-formed or hot-formed to have a suitable curved shape).

[0151] As shown in FIG. 2, the glass article 400 includes at least a substrate 450 and an opaque layer 500, optionally with a light management layer 460. The substrate 450 has a first major surface 470 facing the viewer and a second major surface 480 on which the opaque layer 500 is at least partially disposed. As used herein, the term "disposing" includes coating, depositing, and / or forming a material on a surface using any method known in the art. The disposed material may constitute a layer, as defined herein. As used herein, the phrase "disposed on" includes instances where a material is formed on a surface such that the material is in direct contact with the surface, and also includes instances where a material is formed on a surface with one or more intervening materials between the disposed material and the surface. The intervening materials may constitute a layer, as described herein. The term "layer" may include a single layer or may include one or more sublayers. Such sublayers may be in direct contact with each other. The sublayers may be formed from the same material or from two or more different materials. In one or more alternative embodiments, such sublayers may have intervening layers of different materials disposed therebetween. In one or more embodiments, a layer may include one or more adjacent continuous layers and / or one or more discontinuous interrupted layers (i.e., layers having different materials formed adjacent to one another). The layers or sublayers may be formed by any method known in the art, including separate deposition processes or sequential deposition processes. In one or more embodiments, the layers may be formed using only sequential deposition processes or only separate deposition processes.

[0152] In an embodiment, the substrate 450 is a glass substrate, optionally chemically strengthened, having a thickness of 0.05 to 2.0 mm. In one or more embodiments, the substrate 450 may be a transparent plastic, such as PMMA, polycarbonate, or may be a glass material (which may be strengthened, if desired).

[0153] The various glass substrates of the glass articles described herein, such as substrate 450, may be formed from any suitable glass composition, including soda-lime glass, aluminosilicate glass, borosilicate glass, aluminoborosilicate glass, alkali-containing aluminosilicate glass, alkali-containing borosilicate glass, and alkali-containing aluminoborosilicate glass.

[0154] Unless otherwise stated, the glass compositions disclosed herein are listed in mole percent (mol %) as analyzed on an oxide basis.

[0155] In one or more embodiments, the glass composition may include SiO2 in an amount in the range from about 66 mol% to about 80 mol%, about 67 mol% to about 80 mol%, about 68 mol% to about 80 mol%, about 69 mol% to about 80 mol%, about 70 mol% to about 80 mol%, about 72 mol% to about 80 mol%, about 65 mol% to about 78 mol%, about 65 mol% to about 76 mol%, about 65 mol% to about 75 mol%, about 65 mol% to about 74 mol%, about 65 mol% to about 72 mol%, or about 65 mol% to about 70 mol%, and all ranges and sub-ranges therebetween.

[0156] In one or more embodiments, the glass composition includes Al2O3 in an amount greater than about 4 mol%, or greater than about 5 mol%. In one or more embodiments, the glass composition includes Al2O3 in a range from greater than about 7 mol% to about 15 mol%, from greater than about 7 mol% to about 14 mol%, from about 7 mol% to about 13 mol%, from about 4 mol% to about 12 mol%, from about 7 mol% to about 11 mol%, from about 8 mol% to about 15 mol%, from about 9 mol% to about 15 mol%, from about 9 mol% to about 15 mol%, from about 10 mol% to about 15 mol%, from about 11 mol% to about 15 mol%, or from about 12 mol% to about 15 mol%, and all ranges and sub-ranges therebetween. In one or more embodiments, the upper limit of Al2O3 may be about 14 mol%, 14.2 mol%, 14.4 mol%, 14.6 mol%, or 14.8 mol%.

[0157] In one or more embodiments, the glass layer herein is described as being made as an aluminosilicate glass article or from an aluminosilicate glass composition. In such embodiments, the glass composition or article formed therefrom includes SiO2 and Al2O3 and is not a soda-lime silicate glass. In that regard, the glass composition or article formed therefrom includes Al2O3 in an amount of about 2 mol% or more, 2.25 mol% or more, 2.5 mol% or more, about 2.75 mol% or more, or about 3 mol% or more.

[0158] In one or more embodiments, the glass composition includes B2O3 (e.g., about 0.01 mol% or more). In one or more embodiments, the glass composition includes B2O3 in an amount ranging from about 0 mol% to about 5 mol%, from about 0 mol% to about 4 mol%, from about 0 mol% to about 3 mol%, from about 0 mol% to about 2 mol%, from about 0 mol% to about 1 mol%, from about 0 mol% to about 0.5 mol%, from about 0.1 mol% to about 5 mol%, from about 0.1 mol% to about 4 mol%, from about 0.1 mol% to about 3 mol%, from about 0.1 mol% to about 2 mol%, from about 0.1 mol% to about 1 mol%, from about 0.1 mol% to about 0.5 mol%, and all ranges and sub-ranges therebetween. In one or more embodiments, the glass composition is substantially free of B2O3.

[0159] As used herein, the phrase "substantially free" with respect to a component of a composition means that the component is not actively or intentionally added to the composition during initial batch formulation, but may be present as an impurity in an amount less than about 0.001 mole percent.

[0160] In one or more embodiments, the glass composition optionally includes P2O5 (e.g., about 0.01 mol% or more). In one or more embodiments, the glass composition includes P2O5 in a non-zero amount up to 2 mol%, up to 1.5 mol%, up to 1 mol%, or up to 0.5 mol%. In one or more embodiments, the glass composition is substantially free of P2O5.

[0161] In one or more embodiments, the glass composition may include R2O (the sum of alkali metal oxides, such as Li2O, Na2O, KO, Rb2O, and Cs2O) in a total amount of about 8 mol% or more, about 10 mol% or more, or about 12 mol% or more. In some embodiments, the glass composition includes R2O in a total amount in the range from about 8 mol% to about 20 mol%, about 8 mol% to about 18 mol%, about 8 mol% to about 16 mol%, about 8 mol% to about 14 mol%, about 8 mol% to about 12 mol%, about 9 mol% to about 20 mol%, about 10 mol% to about 20 mol%, about 11 mol% to about 20 mol%, about 12 mol% to about 20 mol%, about 13 mol% to about 20 mol%, about 10 mol% to about 14 mol%, or 11 mol% to about 13 mol%, and all ranges and sub-ranges therebetween. In one or more embodiments, the glass composition may be substantially free of Rb2O, Cs2O, or both Rb2O and Cs2O. In one or more embodiments, R2O may include only the total amounts of Li2O, Na2O, and K2O. In one or more embodiments, the glass composition may include at least one alkali metal oxide selected from Li2O, Na2O, and K2O, where the alkali metal oxide is present in an amount of about 8 mol % or greater.

[0162] In one or more embodiments, the glass composition includes Na2O in an amount of about 8 mol% or more, about 10 mol% or more, or about 12 mol% or more. In one or more embodiments, the glass composition includes Na2O in an amount of about 8 mol% to about 20 mol%, about 8 mol% to about 18 mol%, about 8 mol% to about 16 mol%, about 8 mol% to about 14 mol%, about 8 mol% to about 12 mol%, about 9 mol% to about 20 mol%, about 10 mol% to about 20 mol%, about 11 mol% to about 20 mol%, about 12 mol% to about 20 mol%, about 13 mol% to about 20 mol%, about 10 mol% to about 14 mol%, or 11 mol% to about 13 mol%, and all ranges and sub-ranges therebetween.

[0163] In one or more embodiments, the glass composition includes less than about 4 mol% K2O, less than about 3 mol% K2O, or less than about 1 mol% K2O. In some cases, the glass composition may include KO in an amount in the range from about 0 mol% to about 4 mol%, from about 0 mol% to about 3.5 mol%, from about 0 mol% to about 3 mol%, from about 0 mol% to about 2.5 mol%, from about 0 mol% to about 2 mol%, from about 0 mol% to about 1.5 mol%, from about 0 mol% to about 1 mol%, from about 0 mol% to about 0.5 mol%, from about 0 mol% to about 0.2 mol%, from about 0 mol% to about 0.1 mol%, from about 0.5 mol% to about 4 mol%, from about 0.5 mol% to about 3.5 mol%, from about 0.5 mol% to about 3 mol%, from about 0.5 mol% to about 2.5 mol%, from about 0.5 mol% to about 2 mol%, from about 0.5 mol% to about 1.5 mol%, or from about 0.5 mol% to about 1 mol%, and all ranges and sub-ranges therebetween. In one or more embodiments, the glass composition is substantially free of K2O.

[0164] In one or more embodiments, the glass composition is substantially free of Li2O.

[0165] In one or more embodiments, the amount of Na2O in the composition may be greater than the amount of Li2O. In some cases, the amount of Na2O may be greater than the combined amount of Li2O and K2O. In one or more alternative embodiments, the amount of Li2O in the composition may be greater than the amount of Na2O or the combined amount of Na2O and K2O.

[0166] In one or more embodiments, the glass composition may include RO (which is the sum of alkaline earth metal oxides, such as CaO, MgO, BaO, ZnO, and SrO) in a total amount ranging from about 0 mol% to about 2 mol%. In some embodiments, the glass composition includes RO in a non-zero amount up to about 2 mol%. In one or more embodiments, the glass composition includes RO in an amount from about 0 mol% to about 1.8 mol%, from about 0 mol% to about 1.6 mol%, from about 0 mol% to about 1.5 mol%, from about 0 mol% to about 1.4 mol%, from about 0 mol% to about 1.2 mol%, from about 0 mol% to about 1 mol%, from about 0 mol% to about 0.8 mol%, from about 0 mol% to about 0.5 mol%, and all ranges and sub-ranges therebetween.

[0167] In one or more embodiments, the glass composition includes CaO in an amount less than about 1 mol%, less than about 0.8 mol%, or less than about 0.5 mol%. In one or more embodiments, the glass composition is substantially free of CaO. In some embodiments, the glass composition includes MgO in an amount from about 0 mol% to about 7 mol%, from about 0 mol% to about 6 mol%, from about 0 mol% to about 5 mol%, from about 0 mol% to about 4 mol%, from about 0.1 mol% to about 7 mol%, from about 0.1 mol% to about 6 mol%, from about 0.1 mol% to about 5 mol%, from about 0.1 mol% to about 4 mol%, from about 1 mol% to about 7 mol%, from about 2 mol% to about 6 mol%, or from about 3 mol% to about 6 mol%, and all ranges and sub-ranges therebetween.

[0168] In one or more embodiments, the glass composition includes ZrO2 in an amount of about 0.2 mol% or less, about 0.18 mol% or less, about 0.16 mol% or less, about 0.15 mol% or less, about 0.14 mol% or less, about 0.12 mol% or less, In one or more embodiments, the glass composition includes ZrO2 in an amount of about 0.01 mol% to about 0.2 mol%, about 0.01 mol% to about 0.18 mol%, about 0.01 mol% to about 0.16 mol%, about 0.01 mol% to about 0.15 mol%, about 0.01 mol% to about 0.14 mol%, about 0.01 mol% to about 0.12 mol%, or about 0.01 mol% to about 0.10 mol%, and all ranges and sub-ranges therebetween.

[0169] In one or more embodiments, the glass composition includes SnO2 in an amount of about 0.2 mol% or less, about 0.18 mol% or less, about 0.16 mol% or less, about 0.15 mol% or less, about 0.14 mol% or less, about 0.12 mol% or less, In one or more embodiments, the glass composition includes SnO2 in an amount of about 0.01 mol% to about 0.2 mol%, about 0.01 mol% to about 0.18 mol%, about 0.01 mol% to about 0.16 mol%, about 0.01 mol% to about 0.15 mol%, about 0.01 mol% to about 0.14 mol%, about 0.01 mol% to about 0.12 mol%, or about 0.01 mol% to about 0.10 mol%, and all ranges and sub-ranges therebetween.

[0170] In one or more embodiments, the glass composition may include oxides that impart color or tint to the glass article. In some embodiments, the glass composition includes oxides that prevent discoloration of the glass article when exposed to ultraviolet light. Examples of such oxides include, without limitation, oxides of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Ce, W, and Mo.

[0171] In one or more embodiments, the glass composition includes Fe, expressed as Fe2O3, where Fe is present in an amount up to (including) about 1 mol%. In some embodiments, the glass composition is substantially free of Fe. In one or more embodiments, the glass composition includes Fe2O3 in an amount of about 0.2 mol% or less, about 0.18 mol% or less, about 0.16 mol% or less, about 0.15 mol% or less, about 0.14 mol% or less, or about 0.12 mol% or less. In one or more embodiments, the glass composition includes Fe2O3 in the range from about 0.01 mol% to about 0.2 mol%, from about 0.01 mol% to about 0.18 mol%, from about 0.01 mol% to about 0.16 mol%, from about 0.01 mol% to about 0.15 mol%, from about 0.01 mol% to about 0.14 mol%, from about 0.01 mol% to about 0.12 mol%, or from about 0.01 mol% to about 0.10 mol%, and all ranges and sub-ranges therebetween.

[0172] When the glass composition includes TiO2, TiO2 may be present in an amount of about 5 mol% or less, about 2.5 mol% or less, about 2 mol% or less, or about 1 mol% or less. In one or more embodiments, the glass composition may be substantially free of TiO2.

[0173] Exemplary glass compositions include SiO2 in an amount ranging from about 65 mol% to about 75 mol%, Al2O3 in an amount ranging from about 8 mol% to about 14 mol%, Na2O in an amount ranging from about 12 mol% to about 17 mol%, K2O in an amount ranging from about 0 mol% to about 0.2 mol%, and MgO in an amount ranging from about 1.5 mol% to about 6 mol%. Optionally, SnO2 may be included in amounts as otherwise disclosed herein.

[0174] In one or more embodiments, the glass substrates herein may be formed from tempered glass sheets or articles. In one or more embodiments, the glass substrates used to form the glass articles described herein may be tempered to have compressive stresses extending from the surface to a depth of compression (DOC). The compressive stress areas are balanced with a central portion exhibiting tensile stress. At the DOC, the stress crosses from positive (compressive) to negative (tensile).

[0175] In one or more embodiments, the glass substrates used to form the glass articles described herein may be mechanically strengthened by exploiting the mismatch in thermal expansion coefficients between portions of the glass to create areas of compressive stress and a central region exhibiting tensile stress. In some embodiments, the glass substrates may be thermally strengthened by heating the glass above its glass transition temperature and then quenching.

[0176] In one or more embodiments, the glass substrates used to form the glass articles described herein may be chemically strengthened by ion exchange. In the ion exchange process, ions at or near the surface of the glass substrate are replaced - i.e., exchanged - with larger ions having the same valence or oxidation state. In embodiments in which the glass substrate is made from an alkali aluminosilicate glass, the ions in the surface layer of the article and the larger ions are Li + , Na + , K + , Rb + , and Cs + Alternatively, the monovalent cations in the surface layer are Ag + In such embodiments, the monovalent ions (or cations) exchanged into the glass substrate create stress.

[0177] The ion exchange process is typically carried out by immersing the glass substrate in a molten salt bath (or two or more molten salt baths) containing the larger ions to be exchanged for the smaller ions in the glass substrate. It should be noted that aqueous salt baths may also be utilized. In addition, the composition of the bath may contain more than one type of larger ion (e.g., Na + and K. + ) or one larger type of ion. It will be appreciated by those skilled in the art that the parameters of the ion exchange process, including but not limited to the bath composition and temperature, immersion time, number of immersions of the glass substrate in the salt bath, use of multiple salt baths, and additional steps such as slow cooling, washing, etc., are generally determined by the composition of the glass substrate (including the article structure and any crystalline phases present) and the desired DOC and CS of the glass layer of the glass substrate resulting from the strengthening.

[0178] Exemplary molten bath compositions may include nitrates, sulfates, and chlorides of larger alkali metal ions. Typical nitrates include KNO3, NaNO3, LiNO3, NaSO4, and combinations thereof. The temperature of the molten salt bath generally ranges from about 380°C to about 450°C, while the immersion time ranges from about 15 minutes to about 100 hours, depending on the thickness of the glass, the temperature of the bath, and the diffusivity of the glass (or monovalent ions). However, temperatures and immersion times different from those described above may also be used.

[0179] According to one or more embodiments, a glass substrate used to form a glass article may be immersed in a molten salt bath of 100% NaNO3, 100% KNO3, or a combination of NaNO3 and KNO3 having a temperature of about 370° C. to about 480° C. In some embodiments, the glass substrate may be immersed in a molten mixed salt bath including about 5% to about 90% KNO3 and about 10% to about 95% NaNO3. In some embodiments, the glass substrate may be immersed in a first bath and then in a second bath. The first and second baths may have different compositions and / or temperatures. The immersion times in the first and second baths may vary. For example, the immersion in the first bath may be longer than the immersion in the second bath.

[0180] According to one or more embodiments, the glass substrate may be immersed in a molten mixed salt bath including NaNO3 and KNO3 (e.g., 49% / 51%, 50% / 50%, 51% / 49%) having a temperature less than about 420° C. (e.g., about 400° C. or about 380° C.) for less than about 5 hours, or even less than about 4 hours.

[0181] The ion exchange conditions can be tailored to increase the gradient, or to provide a "spike," in the stress profile at or near the surface of the resulting glass layer of the glass substrate, which would result in a larger surface CS value. This spike can be achieved with a single bath or multiple baths, which have a single composition or a mixture of compositions due to the specific nature of the glass compositions used in the glass layers of the decorative glass structures described herein.

[0182] In one or more embodiments in which multiple monovalent ions are exchanged into the glass substrate, different monovalent ions may be exchanged to different depths within the glass substrate (producing different amounts of stress within the glass substrate at different depths), and the resulting relative depths of the stress-producing ions can be determined, thereby producing different characteristics of the stress profile.

[0183] CS is measured using means known in the art, such as by a surface stress meter (FSM) using commercially available equipment such as the FSM-6000 manufactured by Orihara Seisakusho Co., Ltd. (Japan). Surface stress measurements rely on precise measurement of the stress optical coefficient (SOC), which is related to the birefringence of the glass. SOC is then measured by methods known in the art, such as the fiber method and the four-point bending method, both of which are described in ASTM standard C770-98 (2013), entitled "Standard Test Method for Measurement of Glass Stress-Optical Coefficient," and the bulk cylinder method, the contents of which are incorporated herein in their entirety by reference. As used herein, CS may be the "maximum compressive stress," which is the highest compressive stress value measured within the compressive stress layer. In some embodiments, the maximum compressive stress is located at the surface of the glass substrate. In other embodiments, the maximum compressive stress may occur at some depth below the surface, giving the compressive profile the appearance of a "buried peak."

[0184] The DOC can be measured by FSM or by a scattered light polariscope (SCALP) (such as the SCALP-04 scattered light polariscope available from GlasStress Ltd., Tallinn, Estonia). If the glass substrate is chemically strengthened by an ion exchange process, then either the FSM or the SCALP can be used depending on which ions are exchanged into the glass substrate. If the stress in the glass substrate is caused by exchanging potassium ions into the glass substrate, then the FSM is used to measure the DOC. If the stress in the glass substrate is caused by exchanging sodium ions into the glass substrate, then the SCALP is used to measure the DOC. If the stress in the glass substrate is caused by exchanging both potassium and sodium ions into the glass substrate, then the DOC is measured by SCALP. Because the exchange depth of the sodium ions is considered to represent the DOC, and the exchange depth of the potassium ions is considered to represent the change in the magnitude of the compressive stress (and not the change in the stress from compressive to tensile); the exchange depth of the potassium ions in such a glass substrate is measured by FSM. Central tension or CT is the maximum tensile stress and is measured by SCALP.

[0185] In one or more embodiments, the glass substrate may be strengthened to exhibit a DOC, expressed as a percentage of the thickness, t, of the glass substrate (as defined herein). For example, in one or more embodiments, the DOC may be about 0.05t or more, about 0.1t or more, about 0.11t or more, about 0.12t or more, about 0.13t or more, about 0.14t or more, about 0.15t or more, about 0.16t or more, about 0.17t or more, about 0.18t or more, about 0.19t or more, about 0.2t or more, or about 0.21t or more. In some embodiments, the DOC may be in the range of about 0.08t to 0.25t, about 0.09t to 0.25t, about 0.18t to 0.25t, about 0.11t to 0.25t, about 0.12t to 0.25t, about 0.13t to 0.25t, about 0.14t to 0.25t, about 0.15t to 0.25t, about 0.08t to 0.24t, about 0.08t to 0.23t, about 0.08t to 0.22t, about 0.08t to 0.21t, about 0.08t to 0.2t, about 0.08t to 0.19t, about 0.08t to 0.18t, about 0.08t to 0.17t, about 0.08t to 0.16t, or about 0.08t to 0.15t. In some cases, the DOC may be about 20 μm or less. In one or more embodiments, the DOC may be about 40 μm or more (e.g., about 40 μm to about 300 μm, about 50 μm to about 300 μm, about 60 μm to about 300 μm, about 70 μm to about 300 μm, about 80 μm to about 300 μm, about 90 μm to about 300 μm, about 100 μm to about 300 μm, about 110 μm to about 300 μm, about 120 μm to about 300 μm, about 140 μm to about 300 μm, about 150 μm to about 300 μm, about 40 μm to about 290 μm, about 40 μm to about 280 μm, about 40 μm to about 260 μm, about 40 μm to about 250 μm, about 40 μm to about 240 μm, about 40 μm to about 230 μm, about 40 μm to about 220 μm, about 40 μm to about 210 μm, about 40 μm to about 200 μm, about 40 μm to about 180 μm, about 40 μm to about 160 μm, about 40 μm to about 150 μm, about 40 μm to about 140 μm, about 40 μm to about 130 μm, about 40 μm to about 120 μm, about 40 μm to about 110 μm, or about 40 μm to about 100 μm).

[0186] In one or more embodiments, the glass substrate may have a CS (which may be found at the surface or at a depth within the glass article) of about 200 MPa or more, 300 MPa or more, 400 MPa or more, about 500 MPa or more, about 600 MPa or more, about 700 MPa or more, about 800 MPa or more, about 900 MPa or more, about 930 MPa or more, about 1000 MPa or more, or about 1050 MPa or more.

[0187] In one or more embodiments, the glass substrate may have a maximum tensile stress or central tension (CT) of about 20 MPa or more, about 30 MPa or more, about 40 MPa or more, about 45 MPa or more, about 50 MPa or more, about 60 MPa or more, about 70 MPa or more, about 75 MPa or more, about 80 MPa or more, or about 85 MPa or more. In some embodiments, the maximum tensile stress or central tension (CT) may be in the range of about 40 MPa to about 100 MPa.

[0188] In an embodiment, the glass article 400 includes a functional surface layer 490. The functional surface layer 490 can be made to provide one or more of a variety of functions. For example, the functional surface layer 490 can be an optical coating made to provide easy-to-clean performance, anti-glare properties, anti-reflective properties, and / or a half-mirror coating. In the case of an anti-reflective functional surface layer, such a layer can be formed using multiple layers having alternating high and low refractive indices. Non-limiting examples of low refractive index films include SiO2, MgF2, and Al2O3, and non-limiting examples of high refractive index films include Nb2O5, TiO2, ZrO2, HfO2, and Y2O3. In an embodiment, the total thickness of such an optical coating (which may be disposed over the anti-glare surface or the smooth substrate surface) is 5 nm to 750 nm. In addition, in an embodiment, the functional surface layer 490 that provides easy-to-clean performance also provides coatings / treatments for enhanced feel and / or fingerprint reduction for touch panels. In some embodiments, the functional surface layer 490 is integral with the first side of the substrate. For example, such a functional surface layer may include an etched surface on the first side of the substrate 450 that provides an anti-glare surface (or a haze of, for example, 2% to 20%).

[0189] The opaque layer 500 is printed onto the light management layer 460, if included. Some existing UV curable inks have been shown to be incompatible with the light management layer 460 (e.g., lacking the necessary adhesion). For example, existing photocurable inks, when used on the opaque layer, can chemically react with the inks of the light management layer 460 (either during deposition or after environmental testing) and change the characteristics (e.g., color, size) of those ink layers. Existing photocurable inks can also diffuse into the light management layer 460 and degrade its performance. The photocurable inks described herein, when used to form the opaque layer 500 and printed onto the light management layer 460, do not suffer from such defects and still provide adequate adhesion to the substrate 450, even when the light management layer 460 is present.

[0190] If included, the light management layer 460 may be printed onto the substrate 450. In an embodiment, the light management layer 460 is formed from a suitable thermally or UV curable ink. The light management layer 460 may generally reduce the transmission of light through the glass article 400 such that the glass article 400 presents a similar appearance to a user whether the display 540 is powered on or off. For example, the light management layer 460 may obscure the edges of the viewing area 520, making the boundaries of the viewing area 520 less noticeable to a viewer when the display is powered off. The light management layer 460 may generally be configured as described in any of International Publication No. WO 2019 / 055458 A1, entitled "Black Deadfront for Display Device and Methods," International Publication No. WO 2020 / 205519 A1, entitled "Decorated Glass Having a Printed Ink Layer," or International Publication No. WO 2021 / 118835 A1, entitled "Display Devices and Articles with Color-Matched Display and Non-Display Areas," each of which is incorporated herein by reference in its entirety.

[0191] opaque layer Still referring to FIG. 2, in embodiments, the opaque layer 500 may be comprised of at least one of the photocurable ink compositions and ink primers described herein. For example, in some embodiments, the opaque layer 500 may be made from a photocurable ink comprising at least 11% by weight of pigment. In other embodiments, the opaque layer may be made from an ink composition comprising at least 11% by weight of pigment and an adhesion promoter. In such embodiments, the adhesion promoter is bonded to the glass substrate and the ink composition is polymerized with the adhesion promoter. Thus, the opaque layer 500 may have a relatively high optical density (e.g., 5 or greater) to block the transmission of light. In embodiments, the opaque layer 500 is used to block light from passing through certain areas of the glass article 400. In embodiments, the opaque layer 500 obscures functional or non-decorative elements provided for the operation of the glass article 400. In an embodiment, the opaque layer 500 is provided to contour backlit icons and / or other graphics (not shown) to increase contrast at the edges of such icons and / or graphics.

[0192] In an embodiment as shown in FIG. 2, the glass article 400 is placed over or in front of the display 540. In one or more embodiments, the display 540 may include a touch-enabled display including a display and a touch panel. Exemplary displays include LED displays, DLP MEMS chips, LCDs, OLEDs, transmissive displays, and the like. The glass article 400 may generally have an average transmittance from 380 nm to 750 nm of 10% or more (e.g., 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more). However, due to the high optical density of the opaque layer 500, the area of ​​the glass article 400 with the opaque layer 500 has a relatively low light transmittance (e.g., an average transmittance of 0.1% or less in the visible spectrum). Thus, the boundaries of the opaque layer 500 may define a display area 520 where the glass article 400 exhibits a relatively high light transmittance to facilitate visibility of the image generated by the display 540.

[0193] In the illustrated embodiment, the opaque layer 500 covers the edges 550 of the display 540 to obscure the edges 550 through the first side 470. The opaque layer 500 may also be used to obscure various other components (e.g., electrical connections, mechanical housings, etc.). The opaque layer 500 generally allows desired portions of the display 540 to be visible to a user viewing the first side 470.

[0194] In embodiments, the opaque layer 500 is applied by inkjet printing onto the light management layer 460 and / or onto the second side 480 of the substrate 450. In embodiments, the opaque layer 500 may be deposited directly onto the second side 480 of the substrate 450 using a suitable inkjet process. In embodiments, prior to deposition of the opaque layer 500, the second side 480 may be primed using a suitable primer (e.g., an acryloxysilane primer) to enhance adhesion of the opaque layer 500 to the substrate 450 in embodiments not using an ink primer as described herein. Any suitable treatment may be used on the second side 480 to enhance adhesion of the opaque layer 500 to the substrate 450.

[0195] As described herein, the opaque layer 500 has relatively high adhesion to glass. In embodiments, the opaque layer 500 exhibits adhesion to a glass substrate of 4B or better after exposure to a temperature of 85° C. at 95% relative humidity for a period of at least 500 hours when tested according to ASTM 3359. In embodiments, the opaque layer 500 exhibits adhesion to a glass substrate of 4B or better after exposure to 500 one-hour cycles of being held at a temperature of −40° C. for 0.5 hours and at 95° C. for 0.5 hours when tested according to ASTM 3359.

[0196] The opaque layer 500 may have a desired thickness of 15 μm or less. In embodiments, the opaque layer 500 may have a thickness of 15 μm or less, or even 10 μm or less. In embodiments, the opaque layer 500 may have a thickness of 1 μm or more, or even 5 μm or more. In embodiments, the opaque layer 500 may have a thickness of 1 μm or more, or even 5 μm or more. In embodiments, the opaque layer 500 may have a thickness of 1 μm or more and 15 μm or less, 1 μm or more and 10 μm or more, 5 μm or more and 15 μm or less, or even 5 μm or more and 10 μm or less, or any and all subranges formed from any of these endpoints.

[0197] In embodiments, the photocurable ink compositions and / or ink primers described herein may be tailored to meet specific appearance requirements related to design needs. The opaque layer 500 can be any color; however, in certain embodiments, the opaque layer 500 is black or gray. For example, a cover glass with an opaque layer comprised of the photocurable ink compositions and / or ink primers described herein may meet any of the black mask color targets in Table 2.

[0198] [Table 2]

[0199] In embodiments, an opaque layer constructed using the photocurable ink compositions and / or ink primers described herein may meet any combination of values ​​contained in Table 2 that are within the tolerances outlined in Table 3 below.

[0200] [Table 3]

[0201] As shown in Tables 2 and 3, glass articles comprising the photocurable ink compositions and / or ink primers described herein, when viewed through the uncoated surface of the cover glass (e.g., from the side of the glass opposite the side on which the display is located), generally have a CIELAB L of 30 or less (29 or less, 28 or less, 27 or less, 25 or less, 25 or less) when illuminated with a CIE D65 light source at an incidence angle of 10°. * CIELAB a value, greater than or equal to -0.05 and less than or equal to 0.15 * value (including the reflectance component), and CIELAB b less than or equal to -0.1 and greater than or equal to -0.3 * If the specular component is eliminated, the glass article may have a CIELAB L value of 1 or less. * CIELAB a values ​​and magnitudes less than or equal to 0.1 * Value and b *Areas of a cover glass coated with the photocurable ink compositions and / or ink primers described herein may exhibit a dark, neutral appearance to facilitate hiding various components from view.

[0202] The photocurable ink compositions and / or ink primers of the present disclosure may also be used to construct an opaque layer on a glass article that exhibits favorable reliability test results when compared to certain existing photocurable inks and / or ink primers. Automotive interior components are exposed to highly variable environmental conditions (e.g., with respect to temperature and relative humidity). In embodiments, the opaque layer may meet one or more of the following criteria when subjected to the reliability tests outlined in Table 4:

[0203] [Table 4]

[0204] Some existing UV curable inkjet compatible inks crack or otherwise fail when exposed to such test conditions, rendering them unsuitable for some automotive interior applications. For example, some existing inks have been found to shrink and / or crack when Test B contained in Table 4 above is performed, whereas opaque layers formed from the photocurable ink compositions and / or ink primers described herein meet the test criteria contained in Table 4.

[0205] In embodiments, the glass article exhibits a maximum ΔE value (both SCI and SCE) of less than 2.0 when measured both before and after 500 one hour cycles of being held at a temperature of -40°C for 0.5 hours and at 95°C for 0.5 hours.

[0206] In addition to meeting the reliability test requirements described above, the photocurable ink compositions and / or ink primers described herein may meet additional requirements that make them suitable for use in certain commercial inkjet printers. For example, the pigments may have the desired L * In order to achieve this, the photocurable ink and / or ink primer may have an average particle size of 200 nm or less, 150 nm or less, 100 nm or less, or even 50 nm or less. In embodiments, the photocurable ink and / or ink primer has a viscosity of 25 dyne / cm (10 -3 N / m) or more and 35 dyne / cm(10 -3 In embodiments, the opaque layer may have a liquid surface tension of 36 dyne / cm (10 -3 In embodiments, the opaque layer may exhibit a cured surface tension of greater than 1×10 N / m, as measured according to ASTM D-257 at 100 V DC. 9 It may exhibit electrical resistivity of Ω / □ or more.

[0207] The opaque layers described herein may also exhibit a pencil hardness of 3H or greater when measured with a pencil at a 45° angle with a mass of 750 g according to ASTM 3363, entitled "Standard Test Method for Film Hardness by Pencil Test," which is incorporated herein in its entirety, after being cured with a narrowband UV LED light source emitting a narrowband (e.g., 20 nm or less bandwidth, 30 nm or less bandwidth) curing light. The use of such UV LEDs saves space and cost and is less environmentally harmful when compared to certain existing UV curing lamps. Certain existing UV curable inks, when meeting the optical density requirements described herein, may not cure sufficiently to have such pencil hardness due to ink opacity inhibiting cure. Photoinitiators for the inks and / or ink primers described herein may be selected to facilitate cure using UV LEDs while still meeting the pencil hardness and optical density requirements described herein.

[0208] Thus, the photocurable inks and / or ink primers described herein provide a relatively high optical density to promote their effectiveness as black matrix layers in displays, while being compatible with high throughput inkjet printing processes and also meeting the stringent reliability testing requirements associated with interior automotive displays. The photocurable inks and / or ink primers described herein provide cost savings in the manufacture of glass articles for displays, while still providing a reliable opacity layer that has been demonstrated to provide consistent color performance over the life of the component.

[0209] Method for manufacturing a glass article Ink composition Referring now to Figure 3, a method of manufacturing a glass article is shown at 600. Method 600 may be performed to manufacture glass article 400 as described herein with respect to Figure 2. Accordingly, reference will be made to various components described with respect to Figure 2 to assist in describing the method. It should be understood that other glass articles may be formed by performance of method 600, and that method 600 is not limited to any particular number or order of process steps.

[0210] At block 602, substrate 450 is manufactured. Any suitable glass manufacturing process may be used, such as fusion downdraw, float, etc. Additional details regarding glass forming methods are provided herein. At block 604, substrate 450 is processed. For example, in an embodiment, substrate 450 is subjected to a strengthening treatment (e.g., ion exchange strengthening, heat strengthening). Additional details regarding strengthening treatments that may be applied to substrate 450 are provided herein.

[0211] In embodiments, the treatment applied to substrate 450 during block 604 may be used to form functional surface layer 490. For example, in embodiments, substrate 450 is chemically etched such that at least first surface 470 exhibits anti-glare properties. A suitable anti-reflective and / or ETC coating may also be deposited on first surface 470 by a suitable deposition process. In embodiments, second surface 480 may be primed (e.g., using a suitable chemical primer or ink) to promote adhesion of opaque layer 500 thereto. In embodiments, light management layer 460 may be deposited on second surface 480 and cured (e.g., a suitable ink may be cured thermally or by exposure to electromagnetic radiation).

[0212] At block 606, a photocurable ink is deposited on the second surface 480 to begin the formation of the opaque layer 500. As described herein, a suitable inkjet printing device may be used to deposit droplets of suitable size on the second surface 480 such that the photocurable ink forms a suitable pattern. The various parameters used to operate the inkjet printing device (e.g., control waveform, travel speed, deposition temperature) will vary depending on the composition of the photocurable ink and the desired deposition pattern. As noted with respect to block 604, the second surface 480 may have an ink primer, such as those described herein, applied thereto prior to deposition of the photocurable ink.

[0213] At block 608, the photocurable ink is cured on the second surface 480 by exposure to electromagnetic radiation produced by the UV LEDs. In an embodiment, the UV LEDs emit radiation having a relatively narrow bandwidth (e.g., 50 nm or less, 40 nm or less, 30 nm or less, 20 nm or less) surrounding a central UV wavelength (e.g., 375 nm, 380 nm, 385 nm, 390 nm, 395 nm, 400 nm). The operating parameters of the UV LEDs (e.g., output intensity, duration of exposure) will vary depending on various aspects of the opaque layer 500 (e.g., thickness, composition).

[0214] In embodiments, blocks 606 and 608 may be performed while substrate 450 has a planar shape. In embodiments, blocks 606 and 608 may be performed while substrate 450 is in a curved shape. For example, after performing at least some of the processes described with respect to block 604, substrate 450 may be cold formed by methods described herein, and opaque layer 500 may be formed on the cold formed glass substrate. In embodiments, a suitable display panel is laminated to the glass substrate such that opaque layer 500 at least partially covers the display panel.

[0215] Given the relatively high pigment concentration in each of the ink compositions, it has been found that a multi-print and cure architecture can be used to cure the photocurable inks to provide favorable adhesion performance while meeting the optical density requirements described herein. Such an architecture includes a process in which the opaque layer 500 (see FIG. 2) is incrementally deposited on a substrate in sublayers that are only a fraction of the desired final thickness of the opaque layer 500 (e.g., 40% or less, 33% or less, 30% or less, 25% or less, 10% or more). After each sublayer is deposited, a relatively low dose (a "pinning dose") of UV radiation is provided to at least partially cure (i.e., "pin") the sublayer. After a sufficient number of sublayers (e.g., 3, 4, 5, 6, 7, or even more) are deposited, a higher dose of UV radiation in a pinning step allows the entire stack (substrate 450 and stacked sublayers) to undergo a final curing step (if necessary).

[0216] An exemplary ink deposition apparatus 1000 for implementing the multiplex printing and curing architecture described herein is shown in FIG. 4. The apparatus 1000 is shown to include multiple deposition and pinning stages 1002 and an optional final curing stage 1003. The number of deposition and pinning stages 1002 may vary depending on the optical density (e.g., pigment concentration) of the ink used and the composition of the photocurable ink (e.g., a formulation containing a highly reactive monomer may require fewer deposition and pinning stages than one containing a less reactive monomer). Each of the deposition and pinning stages 1002 includes a print head 1004 and an ultraviolet light source 1006 (e.g., an ultraviolet lamp or LED). In the illustrated example, a glass substrate 450 is moved relative to stages 1002 and 1003 in a moving direction 1014 (e.g., by a roller in contact with a major surface of the substrate 450 opposite the major surface on which the ink is to be deposited). The print head 1004 may be a commercially available print head made to deposit sublayers 1050 (components of the opaque layer 500) onto the glass substrate 450 in a pattern corresponding to the desired pattern of the opaque layer 500 after deposition is completed. In an embodiment, to deposit each sublayer 1050, the print head 1004 deposits multiple droplets of one of the ink compositions described herein to form a sublayer having a thickness between about 2 μm and 10 μm (e.g., 2 μm or more and 8 μm or less, 2 μm or more and 6 μm or less, 2 μm or more and 4 μm or less). After a sublayer 1050 is deposited by the print head 1004 in a particular deposition and pinning stage, the UV light source 1006 for that stage applies a pinning UV light dose to the deposited sublayer 1050. Staging the deposition of the ink advantageously provides a sufficient UV curing dose at a smaller layer thickness to achieve good UV transmission for the ink to have a very high optical density.

[0217] Whether or not a final curing stage 1003 is required depends on the nature of the ink deposited in the sublayer (reactivity of the monomers present). In an embodiment, the final curing stage 1003 includes a first UV light source 1010, if present, configured to emit UV light directly into the sublayer (after all of the sublayers have been deposited) at a dose greater than (e.g., at least 2 times greater, at least 4 times greater, at least 6 times greater, at least 8 times greater, at least 10 times greater, or even at least 15 times greater) than the dose emitted by the UV light source 1006 in each of the deposition and pinning stages 1002. Additionally, the final curing stage 1003 may also include a second UV light source 1012, if present, configured to emit UV light onto a side of the substrate 450 opposite the side on which the sublayer is deposited. The second UV light source 1012 may provide an additional UV light dose to facilitate complete curing of the deposited ink. In an embodiment, the second UV light source 1012 may provide the same dose as the first UV light source 1010. In an embodiment, the speed at which substrate 450 moves relative to stages 1002 and 1003, and the UV dose of UV sources 1006, 1010 (if present), and 1012 (if present) may be set according to Table 5 below. The particular speed and UV dose selected will depend on the composition of the photocurable ink being deposited on the glass.

[0218] [Table 5]

[0219] Ink primer

[0041] Referring now to Figure 5, a method of making a glass article is shown at 650. Method 650 may be performed to make glass article 400 as described herein with respect to Figure 2. Accordingly, reference is made to various components described with respect to Figure 2 to assist in describing the method. It should be understood that other glass articles may be formed by performance of method 650, and that method 650 is not limited to any particular number or order of process steps.

[0220] The method 650 begins at block 652 with depositing an ink primer onto a first major surface 470 of a glass substrate 450 using a first inkjet printhead at a first deposition temperature of 65° C. or less. The ink primer may be an ink primer described in accordance with embodiments herein. Thus, in embodiments, during deposition (i.e., at the first deposition temperature), the ink primer will have a viscosity of less than 13 cP. The ink primer may include an adhesion promoter designed to bond to glass.

[0221] In an embodiment, the wet thickness of the ink primer deposited on the glass substrate 450 is 8.4 ml / m 2 More than 11ml / m 2 Without intending to be bound by theory, it may be 8.4 ml / m 2 At wet thicknesses below 100 μm, the amount of reactive binding molecules is insufficient, whereas at wet thicknesses above 100 μm (>11 ml / m 2 ) results in non-grafted silanes, which can adversely affect adhesion.

[0222] Returning to FIG. 5, the method 650 continues at block 654 with exposing the ink primer to a first light source to at least partially cure the ink primer. Depending on the ink primer (e.g., an infrared curable ink primer or an ultraviolet curable ink primer), the first light source may be an infrared source or an ultraviolet source. The infrared curable ink primer, when exposed to the first light source, may bond the silane groups of the adhesion promoter to the glass and / or remove the solvent. The ultraviolet curable ink primer, when exposed to the first light source, may polymerize to form a polymer that will copolymerize with monomers from the ink composition.

[0223] Returning to Figure 5, the method 650 optionally continues with heating the ink primer at a first heating temperature at block 656. Heating the ink primer to the first heating temperature may cause the silane groups of the adhesion promoter to bond to the glass. In embodiments where the ink primer is an infrared curable ink primer, heating the ink primer to the first heating temperature may also remove solvent.

[0224] In embodiments, the first heating temperature is from 25° C. to 150° C., from 25° C. to 100° C., from 50° C. to 150° C., or even from 50° C. to 100° C., or any and all subranges formed from any of these endpoints. The ink primer may be heated at the first heating temperature for a period of from 1 second to 1 hour, from 1 second to 30 minutes, from 1 minute to 1 hour, from 1 minute to 30 minutes, from 5 minutes to 1 hour, from 5 minutes to 30 minutes, from 10 minutes to 1 hour, or even from 10 minutes to 30 minutes, or any and all subranges formed from any of these endpoints.

[0225] Returning to Figure 5, the method 650 continues at block 658 with depositing an ink composition onto the ink primer using a second inkjet printhead at a second deposition temperature of 65°C or less. In embodiments, the ink composition may be an ink composition described in accordance with embodiments herein. In embodiments, during deposition (i.e., at the second deposition temperature), the ink composition may have a viscosity of less than 13 cP.

[0226] Returning to Figure 5, the method 650 continues at block 660 with exposing the ink composition to a second light source to at least partially cure the ink composition, thereby forming an opaque layer. In the case of an infrared curable ink primer, the methacrylate groups from the silane groups of the adhesion promoter copolymerize with the monomers of the ink composition during exposure to the second light source. In the case of a UV curable ink primer, the polymers of the ink primer copolymerize with the monomers of the ink composition during exposure to the second light source.

[0227] 5, the method 650 optionally continues with heating the ink primer and ink composition at a second heating temperature at block 662. For example, in embodiments where a UV-curable ink primer is used, if the ink primer was not heated at a first heating temperature prior to depositing the ink composition, then the ink primer and ink composition may be heated at a second heating temperature to bond the silane groups of the adhesion promoter to the glass.

[0228] In embodiments, the second heating temperature is from 25° C. to 150° C., from 25° C. to 100° C., from 50° C. to 150° C., or even from 50° C. to 100° C., or any and all subranges formed from any of these endpoints. The ink primer and ink composition may be heated at the second heating temperature for a period of from 1 second to 1 hour, from 1 second to 30 minutes, from 1 minute to 1 hour, from 1 minute to 30 minutes, from 5 minutes to 1 hour, from 5 minutes to 30 minutes, from 10 minutes to 1 hour, or even from 10 minutes to 30 minutes, or any and all subranges formed from any of these endpoints. EXAMPLES

[0229] So that the various embodiments may be more readily understood, reference is made to the following examples, which are intended to illustrate various embodiments of the ink compositions and ink primers described herein.

[0230] Photocurable ink composition Examples 1 to 3 Photocurable inks having different compositions were formulated. An additional carbon black dispersant was used in the pigment dispersant of each of the inks. The concentration of the pigment was between 10% and 20% by weight of each of the photocurable inks. In Example 1, a pigment dispersant containing a carbon black pigment from Penn Color, Inc. with propoxylated neopentyl glycol diacrylate (PO-PPGDA) as a monomer was used. This carbon black pigment constituted 10% by weight of the photocurable ink. In Example 2, a pigment dispersant containing a carbon black pigment from Penn Color, Inc. with trimethylolpropane triacrylate (TMPTA) as a monomer was used. This carbon black pigment constituted 20% by weight of the photocurable ink. In Example 3, a pigment dispersant containing a carbon black pigment from Sun Chemical® with propoxylated neopentyl glycol diacrylate (PO-PPGDA) as a monomer was used. This carbon black pigment constituted 10% by weight of the photocurable ink. These inks were jetted onto chemically strengthened glass substrates using a research-grade printhead at deposition temperatures between 55° C. and 65° C. An opaque layer was formed on the glass using a Dimatix® inkjet cartridge designed to deposit 10 pL drop volumes at 1270 dpi resolution. The inks were then cured using an ultraviolet LED emitting radiation centered at 395 nm.

[0231] The samples made according to Examples 1-3 were measured for the optical density of the resulting opaque layer using a densitometer. Figure 6 shows a chart 700 of optical density as a function of opaque layer thickness for the various samples made. As shown by point 702, the opaque layer made from Example 2 (having the highest weight percent pigment) produced an optical density of greater than 4.0 at a thickness of less than 8 μm, demonstrating the effectiveness of the photocurable inks described herein. Each of the samples shown in Figure 6 was also tested for adhesion and passed the adhesion test (adhesion of 4B or greater as measured according to ASTM 3359) when the glass was primed with an acryloxysilane primer prior to printing.

[0232] Samples made using the ink composition of Example 1 were subjected to high temperature and humidity testing by heating the samples to 85° C. in a 95% relative humidity environment for a period of 500 hours, and then tested for adhesion according to ASTM 3359. The results of the cross-hatch adhesion test are shown in FIG. 7. As can be seen, the appearance of the opaque layer 802 was not significantly affected by the adhesion test, and only a small portion of the opaque layer (shown on the underside of the tape 804 used in the test) was removed along the cut edge. Such results demonstrate the reliability and durability of the photocurable inks described herein.

[0233] Example 4 Another example was formulated using the composition shown in Table 6. As can be seen, the ink formulated according to Example 4 contained 10% by weight carbon black pigment. The ink was jetted onto chemically strengthened glass using a research grade printhead at 60° C., and the printed parts were cured using UV LEDs and measured for optical density and thickness. The optical density was measured to be 4.2 at a thickness of 21 μm. The ink passed the adhesion test (4B or better as measured according to ASTM 3359). It is believed that higher optical densities may be achieved at smaller thicknesses using pigment dispersants with more dilute monomers.

[0234] [Table 6]

[0235] Example 5 Another example was formulated using the composition shown in Table 7. This example differs from the previous example in that the photoinitiator package was modified to reduce the overall percentage in the composition while maintaining cure, allowing for greater compositional versatility. Sun Chemical D3310-FX-K (25% in IBOA) was observed to have a much lower viscosity than UVDJ207 (25% in PONPGDA), and was therefore more attractive for inkjet printing. A mixed design of experiments was also used to optimize the composition for viscosity, printability, and overall thickness vs. OD. From this work, it was found that dipropylene glycol diacrylate (DPGDA M222) performed better than hydroxyl pivalate neopentyl glycol diacrylate (HPNDA M210), especially when combined with dipentaerythritol hexaacrylate (DPHA M600) and vinyl methyl oxazolidinone (Vmox). DPHA M600 added additional crosslinking to the ink and aided in curing. Vmox replaced n-vinylcaprolactam as a better viscosity modifier while aiding in adhesion. As shown in Table 7, the ink formulated according to Example 5 contained 11.25% by weight of carbon black pigment. The ink was jetted using a production KM1024iSHE printhead at 50° C. onto chemically strengthened glass, and the printed parts were cured using UV LEDs and measured for optical density and thickness.

[0236] The printed parts were formed using a three-pulse waveform (including a first 10 microsecond pulse at 1V, a second 10 microsecond pulse at -1V, and a third 10 microsecond pulse at 0V) with a total duration of 30 microseconds. Drop volumes varied from 2.9 pL to 9.0 pL. Drop velocities varied from 2.67 m / s to 2.86 m / s. Drop angles varied from 0.21° to 0.60°. FIG. 8 shows a plot of optical density as a function of thickness for several samples produced according to Example 5. As can be seen, the composition provided an optical density of greater than 4.0 for thicknesses greater than 10 μm. For example, the optical density was measured to be 4.8 at a thickness of 11 μm. Example 5 was subjected to high temperature and humidity testing by heating the sample to 85° C. in a 95% relative humidity environment for a period of 500 hours, and then tested for adhesion according to ASTM 3359. As shown in FIG. 9, the ink passed the adhesion test (4B or better as measured according to ASTM 3359). The appearance of the opaque layer 1001 was not significantly affected by the adhesion test, with only a small portion of the opaque layer (shown on the underside of the tape 1005 used in the test) being removed along the cut edge. Such results demonstrate the reliability and durability of the photocurable inks described herein.

[0237] [Table 7]

[0238] counterexample Two commercially available UV-curable inks (Inks A and B) were deposited on pre-primed, chemically strengthened glass and tested under high temperature and humidity test conditions (85° C. and 95% relative humidity for 500 hours). Figures 10 and 11 show the samples after testing. As can be seen, both samples showed visible cracks 903, 905 as a result of shrinkage of the opaque layer. The photocurable ink showed no such visible cracks when exposed to high temperature conditions for extended periods of time, demonstrating the improved durability and reliability of the inks described herein.

[0239] Examples 6 to 10 The compositions of Examples 6-10 are given (by weight) in Tables 8 and 9. Examples 6-8 utilized a first pigment dispersant ("Dispersant A") that was more viscous and had a more reactive monomer, while Examples 9-10 utilized a second pigment dispersant ("Dispersant B") that had a reactive monomer that was less reactive and viscous than the first pigment dispersant.

[0240] [Table 8]

[0241] [Table 9]

[0242] As shown in Tables 8 and 9, for ink compositions having relatively reactive monomers (e.g., Examples 6-8 in the Examples section below), a relatively large amount of reactive diluent may be used to reduce viscosity while still providing suitable mechanical properties. Additionally, in such cases, a less reactive difunctional monomer (e.g., 3-methyl-1,5-pentanediyl diacrylate) may be used. For ink compositions having relatively low viscosity pigment dispersants and relatively low reactive reactive monomers (e.g., Examples 9 and 10 in the Examples section below), a more reactive third monomer (e.g., dipropylene glycol diacrylate) may be used. As illustrated, the amount of difunctional monomer relative to reactive diluent and the particular difunctional monomer used may be based on the viscosity and reactivity of the reactive monomer in the pigment dispersant.

[0243] The ink compositions according to Examples 6-10 were measured for viscosity over a temperature range of 25° C. to 65° C. The results are shown in FIG. 12. FIG. 12 includes a first curve 902 representing Example 6, a second curve 904 representing Example 7, a third curve 906 representing Example 8, a fourth curve 908 representing Example 9, and a fifth curve 910 representing Example 10. As can be seen, each of the Examples exhibited a viscosity ranging from 5 cP to 18 cP over an operating temperature range of 30° C. to 50° C. associated with a commercially available inkjet printhead. Examples 6, 7, 8, and 10 exhibited a viscosity ranging from 5 cP to 13 cP over a temperature range of 30° C. to 50° C. These results demonstrate that these inks are suitable for ejection from a production printhead. Indeed, the composition according to Example 6 was successfully inked with a KM1024iSHE printhead at a voltage of 10 V, a pulse width of 5.4 microseconds, and a drop temperature of 45° C., giving a drop velocity of about 5 m / s and a drop volume of 9.7 pL.

[0244] The composition according to Example 6 was deposited on a glass substrate and subjected to four deposition and pinning stages. Each UV source provided 0.24 J / cm2 for each sublayer. 2 After deposition and pinning of all sublayers, both the first and second UV sources were designed to apply a UV dose of 24 J / cm to provide a cross-hatch adhesion of greater than 4B when tested according to ASTM D3359. 2 It has been found that a final cure stage providing a dose of

[0245] The composition according to Example 7 was deposited on a glass substrate and subjected to four deposition and pinning stages without a final curing stage. Each of the UV sources had an output of 5.2 J / cm 2 Such a setup, designed to apply a UV dose of 1000 psi was found to be sufficient to achieve full cure and provide a crosshatch adhesion of greater than 4B when tested according to ASTM D3359 (i.e., no final cure stage was required).

[0246] Images of crosshatch adhesion testing according to ASTM D3359 for cured Examples 6 and 7 are shown below in Figures 13 (Example 6) and 14 (Example 7). These results show that both ink compositions provide crosshatch adhesion of greater than 4B when tested according to ASTM D3359, but the curing conditions required were varied to achieve such adhesion performance.

[0247] Unlike the composition of Example 6, the composition of Example 7 can be cured at a significantly lower UV dose without the need for a high dose final cure pass from either the top or bottom, and still provide favorable adhesion. This difference in cure performance between Examples 6 and 7 is believed to result from the difference in monomers. The composition according to Example 7 contained a higher amount of the first monomer (reactive diluent) compared to the third monomer (difunctional monomer), while the composition according to Example 6 contained a relatively higher amount of the third monomer. The inclusion of a relatively higher proportion of the more reactive diluent in Example 7 improves cure performance. It is believed that when using a pigment dispersant with a high viscosity and a relatively reactive monomer, providing at least 25 wt % of the first monomer will improve cure performance. This improvement in cure has broader implications, as the relatively small UV dose required provides flexibility in the design of the deposition and pinning stage. Eliminating the need for a second light source to illuminate the bottom of the glass allows more freedom and versatility in the roller configuration and size of glass used, as there is no longer an engineering constraint to accommodate a UV lamp between the rollers to allow the UV light to pass through.

[0248] The ink compositions according to each of Examples 6-10 were deposited on a glass substrate. A number of samples were prepared according to each ink composition and measured for thickness and optical density. The results are given in FIG. 15. The curves flatten out at concentrations above 6 due to the failure of the measurement method at such high concentrations. As can be seen, each of the ink compositions can provide an optical density greater than 5 at a thickness of less than 15 μm (e.g., between 10 μm and 12 μm), meeting the stringent requirements of automotive applications described herein. Samples decorated with the ink composition according to Example 6 herein were also subjected to the various tests described in Table 4 herein. The results are given in Table 10 below.

[0249] [Table 10]

[0250] Ink primer Infrared curable ink primer Example 11 The formulation of Example 11 is shown in Table 11 (wt %). The formulation from Example 11 exhibited a viscosity of 7.8 cP at 25° C., which is suitable for inkjet printheads for production purposes. Indeed, the formulation from Example 11 was successfully inked by a KM1024iSHE printhead at a voltage of 10 V, a pulse width of 5.4 microseconds, and a drop temperature of 30° C., giving a drop velocity of about 5 m / s and a drop volume of 9.7 pL.

[0251] [Table 11]

[0252] The formulation according to Example 11 was deposited on a glass substrate and subjected to heating at 110° C. for 1 hour in an oven to bond the adhesion promoter to the substrate. 2 From 13.2ml / m 2) was printed and subjected to 500 1 hour cycles of 0.5 hour at -40°C and 0.5 hour at 95°C, according to ASTM 3359, after which adhesion was determined by cross-hatch adhesion test. An image of the cross-hatch adhesion test is shown in Figure 16. 2 A wet thickness of 100 μm provided the best adhesion of the UV curable ink composition to the glass substrate.

[0253] Samples of the formulation according to Example 11 were also subjected to various tests as described in Table 4. The results are given in Table 12.

[0254] [Table 12]

[0255] UV-curable ink primer Examples 12 and 13 The formulations of Examples 12 and 13 are shown in Table 13 (wt%). The ink formulations according to Examples 12 and 13 exhibited viscosities between 7 cP and 12 cP at 35° C. to 45° C., which are suitable for inkjet printheads for production purposes. Indeed, the formulations according to Examples 12 and 13 were successfully inked on a KM1024iSHE printhead at a voltage of 10 V, a pulse width of 5.4 microseconds, and a drop temperature of 45° C., giving a drop velocity of about 5 m / s and a drop volume of 9.7 pL.

[0256] [Table 13]

[0257] The formulation according to Example 13 was deposited on a glass substrate at approximately 15 J / cm 2 The primer formulation was cured by exposure to a 395 nm wavelength UV LED lamp at a dose of about 15 J / cm. A UV curable ink composition was then deposited on the primer layer. 2The ink composition was cured by exposure to a 395 nm wavelength UV LED lamp at a dose of 1000 μm, crosslinking the vinyl groups of the polymer to the monomers of the ink. The primer and ink layers were then heated at 85° C. for 20 minutes to covalently bond the Si-O groups of the primer to the glass. As shown in FIGS. 17 and 18, when tested according to ASTM 3359, adhesion was determined by cross-hatch adhesion testing after 500 exposures to 1 hour cycles of 0.5 hours at -40° C. and 0.5 hours at 95° C. As shown in FIGS. 17 and 18, each of the samples had adhesion greater than 4B. Total primer and ink thicknesses of 13.6 μm and 12.48 μm, respectively, and optical densities of 6.18 and 5.83 were achieved, meeting the stringent requirements of the automotive application described herein.

[0258] It will be apparent to those skilled in the art that various modifications and variations can be made to the embodiments described herein without departing from the spirit and scope of the claimed subject matter. Thus, it is intended that this specification cover modifications and variations of the various embodiments described herein, provided such modifications and variations come within the scope of the appended claims and their equivalents. [Explanation of symbols]

[0259] 100, 200, 300 Cabin Systems 110 Center console base 120, 220, 320 curved surface 130, 230, 330, 540 Display 210 Dashboard Base 215 Instrument Panel 310 Dashboard handle base 400 Glass items 450 Substrate 460 Optical Management Layer 470 First main surface 480 Second main surface 490 Functional surface layer 500, 802, 1001 Opaque layer 520 display area Tape used in 804 and 1005 tests 903, 905 Crack 1000 Ink Deposition Device 1002 Deposition and pinning stage 1003 Final hardening stage 1004 Printhead 1006 UV source 1010 First UV source 1012 Second UV source 1014 Direction of movement 1050 sublayer 2000 cabin

Claims

1. In the ultraviolet ray curable ink composition, based on the total mass of the ultraviolet ray curable ink composition, 25% by weight or more and 50% by weight or less of a pigment dispersant, the pigment dispersant comprising at least 30% by weight of a pigment and a reactive monomer, based on the total weight of the pigment dispersant; greater than 0% and less than or equal to 10% by weight of a photoinitiator package comprising a Type I photoinitiator, a Type II photoinitiator, and an amine synergist; 10% by weight or more and 42% by weight or less of a reactive diluent having a viscosity of less than 5 cP at 25° C.; 5% by weight or more and 20% by weight or less of a polyfunctional monomer, and 0% by weight or more and 35% by weight or less of a difunctional monomer; Including, The ultraviolet ray curable ink composition does not contain a resin and does not contain a TPO.

2. 2. The ultraviolet ray curable ink composition according to claim 1, wherein the ultraviolet ray curable ink composition comprises 10% by mass or more and 35% by mass or less of the bifunctional monomer, a total amount of the reactive diluent, the polyfunctional monomer, and the bifunctional monomer is 60% by mass or less, the ultraviolet ray curable ink composition further comprises more than 0% by mass and 10% by mass or less of an adhesion promoter, and the pigment dispersant comprises 35% by mass or more of the pigment based on the total mass of the pigment dispersant, and the pigment is a carbon black pigment.

3. 3. The ultraviolet curable ink composition according to claim 2, wherein the ultraviolet curable ink composition exhibits a viscosity of 8 cP or more and 13 cP or less over a temperature range of 30°C to 50°C.

4. 4. The UV curable ink composition of claim 1, wherein after being deposited on a glass substrate and cured using a UV source to form an opaque layer having a cured thickness of less than 15 μm, the opaque layer exhibits an optical density of greater than 5.

5. In glass articles, a glass substrate having a first major surface and a second major surface opposite the first major surface; and an opaque layer disposed on the second major surface, the opaque layer being made from a photocurable ink having at least 11% by weight pigment; The opaque layer is resin-free and TPO-free; the opaque layer has a thickness of 15 μm or less and an optical density of 5.0 or greater; The opaque layer is cured solely by exposure to ultraviolet ("UV") radiation and then A pencil hardness of 3H or greater, as measured in accordance with ASTM 3363; and an adhesion to said glass substrate of 4B or greater when measured according to ASTM 3359 after exposure to a temperature of 85° C. at 95% relative humidity for a period of at least 500 hours; Indicating an opaque layer, A glass article comprising:

6. 6. The glass article of claim 5, wherein after exposure to 500 one hour cycles of being held at a temperature of -40°C for 0.5 hours and at 95°C for 0.5 hours, the opaque layer exhibits adhesion to the glass substrate of 4B or greater when tested according to ASTM 3359, and the glass article exhibits a maximum ΔE value (both SCI and SCE) of less than 2.0 when measured both before and after the 500 one hour cycles.

7. 1. A method of making a glass article, comprising: depositing an ink primer onto a first major surface of a glass substrate using an inkjet printhead at a first deposition temperature of 65° C. or less, wherein during the depositing step, the ink primer has a viscosity of less than 13 cP, and the ink primer includes 2% by weight or more and 10% by weight or less of an adhesion promoter designed to bond to glass; exposing the ink primer to a first light source to at least partially cure the ink primer; depositing an ink composition onto the ink primer using a second inkjet printhead at a second deposition temperature of 65° C. or less, wherein during the depositing step, the ink composition has a viscosity of less than 13 cP; and exposing the ink composition to a second light source to at least partially cure the ink composition; The method includes:

8. the first light source is an infrared source; The ink primer is resin-free and TPO-free, 2% by weight or more and 10% by weight or less of an adhesion promoter designed to bond to glass, and a solvent designed to promote bonding of the adhesion promoter to the glass, the solvent comprising: 3-methoxy-3-methyl-1-butanol; butanol; ethylene glycol ether; 2-butoxyethanol; propylene glycol monomethyl ether acetate; propylene glycol; 2-butoxyethyl acetate; ethylene glycol; 1,4-butanediol; diethyl succinate; or combinations thereof; The method of claim 7, comprising:

9. the first light source being an ultraviolet light source; The ink primer is greater than 0% and less than or equal to 10% by weight of a photoinitiator package comprising a Type I photoinitiator, a Type II photoinitiator, and an amine synergist; and 30% by weight or more and 45% by weight or less of a monofunctional monomer; The method of claim 7, comprising:

10. The ink composition comprises: 25% by weight or more and 50% by weight or less of a pigment dispersant, the pigment dispersant comprising at least 30% by weight of a pigment and a reactive monomer, based on the total weight of the pigment dispersant; greater than 0% and less than or equal to 10% by weight of a photoinitiator package comprising a Type I photoinitiator, a Type II photoinitiator, and an amine synergist; 10% by weight or more and 42% by weight or less of a reactive diluent having a viscosity of less than 5 cP at 25° C.; 5% by weight or more and 20% by weight or less of a polyfunctional monomer, and 0% by weight or more and 35% by weight or less of a difunctional monomer; 10. The method of claim 7, comprising:

Images