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

Abstract

An ultraviolet ink composition comprising: from 25% to 50% by weight of a pigment dispersion; from greater than 0% to 10% by weight of a photoinitiator package; 10 wt% to 42 wt% of a reactive diluent; 10 wt% to 20 wt% of a polyfunctional monomer; and 0 wt% to 25 wt% of a bifunctional monomer. The ink primer includes from 2% to 10% by weight of an adhesion promoter configured to bond to the glass and from 90% to 98% by weight of a solvent configured to promote bonding of the adhesion promoter to the glass. Another ink primer includes from 2% to 10% by weight of an adhesion promoter configured to bond to glass, greater than 0% to 10% by weight of a photoinitiator package; and 30 wt% to 45 wt% of a monofunctional monomer.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Application Serial No. 63 / 601,925 filed on November 22, 2023 and U.S. Provisional Application Serial No. 63 / 526,560 filed on July 13, 2023, the contents of each of which are relied upon and incorporated herein by reference in their entirety. Technical Field Technical Field

[0004] The present description relates generally to automotive interior glazing products and, more particularly, to photocurable inks and primers for forming an opaque layer on display cover glass having relatively high glass adhesion and high optical density. Technical Background

[0005] An automotive interior may include a display that includes 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 areas of the cover glass to hide various components of the display (e.g., electrical and mechanical connections) and / or to provide a uniform appearance to the display when the display is powered off. Certain existing inks used to decorate display cover glass may have various deficiencies, such as low yield, unsatisfactory optical density, and insufficient adhesion, rendering these inks unsuitable for use in automotive interior applications.

[0006] Therefore, there is a need for an alternative ink that meets the requirements associated with automotive interior display applications. Summary of the invention

[0007] According to the first aspect A1, the UV-curable ink composition comprises: greater than or equal to 25 wt% and less than or equal to 50 wt% of a pigment dispersion, based on the total weight of the UV-curable ink composition, wherein the pigment dispersion comprises at least 30 wt% of a pigment and a reactive monomer, based on the total weight of the pigment dispersion; greater than 0 wt% and less than 10 wt% of a photoinitiator package, the photoinitiator package comprising a Type I photoinitiator, a Type II photoinitiator and an amine synergist; greater than or equal to 10 wt% and less than or equal to 42 wt% of a reactive diluent, the reactive diluent having a viscosity of less than 5 cPs at 25°C; greater than or equal to 5 wt% and less than or equal to 20 wt% of a multifunctional monomer; and greater than or equal to 0 wt% and less than or equal to 35 wt% of a difunctional monomer.

[0008] The second aspect A2 includes the ultraviolet curable ink composition of the first aspect A1, wherein the ultraviolet curable ink composition comprises 10 wt % or more and 35 wt % or less of a bifunctional monomer.

[0009] The third aspect A3 includes the UV curable ink composition of the second aspect A2, wherein the combined amount of the reactive diluent, the multifunctional monomer, and the difunctional monomer is less than or equal to 60 wt%.

[0010] The fourth aspect A4 includes the UV curable ink composition of any one of the first to third aspects A1-A3, wherein the UV curable ink composition further comprises greater than 0 wt % and less than or equal to 10 wt % of an adhesion promoter.

[0011] The fifth aspect A5 includes the UV curable ink composition of any one of the first to fourth aspects A1-A4, wherein the UV curable ink composition contains no resin and no TPO.

[0012] The sixth aspect A6 includes the UV curable ink composition of any one of the first to fifth aspects A1-A5, wherein the UV curable ink composition exhibits a viscosity greater than or equal to 8 cPs and less than or equal to 13 cPs in a temperature range of 30°C to 50°C.

[0013] The seventh aspect A7 includes the UV curable ink composition of any one of the first to sixth aspects A1-A6, wherein the pigment dispersion comprises greater than or equal to 35 wt% of the pigment based on the total weight of the pigment dispersion, and wherein the pigment is a carbon black pigment.

[0014] The eighth aspect A8 includes the UV curable ink composition of any one of the first to seventh aspects A1-A7, wherein after being deposited on a glass substrate and cured using a UV light source to form an opaque layer having a thickness of less than 15 μm after curing, the opaque layer exhibits an optical density greater than 5.

[0015] According to the ninth aspect A9, a glass substrate has a first major surface and a second major surface, the second major surface being opposite to the first major surface; and an opaque layer is arranged on the second major surface, the opaque layer includes a photocurable ink, the photocurable ink contains at least 11 weight % of a pigment, wherein: the opaque layer is resin-free and TPO-free, the opaque layer has a thickness less than or equal to 15 μm and an optical density greater than or equal to 5.0, and after being cured only by exposure to ultraviolet (“UV”) radiation, the opaque layer exhibits: a pencil hardness greater than or equal to 3H when measured according to ASTM 3363, and an adhesion to the glass substrate greater than or equal to 4B after being subjected to at least 500 hours at a temperature of 85°C and a relative humidity of 95% when tested according to ASTM 3359.

[0016] The tenth aspect A10 includes the glass article of the ninth aspect A9, wherein the average particle size of the pigment is less than or equal to 200 nm.

[0017] An eleventh aspect A11 includes the glass article of any of the ninth to tenth aspects A9-A10, wherein the opaque layer exhibits a cured surface tension greater than 36 dynes / cm.

[0018] The twelfth aspect A12 includes the glass article of any of the ninth to eleventh aspects A9-A11, wherein the opaque layer exhibits a relative humidity greater than or equal to 1×10 9 Resistivity of Ω / sq.

[0019] The thirteenth aspect A13 includes the glass article of any of the ninth through twelfth aspects A9-A12, wherein the glass article exhibits a CIELAB SCI L* value of less than or equal to 30 when illuminated with a D65 light source at an angle of 10°.

[0020] The fourteenth aspect A14 includes the glass article of any of the ninth to thirteenth aspects A9-A13, wherein when illuminated with a D65 light source at a 10° angle, the glass article exhibits a CIELAB SCI a* value greater than or equal to -0.05 and less than or equal to 0.15 and a CIELAB SCI b* value greater than or equal to -0.3 and less than or equal to -0.1.

[0021] The fifteenth aspect A15 includes the glass article of any one of the ninth to fourteenth aspects A9-A14, wherein after 500 1-hour cycles of maintaining a temperature of -40°C for 0.5 hours and maintaining a temperature of 95°C for 0.5 hours, when tested according to ASTM3359, the opaque layer exhibits an adhesion to the glass substrate of greater than or equal to 4B when tested according to ASTM3359.

[0022]

[0066] A sixteenth aspect A16 includes the glass article of the fifteenth aspect A15, wherein the glass article exhibits a maximum ΔE value (SCI and SCE) measured before and after 500 one hour cycles of less than 2.0.

[0023] The seventeenth aspect A17 includes the glass article of any one of the ninth to sixteenth aspects A9-A16, wherein the glass substrate includes at least one of soda-lime glass, aluminosilicate glass, borosilicate glass, boroaluminosilicate glass, alkali-containing aluminosilicate glass, and alkali-containing borosilicate glass.

[0024] According to the eighteenth aspect A18, a method for manufacturing a glass article comprises: depositing a plurality of sub-layers of a UV-curable ink composition onto a first major surface of a glass substrate using an inkjet print head at a deposition temperature of less than or equal to 65° C., wherein during deposition, the UV-curable ink composition has a viscosity of less than 13 cPs, wherein the UV-curable ink composition comprises: greater than or equal to 25 wt % and less than or equal to 50 wt % of a pigment dispersion, wherein the pigment dispersion comprises at least 30 wt % of a pigment and a reactive monomer; greater than or equal to 10 wt % and less than or equal to 0 wt % of a polyol; wt % of a photoinitiator package; greater than or equal to 10 wt % and less than or equal to 42 wt % of a reactive diluent, the reactive diluent comprising a viscosity of less than 5 cPs at 25° C.; greater than or equal to 10 wt % and less than or equal to 20 wt % of a multifunctional monomer; and greater than or equal to 0 wt % and less than or equal to 35 wt % of a difunctional monomer; and between deposition of adjacent ones of the plurality of sublayers, pinning each of the plurality of sublayers by exposing the plurality of sublayers to UV light from a UV light source to at least partially cure an ultraviolet curable ink composition constituting the sublayers.

[0025] The nineteenth aspect A19 includes the method of the eighteenth aspect A18, wherein each of the plurality of sub-layers comprises a thickness greater than or equal to 2 μm and less than or equal to 4 μm after pinning.

[0026] The twentieth aspect A20 includes the method of the nineteenth aspect A19, wherein the deposition and pinning occur in three or more deposition and pinning stages, wherein each deposition and pinning stage comprises an inkjet print head for depositing one of a plurality of sub-layers and a UV light source for pinning the sub-layer.

[0027] The twenty-first aspect A21 includes the method of the twentieth aspect A20, wherein during the deposition and the pinning, the glass substrate is moved relative to the deposition and the pinning stages at a translation speed greater than or equal to 1 m / min and less than or equal to 5 m / min.

[0028] The twenty-second aspect A22 includes the method of the twenty-first aspect A21, wherein the glass substrate moves on a plurality of rollers that contact a second major surface of the glass substrate opposite the first major surface.

[0029] A twenty-third aspect A23 includes the method of any of the twenty-first to twenty-second aspects A21-A22, wherein the UV light source in each of the deposition and pinning stages is configured to apply greater than or equal to 0.2 J / cm to the sublayer. 2 And less than or equal to 10J / cm 2 The pinning dose of UV light.

[0030] The twenty-fourth aspect A24 includes the method of the twenty-third aspect A23, wherein after deposition and pinning through the deposition and pinning stages, the multiple sub-layers form an opaque layer having a thickness of less than 15 μm and exhibiting: an optical density greater than 5 and an adhesion to the glass substrate greater than or equal to 4B when tested according to ASTM 3359, without applying any additional ultraviolet light thereto outside the deposition and pinning stages.

[0031] Aspect 25 A25 includes the method of any one of Aspects 21 to 23 A21-A23, further comprising exposing the sublayer to additional ultraviolet light in a final curing stage after the deposition and pinning stages, wherein the final curing stage includes a first UV light source configured to directly expose the sublayer to greater than or equal to 10 J / cm 2 And less than or equal to 100J / cm 2 The curing dose of UV light.

[0032] The twenty-sixth aspect A26 includes the method of the twenty-fifth aspect A25, wherein after exposure to a curing dose, the multiple sub-layers form an opaque layer having a thickness less than 15 μm and exhibiting: an optical density greater than 5 and an adhesion to a glass substrate greater than or equal to 4B when tested in accordance with ASTM3359.

[0033] The twenty-seventh aspect A27 includes the method of the twenty-sixth aspect A26, wherein the adhesion is exhibited without exposure to ultraviolet rays from the side of the second major surface of the glass substrate opposite to the first major surface.

[0034] The twenty-eighth aspect A28 includes the method of the twenty-sixth aspect A26, wherein the final curing stage includes a second UV light source configured to expose the sublayer to ultraviolet light through the glass substrate from a side of the second major surface of the glass substrate opposite the first major surface.

[0035] According to the twenty-ninth aspect A29, based on the total weight of the ink primer, the ink primer contains: greater than or equal to 2 weight % and less than or equal to 10 weight % of an adhesion promoter configured to bond to glass; and greater than or equal to 90 weight % and less than or equal to 98 weight % of a solvent configured to promote the adhesion promoter bonding to the glass.

[0036] The 30th aspect A30 comprises the ink primer of the 29th aspect A29, wherein the adhesion promoter comprises an organofunctional silane.

[0037] The thirty-first aspect A31 comprises the ink primer of the twenty-ninth aspect A29 or the thirtieth aspect A30, wherein the ink primer is an infrared curable ink primer.

[0038] The thirty-second aspect A32 includes the ink primer of any one of the twenty-ninth to thirty-first aspects A29-A31, 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 a combination of the above items.

[0039] The thirty-third aspect A33 includes the ink primer of any one of the twenty-ninth to thirty-second aspects A29-A32, wherein the ink primer is resin-free and TPO-free.

[0040] The thirty-fourth aspect A34 includes the ink primer of any of the twenty-ninth to thirty-third aspects A29-A33, wherein the ink primer exhibits a viscosity greater than or equal to 8 cPs and less than or equal to 13 cPs in the temperature range of 30°C to 50°C.

[0041] According to the thirty-fifth aspect A35, based on the total weight of the ink primer, the ink primer comprises: greater than or equal to 2 weight % and less than or equal to 10 weight % of an adhesion promoter configured to bond to glass; greater than 0 weight % and less than or equal to 10 weight % of a photoinitiator package, the photoinitiator package comprising a Type I photoinitiator, a Type II photoinitiator and an amine enhancer; and greater than or equal to 30 weight % and less than or equal to 45 weight % of a monofunctional monomer.

[0042] The thirty-sixth aspect A36 comprises the ink primer of the thirty-fifth aspect A35, wherein the adhesion promoter comprises an organofunctional silane.

[0043] The thirty-seventh aspect A37 comprises the ink primer of the thirty-fifth aspect A35 or the thirty-sixth aspect A36, wherein the ink primer is a UV curable ink primer.

[0044] The thirty-eighth aspect A38 includes the ink primer of any of the thirty-fifth to thirty-seventh aspects A35-A37, wherein the ink primer comprises greater than or equal to 4 wt% and less than or equal to 10 wt% of the adhesion promoter.

[0045] The thirty-ninth aspect A39 includes the ink primer of any one of the thirty-fifth to thirty-eighth aspects A35-A38, wherein the Type I photoinitiator includes phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide; 1-hydroxycyclohexyl-phenyl ketone; (2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; 2,2-dimethoxy-2-phenylacetophenone; (2,4,6-trimethylbenzoyl)diphenylphosphine oxide; ethoxy(2,4,6-trimethylbenzoyl)phenylphosphine oxide; or a combination of the above items.

[0046] The fortieth aspect A40 includes the ink primer of any one of the thirty-fifth to thirty-ninth aspects A35-A39, wherein the type II photoinitiator includes isopropylthioxanthone, benzophenone, 4-phenylbenzophenone, methyl-2-benzoylbenzoate, ketosulfone, or a combination thereof.

[0047] The forty-first aspect A41 includes the ink primer of any one of the thirty-fifth to fortieth aspects A35-A40, wherein the amine synergist includes ethyl 4-(dimethylamino)benzoate; N,N-[2-(4-dimethylaminobenzoyl)oxyethylene-1-yl]methanamine; N-methyldiethanolamine; ethyl-4-dimethylamino benzoate; 2-ethylhexyl-4-dimethylamino benzoate; or a combination of the above items.

[0048] The forty-second aspect A42 includes the ink primer of any one of the thirty-fifth to forty-first aspects A35-A41, wherein the monofunctional monomer includes isobornyl acrylate.

[0049] The forty-third aspect A43 includes the ink primer of any one of the thirty-fifth to forty-second aspects A35-A42, wherein the ink primer further comprises greater than 0 wt% and less than or equal to 30 wt% of a reactive diluent having a viscosity of less than 5 cPs at 25°C.

[0050] The forty-fourth aspect A44 includes the ink primer of the forty-third aspect A43, wherein the reactive diluent includes vinylmethyloxazolidinone; 5-methyl-3-vinyloxazolidin-2-one; an N-vinyl monomer; or a combination thereof.

[0051] The forty-fifth aspect A45 includes the ink primer of any of the thirty-fifth to forty-fourth aspects A35-A44, wherein the ink primer further comprises greater than 0 wt% and less than or equal to 35 wt% of a difunctional monomer.

[0052] The forty-sixth aspect A46 includes the ink primer of the forty-fifth aspect A45, wherein the difunctional monomer includes 3-methyl-1,5-pentanediyl diacrylate; dipropylene glycol diacrylate; or a combination thereof.

[0053] The forty-seventh aspect A47 includes the ink primer of any one of the thirty-fifth to forty-sixth aspects A35-A46, wherein the ink primer further comprises greater than or equal to 5 wt% and less than or equal to 10 wt% of a solvent.

[0054] The forty-eighth aspect A48 includes the ink primer of the forty-seventh aspect A47, 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 of the above items.

[0055] The forty-ninth aspect A49 comprises the ink primer of any one of the thirty-fifth to forty-eighth aspects A35-A48, wherein the ink primer is resin-free and TPO-free.

[0056] The fiftieth aspect A50 comprises the ink primer of any one of the thirty-fifth to forty-ninth aspects A35-A49, wherein the ink primer exhibits a viscosity greater than or equal to 8 cPs and less than or equal to 13 cPs in the temperature range of 30°C to 50°C.

[0057] According to the fifty-first aspect A51, a glass article includes: a glass substrate having a first major surface and a second major surface, the second major surface being opposite to the first major surface; and an opaque layer disposed on the second major surface, the opaque layer including an ink composition, the ink composition comprising at least 11 weight percent of a pigment and an adhesion promoter, the adhesion promoter being bonded to the glass substrate and the ink composition being polymerized with the adhesion promoter, wherein: the opaque layer has a thickness less than or equal to 15 μm and an optical density greater than or equal to 5.0, and the opaque layer exhibits adhesion to the glass substrate of greater than or equal to 4B after 500 1-hour cycles of keeping at -40°C for 0.5 hour and keeping at 95°C for 0.5 hour when tested according to ASTM 3359.

[0058] The fifty-second aspect A52 includes the glass article of the fifty-first aspect A51, wherein the adhesion promoter includes an organofunctional silane.

[0059] The fifty-third aspect A53 includes the glass article of the fifty-first aspect A51 or the fifty-second aspect A52, wherein the opaque layer contains no resin and no TPO.

[0060] Fifty-fourth A54 includes the glass article of any of the fifty-first to fifty-third aspects A51-A53, wherein the glass article exhibits a maximum ΔE value (SCI and SCE) measured before and after 500 one-hour cycles of less than 2.0.

[0061] The fifty-fifth aspect A55 includes the glass article of any one of the fifty-first to fifty-fourth aspects A51-A54, wherein the glass substrate includes at least one of soda-lime glass, aluminosilicate glass, borosilicate glass, boroaluminosilicate glass, alkali-containing aluminosilicate glass, and alkali-containing borosilicate glass.

[0062] According to aspect fifty-six A56, a method for manufacturing a glass article comprises: using a first inkjet print head to deposit an ink primer onto a first major surface of a glass substrate at a first deposition temperature of less than or equal to 65°C, wherein during deposition, the viscosity of the ink primer is less than 13 cPs, wherein the ink primer comprises: greater than or equal to 2 weight % and less than or equal to 10 weight % of an adhesion promoter configured to bind to glass; exposing the ink primer to a first light source to at least partially cure the ink primer; using a second inkjet print head to deposit an ink composition onto the ink primer at a second deposition temperature of less than or equal to 65°C, wherein during deposition, the viscosity of the ink composition is less than 13 cPs; and exposing the ink composition to a second light source to at least partially cure the ink composition.

[0063] The fifty-seventh aspect A57 includes the method of the fifty-sixth aspect A56, wherein the first light source is an infrared light source.

[0064] The fifty-eighth aspect A58 includes the method of the fifty-sixth aspect A56, wherein the first light source is an ultraviolet light source.

[0065] The fifty-ninth aspect A59 includes the method of the fifty-sixth aspect, wherein the ink primer further comprises: greater than 0 weight % and less than or equal to 10 weight % of a photoinitiator package, the photoinitiator package comprising a Type I photoinitiator, a Type II photoinitiator and an amine enhancer; and greater than or equal to 30 weight % and less than or equal to 45 weight % of a monofunctional monomer.

[0066] The sixtieth aspect A60 includes the method of any one of the fifty-sixth to fifty-ninth aspects A56-A59, wherein the method further comprises, before depositing the ink composition, heating the ink primer at a first heating temperature greater than or equal to 25° C. and less than or equal to 150° C. for a period of time greater than or equal to 1 second and less than or equal to 1 hour.

[0067] The sixty-first aspect A61 includes the method of any one of the fifty-sixth aspect A56, the fifty-eighth aspect A58 or the fifty-ninth aspect A59, wherein the method further comprises, after depositing the ink composition, heating the ink primer and the ink composition at a second heating temperature greater than or equal to 25° C. and less than or equal to 150° C. for a period of time greater than or equal to 1 second and less than or equal to 1 hour.

[0068] Additional features and advantages of the photocurable inks and primers described herein and glass products containing the same will be set forth in the detailed description below, and in part will be readily apparent to those skilled in the art from the description or recognized by practicing the embodiments described herein, including the detailed description below, the claims, and the accompanying drawings.

[0069] It should be understood that the above 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 the 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

[0070] Figure 1 is a perspective view of a vehicle interior having a vehicle interior system with a display according to one or more embodiments of the present disclosure;

[0071] Figure 2 One or more embodiments according to the present disclosure are schematically described. Figure 1 A cross-sectional view of a display of a vehicle interior system along line 2-2 shown in FIG.

[0072] Figure 3 A flow chart describing a method of forming a glass article having an opaque layer according to one or more embodiments of the present disclosure;

[0073] Figure 4 schematically depicts an apparatus for depositing an opaque layer onto a glass substrate according to one or more embodiments of the present disclosure;

[0074] Figure 5 A flow chart depicting another method of forming a glass article having an opaque layer according to one or more embodiments of the present disclosure;

[0075] Figure 6 depicts a graph of measured optical density (y-axis) of an example photocurable ink as a function of opaque layer thickness (x-axis; in mm) according to one or more embodiments of the present disclosure;

[0076] Figure 7 depicts a photograph of a sample formed from an example photocurable ink after being subjected to a cross-hatch adhesion test according to one or more embodiments of the present disclosure;

[0077] Figure 8is a graph showing optical density (y-axis) of samples formed from example photocurable inks as a function of opaque layer thickness (x-axis; in μm) according to one or more embodiments of the present disclosure;

[0078] Fig. 9 depicts photographs of samples formed from example photocurable inks after being subjected to a cross-hatch adhesion test according to one or more embodiments of the present disclosure;

[0079] Fig.10 depicts a photograph of a sample coated with a first commercially available UV curable ink after testing at high temperature and high humidity;

[0080] Fig.11 depicts a photograph of a sample coated with a second commercially available UV curable ink after testing at high temperature and high humidity;

[0081] Fig.12 Described is a viscosity versus temperature graph of an example photocurable ink according to one or more embodiments of the present disclosure;

[0082] Fig.13 is a photograph of a sample having an example ink composition deposited thereon after being subjected to a cross-hatch adhesion test according to one or more embodiments of the present disclosure;

[0083] Fig.14 is a photograph of a sample having an example ink composition deposited thereon after being subjected to a cross-hatch adhesion test according to one or more embodiments of the present disclosure;

[0084] Fig.15 is a graph of optical density (y-axis) versus thickness (x-axis; in μm) of an opaque layer formed using an example ink formulation according to one or more embodiments of the present disclosure;

[0085] Fig.16 is a photograph of a sample having an example ink primer and an example ink formulation deposited thereon after being subjected to a cross-hatch adhesion test;

[0086] Fig.17 is a photograph of a sample having an example ink primer and an example ink formulation deposited thereon after being subjected to a cross-hatch adhesion test; and

[0087] Fig.18 is a photograph of a sample having an example ink primer and an example ink formulation deposited thereon after being subjected to a cross hatch adhesion test. DETAILED DESCRIPTION

[0088] Reference will now be made in detail to various embodiments of photocurable inks and ink primers for forming an opaque layer on a display cover glass, the opaque layer having relatively high glass adhesion and high optical density. In some embodiments, the UV ink composition comprises greater than or equal to 25 wt% and less than or equal to 50 wt% of a pigment dispersion, greater than 0 wt% and less than or equal to 10 wt% of a photoinitiator package, greater than or equal to 10 wt% and less than or equal to 42 wt% of a reactive diluent, greater than or equal to 10 wt% and less than or equal to 20 wt% of a multifunctional monomer, and greater than or equal to 0 wt% and less than or equal to 35 wt% of a difunctional monomer, based on the total weight of the pigment dispersion. The pigment dispersion comprises at least 30 wt% of a pigment and a reactive monomer, based on the total weight of the pigment dispersion. 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 cPs at 25°C.

[0089] In other embodiments, the glass article includes a glass substrate having a first major surface and a second major surface, the second major surface being opposite to 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 containing at least 11% by weight of a pigment. The opaque layer is resin-free and TPO-free. The opaque layer has a thickness less than or equal to 15 μm and an optical density greater than or equal to 5.0. After curing solely by exposure to ultraviolet (“UV”) radiation, the opaque layer exhibits a pencil hardness greater than or equal to 3H when measured in accordance with ASTM 3363, and an adhesion to the glass substrate greater than or equal to 4B after being subjected to at least 500 hours at a temperature of 85° C. and 95% relative humidity when tested in accordance with ASTM 3359.

[0090] In some embodiments, a method of manufacturing a glass article includes depositing a plurality of sub-layers of an ultraviolet curable ink composition onto a first major surface of a glass substrate using an inkjet print head at a deposition temperature of less than or equal to 65° C., and pinning each of the plurality of sub-layers by exposing the plurality of sub-layers to UV light from a UV light source to at least partially cure the ultraviolet curable ink composition constituting the sub-layer between depositions of adjacent sub-layers of the plurality of sub-layers. During deposition, the viscosity of the photocurable ink is less than 13 cPs. Based on the total weight of the ultraviolet ink composition, the ultraviolet curable ink composition comprises greater than or equal to 25 wt % and less than or equal to 50 wt %, greater than 0 wt % and less than or equal to 10 wt % of a photoinitiator package, greater than or equal to 10 wt % and less than or equal to 42 wt % of a reactive diluent, greater than or equal to 10 wt % and less than or equal to 20 wt % of a multifunctional monomer, and greater than or equal to 0 wt % and less than or equal to 35 wt % of a difunctional monomer. Based on the total weight of the pigment dispersion, the pigment dispersion comprises at least 30 wt % of the pigment and the reactive monomer. The reactive diluent has a viscosity of less than 5 cPs at 25°C.

[0091] In other embodiments, the ink primer includes greater than or equal to 2 wt % and less than or equal to 10 wt % of an adhesion promoter configured to bond to glass and greater than or equal to 90 wt % and less than or equal to 98 wt % of a solvent configured to promote bonding of the adhesion promoter to the glass.

[0092] In some embodiments, the ink primer comprises greater than or equal to 2 wt % and less than or equal to 10 wt % of an adhesion promoter configured to bond to glass, greater than 0 wt % and less than or equal to 10 wt % of a photoinitiator package, and greater than or equal to 30 wt % and less than or equal to 45 wt % of a monofunctional monomer. The photoinitiator package includes a Type I photoinitiator, a Type II photoinitiator, and an amine synergist.

[0093] In other embodiments, a glass article includes a glass substrate having a first major surface and a second major surface, the second major surface being opposite to the first major surface, and an opaque layer disposed on the second major surface. The opaque layer includes an ink composition containing at least 11 weight percent of a pigment and an adhesion promoter. The adhesion promoter is bonded to the glass substrate, and the ink composition and the adhesion promoter are polymerized. The opaque layer has a thickness less than or equal to 15 μm and an optical density greater than or equal to 5.0. After 500 one-hour cycles of 0.5 hours at -40°C and 0.5 hours at 95°C, the opaque layer exhibits adhesion to the glass substrate greater than or equal to 4B.

[0094] In some embodiments, a method of making a glass article includes: depositing an ink primer onto a first major surface of a glass substrate using a first inkjet print head at a first deposition temperature of less than or equal to 65° C., 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 print head at a second deposition temperature of less than or equal to 65° C., and exposing the ink composition to a second light source to at least partially cure the ink composition. During deposition, the viscosity of the ink primer is less than 13 cPs. The ink primer includes greater than or equal to 2 wt % and less than or equal to 10 wt % of an adhesion promoter configured to bond to glass. During deposition, the viscosity of the ink composition is less than 13 cPs.

[0095] Various embodiments of photocurable inks and primers and glass articles including the same will be described herein with specific reference to the accompanying drawings.

[0096] Ranges may be expressed herein as from "about" one particular value and / or to "about" another particular value. When such ranges are expressed, another embodiment includes from the one particular value and / or to the other particular value. Similarly, when a value is expressed as an approximation by using the antecedent "about," it is understood that the particular value forms another embodiment. It is also understood that each of the end values ​​in a range is meaningful relative to the other end value and independently of the other end value.

[0097] Directional terms used herein (eg, up, down, right, left, front, back, top, bottom) refer only to the drawings in which they are drawn and do not imply absolute directions.

[0098] Unless otherwise expressly stated, any method described herein shall not be construed as requiring that its steps be performed in a particular order, nor as requiring a particular orientation of any apparatus. Thus, in the absence of a method claim actually reciting an order in which its steps are to be followed, or any apparatus claim actually reciting an order or orientation of individual components, or in the absence of another specific statement in the claims or specification that the steps are to be limited to a particular order, or in the absence of a particular order or orientation of components of an apparatus, no order or orientation is intended to be inferred in any respect. This applies to any possible non-expressive basis for interpretation, including: logical issues regarding arrangement of steps, operational flow, order of components, or orientation of components; clear meaning derived from grammatical organization or punctuation; and the number or type of embodiments described in this specification.

[0099] As used herein, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a" component includes aspects having two or more such components unless the context clearly dictates otherwise.

[0100] As used herein, "deposition temperature" refers to the temperature of the ink when it is ejected from the printhead.

[0101] As used herein, "optical density" refers to the degree to which a material reduces the power of light passing through the material per unit thickness as measured by a densitometer.

[0102] As used herein, "adhesion" refers to the adhesion of a material after being subjected to given conditions when tested according to ASTM 3359.

[0103] As used herein, "pencil hardness" is measured according to ASTM 3363.

[0104] As used herein, "viscosity" is measured according to ASTM D445 at a given temperature.

[0105] As used herein, the term "free of," 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.

[0106] The interior of an automobile may include a display that includes 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 areas of the cover glass to hide various components of the display (e.g., electrical and mechanical connections) and / or to provide a uniform appearance to the display when the display is powered off.

[0107] Certain existing inks used to decorate display cover glass may have various deficiencies that render these inks unsuitable for automotive interior applications. For example, some existing inks may be applied through a screen printing process, which may require multiple layers to provide the desired optical density. Such inks may have a relatively low yield in production. Other existing inks (e.g., UV curable inks) may not provide the desired optical density and / or may not provide adequate adhesion to the cover glass, either initially or after environmental testing related to various environmental conditions (e.g., temperature or humidity) to which automotive interior components are exposed. As the amount of pigment in the ink increases, it may be more difficult to achieve adequate adhesion.

[0108] Disclosed herein are ink compositions and ink primers that mitigate the above-mentioned problems. Specifically, the UV light-curable inks described herein can be used to form an opaque layer on a display cover glass through a high-throughput curing process. Once the light-curable ink is cured, the opaque layer can have relatively high glass adhesion and high optical density. With respect to adhesion, the ink primers described herein that include an adhesion promoter can be used to adequately adhere an ink composition comprising at least 11 wt % 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.

[0109] Ink composition

[0110] The ink composition described herein can be used to form an opaque layer having a desired post-curing 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 can have a relatively high glass adhesion (e.g., greater than or equal to 4B) and a high optical density (e.g., greater than 5). The terms "photocurable ink," "ink composition," and "photocurable ink composition" are used interchangeably throughout the text.

[0111] The ink composition described herein may be a UV curable ink composition.The ink composition may generally be described as comprising a pigment dispersion, a photoinitiator package, a reactive diluent, a multifunctional monomer, and optionally a difunctional monomer.

[0112] The pigment dispersion imparts the desired optical density to the resulting opaque layer. The ink composition may include a minimum amount of pigment dispersion (e.g., greater than or equal to 25 wt %) to ensure that the desired optical density (e.g., greater than 5) is achieved at the desired thickness after curing (e.g., less than 15 μm). The amount of pigment dispersion in the ink composition may be limited (e.g., less than or equal to 50 wt %) to ensure that the ink composition is curable. Therefore, in an embodiment, the ink composition may include greater than or equal to 25 wt % and less than or equal to 50 wt % of the pigment dispersion based on the total weight of the ink composition. In an embodiment, the amount of pigment dispersion in the ink composition may be greater than or equal to 25 wt %, greater than or equal to 30 wt %, or even greater than or equal to 35 wt %, based on the total weight of the ink composition. In an embodiment, the amount of pigment dispersion in the ink composition may be less than or equal to 50 wt %, less than or equal to 45 wt %, or even less than or equal to 40 wt %, based on the total weight of the ink composition. In embodiments, the amount of pigment dispersion in the ink composition can be greater than or equal to 25 wt % and less than or equal to 50 wt %, greater than or equal to 25 wt % and less than or equal to 45 wt %, greater than or equal to 25 wt % and less than or equal to 40 wt %, greater than or equal to 30 wt % and less than or equal to 50 wt %, greater than or equal to 30 wt % and less than or equal to 45 wt %, greater than or equal to 30 wt % and less than or equal to 40 wt %, greater than or equal to 35 wt % and less than or equal to 50 wt %, greater than or equal to 35 wt % and less than or equal to 45 wt %, or even greater than or equal to 35 wt % and less than or equal to 40 wt %, based on the total weight of the ink composition, or any and all subranges formed by any of these endpoints.

[0113] In an embodiment, the pigment dispersion comprises a pigment and a reactive monomer. In an embodiment, the pigment may include carbon black, iron oxide, carbon nanotubes, graphene, carbon fiber, titanium dioxide (black), or a combination of the above. In an embodiment, 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 of the above. The pigment dispersion may include a minimum amount of pigment (e.g., at least 30% by weight) to ensure that the desired optical density (e.g., greater than 5) is achieved at the desired thickness after curing (e.g., less than 15 μm). The amount of pigment in the pigment dispersion may be limited (e.g., less than or equal to 40% by weight) to maintain UV curability and flexibility in the composition space. Therefore, in an embodiment, based on the gross weight of the pigment dispersion, the amount of pigment in the pigment dispersion may be greater than or equal to 30% by weight, greater than or equal to 33% by weight, or even greater than or equal to 35% by weight. In an embodiment, the amount of pigment in the pigment dispersion may be less than or equal to 40 wt % or even less than or equal to 37 wt %, based on the total weight of the pigment dispersion. In an embodiment, the amount of pigment in the pigment dispersion may be greater than or equal to 30 wt % and less than or equal to 40 wt %, greater than or equal to 30 wt % and less than or equal to 37 wt %, greater than or equal to 33 wt % and less than or equal to 40 wt %, greater than or equal to 33 wt % and less than or equal to 37 wt %, greater than or equal to 35 wt % and less than or equal to 40 wt %, or even greater than or equal to 35 wt % and less than or equal to 37 wt %, based on the total weight of the pigment dispersion, or any and all subranges formed by any of these endpoints.

[0114] In embodiments, the ink composition may include at least 11 wt% of a pigment based on the total weight of the ink composition to facilitate an opaque layer formed therefrom having a relatively high optical density (e.g., greater than or equal to 5) at a relatively low thickness (e.g., less than or equal to 15 μm, after curing). In embodiments, the amount of pigment in the ink composition may be greater than or equal to 11 wt%, greater than or equal to 13 wt%, greater than or equal to 15 wt%, greater than or equal to 17 wt%, or even greater than or equal to 20 wt%, based on the total weight of the ink composition.

[0115] In embodiments, the remainder of the pigment dispersion comprises reactive monomers. Thus, in embodiments, the amount of reactive monomers in the pigment dispersion can be greater than or equal to 60 wt % and less than or equal to 70 wt %, greater than or equal to 60 wt % and less than or equal to 67 wt %, greater than or equal to 60 wt % and less than or equal to 65 wt %, greater than or equal to 63 wt % and less than or equal to 70 wt %, greater than or equal to 63 wt % and less than or equal to 67 wt %, or even greater than or equal to 63 wt % and less than or equal to 65 wt %, based on the total weight of the pigment dispersion, or any and all subranges formed by any of these endpoints.

[0116] In an embodiment, 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 a combination thereof.

[0117] The photoinitiator package of the ink composition promotes the curing of the ink composition, for example, by using a UV LED. The ink composition may include a minimum amount of the photoinitiator package (e.g., greater than 0 wt %) to ensure the curability of the ink composition. The amount of the photoinitiator package may be limited (e.g., less than or equal to 10 wt %) to maintain flexibility of the remaining components in the composition space while still providing favorable ultraviolet curing performance. Therefore, in an embodiment, the ink composition may include greater than 0 wt % and less than or equal to 10 wt % of the photoinitiator package based on the total weight of the ink composition. In an embodiment, the amount of the photoinitiator package in the ink composition may be greater than 0 wt %, greater than or equal to 1 wt %, greater than or equal to 2 wt %, greater than or equal to 3 wt %, or even greater than or equal to 4 wt %, based on the total weight of the ink composition. In an embodiment, the amount of the photoinitiator package in the ink composition may be less than or equal to 10 wt % or even less than or equal to 8 wt %, based on the total weight of the ink composition. In embodiments, the amount of the photoinitiator package in the ink composition can be greater than 0 wt % and less than 10 wt %, greater than 0 wt % and less than 8 wt %, greater than 1 wt % and less than 10 wt %, greater than 1 wt % and less than 8 wt %, greater than 2 wt % and less than 10 wt %, greater than 2 wt % and less than 8 wt %, greater than 3 wt % and less than 10 wt %, greater than 3 wt % and less than 8 wt %, greater than 4 wt % and less than 10 wt %, or even greater than 4 wt % and less than 8 wt %, based on the total weight of the ink composition, or any and all subranges formed by any of these endpoints.

[0118] The photoinitiator package of the ink composition may include a Type I photoinitiator, a Type II photoinitiator, and an amine synergist.

[0119] In an embodiment, the Type I photoinitiator 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 mixtures 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 a combination of the above.

[0120] In embodiments, the amount of Type I photoinitiator in the ink composition may be greater than, or equal to, 2 wt % and less than, or equal to, 8 wt %, greater than, or equal to, 2 wt % and less than, or equal to, 6 wt %, greater than, or equal to, 4 wt % and less than, or equal to, 8 wt %, or even greater than, or equal to, 4 wt % and less than, or equal to, 6 wt %, based on the total weight of the ink composition, or any and all subranges formed by any of these endpoints.

[0121] In an embodiment, the Type II photoinitiator may include isopropylthioxanthone, benzophenone, 4-phenylbenzophenone, methyl-2-benzoylbenzoate, ketosulfone, or a combination thereof.

[0122] In embodiments, the amount of Type II photoinitiator in the ink composition may be greater than or equal to 1 wt% and less than or equal to 4 wt%, greater than or equal to 1 wt% and less than or equal to 3 wt%, greater than or equal to 2 wt% and less than or equal to 4 wt%, or even greater than or equal to 2 wt% and less than or equal to 3 wt%, based on the total weight of the ink composition, or any and all subranges formed by any of these endpoints. In embodiments, the amount of Type I photoinitiator in the ink composition may be greater than the amount of Type II photoinitiator to facilitate photopolymerization.

[0123] In an embodiment, the amine synergist may include ethyl 4-(dimethylamino)benzoate; N,N-[2-(4-dimethylaminobenzoyl)oxyethylene-1-yl]methanamine; N-methyldiethanolamine; ethyl-4-dimethylaminobenzoate; 2-ethylhexyl-4-dimethylaminobenzoate; or a combination of the above.

[0124] In embodiments, the amount of amine synergist in the ink composition may be greater than or equal to 1 wt % and less than or equal to 4 wt %, greater than or equal to 1 wt % and less than or equal to 3 wt %, greater than or equal to 2 wt % and less than or equal to 4 wt %, or even greater than or equal to 2 wt % and less than or equal to 3 wt %, based on the total weight of the ink composition, or any and all subranges formed by any of these endpoints.

[0125] The reactive diluent in the ink composition imparts a relatively low viscosity (e.g., less than 5 cPs at 25° C.), thereby improving curing performance, while also helping to provide a low overall 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.

[0126] The ink composition may include a minimum amount of reactive diluent (e.g., greater than or equal to 10 wt %) to ensure that the ink composition will cure. Thus, in embodiments, the ink composition may include greater than or equal to 10 wt % and less than or equal to 42 wt % 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 greater than or equal to 10 wt %, greater than or equal to 15 wt %, greater than or equal to 20 wt %, or even greater than or equal to 25 wt %, based on the total weight of the ink composition. In embodiments, the amount of reactive diluent in the ink composition may be less than or equal to 42 wt %, less than or equal to 40 wt %, less than or equal to 35 wt %, less than or equal to 30 wt %, less than or equal to 25 wt %, or even less than or equal to 20 wt %, based on the total weight of the ink composition. In an embodiment, the amount of the reactive diluent in the ink composition may be greater than or equal to 10 wt % and less than or equal to 42 wt %, greater than or equal to 10 wt % and less than or equal to 40 wt %, greater than or equal to 10 wt % and less than or equal to 35 wt %, greater than or equal to 10 wt % and less than or equal to 30 wt %, greater than or equal to 10 wt % and less than or equal to 25 wt %, greater than or equal to 10 wt % and less than or equal to 20 wt %, greater than or equal to 15 wt % and less than or equal to 42 wt %, greater than or equal to 15 wt % and less than or equal to 40 wt %, greater than or equal to 15 wt % and less than or equal to 35 wt %, greater than or equal to 15 ...%. % and less than or equal to 42 wt %, greater than or equal to 20 wt % and less than or equal to 40 wt %, greater than or equal to 20 wt % and less than or equal to 35 wt %, greater than or equal to 20 wt % and less than or equal to 30 wt %, greater than or equal to 20 wt % and less than or equal to 25 wt %, greater than or equal to 25 wt % and less than or equal to 42 wt %, greater than or equal to 25 wt % and less than or equal to 40 wt %, greater than or equal to 25 wt % and less than or equal to 35 wt %, greater than or equal to 20 wt % and less than or equal to 30 wt %, greater than or equal to 20 wt % and less than or equal to 25 wt %, greater than or equal to 25 wt % and less than or equal to 42 wt %, greater than or equal to 25 wt % and less than or equal to 40 wt %, greater than or equal to 25 wt % and less than or equal to 35 wt %, or even greater than or equal to 25 wt % and less than or equal to 30 wt %, or any and all subranges formed by these endpoints.

[0127] The multifunctional monomers of the ink composition promote curing through high crosslinking, thereby improving the mechanical properties of the opaque layer. In embodiments, the multifunctional monomer may include dipentaerythritol hexaacrylate (e.g., M600DPHA). Other suitable amide and acrylate compositions for use as reactive diluents and multifunctional monomers may be found in U.S. Pat. No. 7,423,105 B2, entitled "Rapid Curing Primary Optical Fiber Coatings," which is incorporated herein by reference in its entirety.

[0128] Examples of multifunctional acrylate monomers that can 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, di(pentaerythritol) hexaacrylate, 3-methylpentanediol diacrylate, and acrylates of ethoxylated or propoxylated diols and polyols, such as propoxylated neopentyl glycol diacrylate, ethoxylated trimethylolpropane triacrylate, and mixtures thereof.

[0129] In addition, suitable multifunctional methacrylate monomers may also include esters of methacrylic acid (ie, methacrylates), such as hexanediol dimethacrylate, trimethylolpropane trimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, ethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, and mixtures thereof.

[0130] In an embodiment, 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.

[0131] The ink composition may include a minimum amount of multifunctional monomer (e.g., greater than or equal to 5 wt %) to ensure that the ink composition will solidify. The amount of multifunctional monomer may be limited (e.g., less than or equal to 20 wt %) to impart a relatively low viscosity, thereby maintaining jettability. Thus, in an embodiment, the ink composition may include greater than or equal to 5 wt % and less than or equal to 20 wt % of the multifunctional monomer, based on the total weight of the ink composition. In an embodiment, the amount of multifunctional monomer in the ink composition may be greater than or equal to 5 wt %, greater than or equal to 7 wt %, or even greater than or equal to 10 wt %, based on the total weight of the ink composition. In an embodiment, the amount of multifunctional monomer in the ink composition may be less than or equal to 20 wt %, less than or equal to 16 wt %, or even less than or equal to 12 wt %, based on the total weight of the ink composition. In embodiments, the amount of the multifunctional monomer in the ink composition may be greater than, or equal to, 5 wt% and less than, or equal to, 20 wt%, greater than, or equal to, 5 wt% and less than, or equal to, 16 wt%, greater than, or equal to, 5 wt% and less than, or equal to, 12 wt%, greater than, or equal to, 7 wt% and less than, or equal to, 20 wt%, greater than, or equal to, 7 wt% and less than, or equal to, 16 wt%, greater than, or equal to, 7 wt% and less than, or equal to, 12 wt%, greater than, or equal to, 10 wt% and less than, or equal to, 20 wt%, greater than, or equal to, 10 wt% and less than, or equal to, 16 wt%, or even greater than, or equal to, 10 wt% and less than, or equal to, 12 wt%, based on the total weight of the ink composition, or any and all subranges formed by any of these endpoints.

[0132] The ink composition may also include a bifunctional monomer to establish mechanical properties while maintaining low viscosity. In an embodiment, the bifunctional monomer may include a bifunctional acrylate and a methacrylate, such as 3-methyl-1,5-pentanediyl diacrylate, dipropylene glycol diacrylate, or a combination of the above. In an embodiment, the ink composition may include greater than or equal to 0 wt% and less than or equal to 35 wt% of the bifunctional monomer based on the total weight of the ink composition. In an embodiment, the ink composition may include greater than or equal to 10 wt% and less than or equal to 35 wt% of the bifunctional monomer based on the total weight of the ink composition. In an embodiment, the amount of the bifunctional monomer in the ink composition may be greater than or equal to 0 wt%, greater than or equal to 5 wt%, greater than or equal to 10 wt%, or even greater than or equal to 15 wt%, based on the total weight of the ink composition. In an embodiment, the amount of the bifunctional monomer in the ink composition may be less than or equal to 35 wt%, less than or equal to 25 wt%, or even less than or equal to 15 wt%, based on the total weight of the ink composition. In embodiments, the amount of the difunctional monomer in the ink composition may be greater than or equal to 0 wt % and less than or equal to 35 wt %, greater than or equal to 0 wt % and less than or equal to 25 wt %, greater than or equal to 0 wt % and less than or equal to 15 wt %, greater than or equal to 5 wt % and less than or equal to 35 wt %, greater than or equal to 5 wt % and less than or equal to 25 wt %, greater than or equal to 5 wt % and less than or equal to 15 wt %, greater than or equal to 10 wt % and less than or equal to 35 wt %, greater than or equal to 10 wt % and less than or equal to 25 wt %, greater than or equal to 10 wt % and less than or equal to 15 wt %, greater than or equal to 15 wt % and less than or equal to 35 wt %, or even greater than or equal to 15 wt % and less than or equal to 25 wt %, based on the total weight of the ink composition, or any and all subranges formed by any of these endpoints.

[0133] The relative amounts of reactive diluent, multifunctional monomer, and difunctional monomer can be tailored according to the characteristics of the reactive monomers in the pigment dispersion. That is, the amount of difunctional monomer relative to the reactive diluent and the specific difunctional monomer used can be based on the viscosity and reactivity of the reactive monomers in the pigment dispersion, as exemplified in the Examples section below.

[0134] In an embodiment, the combined amount of the reactive diluent, the multifunctional monomer, and the difunctional monomer may be less than or equal to 60 wt % to achieve a relatively low viscosity (e.g., less than 5 cPs at 25° C.) while providing sufficient composition space for other components to promote UV curability and achieve a desired optical density (e.g., greater than 5). In an embodiment, the combined amount of the reactive diluent, the multifunctional monomer, and the difunctional monomer may be less than or equal to 60 wt %, less than or equal to 50 wt %, less than or equal to 40 wt %, or even less than or equal to 30 wt %.

[0135] The ink composition may also include an adhesion promoter to promote the bonding of the ink to the glass without the use of a primer. Suitable adhesion promoters may include 3-(methacryloxy)propyltrimethoxysilane, 3-(acryloxy)propyltrimethoxysilane, (3-mercaptopropyl)trimethoxysilane, allyltrimethylsilane, and any other acrylated silane. Other suitable adhesion promoters may be found in U.S. Patent Application Serial No. 15 / 337,459, filed on October 28, 2016, which is incorporated herein by reference in its entirety. In an embodiment, the ink composition further includes greater than 0 wt % and less than or equal to 10 wt % of an adhesion promoter.

[0136] In embodiments, the ink compositions described herein are free of resin, which helps maintain a low viscosity suitable for inkjet printing, and free of TPO, which complies with REACH requirements.

[0137] The ink compositions described herein may also meet various environmental compliance standards. For example, in an embodiment, the ink compositions described herein may contain less than 10% by weight of volatile organic compounds, thereby meeting GB 35807-2020 entitled "Limits of Volatile Organic Compounds (VOC) in Printing Inks", which is incorporated herein by reference in its entirety. In addition, the ink compositions described herein may be free of halogenated hydrocarbons and free of solvents identified by the CAS registration number in Table 1.

[0138] Table 1

[0139] Components CAS 1 Ethylbenzene 100-41-4 2 Propylene oxide (ethylene oxide, methyl-) 75-56-9 3 Styrene (Benzene, Vinyl-) 100-42-5 4 benzene 71-43-2 5 Isopropyl nitrite 541-42-4 6 Butyl nitrite 544-16-1 7 Ethylene glycol monoethyl ether (2-ethoxyethanol) 110-80-5 8 Glycol ether acetate 111-15-9 9 Ethylene glycol monomethyl ether (2-methoxyethanol) 109-86-4 10 Ethylene glycol formaldehyde acetate (2-methoxyethyl acetate) 110-49-6 11 2-Nitropropane 79-46-9 12 N-Methyl-2-pyrrolidone 872-50-4 13 Triethylene glycol dimethyl ether 112-49-2 14 Ethylene glycol dimethyl ether 110-71-4 15 Ethylene glycol diethyl ether 629-14-1 16 Toluene 108-88-3 17 Xylene 1330-20-7

[0140] Such solvents are known to have potentially harmful effects on the environment and / or human health. Certain existing ink compositions incorporate the solvents listed in Table 1 to provide UV-curable inks with relatively high optical density that are compatible with inkjet printing. The ink compositions described herein provide such advantageous properties without such harmful solvents. The ink compositions of the present disclosure provide uncured viscosities suitable for inkjet printing without the addition of harmful solvents, and thus facilitate relatively high throughput (e.g., greater than 20 m / s) using commercially available print heads.2 / hour, more than 30m 2 / hour, less than 40m 2 / hour, more than 50m 2 Unlike some other inks based on ceramic frits that require relatively high curing temperatures, the inkjet printing process is advantageously compatible with chemically strengthened cover glasses.

[0141] In embodiments, the ink composition may have a viscosity greater than or equal to 1 cPs and less than or equal to 100 cPs in a temperature range of 30° C. to 50° C. In embodiments, the ink composition described herein may be compatible with commercially available inkjet printing processes (e.g., having an uncured viscosity of less than 25 cPs at a temperature less than or equal to 60° C. or from 30° C. to 50° C.) to facilitate a relatively low-cost, high-throughput production process. In embodiments, the ink composition may exhibit a viscosity greater than or equal to 8 cPs and less than or equal to 13 cPs in a temperature range of 30° C. to 50° C.

[0142] Ink Primer

[0143] As discussed herein, as the amount of pigment in the ink composition increases, it may be more difficult to achieve adequate adhesion of the ink composition to the glass substrate. The ink primers described herein include an adhesion promoter to adequately adhere the ink composition including at least 11% by weight of the pigment to the 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. Although the ink primers described herein may be discussed with respect to the ink compositions described herein, those skilled in the art will appreciate that other suitable ink compositions may be used in combination with the disclosed ink primers.

[0144] In embodiments, the ink primers described herein may be resin-free, which helps maintain a low viscosity suitable for inkjet printing, and TPO-free, which complies with REACH requirements.

[0145] In embodiments, the ink primer may have a viscosity greater than or equal to 1 cPs and less than or equal to 100 cPs in a temperature range of 30° C. to 50° C. In embodiments, the ink primer described herein may be compatible with commercially available inkjet printing processes (e.g., having an uncured viscosity of less than 25 cPs at a temperature less than or equal to 60° C. or from 30° C. to 50° C.) to facilitate a relatively low-cost, high-throughput production process. In embodiments, the ink composition may exhibit a viscosity greater than or equal to 8 cPs and less than or equal to 13 cPs in a temperature range of 30° C. to 50° C.

[0146] Infrared curable ink primer

[0147] In some embodiments, the ink primer can be generally described as comprising an adhesion promoter and a solvent, such as an infrared curable ink primer. The adhesion promoter can be configured to bind to the glass and the solvent can be configured to promote the adhesion promoter to bind to the glass. For example, in order to fully bind, the hydrolysis and condensation of the silane molecules of the adhesion promoter should occur on the glass, so that the silane molecules form a covalently bound layer with the surface. The polymerization of the silane before 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.

[0148] The adhesion promoter may include an organofunctional silane. Suitable adhesion promoters may be found in U.S. Patent Application Serial No. 15 / 337,459, filed on October 28, 2016. For example, in an embodiment, the adhesion promoter is a silane having the general formula R n SiX 4-n An organofunctional silane compound wherein R is a non-hydrolyzable organic group having a functional group that enables the adhesion promoter to physically or chemically interact with organic resins and polymers, X is a hydrolyzable group such as an alkoxy group, an acyloxy group, an amine or a halogen (such as chlorine), and n is an integer from 0 to 4 or from 1 to 3.

[0149] Representative organofunctional silane adhesion promoters include, but are not limited to, alkyltrialkoxysilanes, methyltriethoxysilane, methyltrimethoxysilane, octyltrimethoxysilane, octadecyltrimethoxysilane, polyalkoxysiloxane compounds, aminoalkyltrialkoxysilanes, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, trimethoxysilane, 13-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, mercaptoalkyltrialkoxysilane, γ-mercaptopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, 3-azidopropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane and 1,4-bis(trimethoxysilylethyl)benzene.

[0150] The ink primer may have a minimum amount of adhesion promoter (e.g., greater than or equal to 2 wt %) to ensure adequate adhesion. Thus, in an embodiment, the ink primer may contain greater than or equal to 2 wt % and less than or equal to 10 wt % of adhesion promoter based on the total weight of the ink primer. In an embodiment, the amount of adhesion promoter in the ink primer may be greater than or equal to 2 wt %, greater than or equal to 4 wt %, or even greater than or equal to 6 wt %, based on the total weight of the ink primer. In an embodiment, the amount of adhesion promoter in the ink primer may be less than or equal to 10 wt % or even less than or equal to 8 wt %, based on the total weight of the ink primer. In embodiments, the amount of adhesion promoter in the ink primer may be greater than or equal to 2 wt % and less than or equal to 10 wt %, greater than or equal to 2 wt % and less than or equal to 8 wt %, greater than or equal to 4 wt % and less than or equal to 10 wt %, greater than or equal to 4 wt % and less than or equal to 8 wt %, greater than or equal to 6 wt % and less than or equal to 10 wt %, or even greater than or equal to 6 wt % and less than or equal to 8 wt %, based on the total weight of the ink primer, or any and all subranges formed by any of these endpoints.

[0151] In an embodiment, 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 a combination of the above.

[0152] In an embodiment, the ink primer may contain greater than or equal to 90 wt % and less than or equal to 98 wt % of solvent, based on the total weight of the ink primer. In an embodiment, the amount of solvent in the ink primer may be greater than or equal to 90 wt % or even greater than or equal to 92 wt % based on the total weight of the ink primer. In an embodiment, the amount of solvent in the ink primer may be less than or equal to 98 wt %, less than or equal to 96 wt %, or even less than or equal to 94 wt %, based on the total weight of the ink primer. In an embodiment, the amount of solvent in the ink primer may be greater than or equal to 90 wt % and less than or equal to 98 wt %, greater than or equal to 90 wt % and less than or equal to 96 wt %, greater than or equal to 90 wt % and less than or equal to 94 wt %, greater than or equal to 92 wt % and less than or equal to 98 wt %, greater than or equal to 92 wt % and less than or equal to 96 wt %, or even greater than or equal to 92 wt % and less than or equal to 94 wt %, or any and all subranges formed by any of these endpoints, based on the total weight of the ink primer.

[0153] UV Curable Ink Primer

[0154] In other embodiments, an ink primer may generally be described as comprising an adhesion promoter, a photoinitiator package, and a monofunctional monomer, such as a UV curable ink primer.

[0155] The type and / or amount of adhesion promoter in the UV curable ink primer can be the same or similar to the type and / or amount of adhesion promoter described above for the infrared curable ink primer. For example, in an embodiment, the ink primer can include greater than or equal to 2 wt % and less than or equal to 10 wt % of adhesion promoter based on the total weight of the ink primer. In an embodiment, the adhesion promoter can include an organofunctional silane.

[0156] The photoinitiator package of the ink primer promotes the curing of the ink primer, for example, by using a UV LED. The ink primer may include a minimum amount of the photoinitiator package (e.g., greater than 0 wt %) to ensure the curability of the ink primer. The amount of the photoinitiator package may be limited (e.g., less than or equal to 10 wt %) to maintain flexibility of the remaining components in the composition space while still providing favorable ultraviolet curing performance. Therefore, in an embodiment, the ink primer may include a photoinitiator package greater than 0 wt % and less than or equal to 10 wt % based on the total weight of the ink composition. In an embodiment, the amount of the photoinitiator package in the ink primer may be greater than 0 wt %, greater than or equal to 1 wt %, greater than or equal to 2 wt %, greater than or equal to 3 wt %, or even greater than or equal to 4 wt %, based on the total weight of the ink primer. In an embodiment, the amount of the photoinitiator package in the ink primer may be less than or equal to 10 wt % or even less than or equal to 8 wt %, 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 wt % and less than 10 wt %, greater than 0 wt % and less than 8 wt %, greater than 1 wt % and less than 10 wt %, greater than 1 wt % and less than 8 wt %, greater than 2 wt % and less than 10 wt %, greater than 2 wt % and less than 8 wt %, greater than 3 wt % and less than 10 wt %, greater than 3 wt % and less than 8 wt %, greater than 4 wt % and less than 10 wt %, or even greater than 4 wt % and less than 8 wt %, based on the total weight of the ink primer, or any and all subranges formed by any of these endpoints.

[0157] The photoinitiator package for the ink primer may include a Type I photoinitiator, a Type II photoinitiator, and an amine synergist.

[0158] In an embodiment, the Type I photoinitiator 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 mixtures 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 a combination of the above.

[0159] In embodiments, the amount of Type I photoinitiator in the ink primer may be greater than, or equal to, 2 wt % and less than, or equal to, 8 wt %, greater than, or equal to, 2 wt % and less than, or equal to, 6 wt %, greater than, or equal to, 4 wt % and less than, or equal to, 8 wt %, or even greater than, or equal to, 4 wt % and less than, or equal to, 6 wt %, based on the total weight of the ink primer, or any and all subranges formed by any of these endpoints.

[0160] In an embodiment, the Type II photoinitiator may include isopropylthioxanthone, benzophenone, 4-phenylbenzophenone, methyl-2-benzoylbenzoate, ketosulfone, or a combination thereof.

[0161] In embodiments, the amount of Type II photoinitiator in the ink primer may be greater than or equal to 1 wt% and less than or equal to 4 wt%, greater than or equal to 1 wt% and less than or equal to 3 wt%, greater than or equal to 2 wt% and less than or equal to 4 wt%, or even greater than or equal to 2 wt% and less than or equal to 3 wt%, or any and all subranges formed by any of these endpoints, based on the total weight of the ink primer. In embodiments, the amount of Type I photoinitiator in the ink primer is greater than the amount of Type II photoinitiator to facilitate photopolymerization.

[0162] In an embodiment, the amine synergist may include ethyl 4-(dimethylamino)benzoate; N,N-[2-(4-dimethylaminobenzoyl)oxyethylene-1-yl]methanamine; N-methyldiethanolamine; ethyl-4-dimethylaminobenzoate; 2-ethylhexyl-4-dimethylaminobenzoate; or a combination of the above.

[0163] In embodiments, the amount of amine synergist in the ink primer may be greater than or equal to 1 wt % and less than or equal to 4 wt %, greater than or equal to 1 wt % and less than or equal to 3 wt %, greater than or equal to 2 wt % and less than or equal to 4 wt %, or even greater than or equal to 2 wt % and less than or equal to 3 wt %, based on the total weight of the ink primer, or any and all subranges formed by any of these endpoints.

[0164] The monofunctional monomers of the ink primer reduce viscosity and reduce crosslinking, allowing the acrylates of the ink primer to copolymerize with the subsequent ink layer. This is different from the ink compositions described herein, which may include multifunctional monomers to promote curing through high crosslinking, thereby improving the mechanical properties of the resulting opaque layer.

[0165] In an embodiment, the monofunctional monomer may include isobornyl acrylate. Other suitable monofunctional monomers may be found in U.S. Patent Application Serial No. 15 / 337,459, filed on October 28, 2016. For example, exemplary monofunctional monomers include, but are not limited to, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 2-hydroxybutyl acrylate; long and short chain alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, amyl acrylate, isobutyl acrylate, tert-butyl acrylate, amyl 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 FA10 available from CPS Chemical Co.), undecyl acrylate, dodecyl acrylate, tridecyl acrylate (e.g., SR489 available from Sartomer Company, Inc.), lauryl acrylate (e.g., SR490 available from Sartomer Company, Inc.), Company, Inc., SR335, Ageflex FA12, available from CPS Chemical Co. (Old Bridge, NJ), and 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; alkoxyalkyl acrylates, such as butoxyethyl acrylate, phenoxyethyl acrylate (e.g., SR339, available from Sartomer Company, Inc., Ageflex PEA, available from CPS Chemical Co., and Photomer 4035, available from IGM Resins), phenoxyglycidyl acrylate (e.g., CN131, available from Sartomer Company, Inc.), lauryl glycidyl acrylate (e.g., CN130, available from Sartomer Company, Inc.), and ethoxyethoxyethyl acrylate (e.g., available from Sartomer Company, Inc.); Company, Inc.SR256 available from Sartomer Company, Inc.); monocyclic and polycyclic aromatic or non-aromatic acrylates, such as cyclohexyl acrylate, benzyl acrylate, dicyclopentadiene acrylate, dicyclopentyl acrylate, tricyclodecyl 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., SR285 available from Sartomer Company, Inc.), caprolactone acrylate (e.g., SR495 available from Sartomer Company, Inc.; and Tone acrylate available from Union Carbide Company, Danbury, Conn. M100), and acryloyl morpholine; alcohol acrylates, such as polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, methoxyethylene glycol acrylate, methoxypolypropylene glycol acrylate, methoxypolyethylene glycol acrylate, ethoxydiethylene glycol acrylate, and various alkoxylated alkylphenol acrylates, such as ethoxylated (4) nonylphenol acrylate (e.g., Photomer 4003 available from IGM Resins; and SR504 available from Sartomer Company, Inc.) and propoxylated nonylphenol acrylate (e.g., Photomer 4960 available from IGM Resins); acrylamides, such as diacetone acrylamide, isobutoxymethyl acrylamide, N,N'-dimethylaminopropyl acrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, and tert-octyl acrylamide; vinyl compounds, such as N-vinyl pyrrolidone and N-vinyl caprolactam (both available from Ashland Inc., Covington, Ky.); and acid esters, such as maleates and fumarates.

[0166] The ink primer may include a minimum amount of monofunctional monomers (e.g., greater than or equal to 30 wt %) to achieve relatively low viscosity and tack. The amount of monofunctional monomers may be limited (e.g., less than or equal to 45 wt %) so that the ink primer and the resulting opaque layer are not too soft and have desired mechanical properties. Therefore, in an embodiment, the ink primer may include greater than or equal to 30 wt % and less than or equal to 45 wt % of monofunctional monomers based on the total weight of the ink primer. In an embodiment, the amount of monofunctional monomers in the ink primer may be greater than or equal to 30 wt % or even greater than or equal to 35 wt % based on the total weight of the ink primer. In an embodiment, the amount of monofunctional monomers in the ink primer may be less than or equal to 45 wt % or even less than or equal to 40 wt % based on the total weight of the ink primer. In embodiments, the amount of monofunctional monomer in the ink primer may be greater than, or equal to, 30 wt % and less than, or equal to, 30 wt % and less than, or equal to, 35 wt % and less than, or equal to, 45 wt %, or even greater than, or equal to, 35 wt % and less than, or equal to, 40 wt %, based on the total weight of the ink primer, or any and all subranges formed by any of these endpoints.

[0167] The ink primer may also include a reactive diluent to impart a relatively low viscosity (e.g., less than 5 cPs at 25°C) to improve curing performance while also helping to provide a low overall 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.

[0168] The ink primer may include a minimum amount of reactive diluent (e.g., greater than 0 wt %) to ensure that the ink composition will cure. Thus, in an embodiment, the ink primer may include greater than 0 wt % and less than or equal to 30 wt % reactive diluent based on the total weight of the ink primer. In an embodiment, the amount of reactive diluent in the ink primer may be greater than or equal to 0 wt %, greater than or equal to 5 wt %, greater than or equal to 10 wt %, or even greater than or equal to 15 wt %, based on the total weight of the ink primer. In an embodiment, the amount of reactive diluent in the ink primer may be less than or equal to 30 wt % or even less than or equal to 25 wt %, based on the total weight of the ink primer. In embodiments, the amount of reactive diluent in the ink primer may be greater than or equal to 0 wt % and less than or equal to 30 wt %, greater than or equal to 0 wt % and less than or equal to 25 wt %, greater than or equal to 5 wt % and less than or equal to 30 wt %, greater than or equal to 5 wt % and less than or equal to 25 wt %, greater than or equal to 10 wt % and less than or equal to 30 wt %, greater than or equal to 10 wt % and less than or equal to 25 wt %, greater than or equal to 15 wt % and less than or equal to 30 wt %, or even greater than or equal to 15 wt % and less than or equal to 25 wt %, based on the total weight of the ink primer, or any and all subranges formed by any of these endpoints.

[0169] The ink primer may also include a difunctional monomer to establish mechanical properties while maintaining low viscosity. In an embodiment, the difunctional monomer may include a difunctional acrylate and a methacrylate, such as 3-methyl-1,5-pentanediyl diacrylate, dipropylene glycol diacrylate, or a combination of the above. In an embodiment, the ink primer may include greater than or equal to 0 wt % and less than or equal to 35 wt % of the difunctional monomer based on the total weight of the ink primer. In an embodiment, the amount of the difunctional monomer in the ink primer may be greater than or equal to 0 wt %, greater than or equal to 5 wt %, greater than or equal to 10 wt %, or even greater than or equal to 15 wt %, based on the total weight of the ink primer. In an embodiment, the amount of the difunctional monomer in the ink primer may be less than or equal to 35 wt %, less than or equal to 25 wt %, or even less than or equal to 15 wt %, based on the total weight of the ink primer. In embodiments, the amount of difunctional monomer in the ink primer may be greater than or equal to 0 wt % and less than or equal to 35 wt %, greater than or equal to 0 wt % and less than or equal to 25 wt %, greater than or equal to 0 wt % and less than or equal to 15 wt %, greater than or equal to 5 wt % and less than or equal to 35 wt %, greater than or equal to 5 wt % and less than or equal to 25 wt %, greater than or equal to 5 wt % and less than or equal to 15 wt %, greater than or equal to 10 wt % and less than or equal to 35 wt %, greater than or equal to 10 wt % and less than or equal to 25 wt %, greater than or equal to 10 wt % and less than or equal to 15 wt %, greater than or equal to 15 wt % and less than or equal to 35 wt %, or even greater than or equal to 15 wt % and less than or equal to 25 wt %, based on the total weight of the ink primer, or any and all subranges formed by any of these endpoints.

[0170] The ink primer may also include a solvent. The type of solvent in the UV curable ink primer may be the same or similar to the type of solvent described above for the infrared ink primer. For example, in an embodiment, 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 a combination of the above.

[0171] In an embodiment, the ink primer may include greater than or equal to 5 wt % and less than or equal to 10 wt % of a solvent based on the total weight of the ink primer.

[0172] Glass products

[0173] Reference now Figure 1, showing a vehicle interior 2000 including three different vehicle interior systems 100, 200, 300. The vehicle interior system 100 includes a center console base 110 having a curved surface 120, the curved surface including a display 230. The vehicle interior system 200 includes a dashboard base 210 having a curved surface 220, the curved surface including a display 230. The dashboard base 210 generally includes an instrument panel 215, which may also include a curved display. The vehicle interior system 300 includes an instrument panel steering wheel base 310 having a curved surface 320 and a display 330. In an embodiment, the vehicle interior system may include a base that is an armrest, pillar, seat back, floor, headrest, door panel, or any part of the vehicle interior 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 an embodiment, one or more of the displays 130, 230, 330 are curved, and the curved display may include a curved cover glass that can be hot-formed or cold-formed to have such a curvature. For example, such an embodiment may incorporate an opaque layer formed from the photocurable ink composition described herein disposed on a cold-formed glass substrate. Such cold forming may involve any of the techniques described in U.S. Pre-Grant Publication No. 2019 / 0329531A1, entitled "Laminating Thin Strengthened Glass to Curved Molded Plastic Surfaces for Decorative and Display Cover Applications," U.S. Pre-Grant Publication No. 2019 / 0315648A1, entitled "Cold-Formed Glass Articles and Assembly Processes Thereof," U.S. Pre-Grant Publication No. 2019 / 0012033A1, entitled "Vehicle Interior System with Curved Cover Glass and Display or Touch Panel and Method of Forming the Same," and U.S. Patent Application No. 17 / 214,124, entitled "Curved Glass Structure and Method of Forming the Same," which are incorporated herein by reference in their entirety.

[0174] Embodiments of the glass articles described herein may be used in any or all of the vehicle interior systems 100, 200, and 300. Figure 1 An automotive interior is shown, but various embodiments of the vehicle interior system may be incorporated into any type of vehicle, such as trains, automobiles (e.g., cars, trucks, buses, etc.), marine vessels (ships, ships, submarines, etc.), and aircraft (e.g., drones, airplanes, jets, helicopters, etc.), including manned vehicles, semi-autonomous vehicles, and fully autonomous vehicles. In addition, while the description herein is primarily directed to the use of glass articles in vehicle displays, it should be understood that the various embodiments discussed herein may be used in any type of display application.

[0175] Figure 2 Schematically depicts an example embodiment in which the display 230 is flat. Figure 1A cross-sectional view of the display 230 is shown along line 2-2. Figure 2 An example of a display 230 is depicted, but it should be understood that references herein to Figure 1 The displays 130, 330 described herein may have similar cross-sectional structures and incorporate the light-curable inks described herein in a similar manner. Figure 2 In the illustrated embodiment, the display 230 is flat, but embodiments are also contemplated in which the display 230 is curved and the glass article 400 includes one or more curved surfaces (eg, due to cold forming or hot forming to have a suitable curved shape).

[0176] like Figure 2 As shown, the glass article 400 includes at least a substrate 450 and an opaque layer 500, and optionally includes 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 "disposed" includes coating, depositing and / or forming a material onto a surface using any known method in the art. The disposed material may constitute a layer as defined herein. As used herein, the phrase "disposed on..." includes the case where a material is formed on a surface so that the material is in direct contact with the surface, and also includes the case where the material is formed on a surface, wherein one or more intermediate materials are located between the disposed material and the surface. The intermediate material may constitute a layer as defined herein. The term "layer" may include a single layer or may include one or more sublayers. These sublayers may be in direct contact with each other. The sublayers may be formed of the same material or two or more different materials. In one or more alternative embodiments, an intermediate layer of different materials may be disposed between such sublayers. In one or more embodiments, the layer may include one or more continuous and uninterrupted layers and / or one or more discontinuous and discontinuous layers (i.e., layers of different materials formed adjacent to each other). The layer or sublayer may be formed by any method known in the art, including discrete deposition or continuous deposition processes. In one or more embodiments, the layer may be formed using only a continuous deposition process or, alternatively, only a discrete deposition process.

[0177] In an embodiment, the substrate 450 is a glass substrate, which is optionally chemically strengthened and has 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, etc., or may be a glass material (which may be optionally strengthened).

[0178] The various glass substrates of the glass articles discussed herein (e.g., substrate 450) may be formed from any suitable glass composition, including soda-lime glass, aluminosilicate glass, borosilicate glass, boroaluminosilicate glass, alkali-containing aluminosilicate glass, alkali-containing borosilicate glass, and alkali-containing boroaluminosilicate glass.

[0179] Unless otherwise indicated, the glass compositions disclosed herein are described in terms of mole percent (mol %) analyzed on an oxide basis.

[0180] In one or more embodiments, the glass composition may include SiO2 in an amount of 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.

[0181] 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 of greater than about 7 mol% to about 15 mol%, greater than about 7 mol% to about 14 mol%, about 7 mol% to about 13 mol%, about 4 mol% to about 12 mol%, about 7 mol% to about 11 mol%, about 8 mol% to about 15 mol%, 9 mol% to about 15 mol%, about 9 mol% to about 15 mol%, about 10 mol% to about 15 mol%, about 11 mol% to about 15 mol%, or about 12 mol% to about 15 mol% and all ranges and sub-ranges therebetween. In one or more embodiments, the upper limit of Al2O3 can be about 14 mol%, 14.2 mol%, 14.4 mol%, 14.6 mol%, or 14.8 mol%.

[0182] In one or more embodiments, the glass layer herein is described as an aluminosilicate glass article or comprises an aluminosilicate glass composition. In such embodiments, the glass composition or an article formed therefrom comprises SiO2 and Al2O3 and is not a soda-lime silicate glass. In this regard, the glass composition or an article formed therefrom comprises 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, about 3 mol% or more.

[0183] 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 of about 0 mol% to about 5 mol%, about 0 mol% to about 4 mol%, about 0 mol% to about 3 mol%, about 0 mol% to about 2 mol%, about 0 mol% to about 1 mol%, about 0 mol% to about 0.5 mol%, about 0.1 mol% to about 5 mol%, about 0.1 mol% to about 4 mol%, about 0.1 mol% to about 3 mol%, about 0.1 mol% to about 2 mol%, about 0.1 mol% to about 1 mol%, 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.

[0184] 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 compounding, but may be present as an impurity in an amount less than about 0.001 mol%.

[0185] 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 a non-zero amount of P2O5, including up to 2 mol%, 1.5 mol%, 1 mol%, or 0.5 mol%. In one or more embodiments, the glass composition is substantially free of P2O5.

[0186] In one or more embodiments, the glass composition may include a total amount of RO (which is the total amount of alkali metal oxides such as Li2O, Na2O, K2O, Rb2O, and Cs2O) greater than or equal to about 8 mol%, greater than or equal to about 10 mol%, or greater than or equal to about 12 mol%. In some embodiments, the glass composition includes RO in a total 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 about 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 Rb2O and Cs2O. In one or more embodiments, R2O may include only the total amount of Li2O, Na2O, and KO. In one or more embodiments, the glass composition may include at least one alkali metal oxide selected from Li2O, Na2O, and KO, wherein the alkali metal oxide is present in an amount greater than about 8 mol% or more.

[0187] In one or more embodiments, the glass composition includes Na2O in an amount greater than or equal to about 8 mol%, greater than or equal to about 10 mol%, or greater than or equal to about 12 mol%. In one or more embodiments, the composition includes Na2O in a 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 about 11 mol% to about 16 mol% and all ranges and sub-ranges therebetween.

[0188] In one or more embodiments, the glass composition includes less than about 4 mol % K2 O, less than about 3 mol % K2 O, or less than about 1 mol % K2 O. In some cases, the glass composition may include K2 O in an amount of about 0 mol % to about 4 mol %, about 0 mol % to about 3.5 mol %, about 0 mol % to about 3 mol %, about 0 mol % to about 2.5 mol %, about 0 mol % to about 2 mol %, about 0 mol % to about 1.5 mol %, about 0 mol % to about 1 mol %, about 0 mol % to about 0.5 mol %, about 0 mol % to about 0.2 mol %, about 0 mol % to about 0.1 mol %, about 0.5 mol % to about 4 mol %, about 0.5 mol % to about 3.5 mol %, about 0.5 mol % to about 3 mol %, about 0.5 mol % to about 2.5 mol %, about 0.5 mol % to about 2 mol %, about 0.5 mol % to about 1.5 mol %, or about 0.5 mol % to about 1 mol % and all ranges and subranges therebetween. In one or more embodiments, the glass composition may be substantially free of K2O.

[0189] In one or more embodiments, the glass composition is substantially free of Li2O.

[0190] 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.

[0191] In one or more embodiments, the glass composition may include a total amount of RO (which is the total amount of alkaline earth metal oxides such as CaO, MgO, BaO, ZnO, and SrO) in the range of about 0 mol% to about 2 mol%. In some embodiments, the glass composition includes a non-zero amount of RO up to about 2 mol%. In one or more embodiments, the glass composition includes RO in an amount of about 0 mol% to about 1.8 mol%, about 0 mol% to about 1.6 mol%, about 0 mol% to about 1.5 mol%, about 0 mol% to about 1.4 mol%, about 0 mol% to about 1.2 mol%, about 0 mol% to about 1 mol%, about 0 mol% to about 0.8 mol%, about 0 mol% to about 0.5 mol%, and all ranges and sub-ranges therebetween.

[0192] 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 of about 0 mol% to about 7 mol%, about 0 mol% to about 6 mol%, about 0 mol% to about 5 mol%, about 0 mol% to about 4 mol%, about 0.1 mol% to about 7 mol%, about 0.1 mol% to about 6 mol%, about 0.1 mol% to about 5 mol%, about 0.1 mol% to about 4 mol%, about 1 mol% to about 7 mol%, about 2 mol% to about 6 mol%, or about 3 mol% to about 6 mol% and all ranges and sub-ranges therebetween.

[0193] In one or more embodiments, the glass composition includes ZrO2 in an amount equal to or less than about 0.2 mol%, less than about 0.18 mol%, less than about 0.16 mol%, less than about 0.15 mol%, less than about 0.14 mol%, less than about 0.12 mol%. In one or more embodiments, the glass composition includes ZrO2 in a range 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.

[0194] In one or more embodiments, the glass composition includes SnO2 in an amount equal to or less than about 0.2 mol%, less than about 0.18 mol%, less than about 0.16 mol%, less than about 0.15 mol%, less than about 0.14 mol%, less than about 0.12 mol%. In one or more embodiments, the glass composition includes SnO2 in a range 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.

[0195] In one or more embodiments, the glass composition may include an oxide that imparts color or hue to the glass article. In some embodiments, the glass composition includes an oxide that prevents the glass article from discoloring when the glass article is exposed to ultraviolet radiation. Examples of such oxides include, but are not limited to, the following oxides: Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Ce, W, and Mo.

[0196] In one or more embodiments, the glass composition comprises Fe expressed as Fe2O3, wherein Fe is present in an amount up to (and including) about 1 mol%. In some embodiments, the glass composition is substantially free of Fe. In one or more embodiments, the glass composition comprises Fe2O3 in an amount equal to or less than about 0.2 mol%, less than about 0.18 mol%, less than about 0.16 mol%, less than about 0.15 mol%, less than about 0.14 mol%, less than about 0.12 mol%. In one or more embodiments, the glass composition comprises Fe2O3 in a range 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.

[0197] 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.

[0198] The exemplary glass composition includes SiO2 in an amount of about 65 mol% to about 75 mol%, Al2O3 in an amount of about 8 mol% to about 14 mol%, Na2O in an amount of about 12 mol% to about 17 mol%, K2O in an amount of about 0 mol% to about 0.2 mol%, and MgO in an amount of about 1.5 mol% to about 6 mol%. Optionally, SnO2 can be included in an amount otherwise disclosed herein.

[0199] In one or more embodiments, the glass substrates herein may be formed from strengthened glass sheets or articles. In one or more embodiments, the glass substrates used to form the glass articles discussed herein may be strengthened to contain compressive stress extending from the surface to a depth of compression (DOC). The compressive stress region is balanced by a central portion exhibiting tensile stress. At the DOC, the stress transitions from positive (compressive) stress to negative (tensile) stress.

[0200] In one or more embodiments, the glass substrate used to form the glass articles discussed herein can be mechanically strengthened by exploiting the mismatch in thermal expansion coefficients between glass portions to produce regions of compressive stress and a central region exhibiting tensile stress. In some embodiments, the glass substrate can be thermally strengthened by heating the glass to a temperature above the glass transition point and then rapidly quenching.

[0201] In one or more embodiments, the glass substrate used to form the glass articles discussed herein can be chemically strengthened by ion exchange. During the ion exchange process, ions at or near the surface of the glass substrate are replaced or exchanged with larger ions of the same valence or oxidation state. In those embodiments where the glass substrate comprises an alkali aluminosilicate glass, the ions and larger ions in the surface layer of the article are monovalent alkali metal cations, such as Li+, Na+, K+, Rb+, and Cs+. Alternatively, the monovalent cations in the surface layer can be replaced with monovalent cations other than alkali metal cations, such as Ag+, etc. In such embodiments, the monovalent ions (or cations) exchanged into the glass substrate generate stress.

[0202] The ion exchange process is typically performed by immersing the glass substrate in a molten salt bath (or two or more molten salt baths) containing larger ions to exchange with smaller ions in the glass substrate. It should be noted that aqueous salt baths may also be used. In addition, the composition of the bath may contain more than one larger ion (e.g., Na+ and K+) or a single larger ion. Those skilled in the art will appreciate that the parameters of the ion exchange process include, but are not limited to, bath composition and temperature, immersion time, number of immersions of the glass substrate in the salt bath, use of multiple salt baths, additional steps such as annealing, washing, etc., and are typically determined by the composition of the glass substrate (including the structure of the article and any crystalline phases present) and the desired DOC and CS of the glass layer of the glass substrate obtained by strengthening.

[0203] 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 is typically in the range of about 380°C to about 450°C, and the immersion time is in the range of about 15 minutes to about 100 hours, depending on the glass thickness, bath temperature, and glass (or monovalent ion) diffusivity. However, temperatures and immersion times different from those described above may also be used.

[0204] In one or more embodiments, a glass substrate for forming a glass article may be immersed in a molten salt bath of 100% NaNO3, 100% KNO3, or a combination of NaNO3 and KNO3 at 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 containing about 5% to about 90% KNO3 and about 10% to about 95% NaNO3. In one or more embodiments, the glass substrate may be immersed in a second bath after being immersed in the first bath. The first bath and the second bath may have different compositions and / or temperatures from each other. The immersion times in the first bath and the second bath may vary. For example, the immersion in the first bath may be longer than the immersion in the second bath.

[0205] In one or more embodiments, the glass substrate may be immersed in a molten mixed salt bath containing NaNO3 and KNO3 (e.g., 49% / 51%, 50% / 50%, 51% / 49%) at a temperature below about 420°C (e.g., about 400°C or about 380°C) for less than about 5 hours, or even about 4 hours or less.

[0206] The ion exchange conditions can be tailored to provide a "spike" or increase the slope of the stress profile at or near the surface of the resulting glass layer of the glass substrate. The spike may result in a greater surface CS value. Due to the unique properties of the glass compositions used in the glass layers of the decorative glass structures described herein, the spike can be achieved by a single bath or multiple baths, where the baths have a single composition or a mixed composition.

[0207] In one or more embodiments, when more than one monovalent ion is exchanged into the glass substrate, different monovalent ions may be exchanged to different depths within the glass substrate (and produce different amounts of stress at different depths in the glass substrate). The final relative depths of the stress-producing ions may be determined and result in different characteristics of the stress distribution.

[0208] CS is measured using those means known in the art, such as by a surface stress meter (FSM) using a commercially available instrument, such as the FSM-6000 manufactured by Orihara Industrial Co., Ltd. (Japan). Surface stress measurements rely on accurate measurements of the stress optical coefficient (SOC), which is related to the birefringence of the glass. SOC is in turn measured by those methods known in the art, such as fiber and four-point bending methods, both of which are described in ASTM Standard C770-98 (2013) entitled "Standard Test Method for Measurement of Stress Optical Coefficient of Glass," the contents of which are incorporated herein by reference in their entirety, and the integral cylinder method. As used herein, CS may be "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 a depth below the surface, giving the compression profile a "buried peak" appearance.

[0209] DOC can be measured by FSM or scattered light polarimeter (SCALP) (such as SCALP-04 scattered light polarimeter provided by GlasStress Ltd. located in Tallinn, Estonia), depending on the strengthening method and conditions. When the glass substrate is chemically strengthened by ion exchange treatment, FSM or SCALP can be used, depending on which ions are exchanged into the glass substrate. When the stress in the glass substrate is generated by exchanging potassium ions into the glass substrate, FSM is used to measure DOC. When the stress is generated by exchanging sodium ions into the glass substrate, SCALP is used to measure DOC. When the stress in the glass substrate is generated by exchanging potassium ions and sodium ions into the glass, DOC is measured by SCALP because it is believed that the exchange depth of sodium indicates DOC, while the exchange depth of potassium ions indicates the change in the magnitude of compressive stress (but not the change in stress from compression to tension); the exchange depth of potassium ions in such glass substrates is measured by FSM. Central tension or CT is the maximum tensile stress and is measured by SCALP.

[0210] In one or more embodiments, the glass substrate may be strengthened to exhibit a DOC (as described herein) that describes a fraction of the thickness t of the glass article. For example, in one or more embodiments, the DOC may be equal to or greater than about 0.05t, equal to or greater than about 0.1t, equal to or greater than about 0.11t, equal to or greater than about 0.12t, equal to or greater than about 0.13t, equal to or greater than about 0.14t, equal to or greater than about 0.15t, equal to or greater than about 0.16t, equal to or greater than about 0.17t, equal to or greater than about 0.18t, equal to or greater than about 0.19t, equal to or greater than about 0.2t, equal to or greater than about 0.21t. In some embodiments, the DOC may be in the range of about 0.08t to about 0.25t, about 0.09t to about 0.25t, about 0.18t to about 0.25t, about 0.11t to about 0.25t, about 0.12t to about 0.25t, about 0.13t to about 0.25t, about 0.14t to about 0.25t, about 0.15t to about 0.25t, about 0.08t to about 0.24t, about 0.08t to about 0.23t, about 0.08t to about 0.22t, about 0.08t to about 0.21t, about 0.08t to about 0.2t, about 0.08t to about 0.19t, about 0.08t to about 0.18t, about 0.08t to about 0.17t, about 0.08t to about 0.16t, or about 0.08t to about 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 greater (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). 0 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.

[0211] In one or more embodiments, the CS of the glass substrate (which may be found at the surface or at depth of the glass article) may be about 200 MPa or greater, 300 MPa or greater, 400 MPa or greater, about 500 MPa or greater, about 600 MPa or greater, about 700 MPa or greater, about 800 MPa or greater, about 900 MPa or greater, about 930 MPa or greater, about 1000 MPa or greater, or about 1050 MPa or greater.

[0212] In one or more embodiments, the maximum tensile stress or central tension (CT) of the glass substrate may be about 20 MPa or more, 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.

[0213] In an embodiment, the glass article 400 includes a functional surface layer 490. The functional surface layer 490 may be configured to provide one or more of a variety of functions. For example, the functional surface layer 490 may be an optical coating configured to provide easy-to-clean performance, anti-glare performance, anti-reflection performance and / or a semi-mirror coating. Such an optical coating may be created using a single layer or multiple layers. In the case of an anti-reflection functional surface layer, multiple layers having alternating high and low refractive indices may be used to form such a layer. 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 on an anti-glare surface or a smooth substrate surface) is 5nm to 750nm. In addition, in an embodiment, the functional surface layer 490 providing easy-to-clean performance also provides enhanced feel and / or coating / processing for the touch screen to reduce fingerprints. In some embodiments, the functional surface layer 490 is integral with the first surface of the substrate. For example, such a functional surface layer may include an etched surface in the first surface of the substrate 450, providing an anti-glare surface (or a haze of, for example, 2% to 20%).

[0214] When the opaque layer 500 is included, it is printed onto the photomanagement layer 460. Certain existing UV curable inks have been shown to be incompatible with the photomanagement layer 460 (e.g., lacking the necessary adhesion). For example, when used for the opaque layer, existing photocurable inks may chemically react with the ink of the photomanagement layer 460 (either upon deposition or after environmental testing) to change the properties of the ink layer (e.g., color, size). Existing photocurable inks may also diffuse into the photomanagement layer 460 and degrade its performance. When used to form the opaque layer 500 and printed on the photomanagement layer 460, the photocurable ink composition described herein does not have such defects and still provides sufficient adhesion to the substrate 450 even in the presence of the photomanagement layer 460.

[0215] When the light management layer 460 is included, it can be printed on the substrate 450. In an embodiment, the light management layer 460 is formed of a suitable heat or ultraviolet curable ink. The light management layer 460 can generally reduce the light transmittance of the glass article 400 so that the glass article 400 presents a similar appearance to the user regardless of whether the display 540 is powered on or off. For example, the light management layer 460 may block the edge of the display area 520 so that the boundary of the display area 520 is not obvious to the viewer when the display is powered off. The light management layer 460 can generally be constructed as described in any of International Patent Application Publication Nos. WO 2019 / 055458 A1 entitled "Black Dead Front End for Display Devices and Methods", WO 2020 / 205519 A1 entitled "Decorative Glass with Printed Ink Layer", or WO 2021 / 118835 A1 entitled "Display Devices and Products with Color Matching Display and Non-Display Areas", each of which is incorporated herein by reference in its entirety.

[0216] Opaque layer

[0217] Still reference Figure 2In an embodiment, the opaque layer 500 may be composed of at least one of the photocurable ink composition and the ink primer described herein. For example, in some embodiments, the opaque layer 500 may include a photocurable ink containing at least 11% by weight of a pigment. In other embodiments, the opaque layer may include an ink composition containing at least 11% by weight of a pigment and an adhesion promoter. In such an embodiment, the adhesion promoter is bonded to the glass substrate and the ink composition is polymerized with the adhesion promoter. Therefore, the opaque layer 500 may include a relatively high optical density (e.g., greater than or equal to 5) to block light transmission. In an embodiment, the opaque layer 500 is used to block light from passing through certain areas of the glass article 400. In an embodiment, the opaque layer 500 shields functional or non-decorative elements provided for the operation of the glass article 400. In an embodiment, the opaque layer 500 is provided to outline backlit icons and / or other graphics (not depicted) to increase the contrast of the edges of these icons and / or graphics.

[0218] In an embodiment, if Figure 2 As shown, the glass article 400 is placed above or in front of the display 540. In one or more embodiments, the display 540 may include a display with touch functionality, which includes 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 greater than or equal to 10% (e.g., greater than or equal to 20%, greater than or equal to 30%, greater than or equal to 40%, greater than or equal to 50%, greater than or equal to 60%, greater than or equal to 70%). However, the high optical density of the opaque layer 500 causes the area of ​​the glass article 400 containing the opaque layer 500 to have a relatively low light transmittance (e.g., an average transmittance of less than or equal to 0.1% in the visible spectrum). Therefore, the boundary of the opaque layer 500 may define a display area 520, in which the glass article 400 exhibits a relatively high optical transmittance to facilitate visibility of an image generated by the display 540.

[0219] In the illustrated embodiment, the opaque layer 500 covers the edge 550 of the display 540, thereby hiding the edge 550 from being seen through the first surface 470. The opaque layer 500 can also be used to shield various other components (e.g., electrical connections, mechanical housings, etc.) from view. The opaque layer 500 generally facilitates viewing of the desired portion of the display 540 by a user viewing the first surface 470.

[0220] In an embodiment, the opaque layer 500 is applied to the light management layer 460 and / or the second surface 480 of the substrate 450 by inkjet printing. In an embodiment, the opaque layer 500 may be deposited directly onto the second surface 480 of the tether 450 using a suitable inkjet process. In an embodiment, prior to depositing the opaque layer 500, in embodiments where an ink primer as described herein is not used, the second surface 480 may be primed using a suitable primer (e.g., an acryloxysilane primer) to promote adhesion of the opaque layer 500 to the substrate 450. Any suitable treatment may be applied to the second surface 480 to promote adhesion of the opaque layer 500 to the substrate 450.

[0221] As described herein, the opaque layer 500 has relatively high adhesion to glass. In an embodiment, when tested according to ASTM 3359, the opaque layer 500 exhibits adhesion to the glass substrate of greater than or equal to 4B after being subjected to a temperature of 85°C and a relative humidity of 95% for at least 500 hours. In an embodiment, when tested according to ASTM 3359, the opaque layer 500 exhibits adhesion to the glass substrate of greater than or equal to 4B after 500 1-hour cycles of maintaining a temperature of -40°C for 0.5 hours and maintaining a temperature of 95°C for 0.5 hours.

[0222] The opaque layer 500 may have a desired thickness of less than or equal to 15 μm. In an embodiment, the opaque layer 500 may have a thickness of less than or equal to 15 μm or even less than or equal to 10 μm. In an embodiment, the opaque layer 500 may have a thickness of greater than or equal to 1 μm or even greater than or equal to 5 μm. In an embodiment, the opaque layer 500 may have a thickness of greater than or equal to 1 μm and less than or equal to 15 μm, greater than or equal to 1 μm and less than or equal to 10 μm, greater than or equal to 5 μm and less than or equal to 15 μm, or even greater than or equal to 5 μm and less than or equal to 10 μm, or any and all sub-ranges formed by any of these endpoints.

[0223] In embodiments, the photocurable ink composition and / or ink primer described herein can be customized to meet specific appearance requirements related to design needs. The opaque layer 500 can be any color; however, in a specific embodiment, the opaque layer 500 is black or gray. For example, a cover glass including an opaque layer composed of the photocurable ink composition and / or ink primer described herein can meet any black mask color target in Table 2.

[0224] Table 2

[0225]

[0226] 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 within the tolerance ranges listed in Table 3 below.

[0227] Table 3

[0228] OD ΔE within the part L*Tolerance a*Tolerance b*Tolerance ≥4 0.6 ±0.10 ±0.10 ±0.10

[0229] As shown in Tables 2 and 3, when viewed from the uncoated surface of the cover glass (e.g., from the side of the glass opposite to the side where the display is disposed), the glass article including the photocurable ink composition and / or ink primer described herein can generally have a CIELAB L* value of less than or equal to 30 (less than or equal to 29, less than or equal to 28, less than or equal to 27, less than or equal to 25, less than or equal to 25) when illuminated with a CIED65 light source at an incident angle of 10°, a CIELAB a* value (including specular component) greater than or equal to -0.05 and less than or equal to 0.15, and a CIELAB b* value (including specular component) less than or equal to -0.1 and greater than or equal to -0.3. When excluding the specular component, the glass article can exhibit a CIE L* value less than or equal to 1, and CIELAB a* and b* values ​​less than or equal to 0.1. Areas of the cover glass coated with the photocurable ink composition and / or ink primer described herein can exhibit a dark, neutral appearance to facilitate hiding various components from view.

[0230] The photocurable ink compositions and / or ink primers of the present disclosure can also be used to construct opaque layers on glass articles, which show good reliability test results compared to some existing photocurable inks and / or ink primers. Automotive interior components are subject to highly variable environmental conditions (e.g., in terms of temperature and relative humidity). In embodiments, when subjected to the reliability tests summarized in Table 4, the opaque layer may meet one or more of the following criteria.

[0231] Table 4

[0232]

[0233]

[0234]

[0235]

[0236] Certain existing UV-curable inkjet compatible inks can crack or otherwise fail when subjected to such test conditions, rendering these inks unsuitable for certain automotive interior applications. For example, certain existing inks have been found to shrink and / or crack when subjected to Test B contained in Table 4 above, while the opaque layer formed from the photocurable ink composition and / or ink primer described herein meets the test criteria contained in Table 4.

[0237] In an embodiment, the glass article exhibits a maximum ΔE value (SCI and SCE) of less than 2.0 measured before and after 500 cycles of 0.5 hours at -40°C and 0.5 hours at 95°C for 1 hour.

[0238] In addition to meeting the above-mentioned reliability testing requirements, the photocurable ink composition and / or ink primer described herein may also meet other requirements to make it suitable for use with certain commercially available inkjet printers. For example, the pigment may include an average particle size of less than or equal to 200nm, less than or equal to 150nm, less than or equal to 100nm, or even less than or equal to 50nm to achieve the desired L*. In an embodiment, the photocurable ink and / or ink primer may include a liquid surface tension greater than or equal to 25 dynes / cm and less than or equal to 35 dynes / cm. In an embodiment, the opaque layer may exhibit a cured surface tension greater than 36 dynes / cm. In an embodiment, the opaque layer may exhibit a cured surface tension greater than or equal to 1x10 when measured at 100V DC in accordance with ASTM D-257. 9 Resistivity of Ω / sq.

[0239] The opaque layer described herein may also exhibit a pencil hardness of greater than or equal to 3H when measured according to ASTM 3363 (entitled "Standard Test Method for Film Hardness by Pencil Test," which is incorporated herein by reference in its entirety) after being cured using a narrow-band UV LED light source that emits narrow-band (e.g., less than or equal to 20 nm bandwidth, less than or equal to 30 nm bandwidth) curing light. Using such UV LEDs saves space, cost, and is less harmful to the environment than certain existing UV curing lamps. When meeting the optical density requirements described herein, certain existing UV curable inks may not be fully cured to such a pencil hardness because the opacity of the ink inhibits curing. The photoinitiator of the ink and / or ink primer described herein can be selected to facilitate curing using a UV LED while still meeting the pencil hardness and optical density requirements described herein.

[0240] Thus, the photocurable inks and / or ink primers described herein are able to provide relatively high optical density to facilitate efficacy as a black matrix layer in a display while being compatible with high throughput inkjet printing processes and also meeting the stringent reliability testing requirements associated with automotive interior displays. The photocurable inks and / or ink primers described herein save manufacturing costs for display glass articles while still providing a highly reliable opaque layer that has proven to provide consistent color performance over the life of the part.

[0241] Method for manufacturing glass products

[0242] Ink composition

[0243] Reference now Figure 3 , the method for manufacturing a glass product is shown in 300. The method 600 can be performed to manufacture the glass product described herein. Figure 2 Therefore, reference will be made to the glass article 400 described herein. Figure 2 Various components are described to aid in describing the method. It should be understood that other glass articles may be formed by performing the method 600 and that the method 600 is not limited to a particular number or order of process steps.

[0244] At block 602, a substrate 450 is manufactured. Any suitable glass production process may be used, such as a fusion down-draw process, a float process, etc. Additional details regarding the glass forming method are provided herein. At block 604, the substrate 450 is treated. For example, in an embodiment, the substrate 450 is subjected to a strengthening treatment (e.g., ion exchange strengthening, thermal strengthening). Additional details regarding the strengthening treatment that may be provided to the substrate 450 are provided herein.

[0245] In an embodiment, the treatment applied to the substrate 450 during block 604 can be used to form the functional surface layer 490. For example, in an embodiment, the substrate 450 is chemically etched so that at least the first surface 470 exhibits anti-glare properties. A suitable anti-reflective coating and / or ETC coating can also be deposited on the first surface 470 by a suitable deposition process. In an embodiment, the second surface 480 can be primed (e.g., using a suitable chemical primer or ink) to promote adhesion of the opaque layer 500 thereto. In an embodiment, the light management layer 460 can be deposited and cured on the second surface 480 (e.g., a suitable ink can be cured thermally or by exposure to electromagnetic radiation).

[0246] At block 606, the photocurable ink is deposited on the second surface 480 to begin forming the opaque layer 500. As described herein, a suitable inkjet printing device can be used to deposit droplets of suitable size onto the second surface 480 so that the photocurable ink forms a suitable pattern. Various parameters for operating the inkjet printing device (e.g., control waveform, translation rate, deposition temperature) can vary depending on the composition of the photocurable ink and the desired deposition pattern. As described with respect to block 604, the second surface 480 can have an ink primer applied thereto prior to depositing the photocurable ink, such as those described herein.

[0247] At block 608, the light-curable ink is cured on the second surface 480 by exposure to electromagnetic radiation generated by the UV LED. In an embodiment, the UV LED emits radiation having a relatively narrow bandwidth (e.g., less than or equal to 50 nm, less than or equal to 40 nm, less than or equal to 30 nm, less than or equal to 20 nm) around a central UV wavelength (e.g., 375 nm, 380 nm, 385 nm, 390 nm, 395 nm, 400 nm). The operating parameters of the UV LED (e.g., output intensity, exposure time) can vary depending on various aspects of the opaque layer 500 (e.g., thickness, composition).

[0248] In an embodiment, blocks 606 and 608 may be performed when the substrate 450 comprises a planar shape. In an embodiment, blocks 606 and 608 are performed when the substrate is in a curved shape. For example, after applying at least some of the processing described with respect to block 604, the substrate 450 may be cold-formed by the methods described herein, and the opaque layer 500 may be formed on the cold-formed glass substrate. In an embodiment, a suitable display panel is laminated to the glass article such that the opaque layer 500 at least partially covers the display panel.

[0249] Considering the relatively high pigment concentration in each ink composition, it has been found that a multiple printing and curing architecture can be used to cure the light-curable ink to provide favorable adhesion properties while meeting the optical density requirements described herein. Such an architecture involves a process in which the opaque layer 500 (see Figure 2) are incrementally deposited on the substrate in the form of sub-layers that are only a fraction (e.g., less than or equal to 40%, less than or equal to 33%, less than or equal to 30%, less than or equal to 25%, greater than or equal to 10%) of the desired final thickness of the opaque layer 500. After each sub-layer is deposited, a relatively low dose ("pinning dose") of UV light is provided to at least partially cure (or "pin") the sub-layer. After a sufficient number of sub-layers (e.g., 3, 4, 5, 6, 7, or even more) are deposited, the entire stack (substrate 450 and superimposed sub-layers) can be subjected to a final curing step (if desired) with a higher dose of UV radiation than in the pinning step.

[0250] Figure 4 1000 for implementing the multiple printing and curing architecture described herein. The apparatus 1000 is shown as including multiple deposition and pinning stages 1002 and an optional final curing stage 1003. The number of deposition and pinning stages 1002 can vary depending on the optical density of the ink used (e.g., pigment concentration) and the composition of the photocurable ink (e.g., a formulation including more reactive monomers may require fewer deposition and pinning stages than a formulation including less reactive monomers). Each of the deposition and pinning stages 1002 includes a print head 1004 and a UV light source 1006 (e.g., a UV lamp or LED). In the depicted example, the glass substrate 450 is translated in a translation direction 1014 relative to the stages 1002 and 1003 (e.g., via a roller in contact with a major surface of the substrate 450 opposite to which the ink is disposed). The print head 1004 may be a commercially available print head configured to deposit the sub-layer 1050 (component of the opaque layer 500) on the glass substrate 450 in a pattern corresponding to the desired pattern of the opaque layer 500 after the deposition is completed. In an embodiment, to deposit each sub-layer 1050, the print head 1004 deposits a plurality of droplets of one of the ink compositions described herein to form a sub-layer having a thickness between 2 μm and 10 μm (e.g., greater than or equal to 2 μm and less than or equal to 8 μm, greater than or equal to 2 μm and less than or equal to 6 μm, greater than or equal to 2 μm and less than or equal to 4 μm). After the sub-layer 1050 is deposited by the print head 1004 within a specific deposition and pinning stage, the UV light source 1006 of the stage applies a pinning UV dose to the deposited sub-layer 1050. Since the ink has a very high optical density, the deposition stage of the ink advantageously provides sufficient UV curing dose at a relatively low layer thickness to achieve good UV penetration.

[0251] Whether the final curing stage 1003 is needed depends on the nature of the ink deposited in the sub-layer (the reactivity of the monomers present). In an embodiment, when present, the final curing stage 1003 includes a first UV light source 1010, which is configured to emit UV light directly onto the sub-layer (after all sub-layers are deposited) at a higher dose (e.g., at least two times higher, at least four times higher, at least six times higher, at least eight times higher, at least ten times higher, or even at least fifteen times higher) than the dose emitted by the UV light source 1006 in each of the deposition and pinning stages 1002. In addition, when present, the final curing stage 1003 may also include a second UV light source 1012, which is configured to emit UV light onto the side of the substrate 450 opposite to the side where the sub-layer is disposed. The second UV light source 1012 can provide additional UV dose to promote complete curing of the deposited ink. In an embodiment, the second UV light source 1012 can provide the same dose as the first UV light source 1010. In embodiments, the speed at which substrate 450 moves relative to stages 1002 and 1003, and the UV dose of UV light sources 1006, 1010 (if present), and 1012 (if present) may be configured according to the following Table 5. The specific speed and UV dose selected may depend on the composition of the photocurable ink being deposited on the glass.

[0252] Table 5

[0253] Minimum maximum Glass translation speed (m / min) 1 5 <![CDATA[Pinning dose (J / cm 2 )]]> 0.2 10 <![CDATA[Dose of curing agent (J / cm 2 )]]> 10 100

[0254] Ink Primer

[0255] Reference now Figure 5 , a method for manufacturing a glass product is shown in 650. The method 650 can be performed to manufacture the glass product described herein. Figure 2 Therefore, reference will be made to the glass article 400 described herein. Figure 2 Various components are described to aid in describing the method. It should be understood that other glass articles may be formed by performing the method 600 and that the method 600 is not limited to a particular number or order of process steps.

[0256] The method 650 begins at block 652 by depositing an ink primer onto the first major surface 470 of the glass substrate 450 using a first inkjet print head at a first deposition temperature of less than or equal to 65° C. The ink primer may be an ink primer as described in accordance with embodiments herein. Thus, in embodiments, during deposition (i.e., at the first deposition temperature), the ink primer may have a viscosity of less than 13 cPs. The ink primer may include an adhesion promoter configured to bond to the glass.

[0257] In an embodiment, the wet thickness of the ink primer deposited on the glass substrate 450 may be greater than or equal to 8.4 ml / m2 and less than or equal to >11 ml / m2 Although not wishing to be bound by theory, less than 8.4 ml / m 2 The wet thickness of 11ml / m 2 ) results in ungrafted silane, which may have a negative impact on adhesion.

[0258] Return to reference Figure 5 , method 650 continues at block 654 by 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 light source or an ultraviolet light source. When exposed to the first light source, the infrared curable ink primer may bind the silane groups of the adhesion promoter to the glass and / or may remove the solvent. When exposed to the first light source, the ultraviolet curable ink primer may polymerize to form a polymer that will copolymerize with the monomer from the ink composition.

[0259] Return to reference Figure 5 , method 650 may optionally continue at block 656, where the ink primer is heated at a first heating temperature. Heating the ink primer to the first heating temperature may bond the silane groups of the adhesion promoter to the glass. In embodiments where the ink primer is an infrared curable ink primer, heating the ink primer at the first heating temperature may also remove the solvent.

[0260] In an embodiment, the first heating temperature is greater than or equal to 25° C. and less than or equal to 150° C., greater than or equal to 25° C. and less than or equal to 100° C., greater than or equal to 50° C. and less than or equal to 150° C., or even greater than or equal to 50° C. and less than or equal to 100° C., or any and all sub-ranges formed by any of these endpoints. The ink primer can be heated at the first heating temperature for greater than or equal to 1 second and less than or equal to 1 hour, greater than or equal to 1 second and less than or equal to 30 minutes, greater than or equal to 1 minute and less than or equal to 1 hour, greater than or equal to 1 minute and less than or equal to 30 minutes, greater than or equal to 5 minutes and less than or equal to 1 hour, greater than or equal to 5 minutes and less than or equal to 30 minutes, greater than or equal to 10 minutes and less than or equal to 1 hour, or even greater than or equal to 10 minutes and less than or equal to 30 minutes, or any and all sub-ranges formed by any of these endpoints.

[0261] Return to reference Figure 5, method 650 continues at block 658, where an ink composition is deposited onto the ink primer using a second inkjet print head at a second deposition temperature of less than or equal to 65° C. In embodiments, the ink composition may be an ink composition described according to embodiments herein. In embodiments, during deposition (i.e., at the second deposition temperature), the ink primer may have a viscosity of less than 13 cPs.

[0262] Return to reference Figure 5 The method 650 continues at block 660 by exposing the ink composition to a second light source to at least partially cure the ink composition to form an opaque layer. For an infrared curable ink primer, the methacrylate groups from the silane groups of the adhesion promoter copolymerize with the ink composition monomers during exposure to the second light source. For an ultraviolet curable ink primer, the polymer of the ink primer copolymerizes with the ink composition monomers during exposure to the second light source.

[0263] Return to reference Figure 5 , method 650 may optionally continue at block 662, where the ink primer and the ink composition are heated at a second heating temperature. For example, in embodiments using a UV-curable ink primer, if the ink primer is not heated at a first heating temperature prior to depositing the ink composition, the ink primer and the ink composition may be heated at a second heating temperature to bond the silane groups of the adhesion promoter to the glass.

[0264] In an embodiment, the second heating temperature is greater than or equal to 25° C. and less than or equal to 150° C., greater than or equal to 25° C. and less than or equal to 100° C., greater than or equal to 50° C. and less than or equal to 150° C., or even greater than or equal to 50° C. and less than or equal to 100° C., or any and all subranges formed by any of these endpoints. The ink primer and ink composition can be heated at the second heating temperature for greater than or equal to 1 second and less than or equal to 1 hour, greater than or equal to 1 second and less than or equal to 30 minutes, greater than or equal to 1 minute and less than or equal to 1 hour, greater than or equal to 1 minute and less than or equal to 30 minutes, greater than or equal to 5 minutes and less than or equal to 1 hour, greater than or equal to 5 minutes and less than or equal to 30 minutes, greater than or equal to 10 minutes and less than or equal to 1 hour, or even greater than or equal to 10 minutes and less than or equal to 30 minutes, or any and all subranges formed by any of these endpoints.

[0265] Example

[0266] In order to more readily understand the various embodiments, reference is made to the following examples, which are intended to illustrate various embodiments of the ink compositions and ink primers described herein.

[0267] Photocurable ink composition

[0268] Examples 1-3

[0269] Photocurable inks with different compositions were formulated. An additive carbon black dispersion was used in the pigment dispersion of each ink. The concentration of the pigment was between 10 wt % and 20 wt % of each photocurable ink. In Example 1, a pigment dispersion containing a carbon black pigment from Penn Color, Inc. was used, which included propoxylated neopentyl glycol diacrylate (PO-PPGDA) as a monomer. The carbon black pigment accounted for 10 wt % of the photocurable ink. In Example 2, a pigment dispersion containing a carbon black pigment from Penn Color, Inc. was used, which included trimethylolpropane triacrylate (TMPTA) as a monomer. The carbon black pigment accounted for 20 wt % of the photocurable ink. In Example 3, a pigment dispersion containing a carbon black pigment from Sun Color, Inc. was used. The pigment dispersion of carbon black pigment of the photocurable ink comprises propoxylated neopentyl glycol diacrylate (PO-PPGDA) as a monomer. The carbon black pigment accounts for 10 wt % of the photocurable ink. The ink is jetted onto a chemically strengthened glass substrate at a deposition temperature of 55°C to 65°C using a research grade print head. The ink is deposited using a 10 pL drop volume at a resolution of 1270 dpi. The ink cartridges are jetted to form an opaque layer on the glass. The ink is then cured using a UV LED emitting radiation centered at 395 mm.

[0270] The optical density of the resulting opaque layer of the samples produced according to Examples 1-3 was measured using a densitometer. Figure 6 Graph 700 depicts the optical density of various samples produced as a function of opaque layer thickness. As shown by point 702, the opaque layer produced by Example 2 (having the highest weight % pigment) produced an optical density greater than 4.0 at a thickness of less than 8 μm, demonstrating the efficacy of the photocurable inks described herein. When the glass was primed with an acryloxysilane primer prior to printing, Figure 6 Each sample shown in was also subjected to and passed the adhesion test (adhesion greater than or equal to 4B when measured according to ASTM 3359).

[0271] The samples produced using the ink composition of Example 1 were subjected to high temperature, high humidity temperature testing by heating the samples to 85°C in an environment of 95% relative humidity for 500 hours, and then tested for adhesion according to ASTM 3359. Figure 7The results of the cross-hatch adhesion test are described in . As shown, the appearance of the opaque layer 802 is largely unaffected by the adhesion test, with only a small portion of the opaque layer removed along the cut (shown on the underside of the tape 804 used in the test). Such results demonstrate the reliability and durability of the light-curable inks described herein.

[0272] Example 4

[0273] Another example was formulated using the composition shown in Table 6. As shown, the ink formulated according to Example 4 contained 10% by weight of carbon black pigment. The ink was jetted onto chemically strengthened glass at 60°C using a research grade print head, and the printed parts were cured using UV LEDs, and the optical density and thickness were measured. The optical density was measured to be 4.2 at a thickness of 21 μm. The ink passed the adhesion test (greater than or equal to 4B when measured according to ASTM 3359). It is believed that higher optical density can be achieved at lower thicknesses using pigment dispersions with more diluted monomers.

[0274] Table 6

[0275]

[0276]

[0277] Example 5

[0278] Another example was formulated using the composition shown in Table 7. This example differs from the previous example in that the photoinitiator package was changed to maintain curing while reducing the total percentage in the composition, thereby providing greater composition flexibility. It was observed that Sun Chemical D3310-FX-K (25% in IBOA) had a much lower viscosity than UVDJ207 (25% in PONPGDA), making it more attractive for inkjet printing. A mixture design of experiments was also used to optimize composition viscosity, printability, and total thickness relative to OD. In this work, dipropylene glycol diacrylate (DPGDA M222) was found to perform better than hydroxypivalate neopentyl glycol diacrylate (HPNDA M210), especially when coupled with dipentaerythritol hexaacrylate (DPHA M600) and vinyl methyl oxazolidinone (Vmox). DPHA M600 adds additional crosslinking to the ink and helps with curing. Vmox replaces n-vinyl caprolactam as an even better viscosity modifier while helping with adhesion. The ink formulated according to Example 5 contained 11.25 wt% carbon black pigment as shown in Table 7. The ink was jetted onto chemically strengthened glass using a production purpose KM1024iSHE printhead at 50°C and the printed parts were cured using UV LED and the optical density and thickness were measured.

[0279] A three-pulse waveform with a total duration of 30 μs (including a first 10 μs pulse at 1 V, a second 10 μs pulse at -1 V, and a third 10 μs pulse at 0 V) ​​was used to form printed parts. The droplet volume varied from 2.9 pL to 9.0 pL. The droplet velocity varied from 2.67 m / s to 2.86 m / s. The droplet angle varied from 0.21° to 0.60°. Figure 8 A graph of optical density as a function of thickness for a number of samples prepared according to Example 5 is depicted. As shown, for thicknesses greater than 10 μm, the composition provides an optical density greater than 4.0. For example, at a thickness of 11 μm, the optical density was measured to be 4.8. Example 5 was subjected to high temperature, high humidity temperature testing by heating the sample to 85°C in an environment of 95% relative humidity for 500 hours, and then testing adhesion according to ASTM 3359. As shown Fig. 9 As shown, the ink passed the adhesion test (greater than or equal to 4B when measured according to ASTM 3359). The appearance of the opaque layer 1001 was largely unaffected by the adhesion test, with only a small portion of the opaque layer removed along the cut (shown on the underside of the tape 1005 used in the test). Such results demonstrate the reliability and durability of the light-curable inks described herein.

[0280] Table 7

[0281]

[0282] Counterexample

[0283] Two commercially available UV curable inks (Inks A and B) were deposited onto pre-primed chemically strengthened glass and tested under high temperature, high humidity test conditions (85°C and 95% relative humidity for 500 hours). Fig.10 and 11 The samples after testing are depicted. As shown, both samples exhibited visible cracking 903, 905 due to shrinkage of the opaque layer. The light-curable ink advantageously does not exhibit such visible cracking when subjected to high temperature conditions for a long time, demonstrating the improved durability and reliability of the inks described herein.

[0284] Embodiment 6-10

[0285] The compositions (in weight %) of Examples 6-10 are provided in Tables 8 and 9. Examples 6-8 used a first pigment dispersion ("Dispersion A") that was more viscous and had a more reactive monomer, while Examples 9-10 used a second pigment dispersion ("Dispersion B") that had a less reactive reactive monomer and was not as viscous as the first pigment dispersion.

[0286] Table 8

[0287]

[0288] Table 9

[0289]

[0290] As shown in Tables 8 and 9, for ink compositions with relatively reactive monomers (e.g., Examples 6-8 in the Examples section below), relatively high amounts of reactive diluents can be used to reduce viscosity while also providing adequate mechanical properties. Additionally, less reactive difunctional monomers (e.g., 3-methyl-1,5-pentanediyl diacrylate) can be used in such cases. For ink compositions with relatively low viscosity pigment dispersions 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) can be used. As an example, the amount of difunctional monomer relative to reactive diluent and the specific difunctional monomer used can be based on the viscosity and reactivity of the reactive monomer in the pigment dispersion.

[0291] The viscosity of the ink compositions according to Examples 6-10 was measured in the temperature range of 25°C to 65°C. The results are shown in Fig.12 shown. Fig.12 Included are first curve 902 representing Example 6, second curve 904 representing Example 7, third curve 906 representing Example 8, fourth curve 908 representing Example 9, and fifth curve 910 representing Example 10. As shown, each example exhibits a viscosity ranging from 5 cPs to 18 cPs over an operating temperature range of 30° C. to 50° C. associated with a commercially available inkjet printhead. Examples 6, 7, 8, and 10 exhibit a viscosity ranging from 5 cPs to 13 cPs over a temperature range of 30° C. to 50° C. These results demonstrate that these inks are suitable for inkjetting from a production printhead. In fact, the composition according to Example 6 was successfully jetted with a KM1024iSHE printhead at a voltage of 10 V, a pulse width of 5.4 μs, and a droplet temperature of 45° C., providing a droplet velocity of about 5 m / s and a droplet volume of 9.7 pL.

[0292] The composition according to Example 6 was deposited on a glass substrate and subjected to 4 deposition and pinning stages, wherein each UV light source was configured to apply 0.24 J / cm 2 After deposition and pinning of all sub-layers, it was found that when tested according to ASTM D3359, it was necessary to have a first and second UV light source providing 24 J / cm 2 The final cure stage of the dosage is to provide >4B cross hatch adhesion.

[0293] The composition according to Example 7 was deposited on a glass substrate and subjected to 4 deposition and pinning stages without a final curing stage. When tested according to ASTM D3359 (i.e., without a final curing stage), it was found that each UV light source was configured to apply 5.2 J / cm 2 This setting of UV dosage is sufficient to achieve full cure and provide >4B cross-hatch adhesion.

[0294] The following Fig.13 Images of crosshatch adhesion testing performed according to ASTM D3359 on cured Examples 6 and 7 are depicted in 14 (Example 6) and 14 (Example 7). These results show that both ink compositions provide crosshatch adhesion of >4B when tested according to ASTM D3359, but vary the necessary curing conditions to achieve this adhesion performance.

[0295] Unlike the composition of Example 6, the composition of Example 7 does not require a high dose of final curing from the top or bottom, and can be cured with a significantly lower amount of UV dose while still providing favorable adhesion. It is believed that this difference in curing performance between Examples 6 and 7 is derived from the difference in monomers. Relative to the third monomer (bifunctional monomer), the composition according to Example 7 contains a higher amount of the first monomer (reactive diluent), while the composition according to Example 6 contains a relatively high amount of the third monomer. In Example 7, a more reactive diluent is included at a relatively high percentage to improve the curing performance. When using a pigment dispersion with a high viscosity and a relatively reactive monomer, it is believed that providing at least 25% by weight of the first monomer will improve the curing performance. This improvement in curing has a wider significance because the relatively low amount of UV dose required provides flexibility in the design of the deposition and curing stages. The second light source that does not need to illuminate the bottom of the glass provides more freedom and flexibility in the size of the roller configuration and the glass used, because there is no engineering constraint between the rollers for accommodating a UV lamp to pass UV light.

[0296] The ink composition according to each of Examples 6-10 was deposited on a glass substrate. Multiple samples were prepared according to each ink composition, and the thickness and optical density were measured. The results are provided in Fig.15 Since the measurement method fails at such high densities, the curve flattens out at densities greater than 6. As shown, each ink composition is able to 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 for automotive applications described herein. Samples decorated with ink compositions according to Example 6 herein were also subjected to the various tests described in Table 4 herein. The results are provided in Table 10 below.

[0297] Table 10

[0298]

[0299] Ink Primer

[0300] Infrared curable ink primer

[0301] Embodiment 11

[0302] The formulation of Example 11 is shown in Table 11 (in wt %). The formulation according to Example 11 exhibited a viscosity of 7.8 cPs at 25°C, which is suitable for an inkjet production printhead. In fact, the formulation according to Example 11 was successfully jetted with a KM1024iSHE printhead at a voltage of 10 V, a pulse width of 5.4 μs and a droplet temperature of 30°C, providing a droplet velocity of about 5 m / s and a droplet volume of 9.7 pL.

[0303] Table 11

[0304]

[0305] The formulation according to Example 11 was deposited on a glass substrate and heated in an oven at 110° C. for 1 hour to bind the adhesion promoter to the substrate. Various wet thicknesses (i.e., 3.2 ml / m 2 Up to 13.2 ml / m 2 ), and when tested according to ASTM 3359, the adhesion was determined by the cross-hatch adhesion test after 500 cycles of 0.5 hours at -40°C and 0.5 hours at 95°C for 1 hour. The wet thickness of the primer layer was 8.4 ml / m 2 The image of the cross-hatching adhesion test is as follows: Fig.16 As shown, the best adhesion of the UV curable ink composition to the glass substrate is provided.

[0306] Samples of the formulation according to Example 11 were also subjected to the various tests described in Table 4. The results are provided in Table 12.

[0307] Table 12

[0308]

[0309] UV Curable Ink Primer

[0310] Examples 12 and 13

[0311] The formulations of Examples 12 and 13 are shown in Table 13 (in wt %). The ink formulations according to Examples 12 and 13 exhibited viscosities between 7 cPs and 12 CPs at 35°C to 45°C, which are suitable for inkjet production print heads. In fact, the formulations according to Examples 12 and 13 were successfully jetted with a KM1024iSHE print head at a voltage of 10 V, a pulse width of 5.4 μs and a droplet temperature of 45°C, providing a droplet velocity of about 5 m / s and a droplet volume of 9.7 pL.

[0312] Table 13

[0313]

[0314] The formulation according to Example 13 was deposited on a glass substrate and heated at about 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 2 The glass was exposed to a 395 nm wavelength UV LED lamp at a dose of 1000 nm to cure the ink composition and crosslink the vinyl groups of the polymer with the ink monomers. The primer layer and the ink layer were then heated at 85°C for 20 minutes to covalently bond the Si-O groups of the primer to the glass. Fig.17 and 18 As shown, when tested according to ASTM 3359, adhesion was determined by a cross-hatch adhesion test after 500 1-hour cycles of 0.5 hours at -40°C and 0.5 hours at 95°C. Each sample had an adhesion of greater than 4B. The total thickness of the primer and ink were 13.6 μm and 12.48 μm, respectively, and the optical densities were 6.18 and 5.83, respectively, meeting the stringent requirements for the automotive applications described herein.

[0315] It will be apparent to those skilled in the art that various modifications and changes may be made to the embodiments described herein without departing from the spirit and scope of the subject matter claimed. Therefore, this specification is intended to cover modifications and changes of the various embodiments described herein, as long as such modifications and changes are within the scope of the appended claims and their equivalents.

Claims

1. A UV-curable ink composition, comprising, based on the total weight of the UV-curable ink composition: greater than or equal to 25 wt % and less than or equal to 50 wt % of a pigment dispersion, wherein the pigment dispersion comprises at least 30 wt % of a pigment and a reactive monomer, based on the total weight of the pigment dispersion; greater than 0 wt % and less than or equal to 10 wt % of a photoinitiator package, the photoinitiator package comprising a Type I photoinitiator, a Type II photoinitiator, and an amine synergist; 10% or more and 42% or less by weight of a reactive diluent having a viscosity of less than 5 cPs at 25° C.; 5% by weight or more and 20% by weight or less of a multifunctional monomer; as well as Greater than or equal to 0 wt% and less than or equal to 35 wt% of a difunctional monomer.

2. The ultraviolet curable ink composition according to claim 1, wherein the ultraviolet curable ink composition comprises greater than or equal to 10 wt% and less than or equal to 35 wt% of a bifunctional monomer.

3. The UV curable ink composition of claim 2, wherein the combined amount of the reactive diluent, the multifunctional monomer, and the difunctional monomer is less than or equal to 60 wt%.

4. The UV curable ink composition according to any one of claims 1 to 3, wherein the UV curable ink composition further comprises greater than 0 wt% and less than or equal to 10 wt% of an adhesion promoter.

5. The UV curable ink composition according to any one of claims 1 to 3, wherein the UV curable ink composition contains no resin and no TPO.

6. The ultraviolet curable ink composition according to any one of claims 1 to 3, wherein the ultraviolet curable ink composition exhibits a viscosity greater than or equal to 8 cPs and less than or equal to 13 cPs in a temperature range of 30°C to 50°C.

7. The ultraviolet curable ink composition according to any one of claims 1 to 3, wherein the pigment dispersion comprises greater than or equal to 35 wt% of a pigment based on the total weight of the pigment dispersion, and wherein the pigment is a carbon black pigment.

8. The UV curable ink composition of any one of claims 1 to 3, wherein after being deposited on a glass substrate and cured using a UV light source to form an opaque layer having a thickness of less than 15 μm after curing, the opaque layer exhibits an optical density greater than 5.

9. A glass product comprising: A glass substrate having a first main surface and a second main surface, wherein the second main surface is opposite to the first main surface; as well as an opaque layer disposed on the second major surface, the opaque layer comprising a photocurable ink, the photocurable ink comprising at least 11% by weight of a pigment, wherein: The opaque layer contains no resin and no TPO, The opaque layer has a thickness less than or equal to 15 μm and an optical density greater than or equal to 5.0, and After curing solely by exposure to ultraviolet ("UV") radiation, the opaque layer exhibits: A pencil hardness greater than or equal to 3H when measured according to ASTM 3363, and Adhesion to the glass substrate of greater than or equal to 4B after withstanding for at least 500 hours at a temperature of 85° C. and a relative humidity of 95% when tested according to ASTM 3359.

10. The glass article of claim 9, wherein the average particle size of the pigment is less than or equal to 200 nm.

11. The glass article of any one of claims 9-10, wherein the opaque layer exhibits a cured surface tension greater than 36 dynes / cm.

12. The glass article of any one of claims 9-10, wherein the opaque layer exhibits a relative humidity greater than or equal to 1 x 10 9 Resistivity of Ω / sq.

13. The glass article of any one of claims 9-10, wherein the glass article exhibits a CIELAB SCI L* value of less than or equal to 30 when illuminated with a D65 light source at an angle of 10°.

14. The glass article of any one of claims 9-10, wherein the glass article exhibits a CIELAB SCIa* value greater than or equal to -0.05 and less than or equal to 0.15 and a CIELAB SCIb* value greater than or equal to -0.3 and less than or equal to -0.1 when illuminated with a D65 light source at a 10° angle.

15. The glass article of any one of claims 9-10, wherein the opaque layer exhibits adhesion to the glass substrate of greater than or equal to 4B when tested according to ASTM 3359 after 500 1 hour cycles of -40°C for 0.5 hour and 95°C for 0.5 hour.

16. The glass article of claim 15, wherein the glass article exhibits a maximum ΔE value (SCI and SCE) measured before and after 500 one-hour cycles of less than 2.

0.

17. The glass article of any one of claims 9-10, wherein the adhesion promoter is bonded to the glass substrate and the ink composition is polymerized with the adhesion promoter, wherein the adhesion promoter comprises an organofunctional silane.

18. A method of manufacturing a glass product, the method comprising: depositing an ink primer onto a first major surface of a glass substrate using a first inkjet print head at a first deposition temperature of less than or equal to 65° C., wherein during deposition, the ink primer has a viscosity of less than 13 cPs, wherein the ink primer comprises greater than or equal to 2 wt % and less than or equal to 10 wt % of an adhesion promoter configured 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 print head at a second deposition temperature of less than or equal to 65° C., wherein during deposition, the ink composition has a viscosity of less than 13 cPs; as well as The ink composition is exposed to a second light source to at least partially cure the ink composition.

19. The method of claim 18, wherein: The first light source is an infrared light source, and The ink primer is resin-free and TPO-free and comprises: greater than or equal to 2 wt % and less than or equal to 10 wt % of an adhesion promoter configured to bond to glass; and Greater than or equal to 90 weight percent and less than or equal to 98 weight percent of a solvent configured to promote bonding of an adhesion promoter to glass, wherein the solvent comprises 3-methoxy-3-methyl-1-butanol; butanol; ethylene glycol ethers; 2-butoxyethanol; propylene glycol monomethyl ether acetate; propylene glycol; 2-butoxyethyl acetate; ethylene glycol; 1,4-butanediol; diethyl succinate; or a combination of the above.

20. The method of claim 18, wherein the first light source is an ultraviolet light source.

21. The method of claim 20, wherein the ink primer further comprises: Greater than 0 wt % and less than or equal to 10 wt % 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.

22. The method of any one of claims 17-21, wherein the method further comprises, prior to depositing the ink composition, heating the ink primer at a first heating temperature greater than or equal to 25°C and less than or equal to 150°C for a period of time greater than or equal to 1 second and less than or equal to 1 hour.

23. The method of any one of claims 17-21, wherein the ink composition comprises: greater than or equal to 25 wt % and less than or equal to 50 wt % of a pigment dispersion, wherein the pigment dispersion comprises at least 30 wt % of a pigment and a reactive monomer, based on the total weight of the pigment dispersion; greater than 0 wt % and less than or equal to 10 wt % of a photoinitiator package, the photoinitiator package comprising a Type I photoinitiator, a Type II photoinitiator, and an amine synergist; 10% or more and 42% or less by weight of a reactive diluent having a viscosity of less than 5 cPs at 25° C.; 5% by weight or more and 20% by weight or less of a multifunctional monomer; as well as Greater than or equal to 0 wt% and less than or equal to 35 wt% of a difunctional monomer.

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