WO2020223054A1 - Frit structures for haptics - Google Patents

Abstract

The present disclosure includes a frit paste of an alkali borosilicate glass powder with a solvent and a binder. The frit paste can be precision deposited onto a glass substrate and fired to produce haptics in a variety of shapes and depths.

Description

FRIT STRUCTURES FOR HAPTICS

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority under 35 U.S.C. § 119 of U.S.

Provisional Application Serial No. 62/840261 filed on April 29, 2019 the content of which is relied upon and incorporated herein by reference in its entirety.

BACKGROUND

[0002] This disclosure relates generally to touch sensitive glass displays, and specifically to haptics on such glass displays.

[0003] Automobile and other vehicle interiors are predominantly using glass as a structural and design component, and glass displays are replacing traditional dashboards. Glass displays with touch sensitive technology, such as with haptics, are replacing traditional buttons, knobs, or dials. As the complexity of these glass displays increases, drivers tend to look down at the glass display to see which haptic is needed, which induces distraction while driving.

SUMMARY

[0004] The present disclosure provides a frit-based haptic for a glass display, and a method of making the haptic.

[0005] In one embodiment, a paste includes a frit powder, a binder, and a solvent.

[0006] In a second embodiment, a haptic includes the firing product of the paste including a frit powder, a binder, and a solvent.

[0007] In a third embodiment, an article includes a glass substrate and a haptic comprising the haptic made of a fired paste including a frit powder, a binder, and a solvent, disposed thereon.

[0008] In a fourth embodiment, a method of making an article includes firing a frit paste to give a fired product of the frit paste, and ion exchange treating the substrate and the fired frit paste on the substrate.

[0009] In a fifth embodiment, an article made is made by firing a frit paste to give a fired product of the frit paste, and ion exchange treating the substrate and the frit paste on the substrate. BRIEF DESCRIPTION OF THE FIGURES

[0010] In the drawings, which are not necessarily drawn to scale, like numerals describe substantially similar components throughout the several views. Like numerals having different letter suffixes represent different instances of substantially similar components. The drawings illustrate generally, by way of example, but not by way of limitation, various embodiments discussed in the present document.

[0011] FIG. 1 shows fired frit paste haptics on a glass display.

[0012] FIG. 2 shows fired frit paste haptics on a glass display in a variety of patterns.

DESCRIPTION

[0013] Reference will now be made in detail to certain embodiments of the disclosed subject matter, examples of which are illustrated in part in the accompanying drawings. While the disclosed subject matter will be described in conjunction with the enumerated claims, it will be understood that the exemplified subject matter is not intended to limit the claims to the disclosed subject matter.

Overview

[0014] Haptics are sensors that can be perceived via touch. Raised or patterned surfaces that can be felt through touch are considered passive haptic sensors, while buttons or sensors that can activate a process or subsequent action are considered active haptic sensors.

[0015] Current haptic sensors lack three-dimensional shape relative to the surface of the glass display. The addition of three-dimensional haptics to glass displays can be difficult. Many materials that could be used for haptics have softening or melting points near those of the glass substrate, causing those materials to become molten and not maintain a three- dimensional shape above the surface of the glass display when the glass display is fired and shaped.

[0016] Additionally, three-dimensional haptics are difficult to produce on glass displays because many materials cannot withstand the ion exchange treatment used to strengthen touch sensitive glass displays for automotive or other consumer purposes.

[0017] Three-dimensional haptics on glass displays must maintain a strong bond with the glass substrate for long term durability. The coefficient of thermal expansion of the material used for the haptics should be compatible with the coefficient of thermal expansion of the glass display itself, to avoid thermal stress that can cause breakage.

[0018] Overall, three-dimensional haptics for touch sensitive glass displays should be touch sensitive, create a strong bond with the glass substrate, and maintain height and shape to allow distinction by touch without visual input.

[0019] Haptics can be created, for example, by dispensing and firing a frit paste to form a particular three-dimensional frit shape on a substrate, such as a touch-sensitive glass. In this instance, the haptics can be of varying shapes or patterns to allow for detection and distinction of each haptic by touch alone, without visual review.

Fired Frit Paste

[0020] The fired frit paste from which the haptics are formed should be securely bonded to the substrate on which it resides. Specifically, the frit paste should have a coefficient of thermal expansion (CTE) within a compatible range compared to the substrate.

[0021] A frit paste for haptics can include a frit powder, a binder, and a solvent, combined and then fired. Optionally, the frit paste can further include a dispersant and/or a thixotropic additive. The frit powder can dictate properties of the glass resulting from the paste, such as coefficient of thermal expansion (CTE), softening point, and glass transition temperature.

[0022] The frit powder can be an alkali borosilicate glass powder such as a glass frit in the family of Rx0_y-Zn0-B203-Si02 compounds, where RxO_y represents a metal oxide such as, for example, lithium oxide, sodium oxide, potassium oxide, magnesium oxide, calcium oxide, barium oxide, zinc oxide, aluminum oxide, boron oxide, silicon oxide, zirconium oxide, or combinations thereof, as shown below in Table 1.

Table 1. Chemical Formulae of Metal Oxides in Glass Frit

[0023] The frit powder can, for example, contain between about 3.0-7.0 mol.% LriO,

1.5-22.5 mol.% Na₂0 (e.g., 1.5-12.0 mo.%), 1.0-13.5 mol.% K2O (e.g., 1.3-10.3 mol.%), 2.0- 2.5 mol.% MgO, 1.0-5.0 mol.% CaO (e.g., 2.3-5.0 mol.%), 3.0-3.5 mol.% BaO, 1.0-10.0 mol.% ZnO (e.g., 2.40-5.0 mol.%), 4.0-4.5 mol.% AI2O3, 15.0-50.0 mol.% B2O3 (e.g., 33.3- 44.3 mol.%), 25.0-52.0 mol.% S1O2 (e.g., 34.4-48.5 mol.%), 1.0-2.0 mol.% T1O2 and 3.0-4.0 mol.% Zr0₂.

[0024] The CTE of the frit powder should be compatible with the CTE for the substrate on which the frit paste will be applied. This avoids CTE mismatch and associated stresses, resulting in less breakage due to thermal stress created at the interface between the substrate and the frit paste, as the paste forms the sensor. For example, the frit powder can have a CTE ranging from about 55 xlO ⁷/°C to about 85 xl0⁷/°C, corresponding to the CTE of the particular substrate on which the frit paste is dispensed.

[0025] When applied to the substrate and fired, the frit paste, and the substrate must both hold shape under firing. Thus, the frit powder should have a glass transition temperature that allows for the frit powder to be fired onto the substrate without softening, flowing, and losing shape. For example, the frit powder can have a glass transition temperature in a range from about 400 °C to about 500 °C.

[0026] Additionally, the firing temperature should not substantially exceed the annealing point of the substrate glass, otherwise warpage of the assembly can occur during the process of bonding the haptic to the substrate. Noticeable frit flow typically occurs at or above the softening point, thus, the softening point of the frit powder should not substantially exceed the annealing point of the substrate, otherwise the substrate may warp. The softening point of the frit powder for most automotive glass substrates can be in a range from about 550 °C to about 650 °C.

[0027] The frit powder can be mixed with a solvent and a binder to create the frit paste. Mixing can be accomplished by ordinary means as understood by one of ordinary skill in the art. When in the mixed paste, the frit powder itself can be between about 40 vol.% and about 50 vol.% of the frit paste. The frit powder in the paste can have a density in a range from about 2.00 to about 3.00 g/cm³. The solvent can be an organic solvent making up about 50 vol.% of the paste. The binder can act as an agent to suspend the frit powder in the solvent. Optionally, a surfactant can be added to the paste. The combination of frit powder, solvent, binder, and optionally surfactant should form a stable paste with a controlled paste viscosity.

[0028] The frit paste can be viscous to allow for creation of shapes with height on a substrate. The frit paste should not flow substantially such that it is flattened out when applied to the substrate. For example, the frit paste viscosity can be in a range from about 500 to about 10,000 P.

[0029] Optionally, the frit paste can include a colorant or other pigment for decoration. The colorant can be in a range from about 5 wt. % to about 10 wt. % of the frit paste. Examples of colorants include, but are not limited to, black pigments (such as Ferro V- 7709), blue pigments, green pigments (such as Ferro V-l 1633), and combinations thereof.

Haptic

[0030] The frit paste can be fired into a haptic on a substrate. The paste can be fired at a temperature above the frit powder’s glass transition temperature and softening point but should not be fired at such a high range that the fired frit powder loses its shape. For example, the frit paste can be fired at about 500 to 700 °C for 1 hour. The firing temperature can be, for example, about 50 degrees above the softening temperature of the frit powder, but should not be substantially above the annealing point of the particular substrate on which the frit paste is fired.

[0031] The haptic, made of the fired frit paste, can have height, up to about 2mm.

This allows for raised haptics on a substrate, so that they can be sensed by touch. Additionally, the haptic can have a variety of shapes. The haptic can, for example, be a dot, circle, square, triangle, or other shape, such that the sensor has a substantially circular or a polygonal cross-section. Alternatively, multiple haptics can be placed in a dot pattern or other combination of shapes to create distinct, identifying clusters of haptics.

[0032] The haptic can be made of multiple layers of frit paste. In this case, a first layer of frit paste can be applied and fired. Subsequently, a second layer is applied on top of the first layer and fired. The first and second layers of frit paste can be of the same composition, or of differing compositions, provided their CTE are within a similar range to avoid CTE mismatch. This can be used to create various color and texture effects.

[0033] The haptic can additionally be colored, opaque, transparent, glossy, matte, or translucent. Colorants or other pigments in the frit paste can provide color to differentiate various haptics. Additionally, some fired frit pastes include pore structures that, when fired, make the haptic opaque. The fired paste haptic can be applied to and fused with a glass substrate for touchscreen displays.

Glass Display

[0034] FIG. 1 shows fired frit paste based haptics 12 on a glass display 10. Glass display 10 can be, for example, a glass considered for automotive displays and control panels. Glass display 10 includes haptics 12 on substrate 14. Haptics 12 are described in detail above and are a fired frit paste.

[0035] FIG. 2 shows fired frit paste haptics on a glass substrate, similar to those in

FIG. 1. Fired frit paste haptics can be in a variety of shapes or patterns, as shown in FIG. 2. Here, lines, dots, or combinations thereof are used to create circles, diamonds, arrows, and other patterns or shapes to distinguish various haptic sensors.

[0036] Substrate 14 should be a high strength, scratch and damage resistant, ion- exchangeable glass suitable for touch screen applications, for example, in an automotive or consumer device. Substrate 14 can have a CTE from about 75 xlO ⁷/°C to about 105 xlO ⁷/°C, that is compatible with the CTE of the frit powder in the frit paste that haptics 12 are made of. Examples of suitable substrates include aluminosilicate glasses available from Coming Inc.

[0037] Typically, substrate 14 can have an annealing temp from about 585 °C to about 630 °C. When haptics 12 are attached to substrate 14, the firing temperature is less than the annealing temperature of the substrate, so as to create a glass fusion bond between the haptics 12 and the substrate 14 without deforming or melting either the haptics 12 nor the substrate 14. In some embodiments, an additional adhesive can be used to form a bond between substrate 14 and haptics 12. This may additionally include cleaning the substrate 14 with an organic solvent, such as isopropanol (IP A), and air drying the substrate 14 prior to addition of an adhesive.

[0038] Glass display 10 is prepared through applying the frit paste to the substrate 14, firing the frit paste to create haptics 12, and ion exchange treating the substrate 14 with haptics 12 attached. Next, decorative patterns, such as metal, carbon fiber, wood patterns, etc., including button icons, such as home, music, GPS, fan, A/C, etc., can be printed, such as through screening printing or inkjet printing, on the back side of the substrate 14 opposing haptics 12.

[0039] Optionally, the frit paste can be prepared prior to creating glass display 10.

Preparing the frit paste includes mixing a glass frit powder, a solvent, and a binder, as discussed herein. In some embodiments, other additives, such as colorants or pigments, can be added.

[0040] Next, the frit paste is applied to the substrate 14. The frit paste should be applied precisely to the substrate 14 to create distinct shapes and/or patterns. This can be done by syringe dispensing, pen dispensing, applying by nozzle, extruding, using a doctor blade, 3-D printing, screen printing, or other methods according to one of skill in the art. The frit paste can be applied in a variety of shapes, heights, and patterns on the substrate 14 to create haptics 12 that are distinguishable.

[0041] Subsequently, the frit paste is fired to produce the haptics 12. Firing the frit paste can be done at a temperature not substantially higher than the annealing temperature of substrate 14. For example, the frit paste can be fired at about 650 °C for 1 hour, such that the frit paste softens and flows, but does not flow excessively, retaining its shape.

[0042] After firing, the substrate 14 with applied haptics 12 is chemically strengthened by ion exchange treatment. An ion exchange treatment is a chemical strengthening process that starts with a glass containing smaller ions that are capable of exchange with larger ions in a molten salt bath at elevated temperatures. During the treatment, the larger ions replace the smaller ions in the glass display. The more densely packed larger ions in the glass display 10 surface generate a high compressive stress, which translates to higher strength in glass display 10. The ion exchange treatment of the glass display 10 can be done through one or more ion immersion baths, or other methods as known to one of skill in the art. Optionally, the glass display 10 can also be post-treated in other ways, such as further curing or cleaning, such as cleaning with IPA. In some examples, post treatments include the addition of decorative patterns, such as metal, carbon fiber, wood patterns, etc., including button icons, such as home, music, GPS, fan, A/C, etc., printed (through, for example, screening or inkjet printing) on the back side of the substrate 14 opposing haptics 12.

[0043] These frit powder-based haptics have several advantages, some of which are unexpected. Deposition techniques such as precision dispensing lend themselves to rapid and reproducible laydown of a wide variety of shapes. The formulation of glass frit compositions to be compatible with potential substrate glasses with respect to CTE and firing temperature allows for longer lifespans of glass displays incorporating haptics. In addition, the formulation of glass frit compositions allows haptics to go through the chemical strengthening process by ion exchange treatment that is compatible with potential substrate glasses.

[0044] Throughout this document, values expressed in a range format should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a range of “about 0.1% to about 5%” or“about 0.1% to 5%” should be interpreted to include not just about 0.1% to about 5%, but also the individual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range. The statement“about X to Y” has the same meaning as“about X to about Y,” unless indicated otherwise. Likewise, the statement“about X, Y, or about Z” has the same meaning as“about X, about Y, or about Z,” unless indicated otherwise.

[0045] In this document, the terms“a,”“an,” or“the” are used to include one or more than one unless the context clearly dictates otherwise. The term“or” is used to refer to a nonexclusive“or” unless otherwise indicated. The statement“at least one of A and B” has the same meaning as“A, B, or A and B.” In addition, it is to be understood that the phraseology or terminology employed herein, and not otherwise defined, is for the purpose of description only and not of limitation. Any use of section headings is intended to aid reading of the document and is not to be interpreted as limiting; information that is relevant to a section heading may occur within or outside of that particular section.

[0046] In the methods described herein, the acts can be carried out in any order without departing from the principles of the disclosure, except when a temporal or operational sequence is explicitly recited. Furthermore, specified acts can be carried out concurrently unless explicit claim language recites that they be carried out separately. For example, a claimed act of doing X and a claimed act of doing Y can be conducted simultaneously within a single operation, and the resulting process will fall within the literal scope of the claimed process. [0047] The term“about” as used herein can allow for a degree of variability in a value or range, for example, within 10%, within 5%, or within 1% of a stated value or of a stated limit of a range, and includes the exact stated value or range.

[0048] The term“substantially” as used herein refers to a majority of, or mostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or 100%.

[0049] The term“cure” as used herein refers to exposing to radiation in any form, heating, or allowing to undergo a physical or chemical reaction that results in hardening or an increase in viscosity.

[0050] The term“pore” as used herein refers to a depression, slit, or hole of any size or shape in a solid object. A pore can run all the way through an object or partially through the object. A pore can intersect other pores.

[0051] The term“solvent” as used herein refers to a liquid that can dissolve a solid, liquid, or gas. Non-limiting examples of solvents are silicones, organic compounds, water, alcohols, ionic liquids, and supercritical fluids.

[0052] The term“silicate” as used herein refers to any silicon-containing compound wherein the silicon atom has four bonds to oxygen, wherein at least one of the oxygen atoms bound to the silicon atom is ionic, such as any salt of a silicic acid. The counterion to the oxygen ion can be any other suitable ion or ions. An oxygen atom can be substituted with other silicon atoms, allowing for a polymer structure. One or more oxygen atoms can be double-bonded to the silicon atom; therefore, a silicate molecule can include a silicon atom with 2, 3, or 4 oxygen atoms. Examples of silicates include aluminum silicate. Zeolites are one example of materials that can include aluminum silicate. A silicate can be in the form of a salt or ion.

[0053] The term“room temperature” as used herein refers to a temperature of about

15 °C to 28 °C.

[0054] The term“standard temperature and pressure” as used herein refers to 20 °C and 101 kPa.

[0055] The term“surface” as used herein refers to a boundary or side of an object, wherein the boundary or side can have any perimeter shape and can have any three- dimensional shape, including flat, curved, or angular, wherein the boundary or side can be continuous or discontinuous. While the term surface generally refers to the outermost boundary of an object with no implied depth, when the term‘pores’ is used in reference to a surface, it refers to both the surface opening and the depth to which the pores extend beneath the surface into the substrate.

Examples

[0056] Various embodiments of the present disclosure can be better understood by reference to the following Examples which are offered by way of illustration. The present disclosure is not limited to the Examples given herein.

Examples 1-13

[0057] Thirteen working examples of frit powders are provided for making frit pastes for haptics. Each example is a borosilicate glass, with a varying composition of alkali or metal oxides, such as lithium, sodium, potassium, magnesium, calcium, barium, zinc, or aluminum oxides. The compositions of Examples 1-13 are listed in Tables 2-3 below. All percentages are listed in mol.%.

Table 2. Composition of Examples 1-6

Table 3. Composition of Examples 7-13

[0058] The compositions of Examples 1-13 were specifically chosen due to their glass transition temperature (T_g), coefficient of thermal expansion (CTE), and softening point (Soft. Pt), all of which allowed for a firing temperature below the annealing point of the substrate glass. These properties are shown in Tables 4-5 below.

Table 4. Properties of Examples 1-6

Table 5. Properties of Examples 7-13

[0059] The frit powders of Examples 1-13 can be mixed into an organic solvent with a binder to produce frit pastes. The frit pastes can be precision syringe dispensed or pen dispensed onto glass substrates made from aluminosilicate glasses available from Coming Inc. The frit powders can be syringe dispensed into circles or dots on these substrates. After application to the substrates, each of the frit pastes can be fired at 650 °C for 1 hour to produce haptics fusion bonded to the substrate glass.

Examples 14-21

[0060] Glasses from Example 4 were used to create frit pastes (Examples 14-21) for dispensing on glass, and subsequently fired. The compositions of paste Examples 14-21 is summarized below in Tables 6-8.

Table 6. Properties of Examples 14-16

Table 7. Properties of Examples 17-19

Table 8. Properties of Examples 20-22

[0061] The components of Examples 14-22 were mixed, beginning with the binder and solvent in a high speed disperser, such as a Cowles or Sawblade mixing impeller, so as to shear and disperse the binder in the mixture. The Examples 14-22 were mixed for between 1 and 3 hours at about 1500 to about 1800 rpm. Once the binder was fully dissolved, various additives were added and subsequently mixed with the binder and solvent for an additional 15 minutes. Next, the frit powders were mixed in to create the frit paste. The initial mixing was done with a Mazauraster mixer, followed by a second mixing using a 3 -roll mill in three passes. Further mixing was done by hand.

[0062] After mixing, the frit pastes of Examples 14-22 were packaged, de-aired, and stored on a rotating roller mill until dispensed. The pastes were measured for viscosity at a low shear rate of 1 sec ¹ and a moderate shear rate of 10 sec ¹.

[0063] The Examples 14-22 were dispensed into dots and lines as described below in reference to Examples 23-24. Overall, Examples 14, 15, 16, and 19 had poor dispensing performance. Example 14 flowed out too quickly. Examples 14, 16, and 19 formed stringers. Example 15 was too viscous for dispensing. In contrast, Examples 21 and 22 had good dispensing performance. Both Examples 21 and 22 had good height with little flow out. Examples 17, 18, and 20 have average performance.

Examples 23-24

[0064] In Example 23 and 24, frit pastes were applied to a glass substrate. Frit pastes were precision dispensed onto glass substrates with an air pressure actuated valve on the Nordson Asymtek Spectrum II Dispensing System. The dispensing valve included a syringe with a piston and capped with an air assembly called a receiver and was mounted on a robot for precision dispensing. A GPD Global S Type Nozzle (a 21 gauge) was attached to dispense the frit pastes. [0065] The dispensing of the haptic frit structures was done by forming dots and lines to create different patterns that can be learned and recognized by the touch of a finger. These patterns would then be given a definition as to what operation is assigned to it. The dot sizes that were dispensed were dependent upon the parameters that were set and the rheology of the frit paste.

[0066] The varying parameters that were utilized for dispensing Example 23 (dots) include air pressure acting upon the syringe (e.g., fluid pressure in pounds per square inch (psi)), the length of valve“on” time in seconds, the gauge of the nozzle (e.g., the 21 gauge nozzle was 0.022”/0.564mm inside diameter) and the gap distance between the nozzle tip and the glass surface. The parameters that were used for dispensing Example 24 (lines) additionally include line speeds and pre-move delay. Parameters used to dispense haptic frit in Examples 23 and 24 are summarized in Table 9 below.

Table 9. Parameters of Examples 23 and 24.

[0067] Other factors that determined the final sizes of Example 23 dots, such as height and diameter, and Example 24 lines, such as height and width, were the viscosity of the frit paste and the interaction of the paste with the surface of the glass. Lower viscosity materials flowed out more easily and produced dots that were large in diameter and low in height.

[0068] Aspect (1) pertains to a fired frit comprising: a frit powder; a binder; and a solvent.

[0069] Aspect (2) pertains to the fired frit of Aspect (1), wherein the frit powder comprises an alkali borosilicate glass.

[0070] Aspect (3) pertains to the fired frit of Aspect (2), wherein the alkali borosilicate glass comprises lithium oxide, sodium oxide, potassium oxide, magnesium oxide, calcium oxide, barium oxide, zinc oxide, aluminum oxide, boron oxide, silicon oxide, zirconium oxide, fluoride, or combinations thereof.

[0071] Aspect (4) pertains to the fired flit of any one of Aspects (1) through (3), wherein the frit powder is about 50 vol.% of the fired frit.

[0072] Aspect (5) pertains to the fired frit of any one of Aspects (1) through (4), wherein the frit powder comprises one or more particles each of the one or more particles independently comprising a compound of the formula RxOY-ZnO-IfcC -SiCte, wherein RXOY designates one or more alkali oxides.

[0073] Aspect (6) pertains to the fired frit of Aspect (5), wherein the frit powder comprises in a range from about 30 mole% to about 50 mole% boron trioxide.

[0074] Aspect (7) pertains to the fired frit of any one of Aspects (1) through (6), wherein the frit powder has a glass transition temperature in a range from about 400°C to about 500°C.

[0075] Aspect (8) pertains to the fired frit of any one of Aspects (1) through (7), wherein the frit powder has a coefficient of thermal expansion in a range from about 55 xlO ⁷/°C to about 85 xlO-⁷/°C.

[0076] Aspect (9) pertains to the fired frit of any one of Aspects (1) through (8), wherein the frit powder has a softening point in a range from about 550°C to about 650°C.

[0077] Aspect (10) pertains to the fired frit of any one of Aspects (1) through (9), wherein the frit powder has a density in a range from about 2.00 g/cm³ to about 3.00 g/cm³.

[0078] Aspect (11) pertains to the fired frit of any one of Aspects (1) through (10), wherein the fired frit has a viscosity in a range from about 500 P to about 10,000 P.

[0079] Aspect (12) pertains to the fired frit of any one of Aspects (1) through (11), further comprising a colorant, wherein the colorant is in a range from about 5 wt. % to about 10 wt. % of the fired frit.

[0080] Aspect (13) pertains to a haptic comprising the fired frit of any one of Aspects

(1) through (12).

[0081] Aspect (14) pertains to the haptic of Aspect (13), wherein the fired frit is fired at about 500 °C to about 700°C.

[0082] Aspect (15) pertains to the haptic of Aspect (13) or Aspect (14), wherein the haptic has a height of up to about 2 mm.

[0083] Aspect (16) pertains to the haptic of any one of Aspects (13) through (15), wherein the haptic is colored, transparent, translucent, gloss, matte or opaque. [0084] Aspect (17) pertains to the haptic of any one of Aspects (13) through (16), wherein the haptic has a cross sectional geometry conforming to a substantially circular shape.

[0085] Aspect (18) pertains to the haptic of any one of Aspects (13) through (17), wherein the haptic has a cross sectional geometry conforming to a polygonal shape.

[0086] Aspect (19) pertains to the haptic of any one of Aspects (13) through (18), wherein the haptic comprises two or more layers of the fired frit of claim 1.

[0087] Aspect (20) pertains to the haptic of Aspect (19), wherein the two or more layers of the fired frit have a substantially similar composition.

[0088] Aspect (21) pertains to the haptic of Aspect (19) or Aspect (20), wherein the two or more layers of the fired frit have different compositions.

[0089] Aspect (22) pertains to the haptic of any one of Aspects (13) through (21), wherein the haptic comprises a micro porous structure.

[0090] Aspect (23) pertains to an article comprising: a glass substrate; and a haptic comprising the haptic of any one of claims 13-22disposed thereon.

[0091] Aspect (24) pertains to the article of Aspect (23), wherein the substrate has a coefficient of thermal expansion from about 75 xlO ⁷/°C to about 105 xlO ⁷/°C.

[0092] Aspect (25) pertains to the article of Aspect (23) or Aspect (24), wherein the substrate has an annealing point from about 585°C to about 630°C.

[0093] Aspect (26) pertains to the article of any one of Aspects (23) through (25), wherein a firing temperature is less than an annealing temperature of the substrate.

[0094] Aspect (27) pertains to the article of any one of Aspects (23) through (26), further comprising an adhesive bonding the haptic to the substrate.

[0095] Aspect (28) pertains to the article of any one of Aspects (23) through (27), wherein the haptic is fused to the glass substrate.

[0096] Aspect (29) pertains to a method comprising: firing a frit paste to give a fired product of the frit paste; and ion exchange treating the substrate and the frit paste on the substrate.

[0097] Aspect (30) pertains to the method of Aspect (29), further comprising preparing a frit paste by mixing a glass frit powder, a solvent, and a binder.

[0098] Aspect (31) pertains to the method of Aspect (29) or Aspect (30), further comprising applying the frit paste to the substrate prior to firing. [0099] Aspect (32) pertains to the method of Aspect (31), wherein the applying comprises pipetting, pen dispensing, applying by nozzle, extruding, using a doctor blade, 3-D printing, or screen printing.

[00100] Aspect (33) pertains to the method of any one of Aspects (29) through (32), wherein firing the frit paste comprises firing at about 500 °C to about 700 °C.

[00101] Aspect (34) pertains to the method of any one of Aspects (29) through (33), further comprising post-treating the frit paste on the substrate.

[00102] Aspect (35) pertains to the method of any one of Aspects (29) through (34), further comprising applying one or more decorative patterns or button icons.

[00103] Aspect (36) pertains to an article made by the method of any one of Aspects (29) through (35).

[00104] The terms and expressions that have been employed are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the embodiments of the present disclosure. Thus, it should be understood that although the present disclosure has been specifically disclosed by specific embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those of ordinary skill in the art, and that such modifications and variations are considered to be within the scope of embodiments of the present disclosure.

Additional Embodiments.

[00105] The following exemplary embodiments are provided, the numbering of which is not to be construed as designating levels of importance:

[00106] Embodiment 1 provides a fired frit including a frit powder, a binder, and a solvent.

[00107] Embodiment 2 provides the fired frit of Embodiment 1, wherein the frit powder comprises an alkali borosilicate glass.

[00108] Embodiment 3 provides the fired frit of any one of Embodiments 1-2, wherein the alkali borosilicate glass comprises lithium oxide, sodium oxide, potassium oxide, magnesium oxide, calcium oxide, barium oxide, zinc oxide, aluminum oxide, boron oxide, silicon oxide, zirconium oxide, fluoride, or combinations thereof. [00109] Embodiment 4 provides the fired frit of any one of Embodiments 1-3, wherein the frit powder is about 50 vol.% of the fired frit.

[00110] Embodiment 5 provides the fired frit of any one of Embodiments 1-4 wherein the frit powder comprises one or more particles, each of the one or more particles independently comprising a compound of the formula RxOY-ZnO-EteCb-SiCte, wherein RXOY designates one or more metal oxides, such as an alkali oxide.

[00111] Embodiment 6 provides the fired frit of any one of Embodiments 1-5, wherein the frit powder comprises in a range from about 30 mole% to about 50 mole% boron trioxide.

[00112] Embodiment 7 provides the fired frit of any one of Embodiments 1-6, wherein the frit powder has a glass transition temperature in a range from about 400°C to about 500°C.

[00113] Embodiment 8 provides the fired frit of any one of Embodiments 1-7, wherein the frit powder has a coefficient of thermal expansion in a range from about 55 xl0⁷/°C to about 85 xlO ⁷/°C.

[00114] Embodiment 9 provides the fired frit of any one of Embodiments 1-8, wherein the frit powder has a softening point in a range from about 550°C to about 650°C.

[00115] Embodiment 10 provides the fired frit of any one of Embodiments 1-9, wherein the frit powder has a density in a range from about 2.00 g/cm³ to about 3.00 g/cm³.

[00116] Embodiment 11 provides the fired frit of any one of Embodiments 1-10, wherein the fired frit has a viscosity in a range from about 500 P to about 10,000 P.

[00117] Embodiment 12 provides the fired frit of any one of Embodiments 1-11, further comprising a colorant, wherein the colorant is in a range from about 5 wt. % to about 10 wt. % of the fired frit.

[00118] Embodiment 13 provides a haptic comprising the fired frit of Embodiment 1.

[00119] Embodiment 14 provides the haptic of Embodiment 13, wherein the fired frit is fired at about 500 °C to about 700 °C.

[00120] Embodiment 15 provides the haptic of any one of Embodiments 13-14, wherein the haptic has a height of up to about 2 mm.

[00121] Embodiment 16 provides the haptic of any one of Embodiments 13-15, wherein the haptic is colored, transparent, translucent, glossy, matte, or opaque.

[00122] Embodiment 17 provides the haptic of any one of Embodiments 13-16, wherein the haptic has a cross sectional geometry conforming to a substantially circular shape. [00123] Embodiment 18 provides the haptic of any one of Embodiments 13-17, wherein the haptic has a cross sectional geometry conforming to a polygonal shape.

[00124] Embodiment 19 provides the haptic of any one of Embodiments 13-18, wherein the haptic comprises two or more layers of the fired frit of claim 1.

[00125] Embodiment 20 provides the haptic of any one of Embodiments 13-19, wherein the two or more layers of the fired frit have a substantially similar composition.

[00126] Embodiment 21 provides the haptic of any one of Embodiments 13-20, wherein the two or more layers of the fired frit have different compositions.

[00127] Embodiment 22 provides the haptic of any one of Embodiments 13-21, wherein the haptic comprises a micro porous structure.

[00128] Embodiment 23 provides an article including a glass substrate and a haptic comprising the haptic of Embodiment 13 disposed thereon.

[00129] Embodiment 24 provides the article of Embodiment 23, wherein the substrate has a coefficient of thermal expansion from about 75 xlO ⁷/°C to about 105 xlO ⁷/°C.

[00130] Embodiment 25 provides the haptic of any one of Embodiments 23-24, wherein the substrate has an annealing point from about 585°C to about 630°C.

[00131] Embodiment 26 provides the haptic of any one of Embodiments 23-25, wherein a firing temperature is less than an annealing temperature of the substrate.

[00132] Embodiment 27 provides the haptic of any one of Embodiments 23-26, further comprising an adhesive bonding the haptic to the substrate.

[00133] Embodiment 28 provides the haptic of any one of Embodiments 23-27, wherein the haptic is fused to the glass substrate.

[00134] Embodiment 29 provides a method including firing a frit paste to give a fired product of the frit paste and ion exchange treating the substrate and the frit paste on the substrate.

[00135] Embodiment 30 provides the method of Embodiment 29, further comprising preparing a frit paste by mixing a glass frit powder, a solvent, and a binder.

[00136] Embodiment 31 provides the method of any one of Embodiments 29-30, further comprising applying the frit paste to the substrate prior to firing.

[00137] Embodiment 32 provides the method of any one of Embodiments 29-31, wherein the applying comprises pipetting, pen dispensing, applying by nozzle, extruding, using a doctor blade, 3-D printing, or screen printing. [00138] Embodiment 33 provides the method of any one of Embodiments 29-32, wherein firing the frit paste comprises firing at about 500 °C to about 700 °C.

[00139] Embodiment 34 provides the method of any one of Embodiments 29-33, further comprising post-treating the frit paste on the substrate.

[00140] Embodiment 35 provides an article made by the method of Embodiment 29.

Claims

CLAIMS What is claimed is:

1. A fired frit comprising:

a frit powder;

a binder; and

a solvent.

2. The fired frit of claim 1, wherein the frit powder comprises an alkali borosilicate glass.

3. The fired frit of claim 2, wherein the alkali borosilicate glass comprises lithium oxide, sodium oxide, potassium oxide, magnesium oxide, calcium oxide, barium oxide, zinc oxide, aluminum oxide, boron oxide, silicon oxide, zirconium oxide, fluoride, or combinations thereof.

4. The fired frit of any one of the preceding claims, wherein the frit powder is about 50 vol.% of the fired frit.

5. The fired frit of any one of the preceding claims, wherein the frit powder comprises one or more particles each of the one or more particles independently comprising a compound of the formula RxOY-ZnO-IfcC -SiCte, wherein RXOY designates one or more alkali oxides.

6. The fired frit of claim 5, wherein the frit powder comprises in a range from about 30 mole% to about 50 mole% boron trioxide.

7. The fired frit of any one of the preceding claims, wherein the frit powder has a glass transition temperature in a range from about 400°C to about 500°C.

8. The fired frit of any one of the preceding claims, wherein the frit powder has a coefficient of thermal expansion in a range from about 55 xlO ⁷/°C to about 85 xlO ⁷/°C.

9. The fired frit of any one of the preceding claims, wherein the frit powder has a softening point in a range from about 550°C to about 650°C.

10. The fired frit of any one of the preceding claims, wherein the frit powder has a density in a range from about 2.00 g/cm³ to about 3.00 g/cm³.

11. The fired frit of any one of the preceding claims, wherein the fired frit has a viscosity in a range from about 500 P to about 10,000 P.

12. The fired frit of any one of the preceding claims, further comprising a colorant, wherein the colorant is in a range from about 5 wt. % to about 10 wt. % of the fired frit.

13. A haptic comprising the fired frit of any one of the preceding claims.

14. The haptic of claim 13, wherein the fired frit is fired at about 500 °C to about 700°C.

15. The haptic of claim 13 or claim 14, wherein the haptic has a height of up to about 2 mm.

16. The haptic of any one of claims 13-15, wherein the haptic is colored, transparent, translucent, gloss, matte or opaque.

17. The haptic of any one of claims 13-16, wherein the haptic has a cross sectional geometry conforming to a substantially circular shape.

18. The haptic of any one of claims 13-17, wherein the haptic has a cross sectional geometry conforming to a polygonal shape.

19. The haptic of any one of claims 13-18, wherein the haptic comprises two or more layers of the fired frit of claim 1.

20. The haptic of claim 19, wherein the two or more layers of the fired frit have a substantially similar composition.

21. The haptic of claim 19 or claim 20, wherein the two or more layers of the fired frit have different compositions.

22. The haptic of any one of claims 13-21, wherein the haptic comprises a micro porous structure.

23. An article comprising:

a glass substrate; and

a haptic comprising the haptic of any one of claims 13-22disposed thereon.

24. The article of claim 23, wherein the substrate has a coefficient of thermal expansion from about 75 xlO ⁷/°C to about 105 xlO ⁷/°C.

25. The article of claim 23 or claim 24, wherein the substrate has an annealing point from about 585°C to about 630°C.

26. The article of any one of claims 23-25, wherein a firing temperature is less than an annealing temperature of the substrate.

27. The article of any one of claims 23-26, further comprising an adhesive bonding the haptic to the substrate.

28. The article of any one of claims 23-27, wherein the haptic is fused to the glass substrate.

29. A method comprising:

firing a frit paste to give a fired product of the frit paste; and

ion exchange treating the substrate and the frit paste on the substrate.

30. The method of claim 29, further comprising preparing a frit paste by mixing a glass frit powder, a solvent, and a binder.

31. The method of claim 29 or claim 30, further comprising applying the frit paste to the substrate prior to firing.

32. The method of claim 31 , wherein the applying comprises pipetting, pen dispensing, applying by nozzle, extruding, using a doctor blade, 3-D printing, or screen printing.

33. The method of any one of claims 29-32, wherein firing the frit paste comprises firing at about 500 °C to about 700 °C.

34. The method of any one of claims 29-33, further comprising post-treating the frit paste on the substrate.

35. The method of any one of claims 29-34, further comprising applying one or more decorative patterns or button icons.

36. An article made by the method of any one of claims 29-35.