Lamination of electrochromic device to glass substrates

0001[Cross-reference of related applications] This application is in US Provisional Patent Application No. 60 / 31,001 filed on March 5, 2010 and No. 60 / 41,153 filed on November 10, 2010, the disclosure of which is incorporated herein by reference. , Claim the benefit of the filing date.

0002Glass, especially colored glass, is subject to great stress due to the uneven heating caused by the absorption of solar radiation. These stresses can be large enough to cause cracks or cracks in the glass, which can eventually lead to breakage.

0003The center of the glass (COG) can have a significantly higher temperature than, for example, the edges of the glass that are typically covered or shaded by a frame or other building structure. Of course, the darker the glass is colored, the more sunlight is absorbed and the greater the potential temperature difference between the COG and the glass edge or other shaded area. This results in stress typically along the edges of the glass, which can crack if greater than about 14 to about 28 MPa. Therefore, in normal use, the glass is heat-strengthened or hardened to reduce the rate of cracking. Typically, absorbent glazing can withstand at least about 35 MPa, or ASTM E2431 (Practice for Determining the Resistance of Single Glazed). Annealed Architectural Flat Glass to Thermal Heat treatment or quenching is performed to meet industrial standards such as Loadings)). Of course, this increases manufacturing costs.

0004Like colored glass, electrochromic devices (EC devices) absorb significant amounts of solar radiation, especially when in a completely dark state. In order to withstand the stresses or working loads associated with these temperature differences, it is common practice to use heat-strengthened or hardened glass as the substrate for these devices. This is a viable solution, but the cost of manufacturing devices based on these substrates is high. It is desirable to reduce costs and increase efficiency in the manufacture of EC devices while maintaining its structural stability (ie, the ability to withstand cracks and crevices both during the manufacturing process and when installed in the field).

0005The traditional EC device and the insulating glass unit (IGU) containing it have the structure shown in Figure 1A. As used herein, the term "insulated glass unit" is used so that an insulating air layer (or other gas, such as argon, nitrogen, krypton) is formed between the layers separated by spacers along the edges. Means two or more layers of glass sealed in. IGU 18 includes an internal glass panel 10 and an EC device 19. The EC device 19 comprises an EC stack 11 containing a coating continuously adhered or deposited on the EC substrate 12. The EC substrate 12 traditionally consists of heat-strengthened or hardened glass.

0006To form the IGU 18, the glass panel that will be the EC substrate 12 is first cut to a custom size according to the required dimensions. The cut glass panel 12 is then hardened or heat strengthened to provide sufficient strength to withstand the fabrication stresses and the stresses faced during their useful life (work load). The EC device stack 11, which comprises, for example, a continuous thin film, is then glass paneled 12 by methods known in the art (see, eg, US Pat. Nos. 7,372,610 and 7,593,154, the disclosure of which is incorporated herein by reference). Adhere or deposit on. The glass panel 12 is not cut after quenching or heat strengthening. Similarly, the substrate of EC device 19 is generally not hardened or heat strengthened after depositing the coating forming the EC stack 11 (unless a properly post-quenched EC coating stack and process is used). Then IGU Assemble 18 by combining EC device 19 with another glass panel 10. The two panels are separated by a spacer 17. The panel 10 may contain a thin film coating on both sides (eg, for sunshine conditioning).

0007<figref num="1a">It is a sectional view of a traditional IGU including an EC device.</figref><figref num="1b">FIG. 5 is a cross-sectional view of an IGU containing an EC device, wherein the EC device itself is a laminate of two materials.</figref><figref num="2">It is a plot of the stress distribution of the EC laminate containing the low coefficient of thermal expansion glass laminated on soda-lime glass.</figref><figref num="3a">FIG. 6 is a plot of EC laminates comparing peak edge tensile stresses for several laminates exposed to sunlight.</figref><figref num="3b">A plot of an EC laminate comparing peak edge tensile stresses for several laminates exposed to sunlight.</figref><figref num="4">It is a figure which shows the outline of the impact test as a function of the thickness of an EC substrate, an EC external laminated glass plate, and an intermediate layer.</figref><figref num="5">It is a figure which shows the example of the 4-point bending test which shows the laser cut glass sample under a test condition.</figref><figref num="6">It is a figure which shows the probability plot of the intensity with respect to a glass sample comparing a machine cut panel and a laser cut glass.</figref>

0008Applicants have developed an improved IGU that includes an EC device laminate. The applicant has also developed an improved method for manufacturing EC device laminates and IGUs.

0009In one aspect of the invention, the applicant: (a) a step of preparing an electrochromic substrate; (b) a step of cutting the electrochromic substrate into one or more substrate daughter panes; ( c) Steps to make multiple electrochromic device precursors on each of one or more substrate daughter panels; (d) Steps to cut each of the electrochromic device precursors into individual electrochromic devices. And; (e) A method of making an electrochromic device laminate, further comprising a step of laminating each of the individual electrochromic devices onto a separate outer laminate glass plate ("Cut-Zen" further described herein. -I found an example of the "cut-then-coat-then-cut" process). In one embodiment, the electrochromic device precursor is mechanically cleaved. In another embodiment, the electrochromic device precursor is laser cut. In another embodiment, the EC device is cut by electrothermal cutting.

0010In another embodiment, the individual electrochromic devices have an edge strength of at least about 60 MPa. In another embodiment, the individual electrochromic devices have an edge strength of at least about 69 MPa. In another embodiment, the individual electrochromic devices have an edge strength of at least about 75 MPa. In another embodiment, the individual EC device has an edge strength of at least about 100 MPa.

0011In another embodiment, the individual electrochromic devices are about the same size as the outer laminated glass plate. In another embodiment, the individual electrochromic device has at least one dimension smaller than the outer laminated glass plate. In another embodiment, the individual electrochromic devices are indented from about 0.5 mm to about 3 mm to the outer laminated glass plate in at least one dimension. In another embodiment, the individual electrochromic devices are indented from about 1 mm to about 2.0 mm with respect to the outer laminated glass plate in at least one dimension, preferably all dimensions.

0012In another embodiment, the electrochromic substrate and the outer laminated glass plate contain the same material. In another embodiment, the electrochromic substrate is a different material than the external laminated glass plate. In another embodiment, the material of the electrochromic substrate is selected from the group consisting of low thermal expansion coefficient glass, soda lime float glass, aluminosilicate glass, borofloat glass, boroaluminosilicate glass, other low sodium composition glass, or polymers. Will be done. In another embodiment, the electrochromic substrate has a coefficient of thermal expansion ranging from about 2 ppm / K to about 10 ppm / K for glass substrates and a coefficient of thermal expansion up to about 80 ppm / K for polymer substrate materials. .. In another embodiment, the electrochromic substrate has a coefficient of thermal expansion in the range of about 4 ppm / K to about 8 ppm / K. In another embodiment, the electrochromic substrate has a thickness in the range of about 0.7 mm to about 6 mm.

0013In another embodiment, the material of the outer laminated glass plate is a group consisting of low thermal expansion coefficient glass, soda lime float glass, aluminosilicate glass, borofloat glass, boroaluminosilicate glass, heat reinforced glass, hardened glass, or polymer. Is selected from. In another embodiment, the outer laminated glass plate has a coefficient of thermal expansion in the range of about 2 ppm / K to about 10 ppm / K. For polymer-based substrates, the coefficient of thermal expansion can be up to about 80 ppm / K. In another embodiment, the outer laminated glass plate has a thickness in the range of about 2.3 mm to about 12 mm. In another embodiment, the interlayer material is selected from the group consisting of polyvinyl butyral, ionomer polymers, ethylene vinyl acetate, polyurethane, or mixtures thereof.

0014Another aspect of the invention is a laminate prepared by a "cut-zen-coat-zen-cut" process. In another embodiment, the laminate prepared by the "cut-zen-coat-zen-cut" process comprises a substrate having an edge strength of at least about 60 MPa.

0015In another aspect of the invention, the applicant: (a) a step of preparing an electrochromic substrate; (b) a step of making multiple electrochromic device precursors on an electrochromic substrate; (c) electro Electrochromic device lamination, including cutting each of the chromic device precursors into individual electrochromic devices; (d) laminating each of the individual electrochromic devices onto separate external laminate glass plates. A method of making a body (an example of a "coat-then-cut" process further described herein) has been discovered. The EC device precursor may be mechanically cleaved by laser or by electrothermal cutting.

0016In another embodiment, the individual electrochromic devices have an edge strength of at least about 60 MPa. In another embodiment the edge strength is at least about 69 MPa. In another embodiment the edge strength is at least about 75 MPa. In another embodiment the edge strength is at least about 100 MPa.

0017In another embodiment, the individual electrochromic devices are about the same size as the outer laminated glass plate. In another embodiment, the individual electrochromic device has at least one dimension smaller than the outer laminated glass plate. In another embodiment, the individual electrochromic devices are indented from about 0.5 mm to about 3 mm to the outer laminated glass plate in at least one dimension. In another embodiment, the individual electrochromic devices are indented from about 1 mm to about 2.0 mm with respect to the outer laminated glass plate in at least one dimension.

0018In another embodiment, the annealed glass substrate and the outer laminated glass plate contain the same material. In another embodiment, the electrochromic substrate is a different material than the external laminated glass plate. In another embodiment, the material of the electrochromic substrate is selected from the group consisting of low thermal expansion coefficient glass, soda lime float glass, aluminosilicate glass, borofloat glass, boroaluminosilicate glass, low sodium composition glass, or polymers. .. In another embodiment, the electrochromic substrate has a coefficient of thermal expansion in the range of about 2 ppm / K to about 10 ppm / K. For polymer-based substrates, the coefficient of thermal expansion can be up to about 80 ppm / K. In another embodiment, the electrochromic substrate has a coefficient of thermal expansion in the range of about 4 ppm / K to about 8 ppm / K. In another embodiment, the electrochromic glass substrate has a thickness in the range of about 0.7 mm to about 6 mm.

0019In another embodiment, the material of the outer laminated glass plate is a group consisting of low thermal expansion coefficient glass, soda lime float glass, aluminosilicate glass, borofloat glass, boroaluminosilicate glass, heat reinforced glass, hardened glass, or polymer. Is selected from. In another embodiment, the outer laminated glass plate has a coefficient of thermal expansion in the range of about 2 ppm / K to about 10 ppm / K. In another embodiment, the outer laminated glass plate has a thickness in the range of about 2.3 mm to about 12 mm. In another embodiment, the interlayer material is selected from the group consisting of polyvinyl butyral, ionomer materials, ethylene vinyl acetate, polyurethane, or mixtures thereof.

0020Another aspect of the invention is a laminate prepared by a "coat-zen-cut" process. In another embodiment, the laminate prepared by the coat-zen-cut process comprises a substrate having an edge strength of at least about 60 MPa.

0021In another aspect of the invention, the applicant is: (a) an electrochromic device comprising an electrochromic stack on an annealed glass substrate; (b) an external laminated glass plate; (c) an electrochromic device and An outer laminate We have discovered a laminate with an intermediate layer material sandwiched between glass plates. In some embodiments, the electrochromic device has an edge strength of at least about 60 MPa. In another embodiment the edge strength is at least about 69 MPa. In another embodiment the edge strength is at least about 75 MPa and in other embodiments at least about 100 MPa. In another embodiment, the electrochromic device is prepared by mechanical cutting. In another embodiment, the electrochromic device is prepared by laser cutting. In another embodiment, the electrochromic device is prepared by electrothermal cutting. In another embodiment, the laminate is part of an integrated glass unit.

0022In another embodiment, the annealed glass substrate and the outer laminated glass plate contain the same material. In another embodiment, the annealed glass substrate is a different material than the external laminated glass plate. In another embodiment, the material of the annealed glass substrate is selected from the group consisting of low thermal expansion coefficient glass, soda lime float glass, aluminosilicate glass, borofloat glass, boroaluminosilicate glass, low sodium composition glass, or polymers. Will be done. In another embodiment, the annealed glass substrate has a coefficient of thermal expansion in the range of about 2 ppm / K to about 10 ppm / K. In another embodiment, the annealed glass substrate has a coefficient of thermal expansion in the range of about 4 ppm / K to about 8 ppm / K. In another embodiment, the annealed glass plate has a thickness in the range of about 0.7 mm to about 6 mm. In another embodiment, the annealed glass plate has the same thickness as the outer laminate. In another embodiment, the annealed glass plate has a different thickness than the outer laminate.

0023In another embodiment, the material of the outer laminated glass plate is a group consisting of low thermal expansion coefficient glass, soda lime float glass, aluminosilicate glass, borofloat glass, boroaluminosilicate glass, heat reinforced glass, hardened glass, or polymer. Is selected from. In another embodiment, the outer laminated glass plate has a coefficient of thermal expansion in the range of about 2 ppm / K to about 10 ppm / K. In another embodiment, for polymer-based substrates, the coefficient of thermal expansion can be up to about 80 ppm / K. In another embodiment, the outer laminated glass plate has a thickness in the range of about 2.3 mm to about 12 mm.

0024In another embodiment, the annealed glass substrate is about the same size as the external laminated glass plate. In another embodiment, the annealed glass substrate has at least one dimension smaller than the outer laminated glass plate. In another embodiment, the annealed glass substrate is indented from about 0.5 mm to about 3 mm with respect to the outer laminated glass plate in at least one dimension. In another embodiment, the annealed glass substrate is indented from about 1 mm to about 2.0 mm with respect to the outer laminated glass plate in at least one dimension. In another embodiment, the perimeter of the smaller annealed glass substrate is surrounded on at least one side by an interlayer material such as a polymer containing silicone, urethane, epoxy, and acrylate, or another material.

0025In another embodiment, the interlayer material is selected from the group consisting of polyvinyl butyral, ionomer materials, ethylene vinyl acetate, polyurethane, or mixtures thereof.

0026In another embodiment, the annealed glass substrate is soda lime float glass having a coefficient of thermal expansion of about 8.5 ppm / K, and the outer laminated glass plate has a coefficient of thermal expansion of about 8.5 ppm / K. It is a hardened soda lime float glass, and the intermediate layer material is polyvinyl butyral. In another embodiment, the interlayer material is SentryGlas® Plus (SGP). In another embodiment, the annealed glass substrate is prepared by laser cutting and has an edge strength of at least 69 MPa. In another embodiment, the electrochromic stack is between the annealed glass substrate and the interlayer material. In another embodiment, the electrochromic stack is on the surface of the annealed glass substrate opposite the interlayer material.

0027In another aspect of the invention, the applicant is: (a) an electrochromic device with an electrochromic stack on a substrate; (b) an external laminated glass plate; (c) an electrochromic device and an external laminated glass. It includes an intermediate layer material sandwiched between the plates. In another embodiment, the electrochromic device is prepared by laser cutting or electrothermal cutting.

0028Applicants have requested that the electrochromic device laminates of the invention (or IGUs containing these laminates) be manufactured on a hardened or heat treated glass substrate (or such a traditional electrochromic device). It was unexpectedly found that it can withstand the same stresses faced by IGUs, including traditional electrochromic devices. Therefore, the EC device laminate of the present invention can withstand similar glass center and edge stresses and can withstand stresses of at least about 17 MPa.

0029In some embodiments, tolerating similar stresses means that the electrochromic device laminates or IGUs of the present invention pass approximately the same industry standard tests as traditional electrochromic devices or IGUs. In other embodiments, withstanding similar stresses means that the electrochromic device laminates or IGUs of the present invention (i) safely meet the maximum in-use thermomechanical stresses faced in traditional EC applications. Excessive stress and / or (ii) means that it can withstand at least about 50% of the same working load or stress as a traditional EC device or IGU. Applicants have also surprisingly found that these goals can be achieved using an annealed glass substrate with an electrochromic stack attached or deposited on the surface.

0030Applicants can withstand the same working loads or stresses faced by IGUs produced by traditional means, while the improved manufacturing method provides high manufacturing efficiency and meets industry standards. Unexpectedly found to provide an electrochromic device laminate or IGU.

0031In addition, Applicants have provided an annealed glass substrate to produce sufficiently defect-free edges that are believed to withstand the full range of heat and load stresses that the EC device laminate will experience during its useful life. I unexpectedly discovered that laser cutting is possible. Applicants tested the laser-cut glass and EC device laminates in Figure 1B at the top edge of the thermal and mechanical stress parameter space, and the laser-cut EC device laminates or substrates are very durable. Has been determined to be suitable for use in residential and commercial building applications and other applications.

0032In addition, Applicants can coat large substrate panels by the "Coat-Zen-Cut" and "Cut-Zen-Coat-Zen-Cut" processes, both further described herein, and custom after coating. We found that it would be possible to size. Applicants have also found that this process provides improved process control and better overall uniformity of the coating of EC devices. Indeed, if glass panels, all having approximately the same dimensions, are used, subsequent processing temperatures and sputtering plasma conditions for each and every panel are expected to be approximately the same. This is believed to result in a more efficient continuous coater or sputtering operation without the need to slow or stop production, or to make process adjustments with respect to the desired thickness, coloring, and size of many glasses. Therefore, the throughput and operating time are maximized, resulting in lower and more competitive production costs when manufacturing electrochromic devices or IGUs.

0033EC device laminate One aspect of the present invention comprises an electrochromic device with an electrochromic stack on an EC substrate; an EC external laminated glass plate; and an intermediate layer material sandwiched between the electrochromic device and the external laminated glass plate. It is a device laminate.

0034The EC device laminate 29 and the IGU 30 containing it are shown in Figure 1B. The EC device laminate 29 is composed of an EC device 32 laminated on the EC external laminate glass plate 22. Between the EC device 32 and the EC outer laminate glass plate 22, there is an intermediate layer material 28 that bonds the EC device 32 and the outer laminate plate 22. The EC device 32 itself consists of an EC stack 21 attached or deposited on the EC substrate 31. The completed IGU 30 includes an EC device laminate 29, along with another glass panel 20 separated by a spacer 27. Although FIG. 1B represents a two-plate IGU, the present invention also contemplates an IGU containing three or more plates (additional plates may be of any shape or size and are in the art. Includes known, colored or other coatings).

0035Any EC stack 21 may be used as known to those of skill in the art. An exemplary EC stack is described, for example, in US Pat. Nos. 5,321,544; 5,404,244; 7,372,610; and 7,593,154, the entire disclosure of which is incorporated herein by reference.

0036In one embodiment, at least the EC substrate 31 of the EC device laminate 29 is made of annealed glass. As used herein, the term "annealed glass" means glass produced without the internal stress applied by heat treatment and subsequent rapid cooling. The term includes glass typically classified as annealed or floated glass and excludes only heat-tempered or hardened glass.

0037In other embodiments, the EC substrate 31 and the EC external laminate glass plate 22 are both made of annealed glass. In an embodiment in which the EC substrate 31 and the EC external laminate glass plate 22 are both annealed glass, the annealed glass utilized may be the same (matched) or different (mismatched). The annealed glass substrate used may have the same or different coefficients of thermal expansion, or may have different types and / or amounts of dopants.

0038For example, in the "mismatched" embodiment, the substrate 31 may be made of soda lime float glass, while the EC external laminate glass plate 22 may be low coefficient of thermal expansion glass (low CTE glass). Well, or vice versa. In the "matching" embodiment, for example, the substrate 31 and the EC external laminate glass plate 22 may both be made of soda lime float glass, or both may be made of low CTE glass.

0039In addition to those defined above, the term "mismatch" also refers to the use of glass with different thicknesses, regardless of whether the type of glass is the same or different. For example, the substrate 31 and the outer laminated glass plate 22 can be of the same material but can have different thicknesses. Alternatively, as a mere example, the substrate 31 can be of a different material than the external laminated glass plate 22 and can have a different thickness. Further, as a mere example, the substrate 31 can be of the same type of material as the outer laminated glass plate 22, but can have different coefficients of thermal expansion and / or different thicknesses.

0040The EC substrate 31 of the present invention comprises Guardian Industries (Guardian Global Headquarters, Auburn Hills, MI), Pilkington, North America (Toledo, OH), Cardinal Glass Industries (Eden Prairie, MN), and Cardinal Glass Industries (Eden Prairie, MN), which produce large areas of thin glass. You may choose from traditional glass materials, including soda lime annealed glass such as AGC (AGC Flat Glass, Alpharetta, GI).

0041EC substrate 31 is low CTE borofloat glass, such as available from Schott (Schott North America Elmsford, NY), or Corning 1737 and Corning Eagle XG (from Corning Incorporated, Corning, NY, respectively. It may be selected from materials including boroaluminosilicate glass (available). Further, the EC substrate 31 may be selected from materials including aluminosilicate glass. One of ordinary skill in the art would be able to select other glass substrates suitable for this purpose and satisfying the limitations of the invention set forth in the claims.

0042The EC substrate 31 may consist of a polymer, a copolymer, or a mixture of one or more polymers or copolymers. Non-limiting examples of polymers include polyimide, polyethylene, naphthalate (PEM), polyethylene terephthalate (PET), aramid, or other similar polymeric materials. One of ordinary skill in the art will be able to select other polymeric substrates that are suitable for this purpose and that satisfy the limitations of the invention set forth in the claims.

0043In general, EC31 has any thickness, depending on the desired application (eg, residential building windows, commercial building windows, or even automotive windows) and the desired thermal / structural properties. May be good. Typically, the substrate 31 has a thickness in the range of about 0.7 mm to about 6 mm. In some embodiments, the EC substrate has a thickness in the range of about 1.5 mm to about 2.3 mm.

0044In some embodiments, the annealed glass or soda lime float glass utilized has a coefficient of thermal expansion (CTE) between about 7.0 ppm / K and about 10.0 ppm / K. In other embodiments, the glass utilizing a soda lime float has a CTE between about 8.2 ppm / K and about 9.0 ppm / K. In some embodiments utilizing low CTE glass, the coefficient of thermal expansion ranges from about 2.0 ppm / K to about 6.4 ppm / K. In some specific embodiments that utilize low CTE glass, the coefficients of thermal expansion are: Corning 1737 (about 3.76 ppm / K), Corning Eagle XG (about 3.2 ppm / K), and Schott. Borofloat 33 (approximately 3.3 ppm / K).

0045The EC external laminated glass plate 22 of the present invention may be selected from materials including heat tempered glass, hardened glass, partially heat hardened or hardened glass, or annealed glass. The terms "heat tempered glass" and "hardened glass" are used in both types of glass, as is known in the art, in which heat treatment is performed to induce surface compression and the glass is otherwise tempered. is there. Heat-treated glass is classified as fully hardened or heat-strengthened. According to the federal specification DD-G-1403B, fully hardened glass must have a surface compression of about 69 MPa or more, whereas an edge compression of about 67 MPa or more. It is believed that heat tempered glass must have a surface compression between about 24 and about 69 MPa, or an edge compression between about 38 and about 67 MPa. The fracture properties of heat-tempered glass are expected to vary widely, and cracks can occur at stresses of approximately 41-69 MPa.

0046In general, the EC exterior laminated glass plate 22 has an arbitrary thickness, depending on the desired application (eg, a window for residential construction, or a window for commercial construction) and the desired thermal / structural properties. You may. In some embodiments, the plate 22 of the EC outer laminate may be made of plastic, including polycarbonate. Typically, the EC outer laminate glass plate 22 has a thickness in the range of about 2.3 mm to about 12 mm. In some embodiments, the EC external laminated glass plate 22 has a thickness in the range of about 2.3 mm to about 6 mm. Of course, thicker glass may be utilized if required by the application, for example when used in architectural applications facing high wind loads or ballistic or blast resistant applications.

0047In some embodiments, the annealed glass or soda lime float glass utilized has a coefficient of thermal expansion (CTE) between about 7.0 ppm / K and about 10.0 ppm / K. In other embodiments, the soda lime float glass has a CTE between about 8.2 ppm / K and about 9.0 ppm / K. In some embodiments utilizing low CTE glass, the coefficient of thermal expansion ranges from about 2.0 ppm / K to about 6.4 ppm / K. In some specific embodiments that utilize low CTE glass, the coefficients of thermal expansion are: Corning 1737 , about 3.76 ppm / K; Corning Eagle XG , about 3.2 ppm / K; and Schott Borofloat 33 , approx. 3.3 ppm / K.

0048In some embodiments, the EC substrate 31 and the EC external laminated glass plate 22 have approximately the same coefficient of thermal expansion (CTE). In other embodiments, the EC substrate 31 and the EC external laminated glass plate 22 have different CTEs. In other embodiments, the EC substrate 31 and the EC external laminated glass plate 22 have different coefficients of thermal expansion by less than about 50%. In yet another embodiment, the EC substrate 31 and the EC external laminated glass plate 22 have different coefficients of thermal expansion by less than about 30%. In other embodiments, the EC substrate 31 and the EC external laminated glass plate 22 have different coefficients of thermal expansion by less than about 20%. In yet another embodiment, the EC substrate 31 and the EC external laminated glass plate 22 have different coefficients of thermal expansion by less than about 10%. As discussed herein, the selection of the appropriate intermediate layer material 28 can help relieve any stress caused by CTE inconsistencies.

0049For example, FIG. 2 shows the stress distribution of the laminate when low CTE glass is used as the EC substrate 31, soda-lime glass is used as the plate 22 of the EC external laminate, and polyvinyl butyral is used as the intermediate layer material 28. Shown. This simulation shows the contrast effect of a 25 mm frame surrounding the edges of the panel. The frame is thought to cause a temperature gradient between the edges and the center of the laminate, which is thought to form edge stresses. In the case of laminated structures, CTE inconsistencies cause additional stress as the device is heated by the absorption of sunlight. The effect of this CTE inconsistency is shown in Fig. 3a, which is 1000 W / m.²The sunlight-absorbing low-CTE / soda-lime glass laminates exposed to the incident radiation of the are more than the soda lime / soda lime laminate structures also under the same sunlight absorption conditions, also shown in Figure 3a. Has a high peak stress level. As shown in these examples, the maximum edge stress changes over time to a stress of up to about 20.5 MPa after about 40 minutes as the EC laminate absorbs more solar radiation. For a longer period of time, heat conduction through the glass from the exposed area to the contrast edge area will cause temperature equilibrium and correspondingly reduce the thermal stress from its peak level. These stresses can be reduced when two low CTE panels as shown in FIG. 3b are laminated together under the same edge frame contrast and sunlight absorption conditions as shown in FIG. 3a. it is conceivable that.

0050In a preferred embodiment, the edges of the EC substrate 31 are protected from handling and mechanical damage. Without being bound by any particular theory, it is believed that if the edges of the EC substrate 31 are significantly scratched or chipped, the overall strength of the EC device can be compromised. In some embodiments of the present invention, the EC substrate 31 is indented with respect to the EC external laminated glass plate 22. In other embodiments, the size of the EC substrate 31 is at least one dimension, preferably at least two dimensions, more preferably all dimensions, slightly smaller than the size of the EC external laminated glass plate 22. In some embodiments, the EC substrate 31 is indented with respect to the glass plate 22 from about 0.5 mm to about 3 mm in at least one dimension, preferably from about 0.5 mm to about 3 mm along the periphery. There is. In other embodiments, the EC substrate 31 is indented from about 1 mm to about 2.0 mm, preferably about 1 mm to about 2.0 mm along the periphery of the glass plate 22 in at least one dimension. ..

0051In some embodiments, the indentation depth is determined by the automated mounting tolerance of the two pieces of glass during the lamination layup / manufacturing process, as well as by any slight movement that occurs during the thermal lamination process. In some embodiments, during the heat treatment, the intermediate layer material is flushed around the edges of the EC substrate 31 to provide a protective element that is believed to further protect the EC device laminate 29 from damage during transport and installation. In some embodiments, excess intermediate layer material is added to achieve this. In other embodiments, additional protective material, such as, but not limited to, polymers, such as, but not limited to, epoxies, urethanes, silicones, and acrylates, can be deposited around the perimeter of the EC device. These materials can be adhered in varying amounts to achieve the desired result.

0052The intermediate layer material can be selected from any material capable of laminating the EC device 32 on the EC external laminated glass plate 22 by a method known in the art. In general, the interlayer material 28 is: (a) high optical transparency; (b) less cloudiness; (c) high impact resistance; (d) high penetration resistance; (e) UV resistance; (f) good long term Thermal stability; (g) Sufficient adhesion to glass and / or other polymeric materials / sheets; (h) Low moisture absorption; (i) High moisture resistance; (j) Excellent weather resistance; and (k) ) Should possess a combination of features including high stress bearing loads (eg, impact or wind loads). In some embodiments, the intermediate layer material 28 provides sufficient adhesion to both the EC device 32 and the EC external laminate glass plate 22 to prevent layer peeling during stress loading during use. It is also selected to provide at least and not adversely affect the visual properties of the EC device laminate 29. In other embodiments, the interlayer material should be selected so that industry standard performance standards are met in both load modes (eg ANSI Z97.1 for impact testing, ANSI Z971 for wind load standards). ASTM See E1300).

0053In one embodiment, a suitable intermediate layer material 28 is polyvinyl butyral (PVB), available from Solutia Inc. (St. Louis, Missouri) under the trade name Saflex . PVB is also available from DuPont (Wilmington, DE) under the trade name Butacite . Other suitable materials for the interlayer material 28 include ionomer materials such as DuPont's Sentry Glass Plus (SGP), ethylene vinyl acetate (EVA), and crosslinked polyurethane (eg, cast-in cast-in). -place resin)), or thermoplastic polyurethane is included. Of course, a mixture of any of the materials identified above may be used. In addition, other polymeric materials can be used as the interlayer material 28 as long as at least some of the thermomechanical, adhesive, and optical transparency functional requirements listed above are met. This includes intermediate layer materials composed of composite polymer layers designed for improved acoustic damping, ballistic and blast resistance applications. These materials are readily available to those skilled in the art.

0054In other embodiments, the intermediate layer material 28 may include silicone and epoxy.

0055For example, if both the EC substrate 31 and the EC external laminated glass plate 22 are made of the same material, it is considered that both glass panels may have approximately the same coefficient of thermal expansion. If the materials are different, i.e. inconsistent as shown in Figure 2, then the selection of the appropriate interlayer material 28 is not bound by any particular theory, but the selection of the appropriate interlayer material 28 is between the inconsistent glass panels. It is believed that it may affect the transfer or distribution of stresses and therefore may reduce at least some of the stresses present at various points in the laminate.

0056For laminated structures with a coefficient of thermal expansion (CTE) mismatch between the glass plates, the intermediate layer is flexible enough not to transfer tensile stress from (1) higher CTE glass panels to lower CTE glass panels. As such; or (2) with negligible mechanical relaxation of the polymer at low temperatures, sufficient from the stacking temperature to transfer compressive stresses from high CTE glass panels to low CTE glass panels during cooling. It is considered that it should be selected so that it is rigid.

0057Figures 3a and 3b show a sun-exposed laminate with edges shaded by a 1 window / building frame (in this case, the component panels have thicknesses of 0.7 mm and 6 mm, respectively. ) Provides a comparison of peak edge tensile strength. Examples of matching (low CTE / low CTE; soda lime / soda lime) and unmatched (low CTE / soda lime) are shown as a function of time. Rigid intermediate layer For materials (stress transfer), the effective stress for the low CTE / soda lime combination can be greater than the effective stress for the soda lime / soda lime combination, so the resulting edge stress is that of the intermediate layer material. It is considered that it may depend on the thermomechanical properties.

0058The EC device laminate 29 (or IGU 30 containing these laminates) is a traditional electrochromic device (or such a traditional electrochromic device) manufactured on a hardened or heat treated glass substrate. It is believed to withstand the same stresses that IGUs) face.

0059In some embodiments, tolerating similar stresses means that the EC device laminate 29 or IGU 30 of the present invention passes approximately the same industry standard tests as traditional electrochromic devices or IGUs. In other embodiments, withstanding similar stresses means the EC device laminate 29 or IGU of the present invention. 30 stresses that safely exceed the maximum in-use thermomechanical stresses faced in traditional EC applications, and / or (ii) the same working load or stress as traditional electrochromic devices or IGUs. Means that it can withstand at least about 50% of. In some embodiments, the EC device laminate 29 can withstand a thermal edge stress (or working load) of at least about 17 MPa. In other embodiments, the EC device laminate can withstand thermal edge stresses of at least about 21 MPa. In some embodiments, the EC device 29 has an edge strength of at least about 60 MPa. In other embodiments, the EC device or EC substrate has an edge strength of at least about 69 MPa. In yet other embodiments, the EC device or EC substrate has an edge strength of at least about 75 MPa. In yet another embodiment, the EC device or EC substrate has an edge strength of at least about 100 MPa.

0060In some embodiments, the EC laminate 29 or EC substrate 31 is part of the IGU. The glass panel 20 used to form the IGU may be selected from any material, including glass or plastic traditionally used in IGU construction. For example, any type of glass (soda-lime glass, low CTE glass, hardened glass, and / or annealed glass) or plastic may be used. Further, the glass panel 20 is itself a multi-pane laminate of one or more materials (multi-glass plates, multiple plastic plates, glass plates and plastic plates alternately arranged in any order). May be good. The glass panel 20 may be colored in any color, or may be coated on one or both sides by any traditional method such as chemical or physical vapor deposition coating. The glass panel 20 may be an electrochromic or thermochromic device. The glass panel 20 may be laser cut or mechanically scribed. In addition, the IGU in Figure 1B 30 may be a triple-pane IGU, ie, contains an additional glass (or polymer, eg, acrylic) panel 20 adjacent to one of the glass panel 20 or the EC device laminate 29 but separated by a spacer. IGU. The glass panel 20 may have any thickness or any property, provided that it meets minimum commercial or residential building standards and / or window material standards. ..

0061(Production method) "Coat-Zen-Cut" In one embodiment of the invention presented, the applicant has discovered a manufacturing method having the concept of "coat-zen-cut". One aspect is the step of preparing an electrochromic substrate; the step of producing a plurality of electrochromic device precursors on the substrate; and the step of cutting each of the electrochromic device precursors into individual electrochromic devices. A method of manufacturing an electrochromic device laminate, comprising laminating each of the individual electrochromic devices onto a separate external laminate glass plate. As used herein, an "electrochromic device precursor" is an EC device that is typically a stack of thin films, as described above, attached or deposited on the substrate before cutting the substrate into individual EC devices. Is. Therefore, a large number of EC device precursors are made on any single substrate or, as described herein, on a substrate daughter pane. Typically, the EC precursor layout is designed to incorporate sufficient space between the precursors to cut, preferably without damaging any coating or stack as a whole.

0062In some embodiments, the EC device (or precursor) 32 is typically produced by coating or adhering the EC stack 21 onto a large substrate panel 31 such as annealed glass. Stacks may be attached or deposited by methods known in the art, such as those incorporated herein. The EC device (or precursor) 32 is then subsequently cleaved (by traditional mechanical means, by laser cutting, or by electrothermal cutting, as detailed herein) to the final application. Make the desired dimensions according to your needs. Of course, the panel may be cut to any size or shape. The substrate may be pre-cut from a larger panel. The device 32 is then laminated on the EC external laminate glass plate 22 to preferably provide additional mechanical strength. The EC laminate 29 can be configured with the EC device substrate 32 shown in FIG. 1B (ie, with the EC coating stack 21 outside the EC laminate 29), or the EC laminate 29 is the intermediate layer material 28. It can consist of an oriented EC device substrate 32 with an EC coating stack 21 in contact with (ie, the EC coating stack inside the laminate).

0063After processing the EC device laminate 29, it is optionally combined with the glass 20 to form the IGU 30.

0064In some embodiments, the EC external laminate glass plate is approximately the same size as the EC device. In other embodiments, the EC external laminate glass plate is of a different size than the EC device. In some embodiments, the EC substrate is indented on the outer glass plate as described above. As further detailed herein, the EC outer laminate glass may have the same or different thickness and / or coefficient of thermal expansion as the EC device (or substrate on which the EC device is deposited). .. The outer laminated glass plate may be mechanically cut or laser cut. Another aspect of the present invention is a laminate produced by this method.

0065"Cut-Zen-Coat-Zen-Cut" In another embodiment of the invention presented, the applicant first cuts a large panel of EC substrates into one or more substrate daughter panels, and then one of the "Coat-Zen-Cut" concepts described above. We have discovered a manufacturing method that includes steps to apply to each of the above substrate daughter panels (this process is hereafter referred to as the "cut-zen-coat-zen-cut" process).

0066Thus, another aspect of the invention is the step of preparing an electrochromic substrate; the step of cutting the electrochromic substrate into one or more substrate daughter panels; and one or more of the plurality of electrochromic device precursors. With the steps of making each of the substrate daughter panels on;; with the steps of cutting each of the electrochromic device precursors into individual electrochromic devices; with each of the individual electrochromic devices, separate external laminated glass plates. It is a method of manufacturing an electrochromic device laminated body including the step of laminating with.

0067In some embodiments, a large substrate panel of annealed glass is cut into one or more substrate daughter panels. In another embodiment, a large substrate panel of annealed glass is cut into a plurality of substrate daughter panels. Each of the substrate daughter panels may be approximately the same size and / or shape, or may be of a different size and / or shape. For example, early large EC boards may be cut into three equally sized board daughter panels, or may be cut into three board daughter panels, each with a different size. At least some of the edges of the substrate daughter panel may then undergo an optional edge grinding process, followed preferably by cleaning. In other embodiments, the large substrate panel is cut into a single smaller (at least one dimension) substrate daughter panel.

0068In some embodiments, the substrate daughter panel is a carrier for further processing, i.e. to make an EC device precursor by coating each of the substrate daughter panels with the EC stack described herein. Introduced above. Although any number of substrate daughter panels may be introduced on any single carrier, it is preferred to optimize the surface area of the carriers to fit many substrate daughter panels. Each of the EC device precursors on each of the substrate daughter panels is then further cleaved, such as by laser or electrothermal cutting, or by mechanical means.

0069The cut-zen-coat-zen-cut process is considered to offer several advantages. First, it is typical that the glass substrate is held at a slight angle during the sputtering process (usually between about 5 and 9 degrees from the vertical). This angle can result in deflection and, ultimately, uneven coating due to glass warpage. This warpage of the glass is considered to increase as the size of the glass increases. Therefore, it may help mitigate any potential non-uniformity by applying the coating (eg, EC stack) via sputtering to smaller pieces of glass that were initially cut from a larger substrate panel. There is. In some embodiments, the substrate glass is held vertically during coating. Without being bound by any particular theory, it is possible that warpage can be caused by thermal stress. It is believed that any thermal stress can be similarly reduced by using a substrate daughter panel, preferably a smaller substrate daughter panel.

0070Second, a desired substrate glass size (or shape) is not always available from the manufacturer. For example, glass from the manufacturer can be too large to attach to a carrier or reactive sputtering chamber. In addition, it may be more cost effective to purchase a larger piece of glass and cut it first to fit the carrier.

0071Third, the edges of the glass as received may not always be in a suitable condition for immediate processing. In these cases, it is desirable to first cut the glass into smaller daughter panels with defect-free edges or edges that meet downstream manufacturing and processing requirements.

0072Fourth, any large piece of glass can contain defects. Defect-free (s) glass panels can be cut from large glass panels without wasting large amounts of glass or processing time.

0073Laminating steps in the "coat-zen-cut" and "cut-zen-coat-zen-cut" processes are performed using methods known to those of skill in the art. For example, a typical laminating process involves heating the laminate under moderate pressure to create partial bonds between the glass panels, such as the nip roller process, followed by a long-term bonding process, such as high temperature and high pressure. It involves using an autoclave to complete the bond with the glass, remove residual air or dissolve the air in the polymer structure to form an optically transparent intermediate layer. Other techniques are: (i) a vacuum process in combination with heating to remove air from the interlayer region and bond the glass panels, or (ii) between the glass panels to create a transparent interlayer. Utilize a polymer that is poured into the gap and fills the capillary space in between.

0074(Conventional mechanical scribe or cutting) In a typical glass preparation, a carbide or diamond tip scribe or wheel is used to create a cut in the surface of the glass panel and then a bending moment is applied to propagate the surface cracks along the edges and straighten it. It is conceivable to generate a break. The edges of the glass are often ground using a grinder or a silicon carbide sanding belt.

0075(Laser cutting) In some embodiments of the invention, a laser is used to cut the EC device laminate 29 or the EC substrate 31. As used herein, the term "laser cutting" (i) creates fine cracks perpendicular to the substrate surface that later propagate through the glass by applying a bending moment to produce complete separation. To use a laser, or (ii) to produce a complete separation, means a complete cut through the glass due to a laser-induced crack that propagates along the length of the substrate. The laser cutting process is equally applicable to the "coat-zen-cut" and "cut-zen-coat-zen-cut" processes.

0076Therefore, one aspect of the present invention is the step of preparing an electrochromic substrate; the step of producing a plurality of electrochromic device precursors on the substrate; and the step of laser cutting each of the electrochromic device precursors into individual electrochromic devices. Steps; A method of manufacturing an electrochromic device laminate, comprising laminating each of the individual electrochromic devices onto a separate outer laminate glass plate. In some embodiments, the laser cutting process induces fine surface cracks that propagate to separate later by applying a bending moment, or requires subsequent bending or "breakout". It does not include a complete "cut-through" by initiating and propagating cracks along the substrate for complete separation.

0077More specifically, a thermally tough, innovative laminated external glazing is made using a focused laser beam to facilitate cutting the coated glass substrate into individual daughter panes. Will be done. Without being bound by any particular theory, laser energy is thought to heat the glass locally and then rapidly cool it along the separation line. The result is cracks perpendicular to the glass that result in chips and additional microcrack-free edges that can cause contamination and edge weakening, respectively. The resulting laser-treated edge does not require any additional edge finish.

0078In some embodiments, the laser-cut edge is believed to be able to withstand about two to about three times higher stress than a standard machine-cut edge, with edge strength comparable to heat-tempered glass. It is considered to be. As a result, laser-cut, non-quenched EC device substrates are subject to temperature fluctuations, and thus the stress associated with such temperature fluctuations that typically occurs in the field when the glass is darkly colored. , It is thought that it can withstand.

0079In some embodiments, the laser-cut panel can withstand a stress of at least about 60 MPa. In other embodiments, the laser-cut panel can withstand a stress of at least about 69 MPa. In yet other embodiments, the laser-cut panel can withstand a stress of at least about 75 MPa. In yet other embodiments, the laser-cut panel can withstand a stress of at least about 100 MPa. In yet another embodiment, the laser-cut panel can withstand stresses between about 70 MPa and about 310 MPa.

0080(Electric heat cutting) In some embodiments of the invention, electrothermal cutting (ETC) is used to cut or separate the ED device laminate 20 or EC substrate 31. ETC refers to the method of heating (evaporating, if necessary) a small area within an insulating or semiconductor substrate. In some embodiments, the glass is cut by applying an AC discharge between the two electrodes. Without being bound by any particular theory, it is believed that the high voltage heats the glass locally and the cooling head causes the formation of suitable stresses to create through cracks. The electrode / cooling head assembly is then moved along a defined path to propagate the cracks to the desired pattern defined by the required EC board or custom size of the EC board daughter panel (controlled separation). ).

0081In some embodiments, the ETC-cut panel can withstand the same stresses as those cut by the laser. In other embodiments, the panel cut by ETC can withstand a stress of at least about 60 MPa. In yet other embodiments, the panel cut by ETC can withstand a stress of at least about 69 MPa. In other embodiments, the panel cut by ETC can withstand a stress of at least about 75 MPa. In yet another embodiment, the panel cut by ETC can withstand a stress of at least about 80 MPa. In yet another embodiment, the panel cut by ETC can withstand a stress of at least about 100 MPa.

0082(Experimental data and examples) (Laminate impact test result) Impact tests are as shown in Figure 4: (1) with an EC substrate 31 consisting of annealed soda lime float glass or low CTE glass; (2) an EC exterior consisting of heat tempered glass, hardened glass, or annealed glass. This was done for "mismatched" laminates, including the laminate glass plate 22. The impact data suggests a window with a useful design with respect to the thickness of the EC substrate 31 and the EC external laminate glass plate 22. Polyvinyl butyral (PVB) and ionomer polymer (SGP from DuPont) were tested as intermediate layer material 28. The SGP shows a window with a narrower design compared to PVB in terms of EC board / support board and intermediate layer thickness, which is not bound by any particular theory, but better PVB performance. It is believed to be related to the high adaptability / stretchability of PVB materials.

0083FIG. 4 summarizes the impact test data as a function of the thickness of the EC substrate 31, the EC external laminated glass plate 22, and the intermediate layer 28. FIG. 4 demonstrates different combinations of the thickness of the EC substrate 31, the thickness of the EC external laminated glass plate 22, and the thickness of the intermediate layer material 28. For the 34 "x 76" test geometry required by ANSI Z97.1-2004, the data showed applications over a wide range of glass and intermediate layer thicknesses. PVB is considered to be more robust in terms of glass and intermediate layer thickness.

0084The most widely referred test standards for laminated glazing are published by the American National Standards Institute standard, ANSI Z97.1-2004 (American National Standards Institute for Safety Glazing Materials Used in Buildings-Safety). American National Standard for Safety Glazing Materials Used in Buildings-Safety Performance Specifications Method of Test. This standard establishes both specifications and test methods for safety glazing materials used in buildings and architectural purposes. In this test, a 100-pound bag of lead bullets is impacted, held at the end of the rope and rocked towards the centerline of the laminated glass panel. Consumer Products Safety, which uses the same test method but has slightly different pass / fail criteria There is a further standard, 16CFR1201, issued by the Council) (CPSC).

0085The pass / fail criteria for the Z97.1 and 16CFR1201 exams are slightly different. The Z97.1 test allows breakage and formation of smaller crevices / holes than a 3-inch diameter ball would be considered passable. The 16CFR1201 test further requires that, when the panel is in the horizontal position, a 3-inch ball weighing 4 pounds does not fall into the opening after a duration of 1 second. Although the reported pass / fail data is based on the Z97.1 standard, we believe that the stiffness of the laminate passes 16 CFR1201.

0086Both tests have different categories depending on the height of the bag drop. We present the results of the most extreme tests of dropping from a height of 48 "(400 ft-pounds). A typical test panel size is 34" x 76 ", but another. The size (40 x 40) was also tested. The geometry of 40 x 40 represents a more difficult test. All glass substrates for impact testing in Examples 1-8 shown below are mechanical. The test was performed with SAGE, Faribault, MN, and Cardinal LG, Amery, Wisconsin.

<p num="0087">(Example 1) (EC laminate)</p><p num="0088"><tables num="1"><img id="000002" he="41" wi="159" file="JP5877166B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0089">Production method: The laminated EC structure of Example 1 was manufactured by a "cut-zen-coat" process. Lamination was performed using a conventional nip roller / autoclave process. Equivalent results could be obtained using the vacuum lamination process.</p><p num="0090">result: The laminated EC structure with the components detailed above has passed the ANSI Z97.1 standard for impact testing.</p><p num="0091">(Example 2) (EC laminate)<tables num="2"><img id="000003" he="41" wi="159" file="JP5877166B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0092">Production method: The laminated EC structure of Example 2 was manufactured by a "cut-zen-coat" process. Lamination was performed using a conventional nip roller / autoclave process.</p><p num="0093">result: The laminated EC structure with the components detailed above has passed the ANSI Z97.1 standard for impact testing.</p><p num="0094"> External laminated panels with different thicknesses were tested in Examples 1 and 2, and the resulting laminates both passed the impact test. Equivalent results could be obtained using the vacuum lamination process.</p><p num="0095">(Example 3) (EC laminate)<tables num="3"><img id="000004" he="41" wi="159" file="JP5877166B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0096">Production method: The laminated EC structure of Example 3 was manufactured by a "cut-zen-coat" process. Lamination was performed using a conventional nip roller / autoclave process.</p><p num="0097">result: The laminated EC structure with the components detailed above has passed the ANSI Z97.1 standard for impact testing. Equivalent results could be obtained using the vacuum lamination process.</p><p num="0098">(Example 4) (EC laminate)<tables num="4"><img id="000005" he="40" wi="159" file="JP5877166B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0099">Production method: The laminated EC structure of Example 4 was manufactured by a "cut-zen-coat" process. Lamination was performed using a conventional nip roller / autoclave process.</p><p num="0100">result: The laminated EC structure with the components detailed above has passed the ANSI Z97.1 standard for impact testing.</p><p num="0101"> External laminate panels with different thicknesses were tested in Examples 3 and 4, and the resulting laminates both passed the impact test. Equivalent results could be obtained using the vacuum lamination process.</p><p num="0102">(Example 5) (EC laminate)<tables num="5"><img id="000006" he="40" wi="159" file="JP5877166B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0103">Production method: The laminated EC structure of Example 5 was manufactured by a "cut-zen-coat" process. Lamination was performed using a conventional nip roller / autoclave process.</p><p num="0104">result: The laminated EC structure with the components detailed above has passed the ANSI Z97.1 standard for impact testing. Equivalent results could be obtained using the vacuum lamination process.</p><p num="0105">(Example 6) (EC laminate)<tables num="6"><img id="000007" he="40" wi="159" file="JP5877166B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0106">Production method: The laminated EC structure of Example 6 was manufactured by a "cut-zen-coat" process. Lamination was performed using a conventional nip roller / autoclave process.</p><p num="0107">result: The laminated EC structure with the components detailed above has passed the ANSI Z97.1 standard for impact testing. Equivalent results could be obtained using the vacuum lamination process.</p><p num="0108">(Example 7) (EC laminate)<tables num="7"><img id="000008" he="42" wi="159" file="JP5877166B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0109">Production method: The laminated EC structure of Example 7 was manufactured by a "cut-zen-coat" process. Lamination was performed using a conventional nip roller / autoclave process.</p><p num="0110">result: The laminated EC structure with the components detailed above has passed the ANSI Z97.1 standard for impact testing. Equivalent results could be obtained using the vacuum lamination process.</p><p num="0111">(Example 8) (SageGlass® EC device)<tables num="8"><img id="000009" he="34" wi="159" file="JP5877166B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0112">Production method: The IGU of Example 8 was manufactured by the standard manufacturing process described herein.</p><p num="0113">result: IGUs with the components detailed above have passed the ANSI Z97.1 standard for impact testing.</p><p num="0114"> The laminated IGUs of Examples 1-7 and the traditional IGUs of Example 8 all passed ANSI Z97.1. Therefore, it is believed that the EC device laminates of the invention (and IGUs containing them) can meet / exceed all important industrial machine performance requirements for building applications.</p><p num="0115">(Comparison of edge strength of mechanically scribed and annealed, laser cut and annealed, and heat strengthened soda lime float glass)</p><p num="0116"> We evaluated the edge strength after laser cutting at various glass compositions, substrate thicknesses, and mechanical test sample orientations. The best quantitative measurements of edge strength for laser cut glass were made using a 4-point bending test setting. 4-point bending, or "lying" as shown in Figure 5. In the example using the "down)" sample orientation, it is believed that the entire area under the inner span is subject to the same bending moment, thus making it possible to investigate a wider effective area. We have tested edge strength in both "edge-on" and "lining down" orientations. The "edge-on" orientation was used first because it allows both top and bottom edges to be tested simultaneously under stress conditions similar to those found during use. However, we find good agreement with the data in both test orientations, and "lining down" is easier to test using conventional 4-point bending test fixtures. Therefore, we tested the majority of the test samples in a "lining down" orientation. Typical sample dimensions were 25 mm wide and 330 mm long, with an effective test area of approximately 100 mm. We found standard soda lime float glass from a variety of manufacturers, as well as Eagle 2000 and Eagle XG (Corning) and Borofloat 33 (Schott). Various different glass thicknesses (range about 1 mm to 2.3 mm) and glass composition were tested, including low CTE glass (made of Glass).</p><p num="0117"> We compared our laser-cut edge intensity data for soda-lime glass with the literature values for edge intensity for annealed, heat-hardened, and fully hardened soda-lime glass. Veer et al. Recently published a comprehensive experimental study comparing annealed, heat-hardened and hardened glasses. Veer, FA, PC Louter, and FP Bos, "The strength of annealed, heat-strengthened and fully tempered float glass , Fatigue &amp; Fracture of Engineering Materials &amp; Structures, 32 pp. 18-25 (2009). Due to the minimum size restrictions associated with heat strengthening or quenching, their sample dimensions (10 x 10 x 1000 mm, effective test length about 500 mm) are significantly larger than in our study, and the direct comparison is statistically speaking area. The larger the value, the more likely it is to contain a scratch that has reached its limit size under a given stress, so proper scaling is required. The inventors of the present invention include Vuolio (2003) and Beason and Lignell (2002) Beason, WL and AW Lignell, "A Thermal Stress Evaluation Procedure for Monolithic Annealed Glass", Symp.on the Use of Glass in Buildings, ASTM STP1434, VL. Using a process based on the study of Block (2002), the content is that the intensity of different sample sizes is proportional to the ratio of their edge areas: σ₁/ σ₂= (Area₂/area₁)^{1 / m}It is based on.</p><p num="0118"> The Weibull coefficient m is a measure of the variation in each intensity distribution. The value m = 5.8 determined from the experimental data was used in the calculation. This corresponded to a ratio of 1.7.</p><p num="0119"> Area adjustment data comparing intra-tissue and literature test results are shown in Figure 6. Comparison of intra-tissue and bibliographic data suggests that laser cutting test data is in the middle of the distribution of heat-enhanced (HS) and complete quenching (FT) bibliographic data.</p><p num="0120"> FIG. 6 further shows a comparative probability plot of edge intensities for mechanical and laser scribing. Laser scribed panels are believed to exhibit an intensity of at least 60 MPa. In some embodiments, the intensity of the laser scribed panel is at least 69 MPa, preferably about 75 MPa, more preferably about 100 MPa.</p><p num="0121"> Figure 6 also provides a comparison of experimental tests (mechanical (mechanical scribe) and (laser cutting) and bibliographic data (adjusted for differences in test sample geometry). Our test data on annealed samples made using the scribe and laser cutting processes are shown in FIG. 6 as triangles and squares, respectively. In general, the intensity distribution of laser cut glass (different lasers). Represents all data obtained from five different laser cutting campaigns using a cutting machine.) Can be described as having performance between HS and FT performance.</p><p num="0122">(Example 9) (Laser cutting laminate)<tables num="9"><img id="000010" he="38" wi="159" file="JP5877166B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0123">Production method: The laser-cut laminate of Example 9 was produced by a "coat-zen-cut" process. Lamination was performed using a conventional nip roller / autoclave process. The EC substrate (EC device or device precursor) was laser cut as described herein after the EC stack was deposited. The edge strength of the laser-cut laminate was measured by inducing edge stress by creating a temperature gradient within the sample. The temperature gradient was generated using a silicone heating pad that is similar in lateral dimensions to the laminate. Pads were placed on the surface of the laminate, with an unheated periphery about 25 mm wide. The magnitude of the gradient was controlled by adjusting the power applied to the heating pad (controlled by the Variac variable power supply) while keeping the edges of the laminate near room temperature. The edge stress generated by the evoked temperature gradient was measured directly using photoelastic techniques (Stress Photonics, Inc., Madison, WI).</p><p num="0124">result: The laser-cut laminated EC structure with the components detailed above had an edge strength of at least about 60 MPa after lamination.</p><p num="0125"> We also conducted a process capability study of thermal laser scribe (TLS) processing during production. This study used the mechanical 4-point bending test described above. Data from more than 80 samples from 5 test sessions were collected. Using data representing five different TLS campaigns over a six-month period, we developed process capabilities based on different maximum in-use edge stresses. The process capability Cpk suggested that the strength at the time of manufacture was sufficient to reduce the possibility of failure in an operational stress environment in the application of EC device laminates to windows.</p><p num="0126"> To calculate process capacity using traditional statistical methods, the data had to have a normal distribution. The TLS mechanical test data followed a lognormal distribution and required log conversion to achieve normality. Process capacity values and the corresponding predicted failure rates were calculated for some lower specification limits (ie, maximum edge stresses) to determine the sensitivity of the device to thermal gradients. Maximum edge stress depends on the environmental interaction as well as the design of the window or building frame (eg, a fully insulated frame-to-heat sink design). Capability analysis was calculated using the Minitab 15 statistical software package.<tables num="10"><img id="000011" he="82" wi="159" file="JP5877166B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0127"> Although the present invention has been described herein with reference to specific embodiments, it will be appreciated that these embodiments are merely exemplary of the principles and applications of the invention. Therefore, numerous modifications can be made to the exemplary embodiments and other arrangements are conceivable without departing from the spirit and scope of the invention as defined by the appended claims. Will be understood.</p>