EP3419824A1 - Interlayers having enhanced optical properties - Google Patents

Interlayers having enhanced optical properties

Info

Publication number
EP3419824A1
EP3419824A1 EP17708354.0A EP17708354A EP3419824A1 EP 3419824 A1 EP3419824 A1 EP 3419824A1 EP 17708354 A EP17708354 A EP 17708354A EP 3419824 A1 EP3419824 A1 EP 3419824A1
Authority
EP
European Patent Office
Prior art keywords
interlayer
resin
refractive index
polyvinyl acetal
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP17708354.0A
Other languages
German (de)
French (fr)
Inventor
Lora Lee Spangler
Jeffrey B. HURLBUT
Jun Lu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Solutia Inc
Original Assignee
Solutia Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=58192363&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP3419824(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from US15/051,183 external-priority patent/US20160168353A1/en
Application filed by Solutia Inc filed Critical Solutia Inc
Publication of EP3419824A1 publication Critical patent/EP3419824A1/en
Withdrawn legal-status Critical Current

Links

Classifications

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    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
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    • B32B17/10005Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10559Shape of the cross-section
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    • B32B17/10605Type of plasticiser
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Definitions

  • This disclosure relates to polymer resins and, in particular, to polymer resins suitable for use in polymer interlayers, including those utilized in multiple layer panels.
  • PVB Polyvinyl butyral
  • Safety glass generally refers to a transparent laminate that includes at least one polymer sheet, or interlayer, disposed between two sheets of glass.
  • Safety glass is often used as a transparent barrier in architectural and automotive applications, and one of its primary functions is to absorb energy resulting from impact or a blow without allowing penetration of the object through the glass and to keep the glass bonded even when the applied force is sufficient to break the glass. This prevents dispersion of sharp glass shards, which minimizes injury and damage to people or objects within an enclosed area.
  • Safety glass may also provide other benefits, such as a reduction in ultraviolet (UV) and/or infrared (IR) radiation, and it may also enhance the aesthetic appearance of window openings through addition of color, texture, and the like. Additionally, safety glass with desirable acoustic properties has also been produced, which results in quieter internal spaces.
  • UV ultraviolet
  • IR infrared
  • Laminated safety glass has been used in vehicles equipped with heads- up display (HUD) systems, which project an image of an instrument cluster or other important information to a location on the windshield at the eye level of the vehicle operator.
  • HUD heads- up display
  • Such a display allows the driver to stay focused on the upcoming path of travel while visually accessing dash board information.
  • an interfering double, or reflected "ghost” image is created due to the differences in the position of the projected image as it is reflected off the inside and outside surfaces of the glass.
  • One method of addressing these ghost images has been to include a coating, such as a dielectric coating, on one of the surfaces of the windshield between the glass and the polymeric interlayer.
  • the coating is designed to produce a third ghost image at a location very close to the primary image, while significantly reducing the brightness of the secondary image, so that the secondary image appears to blend into the background.
  • the effectiveness of such a coating can be limited and the coating itself may interfere with the adhesion of the polymeric interlayer to the glass substrates, resulting in optical distortion and other issues.
  • the multiple layer panels utilized in a vehicle which may include, for example, its windshield, side windows, and other panels, make up a notable portion of the total weight of the vehicle - at times up to 5 percent.
  • reduction in the total weight of these panels would generally result in a decrease in the weight of the vehicle and a corresponding increase in fuel efficiency.
  • Most of the weight in these panels is not in the interlayer, but is instead attributable to the substrates, which typically include glass.
  • interlayers suitable for use in HUD applications that can also be utilized in lightweight multiple layer panels.
  • Such interlayers should exhibit desirable optical, acoustic, and visual properties, while reducing double image separation and permitting usage of thinner substrates.
  • One embodiment of the present invention relates a tapered interlayer comprising at least one polymer layer comprising a polyvinyl acetal) resin and at least one plasticizer.
  • the polymer layer has a refractive index of at least about 1.480, and the interlayer comprises a tapered zone having an overall wedge angle of not more than 0.85 mrad.
  • Another embodiment of the present invention relates to a multiple layer panel comprising a pair of rigid substrates; and an interlayer disposed between the substrates.
  • the interlayer comprises a tapered zone having an overall wedge angle of less than 0.85 mrad and the equivalent refractive index of the multiple layer panel is at least 0.010 higher than the refractive index of each of the rigid substrates.
  • Still another embodiment of the present invention relates to a multiple layer panel comprising a pair of rigid substrates and a tapered interlayer disposed between the substrates.
  • the tapered interlayer comprises at least one polymeric resin.
  • the refractive index of the interlayer is at least 5 percent higher than the refractive index of each of the rigid substrates.
  • FIG. 1 is a cross-sectional view of a tapered interlayer configured in accordance with one embodiment of the present invention, where various features of the tapered interlayer are labeled for ease of reference;
  • FIG. 2 is a cross-sectional view of a tapered interlayer having a tapered zone that extends over the entire width of the interlayer, where the entire tapered zone has a constant wedge angle and a linear thickness profile;
  • FIG. 3 is a cross-sectional view of a tapered interlayer having a tapered zone that extends over part of the width of the interlayer and a flat edge zone that extends over part of the width of the interlayer, where the tapered zone includes a constant angle zone and a variable angle zone;
  • FIG. 4 is a cross-sectional view of a tapered interlayer having a tapered zone that extends over part of the width of the interlayer and two flat edge zones that extend over part of the width of the interlayer, where the tapered zone includes a constant angle zone and two variable angle zones;
  • FIG. 5 is a cross-sectional view of a tapered interlayer having a tapered zone that extends over part of the width of the interlayer and two flat edge zones that extend over part of the width of the interlayer, where the tapered zone is formed entirely of a variable angle zone having a curved thickness profile;
  • FIG. 6 is a cross-sectional view of a tapered interlayer having a tapered zone that extends over the entire width of the interlayer, where the tapered includes three constant angle zones spaced apart from one another by two variable angle zones;
  • FIG. 7 is a cross-sectional view of a tapered interlayer having a tapered zone that extends over part of the width of the interlayer and two flat edge zones that extend over part of the width of the interlayer, where the tapered zone includes three constant angle zones and four variable angle zones;
  • FIG. 8a is a plan view of a tapered interlayer configured for use in a vehicle windshield, where the thickness profile of the interlayer is similar to the thickness profile of the interlayer depicted in FIG. 2;
  • FIG. 8b is a cross-sectional view of the interlayer of FIG. 8a, showing the thickness profile of the interlayer
  • FIG. 9 is a schematic diagram of an apparatus used to measure the double image separation distance of a multiple layer panel
  • FIG. 10 is an example of a projection image formed when measuring the double image separation distance of a multiple layer panel using the apparatus of FIG. 9;
  • FIG. 11 is an example of a profile formed by analyzing the projection image shown in FIG. 10 by plotting the number of pixels as a function of intensity;
  • FIG. 12 is a graphical depiction of the results of the double image separation distance analyses performed on several Comparative and Disclosed samples as described in Example 11, particularly showing the double image separation distance of several samples of varying wedge angle as a function of total thickness;
  • FIG. 13 is graphical depiction of the results of the double image separation distance analyses performed on several Comparative and Disclosed samples as described in Example 11, particularly showing the double image separation of several samples of varying glass configuration as a function of wedge angle;
  • FIG. 14 is a graphical depiction of the results of the double image separation distance analysis performed in Example 13, particularly showing the double image separation distance of several panels utilizing panels having varying glass thickness as a function of the equivalent refractive index.
  • Resin compositions, layers, and interlayers can comprise one or more thermoplastic polymers and a refractive index (Rl) balancing agent.
  • Rl refractive index
  • the term "refractive index balancing agent" or “Rl balancing agent” refers to any component or additive included in the composition, layer, or interlayer for adjusting the refractive index of at least one of the resins or layers.
  • the Rl balancing agent may increase or reduce the refractive index of at least one of the resins or layers within an interlayer, which may improve the optical properties of the interlayer, including mottle, haze, and/or clarity, as compared to an identical interlayer formed without an Rl balancing agent.
  • polymer resin composition and “resin composition” refer to compositions including one or more polymer resins. Polymer compositions may optionally include other components, such as plasticizers and/or other additives.
  • polymer resin layer refers to one or more polymer resins, optionally combined with one or more plasticizers, that have been formed into a polymeric sheet. Again, polymer layers can include additional additives, although these are not required.
  • interlayer refers to a single or multiple layer polymer sheet suitable for use with at least one rigid substrate to form a multiple layer panel.
  • single-sheet interlayer and “monolithic” interlayer refer to interlayers formed of one single resin sheet, while the terms “multiple layer” and “multilayer” interlayer refer to interlayers having two or more resin sheets coextruded, laminated, or otherwise coupled to one another.
  • the resin compositions, layers, and interlayers described herein may include one or more thermoplastic polymers.
  • suitable thermoplastic polymers can include, but are not limited to, polyvinyl acetal) resins, polyurethanes (PU), poly(ethylene-co-vinyl) acetates (EVA), polyvinyl chlorides (PVC), poly(vinylchloride-co-methacrylate), polyethylenes, polyolefins, ethylene acrylate ester copolymers, poly(ethylene-co-butyl acrylate), silicone elastomers, epoxy resins, and acid copolymers such as ethylene/carboxylic acid copoloymers and ionomers thereof, derived from any of the previously-listed polymers, and combinations thereof.
  • the thermoplastic polymer can be selected from the group consisting of polyvinyl acetal) resins, polyvinyl chloride, and polyurethanes, or the resin can comprise one or more polyvinyl acetal) resins.
  • polyvinyl acetal resins
  • the above polymer resins could be included with, or in the place of, the polyvinyl acetal) resins described below in accordance with various embodiments of the present invention.
  • the resin compositions, layers, and interlayers described herein include polyvinyl acetal) resins
  • the polyvinyl acetal) resins can be formed according to any suitable method.
  • Polyvinyl acetal resins can be formed by acetalization of polyvinyl alcohol with one or more aldehydes in the presence of an acid catalyst. The resulting resin can then be separated, stabilized, and dried according to known methods such as, for example, those described in U.S. Patent Nos. 2,282,057 and 2,282,026, as well as "Vinyl Acetal Polymers," in the Encyclopedia of Polymer Science & Technology, 3 rd ed., Volume 8, pages 381-399, by B.E. Wade (2003).
  • the resulting polyvinyl acetal) resins may have a total percent acetalization of at least about 50, at least about 60, at least about 70, at least about 75, at least about 80, at least about 85 weight percent, measured according to ASTM D1396, unless otherwise noted.
  • the total amount of aldehyde residues in a polyvinyl acetal) resin can be collectively referred to as the acetal component, with the balance of the polyvinyl acetal) resin being residual hydroxyl and residual acetate groups, which will be discussed in further detail below.
  • the resin composition, layer, or interlayer may include at least one polyvinyl acetal) resin, which may be present in the composition, layer, or interlayer in an amount of at least about 0.5, at least about 1, at least about 2, at least about 3, at least about 5, at least about 10, at least about 15, at least about 20, at least about 30, at least about 40, or at least about 45 weight percent, based on the combined weight of all resins in the composition, layer, or interlayer.
  • the at least one polyvinyl acetal) resins can make up at least about 10, at least about 20, at least about 30, at least about 40, at least about 50, at least about 60, at least about 70, or at least about 80 weight percent of composition, layer, or interlayer, based on the combined weight of all resins.
  • the amount of resins other than the at least one polyvinyl acetal) resin can be not more than about 20, not more than about 15, not more than about 10, not more than about 5, not more than about 2, or not more than about 1 weight percent, based on the combined weight of all resins.
  • the resin composition, layer, or interlayer can include at least a first polyvinyl acetal) resin and a second polyvinyl acetal) resin, each of which may be present in the composition, layer, or interlayer in an amount of at least about 0.5, at least about 1, at least about 2, at least about 3, at least about 5, at least about 10, at least about 15, at least about 20, at least about 30, at least about 40, or at least about 45 weight percent, based on the combined weight of all resins in the composition, layer, or interlayer.
  • the first and second polyvinyl acetal) resins can make up at least about 10, at least about 20, at least about 30, at least about 40, at least about 50, at least about 60, at least about 70, or at least about 80 weight percent of composition, layer, or interlayer, based on the combined weight of all resins.
  • the amount of resins other than the first and second polyvinyl acetal) resins can be not more than about 20, not more than about 15, not more than about 10, not more than about 5, not more than about 2, or not more than about 1 weight percent, based on the combined weight of all resins.
  • one of the first and the second polyvinyl acetal) resins can be present in the composition, layer, or interlayer in an amount of less than 12 weight percent, based on the combined weight of the first and second polyvinyl acetal) resins.
  • the first or the second polyvinyl acetal) resin can be present in the composition, layer, or interlayer in an amount of at least about 0.5, at least about 1, at least about 1.5, at least about 2, at least about 2.5, at least about 3, at least about 3.5, at least about 4, at least about 4.5, at least about 5, at least about 5.5, at least about 6, at least about 6.5, at least about 7 weight percent and/or not more than about 12, not more than about 11.5, not more than about 11, not more than about 10.5, not more than about 10, not more than about 9.5, not more than about 9, not more than about 8.5, not more than about 8, not more than about 7.5 weight percent, based on the combined weight of the first and second polyvinyl acetal) resins.
  • one of the first and second polyvinyl acetal) resins can be present in the composition, layer, or interlayer in an amount in the range of from about 0.5 to about 12, about 1.5 to about 11.5, about 2 to about 11, about 2.5 to about 10 weight percent, based on the combined weight of the first and second polyvinyl acetal) resins.
  • the first and second polyvinyl acetal) resins can include residues of any suitable aldehyde and, in some embodiments, can include residues of at least one Ci to Cio aldehyde, or at least one C 4 to Cs aldehyde.
  • suitable C 4 to Cs aldehydes can include, but are not limited to, n-butyraldehyde, iso-butyraldehyde, 2- methylvaleraldehyde, n-hexyl aldehyde, 2-ethylhexyl aldehyde, n-octyl aldehyde, and combinations thereof.
  • At least one of the first and second polyvinyl acetal) resins can include at least about 20, at least about 30, at least about 40, at least about 50, at least about 60, or at least about 70 weight percent of residues of at least one C 4 to Cs aldehyde, based on the total weight of aldehyde residues of the resin, and/or can include not more than about 90, not more than about 85, not more than about 80, not more than about 75, not more than about 70, or not more than about 65 weight percent of at least one C 4 to Cs aldehyde, or in the range of from about 20 to about 90, about 30 to about 80, or about 40 to about 70 weight percent of at least one C 4 to Cs aldehyde.
  • the C 4 to Cs aldehyde may be selected from the group listed above, or it can be selected from the group consisting of n-butyraldehyde, iso-butyraldehyde, 2- ethylhexyl aldehyde, and combinations thereof.
  • the first and/or second polyvinyl acetal) resin may be a polyvinyl n-butyral (PVB) resin.
  • the first and/or second polyvinyl acetal) resin can be a polyvinyl n-butyral) resin that mainly comprises residues of n-butyraldehyde, and may, for example, include not more than about 50, not more than about 40, not more than about 30, not more than about 20, not more than about 10, not more than about 5, or not more than about 2 weight percent of residues of an aldehyde other than n-butyraldehyde, based on the total weight of all aldehyde residues of the resin.
  • the molecular weight of the resins can be at least about 50,000, at least about 70,000, at least about 100,000 Daltons and/or not more than about 600,000, not more than about 550,000, not more than about 500,000, not more than about 450,000, or not more than 425,000 Daltons, measured by size exclusion chromatography using low angle laser light scattering (SEC/LALLS) method of Cotts and Ouano.
  • the term "molecular weight” refers to weight average molecular weight (M w ).
  • the molecular weight of the first and/or second polyvinyl acetal) resin can be in the range of from about 50,000 to about 600,000, about 70,000 to about 450,000, or about 100,000 to about 425,000 Daltons.
  • first and second polyvinyl acetal) resins Although generally described herein with respect to first and second polyvinyl acetal) resins, it should be understood that, in some embodiments, an equivalent single polyvinyl acetal) resin including first and second acetal moieties may be substituted for the first and second polyvinyl acetal) resins with similar results.
  • polyvinyl acetal) resin component can refer to an individual polyvinyl acetal) resin present in a blend of resins or to an acetal moiety present on a single polyvinyl acetal) resin.
  • the ratio, by weight, of the amount of the first polyvinyl acetal) resin component to the second polyvinyl acetal) resin component in a layer, interlayer, or blend can be in the range of from about 0.5:99.5 to about 99.5:0.5, about 1:99 to 99:1, about 10:90 to about 90:10, about 25:75 to about 75:25, or about 40:60 to about 60:40.
  • At least one resin composition, layer, or interlayer can include at least a first polyvinyl acetal) resin component and a second polyvinyl acetal) resin component.
  • the first and second resin components may comprise first and second polyvinyl acetal) resins that can be physically mixed to form a resin blend, which may be combined with one or more plasticizers or other additives to provide a blended polymer layer or interlayer.
  • the first and second polyvinyl acetal) resin components may be present as respective first and second acetal moieties in a single polyvinyl acetal) resin.
  • this single "hybrid" polyvinyl acetal) resin can be optionally blended with a plasticizer and utilized in polymer layers and interlayers.
  • the first and second polyvinyl acetal) resins may be blended such that one of the first and second resins is dispersed within the other of the first and second resins, which can form domains of one of the first and second polyvinyl acetal) resins within the other of the first and second polyvinyl acetal) resins.
  • Such a blended resin may be used as a single layer interlayer or it may be combined with one or more adjacent layers to form a multilayer interlayer.
  • first and second polyvinyl acetal) resins can be present in adjacent layers of a multilayer interlayer, such that one of the layers of the interlayer includes the first polyvinyl acetal) resin and another layer of the interlayer includes the second polyvinyl acetal) resin. Additional layers can also be present adjacent to at least one of the layers.
  • the resin compositions, layers, and interlayers according to various embodiments of the present invention can further include at least one plasticizer.
  • the plasticizer may be present in an amount of at least about 5, at least about 10, at least about 15, at least about 20, at least about 25, at least about 30, at least about 35, at least about 40, at least about 45, at least about 50, at least about 55, at least about 60 parts per hundred parts of resin (phr) and/or not more than about 120, not more than about 110, not more than about 105, not more than about 100, not more than about 95, not more than about 90, not more than about 85, not more than about 75, not more than about 70, not more than about 65, not more than about 60, not more than about 55, not more than about 50, not more than about 45, or not more than about 40 phr, or in the range of from about 5 to about 120, about 10 to about 110, about 20 to about 90, or about
  • the term "parts per hundred parts of resin” or "phr” refers to the amount of plasticizer present as compared to one hundred parts of resin, on a weight basis. For example, if 30 grams of plasticizer were added to 100 grams of a resin, the plasticizer would be present in an amount of 30 phr. If the resin composition, layer, or interlayer includes two or more resins, the weight of plasticizer is compared to the combined amount of all resins present to determine the parts per hundred resin. Further, when the plasticizer content of a layer or interlayer is provided herein, it is provided with reference to the amount of plasticizer in the mix or melt that was used to produce the layer or interlayer.
  • plasticizers can include, but are not limited to, triethylene glycol di-(2-ethylhexanoate) (“3GEH”), triethylene glycol di-(2- ethylbutyrate), triethylene glycol diheptanoate, tetraethylene glycol diheptanoate, tetraethylene glycol di-(2-ethylhexanoate) (“4GEH”), dihexyl adipate, dioctyl adipate, hexyl cyclohexyladipate, diisononyl adipate, heptylnonyl adipate, di(butoxyethyl) adipate, and bis(2-(2-butoxyethoxy)ethyl) adipate, dibutyl sebacate, dioctyl sebacate, and mixtures thereof.
  • 3GEH triethylene glycol di-(2-ethylhexanoate
  • 4GEH triethylene
  • the plasticizer may be selected from the group consisting of triethylene glycol di-(2-ethylhexanoate) and tetraethylene glycol di-(2- ethylhexanoate), or the plasticizer can comprise triethylene glycol di-(2- ethylhexanoate).
  • the first and second polyvinyl acetal) resins in the compositions, layers, and interlayers described herein can have different compositions.
  • the first polyvinyl acetal) resin can have a residual hydroxyl content and/or residual acetate content that is at least about 2, at least about 3, at least about 4, at least about 5, at least about 6, or at least about 8 weight percent higher or lower than the residual hydroxyl content and/or residual acetate content of the second polyvinyl acetal) resin.
  • residual hydroxyl content and “residual acetate content” refer to the amount of hydroxyl and acetate groups, respectively, that remain on a resin after processing is complete.
  • polyvinyl n-butyral can be produced by hydrolyzing polyvinyl acetate to polyvinyl alcohol, and then acetalizing the polyvinyl alcohol with n-butyraldehyde to form polyvinyl n-butyral. In the process of hydrolyzing the polyvinyl acetate, not all of the acetate groups are converted to hydroxyl groups, and residual acetate groups remain on the resin.
  • the difference between the residual hydroxyl content of the first and second polyvinyl acetal) resins could also be at least about 2, at least about 5, at least about 10, at least about 12, at least about 15, at least about 20, or at least about 30 weight percent.
  • weight percent different or “the difference is at least weight percent” refers to a difference between two given weight percentages, calculated by subtracting the one number from the other.
  • the term “different” can refer to a value that is higher than or lower than another value.
  • At least one of the first and second polyvinyl acetal) resins can have a residual hydroxyl content of at least about 14, at least about 14.5, at least about 15, at least about 15.5, at least about 16, at least about 16.5, at least about 17, at least about 17.5, at least about 18, at least about 18.5, at least about 19, at least about 19.5 and/or not more than about 45, not more than about 40, not more than about 35, not more than about 33, not more than about 30, not more than about 27, not more than about 25, not more than about 22, not more than about 21.5, not more than about 21, not more than about 20.5, or not more than about 20 weight percent, or in the range of from about 14 to about 45, about 16 to about 30, about 18 to about 25, about 18.5 to about 24, or about 19.5 to about 21 weight percent.
  • the other polyvinyl acetal) resin can have a residual hydroxyl content of at least about 8, at least about 9, at least about 10, at least about 11 weight percent and/or not more than about 16, not more than about 15, not more than about 14.5, not more than about 13, not more than about 11.5, not more than about 11, not more than about 10.5, not more than about 10, not more than about 9.5, or not more than about 9 weight percent, or in the range of from about 8 to about 16, about 9 to about 15, or about 9.5 to about 14.5 weight percent, and can be selected such that the difference between the residual hydroxyl content of the first and second polyvinyl acetal) resin is at least about 2 weight percent, as mentioned previously.
  • One or more other polyvinyl acetal) resins may also be present in the resin composition, layer, or interlayer and can have a residual hydroxyl within the ranges provided above. Additionally, the residual hydroxyl content of the one or more other polyvinyl acetal) resins can be the same as or different than the residual hydroxyl content of the first and/or second polyvinyl acetal) resins.
  • At least one of the first and second polyvinyl acetal) resins can have a residual acetate content different than the other.
  • the difference between the residual acetate content of the first and second polyvinyl acetal) resins can be at least about 2, at least about 3, at least about 4, at least about 5, at least about 8, at least about 10 weight percent.
  • One of the polyvinyl acetal) resins may have a residual acetate content of not more than about 4, not more than about 3, not more than about 2, or not more than about 1 weight percent, measured as described above.
  • At least one of the first and second polyvinyl acetal) resins can have a residual acetate content of at least about 5, at least about 8, at least about 10, at least about 12, at least about 14, at least about 16, at least about 18, at least about 20, or at least about 30 weight percent.
  • the difference in the residual acetate content between the first and second polyvinyl acetal) resins can be within the ranges provided above, or the difference can be less than about 3, not more than about 2, not more than about 1, or not more than about 0.5 weight percent.
  • Additional polyvinyl acetal) resins present in the resin composition or interlayer can have a residual acetate content the same as or different than the residual acetate content of the first and/or second polyvinyl acetal) resin.
  • the difference between the residual hydroxyl content of the first and second polyvinyl acetal) resins can be less than about 2, not more than about 1, not more than about 0.5 weight percent and the difference in the residual acetate content between the first and second polyvinyl acetal) resins can be at least about 3, at least about 5, at least about 8, at least about 15, at least about 20, or at least about 30 weight percent.
  • the difference in the residual acetate content of the first and second polyvinyl acetal) resins can be less than about 3, not more than about 2, not more than about 1, or not more than about 0.5 weight percent and the difference in the residual hydroxyl content of the first and second polyvinyl acetal) resins can be at least about 2, at least about 5, at least about 10, at least about 12, at least about 15, at least about 20, or at least about 30 weight percent.
  • the differences in residual hydroxyl and/or residual acetate content of the first and second polyvinyl acetal) resins can be selected to control or provide certain performance properties, such as strength, impact resistance, penetration resistance, processability, or acoustic performance to the final composition, layer, or interlayer.
  • polyvinyl acetal) resins having a higher residual hydroxyl content, usually greater than about 16 weight percent can facilitate high impact resistance, penetration resistance, and strength to a resin composition or layer, while lower hydroxyl content resins, usually having a residual hydroxyl content of less than 16 weight percent, can improve the acoustic performance of the interlayer or blend.
  • Polyvinyl acetal) resins having higher or lower residual hydroxyl contents and/or residual acetate contents may also, when combined with at least one plasticizer, ultimately include different amounts of plasticizer.
  • layers or domains formed of first and second polyvinyl acetal) resins having different compositions may also have different properties within a single polymer layer or interlayer.
  • compatibility of a given plasticizer with a polyvinyl acetal) resin can depend, at least in part, on the composition of the polymer, and, in particular, on its residual hydroxyl content.
  • polyvinyl acetal) resins with higher residual hydroxyl contents tend to exhibit a lower compatibility (or capacity) for a given plasticizer as compared to similar resins having a lower residual hydroxyl content.
  • polyvinyl acetal) resins with higher residual hydroxyl contents tend to be less plasticized and exhibit higher stiffness than similar resins having lower residual hydroxyl contents.
  • polyvinyl acetal) resins having lower residual hydroxyl contents may tend to, when plasticized with a given plasticizer, incorporate higher amounts of plasticizer, which may result in a softer polymer layer that exhibits a lower glass transition temperature than a polymer layer including a similar resin having a higher residual hydroxyl content. Depending on the specific resin and plasticizer, these trends could be reversed.
  • the plasticizer may partition between the polymer layers or domains, such that more plasticizer can be present in the layer or domain having the lower residual hydroxyl content and less plasticizer may be present in the layer or domain having the higher residual hydroxyl content.
  • a state of equilibrium is achieved between the two resins.
  • the correlation between the residual hydroxyl content of a polyvinyl acetal) resin and plasticizer compatibility/capacity can facilitate addition of a proper amount of plasticizer to the polymer resin. Such a correlation also helps to stably maintain the difference in plasticizer content between two or more resins when the plasticizer would otherwise migrate between the resins.
  • a polymer layer or interlayer can include at least a first polymer layer comprising a first polyvinyl acetal) resin and a first plasticizer, and a second polymer layer, adjacent to the first polymer layer, comprising a second polyvinyl acetal) resin and a second plasticizer.
  • the first and second plasticizer can be the same type of plasticizer, or the first and second plasticizers may be different.
  • at least one of the first and second plasticizers may also be a blend of two or more plasticizers, which can be the same as or different than one or more other plasticizers.
  • the difference in plasticizer content between the polymer layers can be at least about 2, at least about 5, at least about 8, at least about 10, at least about 12, or at least about 15 phr.
  • the polymer layer that includes the resin having a lower hydroxyl content can have the higher plasticizer content.
  • the difference in plasticizer content between the first and second polymer layers may be not more than about 40, not more than about 30, not more than about 25, not more than about 20, or not more than about 17 phr.
  • the difference in plasticizer content between the first and second polymer layers can be at least about 40, at least about 50, at least about 60, or at least about 70 phr.
  • the first and second polymer layers can exhibit different glass transition temperatures.
  • the domains of one of the first and second polyvinyl acetal) resins can exhibit a different glass transition temperature than the other of the first and second polyvinyl acetal) resins.
  • Glass transition temperature, or T g is the temperature that marks the transition from the glass state of the polymer to the rubbery state. The glass transition temperatures of the resins and layers described herein were determined by dynamic mechanical thermal analysis (DMTA).
  • the DMTA measures the storage (elastic) modulus (G') in Pascals, loss (viscous) modulus (G") in Pascals, and the tan delta (G"/G') of the specimen as a function of temperature at a given oscillation frequency and temperature sweep rate.
  • the glass transition temperature is then determined by the position of the tan delta peak on the temperature scale. Glass transition temperatures provided herein were determined at an oscillation frequency of 1 Hz under shear mode and a temperature sweep rate of 3°C/min.
  • the difference in the glass transition temperature of the first polymer layer and the second polymer layer, or between various regions of a blended resin or polymer layer, can be at least about 3, at least about 5, at least about 8, at least about 10, at least about 12, at least about 15, at least about 18, at least about 20, at least about 22, or at least about 25°C.
  • One of the first and second polymer layers can have a glass transition temperature of at least about 26, at least about 28, at least about 30, at least about 33, at least about 35°C and/or not more than about 70, not more than about 65, not more than about 60, not more than about 55, not more than about 50°C, or in the range of from about 26 to about 70, about 30 to about 60, about 35 to about 50°C.
  • the other of the first and second polyvinyl acetal) resins can have a glass transition temperature of not more than 25, not more than about 20, not more than about 15, not more than about 10, not more than about 5, not more than about 0, not more than about -5, or not more than about -10°C.
  • first and second polyvinyl acetal) resins are blended with one another such that domains of one resin are dispersed within the other, such differences in plasticizer content and/or glass transition temperature may also exist between domains of the first and second resins.
  • a polymer layer or interlayer may include various domains of higher or lower plasticizer content and/or domains having higher or lower glass transition temperatures, as described previously.
  • At least a portion of the polymer layer or interlayer can have a glass transition temperature of at least about 26, at least about 28, at least about 30, at least about 33, at least about 35°C and/or not more than about 70, not more than about 65, not more than about 60, not more than about 55, not more than about 50°C, or in the range of from about 26 to about 70, about 28 to about 60, about 35 to about 50°C and/or at least a portion of the polymer layer or interlayer can have a glass transition temperature of not more than 25, not more than about 20, not more than about 15, not more than about 10, not more than about 5, not more than about 0°C, not more than about -5°C, or not more than about -10°C.
  • One or more resin blends, layers, and interlayers described herein may include various other additives to impart particular properties or features to the interlayer.
  • additives can include, but are not limited to, dyes, pigments, stabilizers such as ultraviolet stabilizers, antioxidants, anti-blocking agents, flame retardants, IR absorbers or blockers such as indium tin oxide, antimony tin oxide, lanthanum hexaboride (LaBe) and cesium tungsten oxide, processing aides, flow enhancing additives, lubricants, impact modifiers, nucleating agents, thermal stabilizers, UV absorbers, dispersants, surfactants, chelating agents, coupling agents, adhesives, primers, reinforcement additives, and fillers.
  • dyes such as ultraviolet stabilizers, antioxidants, anti-blocking agents, flame retardants, IR absorbers or blockers such as indium tin oxide, antimony tin oxide, lanthanum hexaboride (LaBe) and cesium tungsten oxide
  • ACAs adhesion control agents
  • the amount of ACAs present in a resin composition, layer, or interlayer can be at least about 0.003, at least about 0.01, at least about 0.025 and/or not more than about 0.15, not more than about 0.10, or not more than about 0.04 phr, or in the range of from about 0.003 to about 0.15, about 0.01 to about 0.10, or about 0.025 to about 0.04 phr.
  • Suitable ACAs can include, but are not limited to, sodium acetate, potassium acetate, magnesium bis(2-ethyl butyrate), magnesium bis(2-ethylhexanoate), and combinations thereof, as well as the ACAs disclosed in U.S. Patent No. 5,728,472.
  • Resins having different compositions and plasticized polymer layers having different properties also tend to exhibit different refractive indices, which can reduce the optical quality of the resulting layer or blend.
  • refractive index may cause light that passes through the different polymer layers or domains to be refracted in different directions, which may cause haze in the final product.
  • the absolute value of the difference between the refractive index of the first polyvinyl acetal) resin or layer and the refractive index of the second polyvinyl acetal) resin or layer measured according to ASTM D542 at a wavelength of 589 nm and 25°C, can exceed 0.010.
  • these compositions, layers, or interlayers can have a haze value greater than 5 percent and/or a mottle value greater than 3.
  • compositions, layers, and interlayers comprising a polyvinyl acetal) resin may further include at least one refractive index (Rl) balancing agent for adjusting the refractive index of the composition, layer, or interlayer.
  • Rl refractive index
  • the composition, layer, or interlayer may include at least a first polyvinyl acetal) resin and a second polyvinyl acetal) resin along with at least one Rl balancing agent.
  • the composition, layer, or interlayer ma include a single polyvinyl acetal) resin along with at least one Rl balancing agent.
  • the Rl balancing agent can be any suitable agent present in a resin or a resin blend, layer, or interlayer, or portion thereof, that increases or reduces the refractive index of at least one resin or layer, which may improve the optical properties of the interlayer as compared to an identical interlayer formed without an Rl balancing agent.
  • the resin blend, layer, or interlayer may have a haze value of at least 5 percent when formed in the absence of the Rl balancing agent.
  • the Rl balancing agent can be in any suitable form and may be physically blended with one or more resins or it can be chemically bonded, or reacted, with at least one resin so that the Rl balancing agent is incorporated into the polymer chain.
  • Rl balancing agents can include, but are not limited to, liquid Rl additives, solid Rl additives, and residues of at least one aldehyde present in one or more of the polyvinyl acetal) resins.
  • Various embodiments of Rl balancing agents, as well as resin compositions, layers, and interlayers including the same, will now be discussed in detail below.
  • the Rl balancing agent may be present in the resin, polymer layer, or interlayer in an amount sufficient to modify the refractive index of polyvinyl acetal) resin, polymer layer, or interlayer.
  • the Rl balancing agent may also be present in the composition, layer, or interlayer in an amount sufficient to modify the refractive index of at least one of the two polyvinyl acetal) resins, thereby minimizing the difference between the refractive indices of two polyvinyl acetal) polymer layers having different refractive indices.
  • the Rl balancing agent may also minimize the difference between the refractive index of one or more polyvinyl acetal) resins and one or more plasticizers within a resin composition, layer, or interlayer.
  • the Rl balancing agent may be present in an amount sufficient to reduce the absolute value of the difference between the refractive index the first polyvinyl acetal) polymer layer and the refractive index of the second polyvinyl acetal) polymer layer to not more than 0.010, not more than about 0.009, not more than about 0.008, not more than about 0.007, not more than about 0.006, not more than about 0.005, not more than about 0.004, or not more than about 0.003.
  • the Rl balancing agent may be present in one or both layers and can, in some embodiments, be present in one of the layers in a higher amount than in one or more of the other layers.
  • the Rl balancing agent can comprise one or more residues of an aldehyde having a refractive index of at least 1.421, as measured by ASTM D542 at a wavelength of 589 nm and a temperature of 25°C.
  • the Rl balancing aldehyde which may also be referred to herein as a "high refractive index aldehyde” or “high Rl aldehyde,” can have a refractive index of at least about 1.425, at least about 1.450, at least about 1.475, at least about 1.500, at least about 1.510, or at least about 1.515 and/or not more than about 1.675, not more than about 1.650, or not more than about 1.625, or in the range of from about 1.425 to about 1.675, about 1.475 to about 1.650, or about 1.515 to about 1.625.
  • the high Rl aldehyde may be an aromatic aldehyde that includes at least one aromatic ring or group.
  • aromatic aldehydes can include, but are not limited to, C7 to C30 aromatic aldehydes, Cs to C25 aromatic aldehydes, or Cg to C20 aromatic aldehydes.
  • Specific examples of high Rl aldehydes that can be used as Rl balancing agents in various embodiments of the present invention are listed in Table 1, below. Table 1: Exemplary High Rl Aldehydes
  • At least one of the first and second polyvinyl acetal) resins can include residues of at least one high Rl aldehyde in an amount of at least about 0.5, at least about 1, at least about 5, at least about 10, at least about 15, at least about 20, at least about 25, at least about 30, at least about 35, at least about 40, at least about 45, at least about 50, at least about 55, at least about 60, at least about 65, at least about 70, at least about 75, at least about 80, at least about 85, at least about 90, at least about 95 percent and/or not more than about 99.5, not more than about 99, not more than about 97, not more than about 95, not more than about 90, not more than about 85, not more than about 80, not more than about 75, not more than about 70, not more than about 65, or not more than about 60 weight percent, based on the total weight of aldehyde residues of the
  • At least one of the first and second polyvinyl acetal) resins can include residues of at least one high Rl aldehyde in an amount in the range of from about 0.5 to about 99.5, about 10 to about 90, about 25 to about 75, or about 40 to about 60 weight percent, based on the total weight of aldehyde residues of the first or second polyvinyl acetal) resin.
  • the amount of high Rl aldehyde residues can be determined using a combination of Fourier Transform Infrared Spectroscopy (FT-IR) and Size Exclusion Chromatography (SEC) with UV detection.
  • FT-IR is used to measure residual hydroxyl content of the resin
  • SEC Size Exclusion Chromatography
  • the FT-IR analysis is performed using a Perkin Elmer Spectrum 100 FT-IR Spectrometer (commercially available from Perkin Elmer, Waltham, Massachusetts) with an ATR sampling attachment. The analysis is performed using 8 scans at a 4 cm-1 resolution.
  • a calibration is generated from several polyvinyl n-butyral) samples of varying residual hydroxyl content which have been dried in a desiccator with silica overnight at room temperature to remove excess moisture.
  • the peak maximum wave number of the hydroxyl stretching band is correlated with the molar vinyl alcohol content of each sample, which was previously determined by ASTM D1396, and the resulting linear curve fits are used to predict molar residual hydroxyl content of the samples being analyzed.
  • the SEC analysis is performed using a Waters 2695 Alliance pump and autosampler with a Waters 410 inline differential refractive index detector and a Waters 2998 PDA inline UV detector (commercially available from Waters Corporation, Milford, Massachusetts) with Dionex Chromeleon v. 6.8 data acquisition software with an extension pack (commercially available from Thermo Fischer Scientific, Sunnyvale, CA).
  • the analysis is performed with a PL Gel Mixed C (5 micron) column and Mixed E (3 micron) columns with an injection volume of 50 microliters at a flow rate of 1.0 mL/minute.
  • Samples are prepared by dissolving between 0.03 and 0.09 grams of resin in 10-15 mL of stabilized tetrahydrofuran and then filtering each through a 0.22 micron PTFE filter.
  • Initial calibrations of the chromatograph are performed using a narrow molecular weight polystyrene standard and a polyvinyl acetal) resin including only residues of the high Rl aldehyde, and subsequent samples were calibrated with a broad molecular weight polystyrene (commercially available as PSBR250K from American Polymer Standard Corporation, Mentor, Ohio).
  • only one of the first and second polyvinyl acetal) resins includes residues of the high Rl aldehyde, while, in other embodiments, both of the resins may include such residues.
  • the refractive index of a resin comprising residues of a high Rl aldehyde can be at least about 1.492, at least about 1.495, at least about 1.500, at least about 1.505, at least about 1.510, or at least about 1.515.
  • At least one of the first and second polyvinyl acetal) resins may also include residues of at least one aldehyde having a refractive index of less than 1.421.
  • these aldehydes can include, for example, aliphatic aldehydes such as the C 4 to Cs aldehydes discussed above.
  • the aldehydes having a refractive index of less than 1.421 can be selected from the group consisting of n-butyraldehyde, iso-butyraldehyde, and 2-ethylhexyl aldehyde.
  • the first and/or second polyvinyl acetal) resin can include at least about 10, at least about 15, at least about 20, at least about 25, at least about 30, at least about 35, at least about 40, at least about 45, at least about 50, at least about 55, at least about 60, at least about 65, at least about 70, at least about 75, at least about 80, at least about 85, at least about 90, at least about 95 percent and/or not more than about 99, not more than about 97, not more than about 95, not more than about 90, not more than about 85, not more than about 80, not more than about 75, not more than about 70, not more than about 65, or not more than about 60 weight percent, of these aldehydes, based on the total weight of aldehyde residues of the first or second polyvinyl acetal) resin.
  • the first and/or second polyvinyl acetal) resin can include residues of an aldehyde having a refractive index of less than 1.421 in an amount in the range of from about 10 to about 99, about 25 to about 75, or about 40 to about 60 weight percent, based on the total weight of aldehyde residues of the first or second polyvinyl acetal) resin.
  • the refractive index of one of these resins can be less than about 1.492, less than about 1.491, or less than about 1.490, measured as described previously.
  • one of the first and second polyvinyl acetal) resins primarily includes residues of a high Rl aldehyde, while the other of the first and second polyvinyl acetal) resins primarily includes residues of at least one aldehyde having a refractive index of less than 1.421.
  • the term "primarily" means at least 75 weight percent, so that a polyvinyl acetal) resin primarily including residues of a specified aldehyde includes at least 75 weight percent of residues of the specified aldehyde, based on the total weight of aldehyde residues of that resin.
  • the polyvinyl acetal) resin primarily including residues of a high Rl aldehyde can include not more than about 25, not more than about 20, not more than about 15, not more than about 10, not more than about 5, not more than about 2, or not more than about 1 weight percent of residues of other aldehydes having a refractive index less than 1.421, based on the total weight of aldehyde residues of the resin.
  • the other polyvinyl acetal) resin which can primarily include residues of an aldehyde having a refractive index of less than 1.421, may comprise not more than about 25, not more than about 20, not more than about 15, not more than about 10, not more than about 5, not more than about 2, or not more than about 1 weight percent of residues of a high Rl aldehyde, based on the total weight of aldehyde residues of the resin, and may include at least about 75, at least about 80, at least about 85, at least about 90, at least about 95, at least about 97, or at least about 99 percent of residues of one or more aldehydes having a refractive index less than 1.421.
  • the ratio of the resin primarily including residues of the high Rl aldehyde to the other resin or resins in the composition can be at least about 1:99, at least about 5:95, at least about 10:90, at least about 20:80, at least about 25:75, at least about 30:70, at least about 40:60 and/or not more than about 99:1, not more than about 95:5, not more than about 90:10, not more than about 85:15, not more than about 75:25, not more than about 70:30, or not more than about 60:40, or in the range of from about 1:99 to 99:1, about 10:90 to about 90:10, about 25:75 to 75:25, or about 40:60 to 60:40.
  • At least one of the first and second polyvinyl acetal) resins includes residues of a high Rl aldehyde and at least one aldehyde having a refractive index of less than 1.421, thereby forming a "hybrid" resin that includes residues of both high and low Rl aldehydes.
  • the amounts of the high Rl aldehyde residues and the residues of aldehydes having a refractive index of less than 1.421, as well as the weight ratios of one to the other, in the hybrid resin can be within the same ranges provided above with respect to the resin blends.
  • the other of the two polyvinyl acetal) resins may also include residues of at least one high Rl aldehyde.
  • the other of the two resins may include little or no high Rl aldehyde residues, such that it includes less than about 10, less than about 5, less than about 2, or less than about 1 weight percent of residues of a high Rl aldehyde, with the balance being residues of an aldehyde having a refractive index of less than 1.421, including, for example, aldehydes selected from the group consisting of n-butyraldehyde, iso-butyraldehyde, 2-ethylhexyl aldehyde, and combinations thereof.
  • the interlayer when the interlayer is a multilayer interlayer, it can include at least one polymer layer having at least a first polyvinyl acetal) resin and another polymer layer comprising at least a second polyvinyl acetal) resin, wherein the difference between the residual hydroxyl content of the first polyvinyl acetal) resin and the second polyvinyl acetal) resin is at least 2 weight percent.
  • One or both of the polyvinyl acetal) resins can include residues of a high Rl aldehyde and one of the polymer layers may have a refractive index that is higher or lower than the other by at least about 0.002, at least about 0.003, at least about 0.004 and/or not more than about 0.010, not more than about 0.009, not more than about 0.008, or not more than about 0.007, or by an amount in the range of from about 0.002 to about 0.010, about 0.003 to about 0.009, or about 0.004 to about 0.007.
  • the innermost polymer layer can have the higher refractive index, while in other embodiments, the refractive index of one or both of the outer polymer layers may be higher.
  • only one of the first and second polyvinyl acetal) resins may include residues of the high Rl aldehyde.
  • both of the polyvinyl acetal) resins may include residues of at least one high Rl aldehyde, but the resins can still exhibit a difference in refractive index within the ranges provided above.
  • One or both of the polyvinyl acetal) resins can include residues of at least one high Rl aldehyde.
  • the polymer layer including such a resin may have a glass transition temperature of less than 20, not more than about 15, not more than about 10, not more than about 5, not more than about 0, not more than about -5, or not more than about -10°C and a refractive index of at least about 1.465, at least about 1.470, at least about 1.475, at least about 1.480, at least about 1.485, at least about 1.490, at least about 1.495, at least about 1.500, at least about 1.510, at least about 1.520, at least about 1.525, at least about 1.540, at least about 1.550, at least about 1.575, at least about 1.590, at least about 1.600, at least about 1.615, at least about 1.625,
  • the plasticizer content of the layer can be at least about 50, at least about 55, at least about 60, at least about 65 phr and/or not more than about 120, not more than about 110, not more than about 90, not more than about 85, not more than about 80, or not more than about 75 phr, or in the range of from about 50 to about 120, about 55 to about 110, about 60 to about 90, or about 65 to about 75 phr.
  • the polymer layer including that resin may have a glass transition temperature of at least about 26, at least about 30, at least about 33, or at least about 35°C, and a refractive index of at least about 1.470, at least about 1.475, at least about 1.480, at least about 1.485, at least about 1.490, at least about 1.495, at least about 1.500, at least about 1.510, at least about 1.520, at least about 1.525, at least about 1.540, at least about 1.550, at least about 1.575, at least about 1.590, at least about 1.600, at least about 1.615, at least about 1.625, or at least about 1.650, each measured as described previously.
  • the plasticizer content of the layer can be less than 50 phr, not more than about 45 phr, not more than about 40 phr
  • the refractive index of the entire interlayer can be at least about 1.477, at least about 1.478, at least about 1.480, at least about 1.485, at least about 1.490, at least about at least about 1.495, at least about 1.500, at least about 1.505, at least about 1.510, at least about 1.515, at least about 1.520, at least about 1.540, at least about 1.550, at least about 1.575, at least about 1.580, at least about 1.590, at least about 1.600, at least about 1.610, at least about 1.620, at least about 1.630, at least about 1.640, or at least about 1.650, measured as described previously.
  • the Rl balancing agent can comprise a liquid Rl balancing agent.
  • liquid Rl balancing agent refers to an Rl balancing agent that is liquid at standard conditions of 25°C and 1 atm.
  • the liquid Rl balancing agent can be, for example, a high Rl plasticizer.
  • high Rl plasticizer refers to a plasticizer having a refractive index of at least 1.460, measured as described previously.
  • the high Rl plasticizers suitable for use as Rl balancing agents can have a refractive index of at least about 1.470, at least about 1.480, at least about 1.490, at least about 1.500, at least about 1.510, at least about 1.520 and/or not more than about 1.600, not more than about 1.575, or not more than about 1.550, measured as discussed above.
  • the refractive index of the high Rl plasticizers may be in the range of from about 1.460 to about 1.600, about 1.470 to about 1.575, about 1.480 to about 1.550, about 1.490 to about 1.525.
  • Examples of types or classes of high Rl plasticizers can include, but are not limited to, polyadipates (Rl of about 1.460 to about 1.485); epoxides such as epoxidized soybean oils (Rl of about 1.460 to about 1.480); phthalates and terephthalates (Rl of about 1.480 to about 1.540); benzoates and toluates (Rl of about 1.480 to about 1.550); and other specialty plasticizers (Rl of about 1.490 to about 1.520).
  • polyadipates Rl of about 1.460 to about 1.485
  • epoxides such as epoxidized soybean oils (Rl of about 1.460 to about 1.480); phthalates and terephthalates (Rl of about 1.480 to about 1.540); benzoates and toluates (Rl of about 1.480 to about 1.550); and other specialty plasticizers (Rl of about 1.490 to about 1.520).
  • Rl plasticizers can include, but are not limited to, dipropylene glycol dibenzoate, tripropylene glycol dibenzoate, polypropylene glycol dibenzoate, isodecyl benzoate, 2-ethylhexyl benzoate, diethylene glycol benzoate, butoxyethyl benzoate, butoxyethyoxyethyl benzoate, butoxyethoxyethoxyethyl benzoate, propylene glycol dibenzoate, 2,2,4-trimethyl-l,3-pentanediol dibenzoate, 2,2,4-trimethyl-l,3-pentanediol benzoate isobutyrate, 1,3-butanediol dibenzoate, diethylene glycol di-o-toluate, triethylene glycol di-o-toluate, dipropylene glycol di-o- toluate, 1,2-octyl dibenzoate, tri-2-ethylhex
  • the plasticizer can be present in the layer alone or it can be blended with one or more additional plasticizers.
  • the other plasticizer or plasticizers may also comprise high Rl plasticizers, or one or more may be a lower Rl plasticizer having a refractive index of less than 1.460.
  • the lower Rl plasticizer may have a refractive index of less than about 1.450, less than about 1.445, or less than about 1.442 and can be selected from the group listed previously.
  • the mixture can have a refractive index within one or more of the above ranges.
  • a high Rl plasticizer When used as an Rl balancing agent in a multilayer interlayer, a high Rl plasticizer may be present in different amounts in two or more of the polymer layers. Similarly, when used as an Rl balancing agent in a resin composition or blended polymer layer, the high Rl plasticizer may be partitioned as described previously, such that polymer layers or domains having a lower residual hydroxyl content may have higher amounts of the high Rl plasticizer.
  • At least one layer or portion of a polymer layer or interlayer may comprise a high Rl plasticizer as an Rl balancing agent in an amount of at least about 5, at least about 10, at least about 15, at least about 20, at least about 25, at least about 30, at least about 35 and/or not more than about 50, not more than about 45, or not more than about 40 phr.
  • the high Rl plasticizer can be present in the polymer layer or interlayer in an amount in the range of from about 5 to about 50, about 10 to about 45, about 20 to about 40 phr.
  • one or more other layers or portions can include the high Rl plasticizer in an amount of at least about 50, at least about 55, at least about 60, at least about 65, at least about 70 and/or not more than about 120, not more than about 110, not more than about 100, not more than about 90, or not more than about 75 phr, or in the range of from about 50 to about 120, about 55 to about 110, about 60 to about 90, about 65 to about 75 phr.
  • These amounts may include any other plasticizers present in the composition, including those having a refractive index less than 1.460, or may include only the high Rl plasticizer.
  • the interlayer can include at least one polymer layer having a first polyvinyl acetal) resin and another polymer layer comprising a second polyvinyl acetal) resin, wherein the difference between the residual hydroxyl content of the first polyvinyl acetal) resin and the second polyvinyl acetal) resin is at least 2 weight percent.
  • At least one of the polymer layers can include a high Rl plasticizer in an amount sufficient so that the absolute value of the difference between the refractive index of the polymer layer and the refractive index of the another polymer layer is not more than 0.010.
  • the innermost polymer layer can have a higher refractive index, while in other embodiments, the refractive index of one or both of the outer polymer layers may be higher.
  • At least a portion of the polymer layer can have a glass transition temperature of not more than 25, not more than about 20, not more than about 15, not more than about 10, not more than about 5, not more than about 0, not more than about -5, or not more than about -10°C, and the layer can have a refractive index of at least about 1.465, at least about 1.470, at least about 1.475, at least about 1.480, at least about 1.485, at least about 1.490, at least about 1.495, at least about 1.500, at least about 1.510, at least about 1.520, at least about 1.525, at least about 1.540, at least about 1.550, at least about 1.575, at least about 1.590, at least about 1.600, at least about 1.615, at least about 1.625, or at least about 1.650, measured as described previously.
  • the plasticizer content of this layer in some embodiments, can be at least about 50, at least about 55, at least about 60 phr and/or not more than about 120, not more than about 110, not more than about 90, not more than about 85, not more than about 80, or not more than about 75 phr, or in the range of from about 50 to about 120, about 55 to about 110, about 60 to about 90, or about 60 to about 75 phr.
  • the high Rl plasticizer is present in the polymer layer that comprises the polyvinyl acetal) resin having a higher residual hydroxyl content
  • at least a portion of the layer can have a glass transition temperature of at least about 26, at least about 30, at least about 33, or at least about 35°C
  • the layer can have a refractive index of at least about 1.470, at least about 1.475, at least about 1.480, at least about 1.485, at least about 1.490, at least about 1.495, at least about 1.500, at least about 1.510, at least about 1.520, at least about 1.525, at least about 1.540, at least about 1.550, at least about 1.575, at least about 1.590, at least about 1.600, at least about 1.615, at least about 1.625, or at least about 1.650, measured as described previously.
  • the plasticizer content of this layer can be less than 50 phr, not more than about 45 phr, not more than about 40 phr, not more
  • the Rl balancing agent may be a solid Rl additive present in one or more layers or portions of a layer or interlayer.
  • solid Rl additive refers to an additive used to adjust the refractive index of a polyvinyl acetal) resin, polymer layer, or interlayer and which is solid at ambient conditions of 25°C and 1 atm.
  • the solid Rl additive may have a melting point of at least about 27, at least about 30, at least about 35, at least about 40, at least about 45, at least about 50, at least about 55, at least about 60, at least about 75, at least about 80, at least about 85, at least about 90, at least about 95, or at least about 100°C.
  • the solid Rl additive can be present in an amount sufficient such that the absolute value of the difference between the refractive indices of the first and second polymer layers is not more than about 0.010.
  • the difference between the refractive index of the first and second polymer layers may be greater than 0.010, when formulated into identical polymer layers in the absence of the solid Rl additive.
  • the solid Rl additive can be a high Rl solid additive for increasing the refractive index of at least one polymer layer or interlayer.
  • the refractive index of the high Rl solid additive can be at least about 1.460, at least about 1.465, at least about 1.470, at least about 1.475, at least about 1.480, at least about 1.485, at least about 1.490, at least about 1.495, at least about 1.500, at least about 1.505, at least about 1.510, at least about 1.525, at least about 1.550, at least about 1.575, or at least about 1.600, measured as described previously.
  • the solid Rl additive may be a Rl lowering solid additive for reducing the refractive index of at least one resin or polymer layer.
  • the Rl lowering solid additive can have a refractive index of less than 1.460, not more than about 1.455, not more than about 1.450, not more than about 1.445, or not more than about 1.440, measured as described previously. Whether higher or lower, the solid Rl additive can have a refractive index that is at least about 0.005, at least about 0.010, at least about 0.050, at least about 0.10 and/or not more than about 0.50, not more than about 0.35, or not more than about 0.20 different than the refractive index of the polyvinyl acetal) resin.
  • the difference in refractive index between the solid Rl additive and the polyvinyl acetal) resin can be in the range of from about 0.005 to about 0.50, about 0.010 to about 0.35, or about 0.050 to about 0.35.
  • the solid Rl additive can be present in a resin composition or interlayer in an amount of at least about 0.5, at least about 1, at least about 1.5, at least about 2, or at least about 5 phr, depending on the specific type of additive and layer or interlayer.
  • the solid Rl additive whether a high Rl additive or an Rl lowering additive, may comprise a physical solid Rl additive capable of being physically mixed or blended with at least one polyvinyl acetal) resin in a resin composition or layer, or it can be a reactive solid Rl additive, which may react with and become incorporated into the backbone of one or more polyvinyl acetal) resins.
  • the solid Rl additive can be used in combination with one or more low Rl plasticizers.
  • low Rl plasticizers can include, but are not limited to, triethylene glycol di-(2-ethylhexanoate) ("3GEH”), triethylene glycol di-(2- ethylbutyrate), triethylene glycol diheptanoate, tetraethylene glycol diheptanoate, tetraethylene glycol di-(2-ethylhexanoate) (“4GEH”), dihexyl adipate, dioctyl adipate, hexyl cyclohexyladipate, diisononyl adipate, heptylnonyl adipate, di(butoxyethyl) adipate, and bis(2-(2-butoxyethoxy)ethyl) adipate, dibutyl sebacate, dioctyl sebacate, and mixtures thereof.
  • the plasticizer may be selected from the group consisting of triethylene glycol di-(2-ethylhexanoate) and tetraethylene glycol di-(2- ethylhexanoate), or the plasticizer can comprise triethylene glycol di-(2- ethylhexanoate).
  • the solid Rl additive can also be used in combination with one or more high Rl plasticizers mentioned previously.
  • the solid Rl additive is a physical solid Rl additive, it may be combined with one or more polyvinyl acetal) resins or layers in an interlayer.
  • the physical solid Rl additive may be present in at least one layer or in an interlayer in an amount of at least about 1, at least about 2, at least about 3, at least about 5, at least about 8, at least about 10, at least about 12, at least about 15, at least about 20 and/or not more than about 60, not more than about 55, not more than about 50, not more than about 45, not more than about 40, not more than about 35, not more than about 30, not more than about 25, not more than about 20, or not more than about 15 phr, or in an amount in the range of from about 1 to about 60, about 5 to about 50, or about 10 to about 45 phr.
  • suitable physical solid high Rl additives can include, but are not limited to, polyadipates, polystyrene having a molecular weight of less than 2500, epoxides, phthalic acid esters, benzoic acid esters, inorganic oxides such as, for example, zirconium oxide, and combinations thereof.
  • Physical solid Rl lowering additives can be selected from the group consisting of halogenated additives, and silicon-containing additives.
  • the physical solid Rl additive may be present in one of the polymer layers in a higher amount than one or more other layers.
  • the difference between the amount of the physical solid Rl additive present in one of the polymer layers and the amount of physical solid Rl additive present in another layer, including, for example, an adjacent layer, can be at least about 2, at least about 5, at least about 8, at least about 10 phr and/or not more than about 30, not more than about 25, or not more than about 20 phr, or it can be in the range of from about 2 to about 30, about 5 to about 25, or about 10 to about 20 phr.
  • At least one of the layers can include at least about 1, at least about 5, at least about 10, at least about 15 phr and/or not more than about 60, not more than about 55, not more than about 50, not more than about 45 phr of the physical solid Rl additive, or the physical solid Rl additive can be present in an amount in the range of from about 1 to about 60, about 10 to about 50, or about 15 to about 45 phr.
  • the physical solid Rl additive can be present in one or more layers in an amount of at least about 5, at least about 10, at least about 15, at least about 20 phr and/or not more than about 60, not more than about 55, not more than about 50 phr, or in an amount in the range of from about 5 to about 60, about 15 to about 55, or about 20 to about 50 phr.
  • the inner, or core, layer or layers can include higher amounts of the physical solid Rl additive than the outer, or skin, layers.
  • the outer skin layers may include higher amounts of the solid Rl additive than the inner core layer.
  • the core layer can include at least about 30, at least about 40, at least about 50, at least about 60, at least about 70, or at least about 80 percent of the total amount of physical solid Rl additive present in the interlayer.
  • the solid Rl additive is a reactive solid Rl additive, it may be reacted with at least one polyvinyl acetal) resin such that at least a portion of the additive is incorporated into the polymer chain.
  • the reactive Rl additive can be an aromatic additive and can comprise, in some embodiments, phthalic anhydrides and phenylalkoxysilanes including, for example, diphenyldimethoxysilane.
  • the reactive Rl additive may be present in one layer of a multilayer interlayer in a higher amount than it is present in one or more other layers of the interlayer. In some embodiments, it may be absent, or substantially absent, from one or more polymer layers.
  • the inner core layer may include at least about 0.5, at least about 1, at least about 1.5, at least about 2, at least about 2.5, at least about 3 and/or not more than about 50, not more than about 30, not more than about 20, not more than about 15, not more than about 12, not more than about 10, or not more than about 8 phr of one or more reactive solid Rl additives, or an amount in the range of from about 0.5 to about 20, about 1 to about 12, or about 2 to about 8 phr.
  • the outer skin layer or layers may include not more than about 10, not more than about 5, not more than about 2, not more than about 1, or not more than about 0.5 phr of the reactive solid Rl additive.
  • the core layer can include at least about 65, at least about 75, at least about 85, at least about 95, or at least about 99 percent of the total amount of the reactive Rl additive present in the interlayer.
  • the interlayer can include at least one polymer layer having a first polyvinyl acetal) resin and another polymer layer comprising a second polyvinyl acetal) resin, wherein the difference between the residual hydroxyl content of the first polyvinyl acetal) resin and the second polyvinyl acetal) resin is at least 2 weight percent.
  • At least one of the polymer layers can include the high Rl additive in an amount sufficient so that the absolute value of the difference between the refractive index of the first polymer layer and the refractive index of the second polymer layer is not more than 0.010.
  • the innermost polymer layer can have a higher refractive index, while in other embodiments, the refractive index of one or both of the outer polymer layers may be higher.
  • the polymer layer can have a glass transition temperature of not more than 25, not more than about 20, not more than about 15, not more than about 10, not more than about 5, not more than about 0, not more than about -5, or not more than about-10°C, and a refractive index of at least about 1.465, at least about 1.470, at least about 1.475, at least about 1.480, at least about 1.485, at least about 1.495, at least about 1.500, at least about 1.510, at least about 1.520, at least about 1.525, at least about 1.540, at least about 1.550, at least about 1.575, at least about 1.590, at least about 1.600, at least about 1.615, at least about 1.625, or at least about 1.650, each measured as described previously.
  • the plasticizer content of this layer in some embodiments, can be at least about 50, at least about 55, at least about 60, at least about 65 phr and/or not more than about 120, not more than about 110, not more than about 90, not more than about 85, not more than about 80, or not more than about 75 phr, or in the range of from about 50 to about 120, about 55 to about 110, about 60 to about 90, about 65 to about 75 phr.
  • the layer can have a glass transition temperature of at least about 26, at least about 30, at least about 33, or at least about 35°C.
  • the layer can have a refractive index of at least about 1.470, at least about 1.475, at least about 1.480, at least about 1.485, at least about 1.490, at least about 1.500, at least about 1.510, at least about 1.520, at least about 1.525, at least about 1.540, at least about 1.550, at least about 1.575, at least about 1.590, at least about 1.600, at least about 1.615, at least about 1.625, or at least about 1.650.
  • the plasticizer content of this layer can be less than 50 phr, not more than about 45 phr, not more than about 40 phr, not more than about 30, or not more than about 20 phr.
  • the refractive index of the interlayer can be greater than 1.475, at least about 1.480, at least about 1.490, at least about 1.500, at least about 1.510, at least about 1.520, at least about 1.530, at least about 1.540, at least about 1.550, at least about 1.560, at least about 1.570, at least about 1.580, at least about 1.590, at least about 1.600, at least about 1.610, at least about 1.620, at least about 1.630, at least about 1.640, at least about 1.650, at least about 1.660, or at least about 1.670, measured as described above.
  • the interlayer can include one or more of the Rl balancing agents described herein, or one or more other Rl balancing agents not specifically mentioned.
  • the interlayer may be a single layer (or monolithic interlayer), or it may comprise two or more layers adjacent to one another, as discussed herein.
  • Resin compositions, layers, and interlayers formulated according to various embodiments of the present invention to include at least two polyvinyl acetal) resins and an Rl balancing agent can exhibit enhanced optical properties without sacrificing other properties such as impact resistance and acoustic performance.
  • an Rl balancing agent due to differences in properties or composition of the resins, such as, for example, residual hydroxyl content, residual acetate content, or aldehyde residues, identical blends of the same resins formulated without the Rl balancing agent may provide compositions, layers, and interlayers with reduced optical performance.
  • Clarity is one parameter used to describe the optical performance of compositions, layers, and interlayers described herein and may be determined by measuring haze value or percent.
  • Haze value represents the quantification of light scattered by a sample in contrast to the incident light.
  • the resin blends, layers, and interlayers described herein may have a haze value of less than 5 percent, less than about 4 percent, less than about 3 percent, less than about 2 percent, less than about 1, or less than about 0.5 percent, as measured in accordance with ASTM D1003-13- Procedure B using llluminant C, at an observer angle of 2 degrees.
  • the test is performed with a spectrophotometer, such as a Hunterlab UltraScan XE instrument (commercially available from Hunter Associates, Reston, VA), on a polymer sample having a thickness of 0.76 mm, which has been laminated between two sheets of clear glass each having a thickness of 2.3 mm (commercially available from Pittsburgh Glass Works of Pennsylvania).
  • a spectrophotometer such as a Hunterlab UltraScan XE instrument (commercially available from Hunter Associates, Reston, VA)
  • a polymer sample having a thickness of 0.76 mm, which has been laminated between two sheets of clear glass each having a thickness of 2.3 mm (commercially available from Pittsburgh Glass Works of Pennsylvania).
  • the polymer layers and interlayers described herein may have a mottle value of not more than 3, not more than 2, or not more than 1.
  • Mottle is another measure of optical quality, which is detected as a texture or graininess. Mottle is a visual defect if the level is too high or too severe, thereby causing objectionable visual appearance. Mottle is assessed and categorized by a side-by-side qualitative comparison of shadowgraph projections for a test laminate with a set of standard laminate shadowgraphs that represent a series, or scale, of mottle values ranging from 1 to 4, with 1 representing a standard of low mottle (i.e., a low number of disruptions) and 4 representing a standard of high mottle (i.e., a high number of disruptions).
  • a model laminate having a single layer interlayer with zero mottle is used to facilitate the evaluation in a test laminate that has a mottle rating lower than the scale of the standard set, such as lower than a rating of 1.
  • a test laminate that shows a shadowgraph projection similar to that of a zero-mottle laminate is assessed to have a mottle rating of zero.
  • the test laminate is prepared with two sheets of clear glass each having a thickness of 2.3 mm (commercially available from Pittsburgh Glass Works of Pennsylvania) and an interlayer.
  • the interlayer typically has a random rough surface R z of about 35 to 40 microns and thickness of 0.76 to 0.86 mm.
  • the mottle values provided herein were determined using a Clear Mottle Analyzer (CMA) that includes a xenon arc lamp, a sample holder, a projection screen, and a digital camera.
  • CMA Clear Mottle Analyzer
  • the xenon arc lamp is used to project a shadowgraph of a laminated sample onto the screen and the camera is configured to capture an image of the resulting shadowgraph.
  • the image is then digitally analyzed using computer imaging software and compared to images of previously-captured standard samples to determine the mottle of the sample.
  • a method of measuring mottle using a CMA is described in detail in U.S. Patent Application Publication No. US 2012-0133764.
  • Another parameter used to determine the optical performance is transparency, or percent visual transmittance (%T V i S ), which is measured using a spectrophotometer, such as a HunterLab UltraScan EX, in accordance with ASTM D1003, Procedure B using llluminant C at an observer angle of 2 degrees.
  • a spectrophotometer such as a HunterLab UltraScan EX, in accordance with ASTM D1003, Procedure B using llluminant C at an observer angle of 2 degrees.
  • the values provided herein were obtained by analyzing a glass laminate samples having an interlayer thickness of about 0.76 mm and a clear glass thickness of 2.3 mm (commercially available from Pittsburgh Glass Works of Pennsylvania).
  • the polymer layers and interlayers of the present invention can have a percent visual transmittance of at least about 70, at least about 75, at least about 80, at least about 81, at least about 82, at least about 83, at least about 84, at least about 85, at least about 85.5, at least about 86, at least about 86.5, at least about 87, at least about 87.5, at least about 88, or at least about 88.5 percent.
  • the polymer layers and interlayers of the present invention have a %T V i S of greater than 85 for the interlayers containing only additives of ACAs, UV stabilizers, and antioxidant, or greater than 80% for the interlayers containing additional additives such as pigments, IR absorbers or blockers as mentioned above.
  • Polymer interlayers containing high levels of pigments and/or dyes may have lower % T V i S values as desired, such as in mass pigmented or colored polymer interlayers.
  • the polymer layers and interlayers described herein may also exhibit acoustic properties within a desirable range.
  • At least a portion of a polymer layer or interlayer may have a glass transition temperature of not more than 25, not more than about 20, not more than about 15, not more than about 10, not more than about 5, not more than about 0, not more than about -5, or not more than about -10°C, which may facilitate acoustic performance of the layer or interlayer.
  • at least a portion of the layer or interlayer may have a glass transition temperature of at least about 26, at least about 30, at least about 35°C, which may facilitate impact resistance properties and strength.
  • a polymer layer or interlayer according to the present invention may have a tan delta value of at least about 0.70.
  • Tan delta is the ratio of the loss modulus (G") in Pascals to the storage modulus (G') in Pascals of a specimen measured by Dynamic Mechanical Thermal Analysis (DMTA).
  • the DMTA is performed with an oscillation frequency of 1 Hz under shear mode and a temperature sweep rate of 3°C/min.
  • the peak value of the G"/G' curve at the glass transition temperature is the tan delta value.
  • Polymer layers or interlayers as described according to various embodiment herein can have a tan delta of at least about 1.0, at least about 1.05, at least about 1.10, at least about 1.25, at least about 1.50, at least about 1.75, at least about 2.0, or at least about 2.25.
  • the polymer layers and interlayers can have a damping loss factor, or loss factor, of at least about 0.10, at least about 0.15, at least about 0.17, at least about 0.20, at least about 0.25, at least about 0.27, at least about 0.30, at least about 0.33, or at least about 0.35.
  • Loss factor is measured by Mechanical Im pedance Measurement as described in ISO Standard 16940. A polymer sample is laminated between two sheets of clear glass, each having a thickness of 2.3 mm, and is prepared to have a width of 25 mm and a length of 300 mm.
  • the laminated sample is then excited at the center point using a vibration shaker, commercially available from Bruel and Kjaer (Naerum, Netherlands) and an impedance head (Bruel and Kjaer) is used to measure the force required to excite the bar to vibrate and the velocity of the vibration.
  • a vibration shaker commercially available from Bruel and Kjaer (Naerum, Netherlands) and an impedance head (Bruel and Kjaer) is used to measure the force required to excite the bar to vibrate and the velocity of the vibration.
  • the resultant transfer function is recorded on a National Instrument data acquisition and analysis system and the loss factor at the first vibration mode is calculated using the half power method.
  • the layer or interlayer when the Rl balancing agent is a high Rl plasticizer, the layer or interlayer may have a loss factor greater than 0.25, greater than 0.27, greater than 0.30, or greater than 0.35 at 20°C, while, in other embodiments, when the Rl balancing agent is a solid Rl additive or residues of at least one high Rl aldehyde, the layer or interlayer may have a loss factor of at least about 0.10, at least about 0.15, at least about 0.20, at least about 0.25, or at least about 0.30°C at 20°C.
  • blending two or more distinct polymer layers or interlayers can often result in the new polymer layer(s) or interlayer(s) having unexpected properties and performance attributes.
  • a polymer layer or interlayer having lower residual hydroxyl content and lower glass transition temperature may be blended with another polymer layer or interlayer having higher residual hydroxyl content and higher glass transition temperature, resulting a new polymer layer or interlayer having soft domains of lower glass transition temperature, which enhances its acoustic performance, and stiff domains of higher glass transition temperature, which imparts enhanced processability, strength, and impact resistance to the polymer layer or interlayer.
  • blending a single sheet interlayer and multilayer interlayer includes blending two multilayer interlayers, or blending one multilayer interlayer into a polymer layer of another multilayer interlayer.
  • the effect arising from blending two materials can also be achieved from blending two or more resins, plasticizers, and other additives according to the contents of the materials.
  • a "blend resin material” or “blend material” refers to the resin composition, polymer layer or interlayer to be blended into another resin composition, polymer layer or interlayer.
  • at least one of the two materials to be blended can include the polymer layer or interlayer of the present invention.
  • both materials can include the polymer layers or interlayers of the present invention.
  • At least a portion of the resin compositions, layers, or interlayers described herein may comprise another resins, layers, or interlayers.
  • at least about 0.5, at least about 1, at least about 5, at least about 10, at least about 15, at least about 20, at least about 25, at least about 30, or at least about 50 percent of the total amount of resin in a composition, layer, or interlayer can originate from a blend resin material.
  • polymer layers and interlayers that include higher levels of blend resin material can be produced by utilizing one or more of the Rl balancing agents discussed above.
  • the Rl balancing agent includes a high Rl plasticizer
  • higher amounts of blend resin materials can be added to a process for producing a resin composition, layer, or interlayer described herein without reducing the clarity or increasing the haze of the final composition, layer, or interlayer.
  • the composition that includes blend materials can include a first polyvinyl acetal) resin and a second polyvinyl acetal) resin, wherein one of the resins has a residual hydroxyl content that can be at least 2 weight percent lower than the residual hydroxyl content of the other resin.
  • Such a composition may further include at least one high Rl plasticizer having a refractive index of 1.460, and, in some embodiments, more than 3 percent of the combined amount of the first and second polyvinyl acetal) resins present in the composition, layer, or interlayer may have originated from a blend composition, layer, or interlayer.
  • the composition that includes more than 0.5 weight percent of blend resin materials may have a haze value of not more than about 5, not more than about 4, not more than about 3, not more than about 2, or not more than about 1, or not more than about 0.5.
  • the high Rl plasticizer used as an Rl balancing agent with blend resin compositions can have a refractive index within one or more of the ranges described previously.
  • the high Rl plasticizer may be added during production of the composition, layer, or interlayer along with the blend material and/or at least a portion of the high Rl plasticizer may be present in the blend resin material added to the process.
  • one or more other plasticizers may also be present in the resin material being blended and/or in the resin composition, layer, or interlayer being produced, including, for example, those having a refractive index less than about 1.450, less than about 1.445, or less than about 1.442, measured as described previously.
  • one or more additional high Rl plasticizers may also be present in the blend material and/or in the resin composition, layer, or interlayer into which the materials are being blended.
  • the resin composition that includes blended resin material as described above can be used to form layers and interlayers according to various embodiments of the present invention.
  • the resin composition including a blend resin material can be used to form a single monolithic interlayer, or it may be used to form one or more layers of a multilayer interlayer.
  • additional plasticizer may be added such that the total amount of plasticizer present in the polymer layer or interlayer can be within the range described previously.
  • the glass transition temperature and refractive indices of polymer layers and interlayers formed from a composition that includes a blend resin material may also be within the ranges provided above.
  • polymer layers and interlayers formed from a composition that includes blended materials may also exhibit acoustic properties as described previously and may be included in any of the applications described below.
  • At least a portion of the resin compositions, layers, or interlayers described herein may comprise one or more recycled resin materials, including, for example, recycled layers or interlayers.
  • recycled means removed from and subsequently returned to a production line. Often, utilizing recycled materials may adversely affect the optical performance of the final composition, layer, or interlayer, as determined by clarity or haze, because of the different compositions and properties of the materials being blended or combined.
  • layers or interlayers as described herein may include at least one recycled resin material, while still exhibiting the same optical and/or acoustic properties as described herein.
  • the type and/or amount of recycle resin material may fall within one or more of the ranges described previously and the layer or interlayer may further include at least one Rl balancing agent. Additionally, the polymer layers and interlayers including recycled resin material may also have optical and/or acoustic performance within one or more of the ranges described below.
  • the resin compositions, layers, and interlayers described above may be produced according to any suitable method.
  • the method for producing these compositions, layers, and interlayers can include providing two or more polyvinyl acetal) resins, blending at least one resin with an Rl balancing agent and, optionally, at least one plasticizer or other additive, to form a blended composition, and forming a layer from the blended composition.
  • the resins provided in the initial steps of the method can be in the form of one or more polyvinyl acetal) resins, while, in other embodiments, one or more resin precursors can also be provided.
  • the blending of the two resins can comprise melt blending and may be performed at a temperature of at least about 140, at least about 150, at least about 180, at least about 200, at least about 250°C.
  • the blending step may include reacting two or more aldehydes with a polyvinyl alcohol to provide a single polyvinyl acetal) resin having two or more aldehyde moieties. Additionally, a portion of the blending step can include blending one or more of the resins with at least one plasticizer and/or with one or more of the Rl balancing agents described previously.
  • the resulting blended resins can then be formed into one or more polymer layers according to any suitable method.
  • Exemplary methods of forming polymer layers and interlayers can include, but are not limited to, solution casting, compression molding, injection molding, melt extrusion, melt blowing, and combinations thereof.
  • Multilayer interlayers including two or more polymer layers may also be produced according to any suitable method such as, for example, co- extrusion, blown film, melt blowing, dip coating, solution coating, blade, paddle, air- knife, printing, powder coating, spray coating, and combinations thereof.
  • the layers or interlayers may be formed by extrusion or co-extrusion.
  • thermoplastic polymers plasticizers, and, optionally, at least one additive, including one or more Rl balancing agents as described previously, can be pre-mixed and fed into an extrusion device.
  • additives such as ACAs, colorants, and UV inhibitors, which can be in liquid, powder, or pellet form, may also be used and may be mixed into the thermoplastic polymers or plasticizers prior to entering the extrusion device.
  • ACAs ACAs, colorants, and UV inhibitors
  • UV inhibitors which can be in liquid, powder, or pellet form
  • These additives can be incorporated into the polymer resin and, by extension, the resultant polymer sheet, thereby enhancing certain properties of the polymer layer or interlayer and its performance in the final multiple layer glass panel or other end product.
  • the thickness, or gauge, of the layers or interlayers can be at least about 10, at least about 15, at least about 20 mils and/or not more than about 100, not more than about 90, not more than about 60, not more than about 50, or not more than about 35 mils, or it can be in the range of from about 10 to about 100, about 15 to about 60, or about 20 to about 35 mils.
  • the thickness of the polymer layers or interlayers can be at least about 0.25, at least about 0.38, at least about 0.51 mm and/or not more than about 2.54, not more than about 2.29, not more than about 1.52, or not more than about 0.89 mm, or in the range of from about 0.25 to about 2.54 mm, about 0.38 to about 1.52 mm, or about 0.51 to about 0.89 mm.
  • the polymer layers or interlayers can comprise flat polymer layers having substantially the same thickness along the length, or longest dimension, and/or width, or second longest dimension, of the sheet, while, in other embodiments, one or more layers of a multilayer interlayer, for example, can be tapered or can have a wedge-shaped profile, such that the thickness of the interlayer changes along the length and/or width of the sheet, such that one edge of the layer or interlayer has a thickness greater than the other.
  • the interlayer is a multilayer interlayer, at least one, at least two, or at least three of the layers of the interlayer can comprise at least one tapered zone.
  • the polymer sheet can be flat or may include at least one tapered zone. Tapered interlayers may be useful in, for example, heads-up-display (HUD) panels in automotive and aircraft applications.
  • HUD heads-up-display
  • FIG. 1 is a cross-sectional view of an exemplary tapered interlayer that includes a tapered zone of varying thickness.
  • the tapered zone has a minimum thickness, Tmin, measured at a first boundary of the tapered zone and a maximum thickness, Tmax, measured at a second boundary of the tapered zone.
  • Tmin can be at least about 0.25, at least about 0.40, or at least about 0.60 millimeters (mm) and/or not more than 1.2, not more than about 1.1, or not more than about 1.0 mm.
  • Tmin can be in the range of 0.25 to 1.2 mm, 0.4 to 1.1 mm, or 0.60 to 1.0 mm.
  • Tmax can be at least about 0.38, at least about 0.53, or at least about 0.76 mm and/or not more than 2.2, not more than about 2.1, or not more than about 2.0 mm. Further, Tmax can be in the range of 0.38 to 2.2 mm, 0.53 to 2.1 mm, or 0.76 to 2.0 mm.
  • the difference between I max anu I min can be at least about 0.13, at least about 0.15, at least about 0.2, at least about 0.25, at least about 0.3, at least about 0.35, at least about 0.4 mm and/or not more than 1.2, not more than about 0.9, not more than about 0.85, not more than about 0.8, not more than about 0.75, not more than about 0.7, not more than about 0.65, or not more than about 0.6 mm. Further, the difference between I max anu I min can be in the range of 0.13 to 1.2 mm, 0.25 to 0.75 mm, or 0.4 to 0.6 mm. In certain embodiments, the distance between the first and second boundaries of the tapered zone (i.e.
  • the "tapered zone width") can be at least about 5, at least about 10, at least about 15, at least about 20, or at least about 30 centimeters (cm) and/or not more than about 200, not more than about 150, not more than about 125, not more than about 100 or not more than about 75 cm. Further, the tapered zone width can be in the range of 5 to 200 cm, 15 to 125 cm, or 30 to 75 cm.
  • the tapered interlayer includes opposite first and second outer terminal edges.
  • the distance between the first and second outer terminal edges i.e., the "interlayer width" can be at least about 20, at least about 40, or at least about 60 cm and/or not more than about 400, not more than about 200, or not more than about 100 cm.
  • the interlayer width can be in the range of 20 to 400 cm, 40 to 200 cm, or 60 to 100 cm.
  • the first and second boundaries of the tapered zone are spaced inwardly from the first and second outer terminal edges of the interlayer. In such embodiments, only a portion of the interlayer is tapered.
  • the ratio of the interlayer width to the tapered zone width can be at least about 0.05:1, at least about 0.1:1, at least about 0.2:1, at least about 0.3:1, at least about 0.4:1 at least about 0.5:1, at least about 0.6:1, or at least about 0.7:1 and/or not more than about 1:1, not more than about 0.95:1, not more than about 0.9:1, not more than about 0.8:1, or not more than about 0.7:1. Further, the ratio of interlayer width to the tapered zone width can be in the range of 0.05:1 to 1:1 or 0.3:1 to 0.9:1. In an alternative embodiment, discussed below, the entire interlayer is tapered. When the entire interlayer is tapered, the tapered zone width is equal to the interlayer width and the first and second boundaries of the tapered zone are located at the first and second terminal edges, respectively.
  • the tapered zone of the interlayer has a wedge angle, which is defined as the angle formed between a first reference line extending through two points of the interlayer where the first and second tapered zone boundaries intersect a first (upper) surface of the interlayer and a second reference line extending through two points where the first and second tapered zone boundaries intersect a second (lower) surface of the interlayer.
  • the wedge angle of the tapered zone can be at least about 0.13, at least about 0.15, at least about 0.2, at least about 0.25, at least about 0.3, at least about 0.35, at least about 0.4 milliradians (mrad) and/or not more than about 1.2, not more than about 1.0, not more than about 0.9, not more than about 0.85, not more than about 0.8, not more than about 0.75, not more than about 0.7, not more than about 0.65, not more than about 0.6, not more than about 0.55, not more than about 0.5, or not more than about 0.45 mrad.
  • the wedge angle of the tapered zone can be in the range of 0.13 to 1.2 mrad, 0.2 to 0.8 mrad, 0.25 to 0.75 mrad, 0.3 to 0.6, or 0.4 to 0.55 mrad.
  • the wedge angle of the tapered zone is simply the angle between the first (upper) and second (lower) surfaces.
  • the tapered zone can include at least one variable angle zone having a curved thickness profile and a continuously varying wedge angle.
  • the tapered zone can include two or more constant angle zones, where the constant angle zones each have a linear thickness profile, but at least two of the constant angle zones have different wedge angles.
  • FIGS. 2-7 illustrate various tapered interlayers configured according embodiments of the present invention.
  • FIG. 2 depicts an interlayer 20 that includes a tapered zone 22 extending entirely from a first terminal edge 24a of the interlayer 20 to a second terminal edge 24b of the interlayer 20.
  • the first and second boundaries of the tapered zone are located at the first and second terminal edges 24a, b of the interlayer.
  • the entire tapered zone 22 of the interlayer 20 depicted in FIG. 2 has a constant wedge angle ⁇ that is simply the angle formed between the first (upper) planar and second (lower) planar surfaces of the interlayer 20.
  • FIG. 3 illustrates an interlayer 30 that includes a tapered zone 32 and a flat edge zone 33.
  • the first boundary 35a of the tapered zone 32 is located at the first terminal edge 34a of the interlayer 30, while the second boundary 35b of the tapered zone 32 is located where the tapered zone 32 and the flat edge zone 33 meet.
  • the tapered zone 32 includes a constant angle zone 36 and a variable angle zone 37.
  • the constant angle zone 36 has a linear thickness profile and a constant wedge angle, 9 C
  • the variable angle zone 37 has a curved thickness profile and a continuously varying wedge angle.
  • the starting wedge angle of the variable angle zone 37 is equal to the constant wedge angle 9 C and the ending wedge angle of the variable angle zone 37 is zero.
  • the interlayer 30 depicted in FIG. 3 has a constant wedge angle 9 C that is greater than the overall wedge angle of the entire tapered zone 32.
  • FIG. 4 illustrates an interlayer 40 that includes a tapered zone 42 located between first and second flat edge zones 43a, b.
  • the first boundary 45a of the tapered zone 42 is located where the tapered zone 42 and the first flat edge zone 43a meet, while the second boundary 45b of the tapered zone 42 is located where the tapered zone 42 and the second flat edge zone 43b meet.
  • the tapered zone 42 includes a constant angle zone 46 located between first and second variable angle zones 47a, b.
  • the first variable angle zone 47a forms a transition zone between the first flat edge zone 43a and the constant angle zone 46.
  • the second variable angle zone 47b forms a transition zone between the second flat edge zone 43b and the constant angle zone 46.
  • the constant angle zone 46 has a linear thickness profile and a constant wedge angle, 9 C , while the first and second variable angle zones 47a, b have curved thickness profiles and continuously varying wedge angles.
  • the starting wedge angle of the first variable angle zone 47a is equal to zero and the ending wedge angle of the first variable angle zone 47b is equal to the constant wedge angle 9 C .
  • the starting wedge angle of the second variable angle zone 47b is equal to the constant wedge angle 9 C and the ending wedge angle of the second variable angle zone 47b is zero.
  • the interlayer 40 depicted in FIG 4 has a constant wedge angle 9 C that is greater than the overall wedge angle of the entire tapered zone 42.
  • FIG. 5 illustrates an interlayer 50 that includes a tapered zone 52 located between first and second flat edge zones 53a, b.
  • the tapered zone 52 of the interlayer 50 does not include a constant angle zone. Rather, the entire tapered zone 52 of the interlayer 50 is a variable angle zone having a curved thickness profile and a continuously varying wedge angle.
  • the overall wedge angle, ⁇ , of the tapered zone 52 is measured as the angle between a first reference line "A" extending through the two points where the first and second boundaries 55a, b of the tapered zone 52 meet the first (upper) surface of the interlayer 50 and a second reference line “B" extending through the two points where the first and second boundaries 55a, b of the tapered zone 52 meet the second (lower) surface of the interlayer 50.
  • the curved thickness profile provides an infinite number of wedge angles, which can be greater than, less than, or equal to the overall wedge angle ⁇ of the entire tapered zone 52.
  • FIG. 6 illustrates an interlayer 60 that does not include any flat end portions. Rather, the tapered zone 62 of the interlayer 60 forms the entire interlayer 60. Thus, the first and second boundaries 65a, b of the tapered zone 60 are located at the first and second terminal edges 64a, b of the interlayer 60.
  • the tapered zone 62 of the interlayer 60 includes first, second, and third constant angle zones 46a, b,c separated by first and second variable angle zones 47a, b.
  • the first, second, and third constant angle zones 46a,b,c each have a linear thickness profile and each have unique first, second, and third constant wedge angles, ⁇ 0 ⁇ , ⁇ 0 2, ⁇ 0 3, respectively
  • the first variable angle zone 47a acts as a transition zone between the first and second constant angle zones 46a, b.
  • the second variable angle zone 47b acts as a transition zone between the second and third constant angle zones 46b,c.
  • the overall wedge angle, ⁇ , of the tapered zone 62 is measured as the angle between a first reference line "A" and a second reference line "B.”
  • the first constant wedge angle 9 c i is less than the overall wedge angle ⁇ of the tapered zone 62.
  • the second constant wedge angle 9 c2 is greater the overall wedge angle ⁇ of the tapered zone 62.
  • the third constant wedge angle 9 c3 is less than the overall wedge angle ⁇ of the tapered zone 62.
  • the wedge angle of the first variable angle zone 47a continuously increases from the first constant wedge angle 9 c i to the second constant wedge angle, 9 c2 .
  • the wedge angle of the second variable angle zone 47b continuously decreases from the second constant wedge angle 9 c2 to the third wedge angle 9 c3 .
  • FIG. 7 illustrates an interlayer 70 that includes a tapered zone 72 located between first and second flat edge zones 73a,b.
  • the first and second boundaries 75a, b of the tapered zone 72 are spaced inwardly from the first and second outer edges 74a, b of the interlayer 70.
  • the tapered zone 72 of the interlayer 70 includes first, second, third, and fourth variable angle zones 77a,b,c,d and first, second, and third constant angle zones 76a, b,c.
  • the first variable angle zone 77a acts as a transition zone between the first flat edge zone 73a and the first constant angle zone 76a.
  • the second variable angle zone 77b acts as a transition zone between the first constant angle zone 76a and the second constant angle zone 76b.
  • the third variable angle zone 77c acts as a transition zone between the second constant angle zone 76b and the third constant angle zone 76c.
  • the fourth variable angle zone 77d acts as a transition zone between the third constant angle zone 76c and the second flat edge zone 73b.
  • the first, second, and third constant angle zones 76a, b,c each have a linear thickness profile and each have unique first, second, and third constant wedge angles, ⁇ 0 ⁇ , ⁇ ⁇ 2 , ⁇ ⁇ 3 , respectively
  • the first, second, third, and fourth variable angle zones 77a,b,c,d have wedge angles that continuously transition from the wedge angle of the constant angle zone on one side of the variable angle zone 77 to the wedge angle of the constant angle zone on the other side of the variable angle zone 77.
  • the tapered interlayer can include one or more constant angle tapered zones, each having a width that is less than the overall width of the entire tapered zone and each having a wedge angle that is the same as or different than the overall wedge angle of the entire tapered zone.
  • the tapered zone can include one, two, three, four, five, or more constant angle tapered zones.
  • the constant angle tapered zones can be separated from one another by variable angle tapered zones that serve to transition between adjacent constant angle tapered zones.
  • the width of each constant angle tapered zone can be at least about 2, at least about 5, at least about 10, at least about 15, or at least about 20 cm and/or not more than about 150, not more than about 100, or not more than about 50 cm.
  • the ratio of the width of each constant angle tapered zone to the overall width of the entire tapered zone can be at least about 0.1:1, at least about 0.2:1, at least about 0.3:1 or at least about 0.4:1 and/or not more than about 0.9:1, not more than about 0.8:1, not more than about 0.7:1, not more than about 0.6:1, or not more than about 0.5:1.
  • the wedge angle of each constant angle tapered zone can be at least about 0.13, at least about 0.15, at least about 0.2, at least about 0.25, at least about 0.3, at least about 0.35, at least about 0.4 mrad and/or not more than about 1.2, not more than about 1.0, not more than about 0.9, not more than about 0.85, not more than about 0.8, not more than about 0.75, not more than about 0.7, not more than about 0.65, or not more than about 0.6 mrad. Further, the wedge angle of each constant angle tapered zone can be in the range of 0.13 to 1.2 mrad, 0.25 to 0.75 mrad, or 0.4 to 0.6 mrad.
  • the wedge angle of at least one constant angle tapered zone is at least about 0.01, at least about 0.05, at least about 0.1, at least about 0.2, at least about 0.3, or at least about 0.4 mrad greater than the overall wedge angle of the entire tapered zone. In certain embodiments, the wedge angle of at least one constant angle tapered zone is at least about 0.01, at least about 0.05, at least about 0.1, at least about 0.2, at least about 0.3, or at least about 0.4 mrad less than the overall wedge angle of the entire tapered zone.
  • the wedge angle of at least one constant angle tapered zone is not more than about 0.4, not more than about 0.3, not more than about 0.2, not more than about 0.1, not more than about 0.05, or not more than about 0.01 mrad greater than the overall wedge angle of the entire tapered zone. In certain embodiments, the wedge angle of at least one constant angle tapered zone is not more than about 0.4, not more than about 0.3, not more than about 0.2, not more than about 0.1, not more than about 0.05, or not more than about 0.01 mrad less than the overall wedge angle of the entire tapered zone.
  • FIGS. 8a and 8b illustrate an interlayer 80 that is similar in thickness profile to the interlayer 30 of FIG. 3.
  • the interlayer 80 of FIGS. 8a and 8b is configured for use in a vehicle windshield by fixing the interlayer between two sheets of glass.
  • the first terminal edge 84a of the interlayer 80 can be located at the bottom of the windshield, while the second terminal edge 84b of the interlayer 80 can be located at the top of the windshield.
  • the tapered zone 82 of the interlayer 80 is positioned in an area of the windshield where a heads-up display is to be located.
  • the tapered zone 82 of interlayer 80 includes a constant angle zone 86 and a variable angle zone 87. As depicted in FIG.
  • the tapered zone 82 extends entirely across the interlayer 80 between a first side edge 88a and a second side edge 88b of the interlayer 80.
  • FIG. 8b which is similar to FIG. 3, shows the thickness profile of the interlayer 80 between the bottom of the windshield and the top of the windshield.
  • the tapered interlayer can be a multilayered interlayer.
  • the tapered interlayer comprises multiple individual layers, all of the individual layers can be tapered, some of the individual layers can be tapered, or only one of the individual layers can be tapered.
  • the glass transition temperatures of the individual layers can be different than another.
  • the interlayer includes a tapered middle layer having a lower glass transition temperature than two tapered outer layers of the interlayer, where the glass transition temperature of one or both of the outer layers exceeds the glass transition temperature of the middle layer by at least about 10, at least about 20, at least about 30, at least about 40, or at least about 50 ° C.
  • the polymer layers or interlayers can comprise flat polymer layers having substantially the same thickness along the length, or longest dimension, and/or width, or second longest dimension, of the sheet, while, in other embodiments, one or more layers of a multilayer interlayer, for example, can be wedge-shaped or can have a wedge-shaped profile, such that the thickness of the interlayer changes along the length and/or width of the sheet, such that one edge of the layer or interlayer has a thickness greater than the other.
  • the interlayer is a multilayer interlayer, at least one, at least two, or at least three of the layers of the interlayer can be wedge-shaped.
  • the interlayer is a monolithic interlayer
  • the polymer sheet can be flat or wedge shaped. Wedge-shaped interlayers may be useful in, for example, heads-up-display (HUD) panels in automotive and aircraft applications.
  • HUD heads-up-display
  • the resin compositions, layers, and interlayers according to embodiments of the present invention may be utilized in a multiple layer panel that comprises a polymer layer or interlayer and at least one rigid substrate.
  • the multilayer panels include a pair of rigid substrates with the resin interlayer disposed therebetween.
  • the total thickness of the panel measured as the combined thickness of the substrates and the interlayer, can be at least about 2, at least about 3, at least about 3.5, at least about 4, at least about 4.5, at least about 4.65, at least about 4.75, or at least about 5 mm and/or not more than about 6.5, not more than about 6.25, not more than about 6.0, not more than about 5.75, not more than about 5.5, or not more than about 5 mm.
  • the thickness of one or both substrates may be substantially less than would be expected for a conventional multiple layer panel.
  • the combined thickness of each of the rigid substrates can be not more than about 4.0, not more than about 3.9, not more than about 3.8, not more than about 3.7, not more than about 3.6, not more than about 3.5, not more than about 3.4 mm.
  • any suitable rigid substrate may be used to form a multiple layer panel, and in some embodiments, the substrates may comprise a material selected from the group consisting of glass, polycarbonate, biaxially oriented PET, copolyesters, acrylic, and combinations thereof.
  • the rigid substrate includes a polymeric material
  • the polymeric material may or may not include a hard coat surface layer.
  • the rigid substrates may have a refractive index less than the refractive index of the interlayer used to form the multiple layer panel.
  • the refractive index of at least one of the rigid substrates can be not more than about 1.550, not more than about 1.545, not more than about 1.540, not more than about 1.535, not more than about 1.530, or not more than about 1.525, measured as described above.
  • the refractive index of at least one of the rigid substrates can be at least about 5, at least about 10, at least about 15, at least about 20 percent lower than the refractive index of the interlayer used to form the multiple layer panel.
  • the refractive index of one or both substrates can be at least about 0.25 units, at least about 0.50 units, at least about 0.75 units, at least about 1.0 units, at least about 1.1 units, or at least about 1.5 units lower than the refractive index of the interlayer.
  • the refractive index of the interlayer is higher than the refractive index of at least one of the substrates by the amounts or percentages described herein.
  • Multiple layer panels may have an equivalent refractive index that is higher than the refractive index of one or more of the rigid substrates.
  • equivalent refractive index refers to the overall refractive index of a composite material, such as, for example, a multiple layer panel.
  • I n the above equations, Q e q is the equivalent incident angle of the composite, ⁇ is the distance light travels through the entire composite, tj is the total thickness of the composite having m layers, /IA is the refractive index of air, ⁇ is the incident angle of light passing through the air-layer 1 interface, n eq is the equivalent refractive index of the composite, t, is the thickness of layer , and ⁇ , is the incident angle of light passing through layer .
  • the equivalent refractive index of a multiple layer panel as described herein can be at least about 1.490, at least about 1.495, at least about 1.500, at least about 1.505, at least about 1.510, at least about 1.515, at least about 1.520, at least about 1.525, at least about 1.530, at least about 1.535, at least about 1.540, or at least about 1.545.
  • the multiple layer panel can have an equivalent refractive index that is at least about 0.25, at least about 0.5, at least about 0.75, at least about 1, or at least about 1.5 percent higher than the refractive index of at least one of the substrates used to form the multiple layer interlayer.
  • the panel can have an equivalent refractive index that is at least 0.010, at least about 0.015, at least about 0.020, or at least about 0.025 higher than the refractive index of one or more rigid substrates used to form the panel.
  • the equivalent refractive index of a multiple layer panel may be less than the refractive index of the interlayer used to form the panel and can be, for example, at least about 0.5, at least about 1, at least about 1.5, at least about 2, at least about 2.5, at least about 3, at least about 5, or at least about 7 percent lower than the refractive index of the interlayer used to form the multiple layer panel.
  • the difference between the refractive index of the interlayer and the equivalent refractive index of the panel can be at least about 0.010, at least about 0.025, at least about 0.050, at least about 0.10, at least about 0.125, at least about 0.50, or at least about 0.75.
  • Multiple layer panels as described herein can be used for a variety of end use applications, including, for example, for automotive windshields and windows, aircraft windshields and windows, panels for various transportation applications such as marine applications, rail applications, etc., structural architectural panels such as windows, doors, stairs, walkways, balusters, decorative architectural panels, weather-resistant panels, such as hurricane glass or tornado glass, ballistic panels, and other similar applications.
  • multiple layer panels as described herein may exhibit a reduction in interfering double or reflected "ghost" images when, for example, used for projecting a heads-up display (HUD) image onto the windshield of an automobile or aircraft.
  • HUD heads-up display
  • ghost images are most problematic when the windshield has a generally uniform thickness profile, due to the differences in position of the projected image when it is reflected off the inside and outside surfaces of the glass.
  • multiple layer panels as described herein can minimize projection of ghost images such that, for example, the panel has a double image separation distance significantly lower than would be exhibited by a conventional panel.
  • the method of determining double image separation includes providing a multiple layer panel that includes at least a pair of rigid substrates and an interlayer disposed therebetween.
  • the interlayer can include any properties of, or may be, any of the interlayers described herein.
  • the interlayer may be a tapered interlayer comprising, for example, at least one tapered zone having a wedge angle of at least 0.05 mrad.
  • the substrates may also include one or more properties of the substrates described herein and, in certain embodiments, may comprise glass.
  • a projection image can be generated by passing light through at least a portion of the panel.
  • the light passing through the panel includes an image such as, for example, a grid, a line, a shape, or a picture.
  • the image may be generated by reflecting a thin film transistor display off of a substantially flat mirrored surface, although other suitable methods of generating images may be used. If the multiple layer panel is formed using a tapered interlayer, at least a portion of the light passing though the panel may be passed through at least a portion of the tapered zone. Alternatively, or in addition, the light may pass through one or more other zones of interest along the panel in order to determine the double image separation formed as light projects through those zones.
  • the projection image can be projected onto a surface and then captured to form a captured image.
  • the projected image displayed on the surface may include a primary image and a secondary "ghost" image, off-set and slightly overlapping the primary image, as shown in FIG. 10.
  • the projected image may be captured using a digital camera or other suitable device, and the capture may include digitizing the projected image to form a digital projection image comprising a plurality of pixels.
  • the captured image can be quantitatively analyzed to form a profile that includes at least one primary image indicator and at least one secondary image indicator.
  • the analyzing may be performed by converting at least a portion of the digital projection image to a vertical image matrix that includes a numerical value representing the intensity of pixels in that portion of the image.
  • a column of the matrix can then be extracted and graphed against pixel number, as shown in FIG. 11, to provide the profile.
  • the primary image indicator of the profile can then be compared with the secondary image indicator of the profile to determine a difference.
  • the primary image indicator may comprise the higher intensity peaks of the graph, while the secondary image indicator may be the lower intensity peaks.
  • any suitable difference between the two indicators can be determined and, in some embodiments, can be the difference in position between the two indicators in the profile graph. Based on the difference, the double image separation distance for the portion of the panel being tested can be calculated. A specific use of the above method for determining double image separation distance is described in Example 11.
  • multiple layer panels configured according to embodiments of the present invention may have a significantly lower double image separation distance than conventionally-formed panels.
  • the double image separation distance of panels as described herein may be at least about 10, at least about 20, at least about 30, at least about 40 percent less than the double image separation distance of panels formed from conventional interlayers such as, for example, those having a refractive index less than 1.480, all other things being equal.
  • the double image separation distance for a given panel may depend, in part, on its specific configuration, including the type and dimensions of its interlayer and substrates. Specific examples of double image separation distances for several inventive and comparative panels are provided in the Examples.
  • the process can include at least the following steps: (1) assembly of the two substrates and the interlayer; (2) heating the assembly via an IR radiant or convective device for a first, short period of time; (3) passing the assembly into a pressure nip roll for the first de-airing; (4) heating the assembly for a short period of time to about 60°C to about 120°C to give the assembly enough temporary adhesion to seal the edge of the interlayer; (5) passing the assembly into a second pressure nip roll to further seal the edge of the interlayer and allow further handling; and (6) autoclaving the assembly at temperature between 135°C and 150°C and pressures between 150 psig and 200 psig for about 30 to 90 minutes.
  • Other methods for de-airing the interlayer-glass interface, as described according to some embodiments in steps (2) through (5) above include vacuum bag and vacuum ring processes, and both may also be used to form interlayers of the present invention as
  • the multiple layer panel may include at least one polymer film disposed on the layer or interlayer, forming a multiple layer panel referred to as a "bilayer."
  • the interlayer utilized in a bilayer may include a multilayer interlayer, while, in other embodiments, a monolithic interlayer may be used.
  • the use of a polymer film in multiple layer panels as described herein may enhance the optical character of the final panel, while also providing other performance improvements, such as infrared absorption.
  • Polymer films differ from polymer layers or interlayers in that the films alone do not provide the necessary penetration resistance and glass retention properties.
  • the polymer film can also be thinner than the sheet, and may have a thickness in the range of from 0.001 to 0.25 mm.
  • PET Poly(ethylene terephthalate)
  • the composition of the resulting resins were measured using either the ASTM D1396 or FT-IR/SEC method described in detail previously.
  • the refractive index and glass transition temperature (T g ) of several of the resins was also measured according to the methods described previously, and the results are provided in Table 2, below.
  • BzCHO Rl 1.545
  • CCHO; Rl 1.620
  • 2-phenylpropionaldehyde (2PHPrCHO; Rl 1.517)
  • polyvinyl acetal resins comprising residues of at least one high refractive index aldehyde, including those listed above, tend to exhibit higher refractive indices than those comprising residues of aldehydes such as n-butyraldehyde, iso-butyraldehyde, and 2-ethylhexyl aldehyde.
  • Comparative and Disclosed Interlayers were formed by mixing and melt blending several of the Comparative Resins listed in Table 2 and several of the Disclosed Resins listed in Table 3 above, with varying amounts of the plasticizer triethylene glycol bis(2-ethylhexanoate) (3GEH).
  • the composition, refractive index, and glass transition temperature of each of the resulting interlayers referred to as Comparative Interlayers CL-1 through CL-14 and Disclosed Interlayers DL-1 through DL-26, were measured as described previously, and the results are respectively summarized in Tables 4 and 5, below.
  • Comparative Interlayers formulated with lower refractive index resins such as the Comparative Resins listed in Table 2. Additionally, as shown by comparison of Disclosed Interlayers DL-1 and DL-2 and DL-6 and DL-23 through DL-25, the amount of plasticizer used to form an interlayer affects both the glass transition temperature and refractive index of the layer, although not necessarily to the same extent for all resins.
  • reducing the amount of plasticizer by about 33 percent increases the glass transition temperature of the interlayer by 11°C (from 1°C to 12°C), but only increases the refractive index by 0.006 (from 1.473 to 1.479).
  • each multilayer interlayer included a pair of outer "skin" layers, having a total thickness of 28 mils, sandwiching an inner "core” layer having a thickness of 5 mils, usually formed of a resin having a lower residual hydroxyl content.
  • interlayers formed from skin and core layers having refractive index differences of 0.010 or more exhibited optical defects, as indicated by the mottle values greater than 5.
  • interlayers formed from skin and core layers having refractive index differences of less than 0.010 exhibited low mottle values of 1 or less.
  • such low mottle values were achievable by interlayers having a core layer with a higher or lower refractive index than the skin layer, as long as the absolute value of the difference between the refractive indices of adjacent layers was less than 0.010.
  • interlayers formed from skin a nd core layers both having high Rl aldehyde residues and having refractive index differences of greater than 0.010 exhibited high mottle values of 5 or greater.
  • Disclosed Interlayer DI-4 (as well as Comparative Interlayers CI-2 and CI-7) exhibited minimal changes in the glass transition temperature of both the skin and core layers of the interlayer at equilibrium. This indicates a minor amount of plasticizer migration between the skin and core layers of each of Interlayers CI-2, Cl- 7, and DI-4. Although Comparative Interlayers CI-2 and CI-7 may be relatively stable, both exhibited a mottle value greater than 5, which would be unacceptable for most optical applications. In contrast, the mottle value exhibited by Disclosed Interlayer Dl- 4 was less than 1.
  • Comparative and Disclosed Resins prepared as described in Example 1 above, were mixed and melt-blended together with 38 phr of 3GEH plasticizer to form Comparative Blended Layers CBL-16 and CBL-17 and Disclosed Blended Layers DBL-27 and DBL-28.
  • Comparative Polymer Layer CL-2 is listed in Table 4. Comparative Polymer Layer CL-15 was formulated with Comparative Resin CR-10 and 38 phr of 3GEH, while Disclosed Polymer layers DL-27 and DL-28 were formulated with Disclosed Resins DR-3 and DR-5, respectively, and 38 phr of 3GEH.
  • Comparative Blended Interlayers CBL-16 and CBL-17 which were formed from a blend of Comparative Resins CR-2 and CR-10, exhibited high haze values and lower percent visual transmittance than single polymer layers of Comparative Resin CR-2 (Comparative Layer CL-2) or CR-10 (Comparative Interlayer CL-15).
  • Disclosed Blended Interlayers DBL-27 and DBL-28 which were formed from a blend of Comparative Resin CR-2 and a high refractive index Disclosed Resin (Resin DR-3 in Layer DBL-27 or Resin DR-5 in Layer DBL-28), exhibited substantially the same haze and percent visual transmittance as Comparative Interlayer CL-2, which was formulated with Comparative Resin CR-2 alone.
  • inventive high refractive index resins to a comparative interlayer does not reduce the optical quality of the resulting interlayer.
  • polyvinyl acetal resins were prepared by acetalizing polyvinyl alcohol with n-butyraldehyde.
  • the resins which had different residual hydroxyl contents, were melt blended with varying amounts of a 3GEH plasticizer and used to form various layers of multilayer interlayers.
  • Each interlayer had an inner "core" layer having a thickness of 5 mils sandwiched between two outer "skin” layers, each having a thickness of 14 mils.
  • the polyvinyl butyral) resin used to form the core layers had a hydroxyl content of 11 weight percent and the resin used for the skin layers had a hydroxyl content of 19 weight percent. Both resins had a residual acetate content of about 2 weight percent.
  • Comparative Interlayers CI-17 through CI-19 were formed with polymer layers plasticized with 3GEH, which was present in varying amounts in the core and skin layers.
  • Disclosed Interlayers DI-30 through Dl- 38 also included varying amounts of two different high refractive index additives, BenzoflexTM 2-45 (diethyleneglycol dibenzoate; commercially available from Eastman Chemical Company, Kingsport, Tennessee) (Additive A-1), which had a melting point of 28°C and a refractive index of 1.542; and BenzoflexTM 352 (1,4-cyclohexane dimethanol dibenzoate; commercially available from Eastman Chemical Company) (Additive A-2), which had a melting point of 118°C and a refractive index of 1.554.
  • the refractive index and glass transition temperatures of each of the layers of Comparative Interlayers CI-17 through CI-19 and Disclosed Interlayers DI-30 through DI-38 were measured and the results are summarized in Table 10
  • the reactive high Rl additive used in Disclosed Layers DL- 29 and DL-30 was diphenyldimethoxysilane (commercially available as SID4535.0 from Gelest, Inc., Morrisville, Pennsylvania), and the reactive high Rl additive used in Disclosed Layer DL-31 (Additive B) was phthalic anhydride (commercially available from Sigma Aldrich Co., St. Louis, Missouri).
  • the refractive index of Comparative Layer CL-16 and each of Disclosed Layers DL-29 through DL-31 was measured and the results are provided in Table 11, below. Table 11: Refractive Index of Comparative and Disclosed Core Polymer Layers
  • Example 8 Various Interlayers with Resin Blends having a High Refractive Index Plasticizer
  • the resulting plasticized resins were then formed into single sheets that included both resins and the plasticizer.
  • the refractive index, haze, and percent visual transmittance was determined for each sheet and the results are provided in Table 12, below.
  • the resin blends including more than 2.2 percent of resin R- 2 that were plasticized with higher refractive index plasticizers P-2 through P-4 each exhibited substantially the same haze value and percent visual transmittance as blends having lower amounts of resin R-2. Therefore, it can be concluded that the resin blends utilizing higher refractive index plasticizers, such as plasticizers P-2 through P-4, may permit higher amounts of lower hydroxyl content resins without adversely impacting the optical properties of the final blend.
  • Example 9 Polyvinyl butyral) Layers including a High Refractive Index Plasticizer
  • polyvinyl n-butyral layers were formed by combining and melt blending three different polyvinyl n-butyral) resins (PVB-1 through PVB-3) with different types and amounts of plasticizer.
  • PVB-1 through PVB-3 had a different residual hydroxyl content, ranging from 11 to 20.4 weight percent, and all three resins had a residual vinyl acetate content of 1 weight percent.
  • 3GEH triethylene glycol di-(2-ethylhexanoate)
  • BenzoflexTM 354 commercially available from Eastman Chemical Company, Kingsport, Tennessee
  • Table 13 Several Poly(vinyl) Butyral Layers with Various Plasticizers
  • Example 11 Measurement of Double Image Separation Distance for Comparative and Disclosed Multiple Layer Panels with Varying Thickness and Wedge Angle
  • interlayers were formed by combining polyvinyl butyral) resin having a residual hydroxyl content of 18.7 weight percent with 38 phr of the plasticizer triethylene glycol bis(2-ethylhexanoate) (3GEH), and extruding the resulting mixture to form single layer sheets.
  • a flat interlayer sheet i.e., with no tapered zone, was formed with a uniform thickness of about 30 mils (about 0.76 mm) and was cut to form several comparative interlayers having a wedge angle of 0°.
  • test apparatus 100 includes a projector 130, an adjustable mirror 140, and a detector 120.
  • the incident angle at which the light from projector 130 hit adjustable mirror 140, shown in FIG. 9 as ⁇ was 30.11°
  • panel 110 was arranged so that the incident angle of the image from mirror 140 onto panel 110, shown in FIG.
  • a Comparative Panel is formed by laminating a PVB interlayer having a uniform thickness of 0.76 mm and a refractive index of 1.475 between glass panels, one of which has a thickness of 1.6 mm and the other of which has a thickness of 2.3 mm.
  • the glass panels each have a refractive index of 1.52, measured according to ASTM
  • a Disclosed Multiple Layer Panel (DP-B) is formed by laminating another PVB interlayer having a uniform thickness of 0.76 mm between two glass panels, each panel having the same thickness as the panels used to form the Comparative Multiple Layer Panel.
  • the PVB interlayer used to form the Disclosed Multiple Layer Panel (DP-B) has a refractive index of 1.65.
  • the equivalent refractive index of the Disclosed Multiple Layer Panel is calculated to be 1.540.
  • This Disclosed Multiple Layer Panel DP-B may represent the practical maximum (or practical limit) of equivalent refractive index achievable in some cases. The results are summarized in Table 17, below.
  • any of the ranges, values, or characteristics given for any single component of the present disclosure can be used interchangeably with any ranges, values or characteristics given for any of the other components of the disclosure, where compatible, to form an embodiment having defined values for each of the components, as given herein throughout.
  • an interlayer can be formed comprising polyvinyl butyral) having a residual hydroxyl content in any of the ranges given in addition to comprising a plasticizers in any of the ranges given to form many permutations that are within the scope of the present disclosure, but that would be cumbersome to list.
  • ranges provided for a genus or a category such as phthalates or benzoates, can also be applied to species within the genus or members of the category, such as dioctyl terephthalate, unless otherwise noted.

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Abstract

A tapered interlayer comprising at least one polymer layer and a having tapered zone with an overall wedge angle of not more than 0.85 mrad is provided. The refractive index of the polymer layer is 1.480 or higher. Multiple layer panels formed from such interlayers may exhibit desirable optical properties, including, for example, less image "ghosting," when used as part of a heads-up-display (HUD) display panel for use in automotive and aircraft applications.

Description

INTERLAYERS HAVING ENHANCED OPTICAL PROPERTIES
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a Continuation-in-Part of U.S. Patent Application Serial No. 14/563,011 filed on December 8, 2014, which is currently pending, the disclosure of which is incorporated herein by reference in its entirety.
BACKGROUND
1. Field of the Invention
[0002] This disclosure relates to polymer resins and, in particular, to polymer resins suitable for use in polymer interlayers, including those utilized in multiple layer panels.
2. Description of Related Art
[0003] Polyvinyl butyral) (PVB) is often used in the manufacture of polymer sheets that can be used as interlayers in multiple layer panels, including, for example, light-transmitting laminates such as safety glass or polymeric laminates. PVB is also used in photovoltaic solar panels to encapsulate the panels which are used to generate and supply electricity for commercial and residential applications.
[0004] Safety glass generally refers to a transparent laminate that includes at least one polymer sheet, or interlayer, disposed between two sheets of glass. Safety glass is often used as a transparent barrier in architectural and automotive applications, and one of its primary functions is to absorb energy resulting from impact or a blow without allowing penetration of the object through the glass and to keep the glass bonded even when the applied force is sufficient to break the glass. This prevents dispersion of sharp glass shards, which minimizes injury and damage to people or objects within an enclosed area. Safety glass may also provide other benefits, such as a reduction in ultraviolet (UV) and/or infrared (IR) radiation, and it may also enhance the aesthetic appearance of window openings through addition of color, texture, and the like. Additionally, safety glass with desirable acoustic properties has also been produced, which results in quieter internal spaces.
[0005] Laminated safety glass has been used in vehicles equipped with heads- up display (HUD) systems, which project an image of an instrument cluster or other important information to a location on the windshield at the eye level of the vehicle operator. Such a display allows the driver to stay focused on the upcoming path of travel while visually accessing dash board information. When projected onto a flat windshield having uniform and consistent thickness, an interfering double, or reflected "ghost," image is created due to the differences in the position of the projected image as it is reflected off the inside and outside surfaces of the glass.
[0006] One method of addressing these ghost images has been to include a coating, such as a dielectric coating, on one of the surfaces of the windshield between the glass and the polymeric interlayer. The coating is designed to produce a third ghost image at a location very close to the primary image, while significantly reducing the brightness of the secondary image, so that the secondary image appears to blend into the background. Unfortunately, at times, the effectiveness of such a coating can be limited and the coating itself may interfere with the adhesion of the polymeric interlayer to the glass substrates, resulting in optical distortion and other issues.
[0007] At the same time, due in part to desire for increased fuel efficiency for vehicles, demand has grown for multiple layer panels that are lighter in weight than traditional panels. In general, the multiple layer panels utilized in a vehicle, which may include, for example, its windshield, side windows, and other panels, make up a notable portion of the total weight of the vehicle - at times up to 5 percent. As a result, reduction in the total weight of these panels would generally result in a decrease in the weight of the vehicle and a corresponding increase in fuel efficiency. Most of the weight in these panels is not in the interlayer, but is instead attributable to the substrates, which typically include glass.
[0008] Therefore, a need exists for polymeric interlayers suitable for use in HUD applications that can also be utilized in lightweight multiple layer panels. Such interlayers should exhibit desirable optical, acoustic, and visual properties, while reducing double image separation and permitting usage of thinner substrates.
SUMMARY
[0009] One embodiment of the present invention relates a tapered interlayer comprising at least one polymer layer comprising a polyvinyl acetal) resin and at least one plasticizer. The polymer layer has a refractive index of at least about 1.480, and the interlayer comprises a tapered zone having an overall wedge angle of not more than 0.85 mrad.
[0010] Another embodiment of the present invention relates to a multiple layer panel comprising a pair of rigid substrates; and an interlayer disposed between the substrates. The interlayer comprises a tapered zone having an overall wedge angle of less than 0.85 mrad and the equivalent refractive index of the multiple layer panel is at least 0.010 higher than the refractive index of each of the rigid substrates.
[0011] Still another embodiment of the present invention relates to a multiple layer panel comprising a pair of rigid substrates and a tapered interlayer disposed between the substrates. The tapered interlayer comprises at least one polymeric resin. The refractive index of the interlayer is at least 5 percent higher than the refractive index of each of the rigid substrates.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] Various embodiments of the present invention are described in detail below with reference to the attached drawing Figures, wherein:
[0013] FIG. 1 is a cross-sectional view of a tapered interlayer configured in accordance with one embodiment of the present invention, where various features of the tapered interlayer are labeled for ease of reference;
[0014] FIG. 2 is a cross-sectional view of a tapered interlayer having a tapered zone that extends over the entire width of the interlayer, where the entire tapered zone has a constant wedge angle and a linear thickness profile; [0015] FIG. 3 is a cross-sectional view of a tapered interlayer having a tapered zone that extends over part of the width of the interlayer and a flat edge zone that extends over part of the width of the interlayer, where the tapered zone includes a constant angle zone and a variable angle zone;
[0016] FIG. 4 is a cross-sectional view of a tapered interlayer having a tapered zone that extends over part of the width of the interlayer and two flat edge zones that extend over part of the width of the interlayer, where the tapered zone includes a constant angle zone and two variable angle zones;
[0017] FIG. 5 is a cross-sectional view of a tapered interlayer having a tapered zone that extends over part of the width of the interlayer and two flat edge zones that extend over part of the width of the interlayer, where the tapered zone is formed entirely of a variable angle zone having a curved thickness profile;
[0018] FIG. 6 is a cross-sectional view of a tapered interlayer having a tapered zone that extends over the entire width of the interlayer, where the tapered includes three constant angle zones spaced apart from one another by two variable angle zones;
[0019] FIG. 7 is a cross-sectional view of a tapered interlayer having a tapered zone that extends over part of the width of the interlayer and two flat edge zones that extend over part of the width of the interlayer, where the tapered zone includes three constant angle zones and four variable angle zones;
[0020] FIG. 8a is a plan view of a tapered interlayer configured for use in a vehicle windshield, where the thickness profile of the interlayer is similar to the thickness profile of the interlayer depicted in FIG. 2;
[0021] FIG. 8b is a cross-sectional view of the interlayer of FIG. 8a, showing the thickness profile of the interlayer;
[0022] FIG. 9 is a schematic diagram of an apparatus used to measure the double image separation distance of a multiple layer panel; [0023] FIG. 10 is an example of a projection image formed when measuring the double image separation distance of a multiple layer panel using the apparatus of FIG. 9;
[0024] FIG. 11 is an example of a profile formed by analyzing the projection image shown in FIG. 10 by plotting the number of pixels as a function of intensity;
[0025] FIG. 12 is a graphical depiction of the results of the double image separation distance analyses performed on several Comparative and Disclosed samples as described in Example 11, particularly showing the double image separation distance of several samples of varying wedge angle as a function of total thickness;
[0026] FIG. 13 is graphical depiction of the results of the double image separation distance analyses performed on several Comparative and Disclosed samples as described in Example 11, particularly showing the double image separation of several samples of varying glass configuration as a function of wedge angle; and
[0027] FIG. 14 is a graphical depiction of the results of the double image separation distance analysis performed in Example 13, particularly showing the double image separation distance of several panels utilizing panels having varying glass thickness as a function of the equivalent refractive index.
DETAILED DESCRIPTION
[0028] Resin compositions, layers, and interlayers according to various embodiments of the present invention can comprise one or more thermoplastic polymers and a refractive index (Rl) balancing agent. As used herein, the term "refractive index balancing agent" or "Rl balancing agent" refers to any component or additive included in the composition, layer, or interlayer for adjusting the refractive index of at least one of the resins or layers. The Rl balancing agent may increase or reduce the refractive index of at least one of the resins or layers within an interlayer, which may improve the optical properties of the interlayer, including mottle, haze, and/or clarity, as compared to an identical interlayer formed without an Rl balancing agent. [0029] As used herein, the terms "polymer resin composition" and "resin composition" refer to compositions including one or more polymer resins. Polymer compositions may optionally include other components, such as plasticizers and/or other additives. As used herein, the terms "polymer resin layer," "polymer layer," and "resin layer" refer to one or more polymer resins, optionally combined with one or more plasticizers, that have been formed into a polymeric sheet. Again, polymer layers can include additional additives, although these are not required. As used herein, the term "interlayer" refers to a single or multiple layer polymer sheet suitable for use with at least one rigid substrate to form a multiple layer panel. The terms "single-sheet" interlayer and "monolithic" interlayer refer to interlayers formed of one single resin sheet, while the terms "multiple layer" and "multilayer" interlayer refer to interlayers having two or more resin sheets coextruded, laminated, or otherwise coupled to one another.
[0030] The resin compositions, layers, and interlayers described herein may include one or more thermoplastic polymers. Examples of suitable thermoplastic polymers can include, but are not limited to, polyvinyl acetal) resins, polyurethanes (PU), poly(ethylene-co-vinyl) acetates (EVA), polyvinyl chlorides (PVC), poly(vinylchloride-co-methacrylate), polyethylenes, polyolefins, ethylene acrylate ester copolymers, poly(ethylene-co-butyl acrylate), silicone elastomers, epoxy resins, and acid copolymers such as ethylene/carboxylic acid copoloymers and ionomers thereof, derived from any of the previously-listed polymers, and combinations thereof. In some embodiments, the thermoplastic polymer can be selected from the group consisting of polyvinyl acetal) resins, polyvinyl chloride, and polyurethanes, or the resin can comprise one or more polyvinyl acetal) resins. Although described herein with respect to polyvinyl acetal) resins, it should be understood that one or more of the above polymer resins could be included with, or in the place of, the polyvinyl acetal) resins described below in accordance with various embodiments of the present invention. [0031] When the resin compositions, layers, and interlayers described herein include polyvinyl acetal) resins, the polyvinyl acetal) resins can be formed according to any suitable method. Polyvinyl acetal) resins can be formed by acetalization of polyvinyl alcohol with one or more aldehydes in the presence of an acid catalyst. The resulting resin can then be separated, stabilized, and dried according to known methods such as, for example, those described in U.S. Patent Nos. 2,282,057 and 2,282,026, as well as "Vinyl Acetal Polymers," in the Encyclopedia of Polymer Science & Technology, 3rd ed., Volume 8, pages 381-399, by B.E. Wade (2003). The resulting polyvinyl acetal) resins may have a total percent acetalization of at least about 50, at least about 60, at least about 70, at least about 75, at least about 80, at least about 85 weight percent, measured according to ASTM D1396, unless otherwise noted. The total amount of aldehyde residues in a polyvinyl acetal) resin can be collectively referred to as the acetal component, with the balance of the polyvinyl acetal) resin being residual hydroxyl and residual acetate groups, which will be discussed in further detail below.
[0032] According to some embodiments, the resin composition, layer, or interlayer may include at least one polyvinyl acetal) resin, which may be present in the composition, layer, or interlayer in an amount of at least about 0.5, at least about 1, at least about 2, at least about 3, at least about 5, at least about 10, at least about 15, at least about 20, at least about 30, at least about 40, or at least about 45 weight percent, based on the combined weight of all resins in the composition, layer, or interlayer. Together, the at least one polyvinyl acetal) resins can make up at least about 10, at least about 20, at least about 30, at least about 40, at least about 50, at least about 60, at least about 70, or at least about 80 weight percent of composition, layer, or interlayer, based on the combined weight of all resins. In some embodiments, the amount of resins other than the at least one polyvinyl acetal) resin can be not more than about 20, not more than about 15, not more than about 10, not more than about 5, not more than about 2, or not more than about 1 weight percent, based on the combined weight of all resins. [0033] In some embodiments, the resin composition, layer, or interlayer can include at least a first polyvinyl acetal) resin and a second polyvinyl acetal) resin, each of which may be present in the composition, layer, or interlayer in an amount of at least about 0.5, at least about 1, at least about 2, at least about 3, at least about 5, at least about 10, at least about 15, at least about 20, at least about 30, at least about 40, or at least about 45 weight percent, based on the combined weight of all resins in the composition, layer, or interlayer. Together, the first and second polyvinyl acetal) resins can make up at least about 10, at least about 20, at least about 30, at least about 40, at least about 50, at least about 60, at least about 70, or at least about 80 weight percent of composition, layer, or interlayer, based on the combined weight of all resins. In some embodiments, the amount of resins other than the first and second polyvinyl acetal) resins can be not more than about 20, not more than about 15, not more than about 10, not more than about 5, not more than about 2, or not more than about 1 weight percent, based on the combined weight of all resins.
[0034] In some embodiments, one of the first and the second polyvinyl acetal) resins can be present in the composition, layer, or interlayer in an amount of less than 12 weight percent, based on the combined weight of the first and second polyvinyl acetal) resins. For example, the first or the second polyvinyl acetal) resin can be present in the composition, layer, or interlayer in an amount of at least about 0.5, at least about 1, at least about 1.5, at least about 2, at least about 2.5, at least about 3, at least about 3.5, at least about 4, at least about 4.5, at least about 5, at least about 5.5, at least about 6, at least about 6.5, at least about 7 weight percent and/or not more than about 12, not more than about 11.5, not more than about 11, not more than about 10.5, not more than about 10, not more than about 9.5, not more than about 9, not more than about 8.5, not more than about 8, not more than about 7.5 weight percent, based on the combined weight of the first and second polyvinyl acetal) resins. In some embodiments, one of the first and second polyvinyl acetal) resins can be present in the composition, layer, or interlayer in an amount in the range of from about 0.5 to about 12, about 1.5 to about 11.5, about 2 to about 11, about 2.5 to about 10 weight percent, based on the combined weight of the first and second polyvinyl acetal) resins.
[0035] The first and second polyvinyl acetal) resins can include residues of any suitable aldehyde and, in some embodiments, can include residues of at least one Ci to Cio aldehyde, or at least one C4 to Cs aldehyde. Examples of suitable C4 to Cs aldehydes can include, but are not limited to, n-butyraldehyde, iso-butyraldehyde, 2- methylvaleraldehyde, n-hexyl aldehyde, 2-ethylhexyl aldehyde, n-octyl aldehyde, and combinations thereof. At least one of the first and second polyvinyl acetal) resins can include at least about 20, at least about 30, at least about 40, at least about 50, at least about 60, or at least about 70 weight percent of residues of at least one C4 to Cs aldehyde, based on the total weight of aldehyde residues of the resin, and/or can include not more than about 90, not more than about 85, not more than about 80, not more than about 75, not more than about 70, or not more than about 65 weight percent of at least one C4 to Cs aldehyde, or in the range of from about 20 to about 90, about 30 to about 80, or about 40 to about 70 weight percent of at least one C4 to Cs aldehyde. The C4 to Cs aldehyde may be selected from the group listed above, or it can be selected from the group consisting of n-butyraldehyde, iso-butyraldehyde, 2- ethylhexyl aldehyde, and combinations thereof.
[0036] I n various embodiments, the first and/or second polyvinyl acetal) resin may be a polyvinyl n-butyral (PVB) resin. I n other embodiments, the first and/or second polyvinyl acetal) resin can be a polyvinyl n-butyral) resin that mainly comprises residues of n-butyraldehyde, and may, for example, include not more than about 50, not more than about 40, not more than about 30, not more than about 20, not more than about 10, not more than about 5, or not more than about 2 weight percent of residues of an aldehyde other than n-butyraldehyde, based on the total weight of all aldehyde residues of the resin. When the first and/or second polyvinyl acetal) resins are PVB resins, the molecular weight of the resins can be at least about 50,000, at least about 70,000, at least about 100,000 Daltons and/or not more than about 600,000, not more than about 550,000, not more than about 500,000, not more than about 450,000, or not more than 425,000 Daltons, measured by size exclusion chromatography using low angle laser light scattering (SEC/LALLS) method of Cotts and Ouano. As used herein, the term "molecular weight" refers to weight average molecular weight (Mw). The molecular weight of the first and/or second polyvinyl acetal) resin can be in the range of from about 50,000 to about 600,000, about 70,000 to about 450,000, or about 100,000 to about 425,000 Daltons.
[0037] Although generally described herein with respect to first and second polyvinyl acetal) resins, it should be understood that, in some embodiments, an equivalent single polyvinyl acetal) resin including first and second acetal moieties may be substituted for the first and second polyvinyl acetal) resins with similar results. As used herein, the term "polyvinyl acetal) resin component" can refer to an individual polyvinyl acetal) resin present in a blend of resins or to an acetal moiety present on a single polyvinyl acetal) resin. In various embodiments, the ratio, by weight, of the amount of the first polyvinyl acetal) resin component to the second polyvinyl acetal) resin component in a layer, interlayer, or blend can be in the range of from about 0.5:99.5 to about 99.5:0.5, about 1:99 to 99:1, about 10:90 to about 90:10, about 25:75 to about 75:25, or about 40:60 to about 60:40.
[0038] In some embodiments, at least one resin composition, layer, or interlayer can include at least a first polyvinyl acetal) resin component and a second polyvinyl acetal) resin component. In some embodiments, the first and second resin components may comprise first and second polyvinyl acetal) resins that can be physically mixed to form a resin blend, which may be combined with one or more plasticizers or other additives to provide a blended polymer layer or interlayer. In other embodiments, the first and second polyvinyl acetal) resin components may be present as respective first and second acetal moieties in a single polyvinyl acetal) resin. As with the resin blend, this single "hybrid" polyvinyl acetal) resin can be optionally blended with a plasticizer and utilized in polymer layers and interlayers.
[0039] In some embodiments, when the resin components include polyvinyl acetal) resins, the first and second polyvinyl acetal) resins may be blended such that one of the first and second resins is dispersed within the other of the first and second resins, which can form domains of one of the first and second polyvinyl acetal) resins within the other of the first and second polyvinyl acetal) resins. Such a blended resin may be used as a single layer interlayer or it may be combined with one or more adjacent layers to form a multilayer interlayer. In other embodiments, the first and second polyvinyl acetal) resins can be present in adjacent layers of a multilayer interlayer, such that one of the layers of the interlayer includes the first polyvinyl acetal) resin and another layer of the interlayer includes the second polyvinyl acetal) resin. Additional layers can also be present adjacent to at least one of the layers.
[0040] The resin compositions, layers, and interlayers according to various embodiments of the present invention can further include at least one plasticizer. Depending on the specific composition of the resin or resins in a composition, layer, or interlayer, the plasticizer may be present in an amount of at least about 5, at least about 10, at least about 15, at least about 20, at least about 25, at least about 30, at least about 35, at least about 40, at least about 45, at least about 50, at least about 55, at least about 60 parts per hundred parts of resin (phr) and/or not more than about 120, not more than about 110, not more than about 105, not more than about 100, not more than about 95, not more than about 90, not more than about 85, not more than about 75, not more than about 70, not more than about 65, not more than about 60, not more than about 55, not more than about 50, not more than about 45, or not more than about 40 phr, or in the range of from about 5 to about 120, about 10 to about 110, about 20 to about 90, or about 25 to about 75 phr. Specific embodiments are discussed in detail shortly.
[0041] As used herein, the term "parts per hundred parts of resin" or "phr" refers to the amount of plasticizer present as compared to one hundred parts of resin, on a weight basis. For example, if 30 grams of plasticizer were added to 100 grams of a resin, the plasticizer would be present in an amount of 30 phr. If the resin composition, layer, or interlayer includes two or more resins, the weight of plasticizer is compared to the combined amount of all resins present to determine the parts per hundred resin. Further, when the plasticizer content of a layer or interlayer is provided herein, it is provided with reference to the amount of plasticizer in the mix or melt that was used to produce the layer or interlayer.
[0042] Examples of suitable plasticizers can include, but are not limited to, triethylene glycol di-(2-ethylhexanoate) ("3GEH"), triethylene glycol di-(2- ethylbutyrate), triethylene glycol diheptanoate, tetraethylene glycol diheptanoate, tetraethylene glycol di-(2-ethylhexanoate) ("4GEH"), dihexyl adipate, dioctyl adipate, hexyl cyclohexyladipate, diisononyl adipate, heptylnonyl adipate, di(butoxyethyl) adipate, and bis(2-(2-butoxyethoxy)ethyl) adipate, dibutyl sebacate, dioctyl sebacate, and mixtures thereof. The plasticizer may be selected from the group consisting of triethylene glycol di-(2-ethylhexanoate) and tetraethylene glycol di-(2- ethylhexanoate), or the plasticizer can comprise triethylene glycol di-(2- ethylhexanoate).
[0043] According to some embodiments, the first and second polyvinyl acetal) resins in the compositions, layers, and interlayers described herein can have different compositions. For example, in some embodiments, the first polyvinyl acetal) resin can have a residual hydroxyl content and/or residual acetate content that is at least about 2, at least about 3, at least about 4, at least about 5, at least about 6, or at least about 8 weight percent higher or lower than the residual hydroxyl content and/or residual acetate content of the second polyvinyl acetal) resin. As used herein, the terms "residual hydroxyl content" and "residual acetate content" refer to the amount of hydroxyl and acetate groups, respectively, that remain on a resin after processing is complete. For example, polyvinyl n-butyral can be produced by hydrolyzing polyvinyl acetate to polyvinyl alcohol, and then acetalizing the polyvinyl alcohol with n-butyraldehyde to form polyvinyl n-butyral. In the process of hydrolyzing the polyvinyl acetate, not all of the acetate groups are converted to hydroxyl groups, and residual acetate groups remain on the resin. Similarly, in the process of acetalizing the polyvinyl alcohol, not all of the hydroxyl groups are converted to acetal groups, which also leaves residual hydroxyl groups on the resin. As a result, most polyvinyl acetal) resins include both residual hydroxyl groups (as vinyl hydroxyl groups) and residual acetate groups (as vinyl acetate groups) as part of the polymer chain. The residual hydroxyl content and residual acetate content are expressed in weight percent, based on the weight of the polymer resin, and are measured according to ASTM D1396, unless otherwise noted.
[0044] The difference between the residual hydroxyl content of the first and second polyvinyl acetal) resins could also be at least about 2, at least about 5, at least about 10, at least about 12, at least about 15, at least about 20, or at least about 30 weight percent. As used herein, the term "weight percent different" or "the difference is at least weight percent" refers to a difference between two given weight percentages, calculated by subtracting the one number from the other. For example, a polyvinyl acetal) resin having a residual hydroxyl content of 12 weight percent has a residual hydroxyl content that is 2 weight percent lower than a polyvinyl acetal) resin having a residual hydroxyl content of 14 weight percent (14 weight percent - 12 weight percent = 2 weight percent). As used herein, the term "different" can refer to a value that is higher than or lower than another value.
[0045] At least one of the first and second polyvinyl acetal) resins can have a residual hydroxyl content of at least about 14, at least about 14.5, at least about 15, at least about 15.5, at least about 16, at least about 16.5, at least about 17, at least about 17.5, at least about 18, at least about 18.5, at least about 19, at least about 19.5 and/or not more than about 45, not more than about 40, not more than about 35, not more than about 33, not more than about 30, not more than about 27, not more than about 25, not more than about 22, not more than about 21.5, not more than about 21, not more than about 20.5, or not more than about 20 weight percent, or in the range of from about 14 to about 45, about 16 to about 30, about 18 to about 25, about 18.5 to about 24, or about 19.5 to about 21 weight percent.
[0046] The other polyvinyl acetal) resin can have a residual hydroxyl content of at least about 8, at least about 9, at least about 10, at least about 11 weight percent and/or not more than about 16, not more than about 15, not more than about 14.5, not more than about 13, not more than about 11.5, not more than about 11, not more than about 10.5, not more than about 10, not more than about 9.5, or not more than about 9 weight percent, or in the range of from about 8 to about 16, about 9 to about 15, or about 9.5 to about 14.5 weight percent, and can be selected such that the difference between the residual hydroxyl content of the first and second polyvinyl acetal) resin is at least about 2 weight percent, as mentioned previously. One or more other polyvinyl acetal) resins may also be present in the resin composition, layer, or interlayer and can have a residual hydroxyl within the ranges provided above. Additionally, the residual hydroxyl content of the one or more other polyvinyl acetal) resins can be the same as or different than the residual hydroxyl content of the first and/or second polyvinyl acetal) resins.
[0047] In some embodiments, at least one of the first and second polyvinyl acetal) resins can have a residual acetate content different than the other. For example, in some embodiments, the difference between the residual acetate content of the first and second polyvinyl acetal) resins can be at least about 2, at least about 3, at least about 4, at least about 5, at least about 8, at least about 10 weight percent. One of the polyvinyl acetal) resins may have a residual acetate content of not more than about 4, not more than about 3, not more than about 2, or not more than about 1 weight percent, measured as described above. In some embodiments, at least one of the first and second polyvinyl acetal) resins can have a residual acetate content of at least about 5, at least about 8, at least about 10, at least about 12, at least about 14, at least about 16, at least about 18, at least about 20, or at least about 30 weight percent. The difference in the residual acetate content between the first and second polyvinyl acetal) resins can be within the ranges provided above, or the difference can be less than about 3, not more than about 2, not more than about 1, or not more than about 0.5 weight percent. Additional polyvinyl acetal) resins present in the resin composition or interlayer can have a residual acetate content the same as or different than the residual acetate content of the first and/or second polyvinyl acetal) resin. [0048] In some embodiments, the difference between the residual hydroxyl content of the first and second polyvinyl acetal) resins can be less than about 2, not more than about 1, not more than about 0.5 weight percent and the difference in the residual acetate content between the first and second polyvinyl acetal) resins can be at least about 3, at least about 5, at least about 8, at least about 15, at least about 20, or at least about 30 weight percent. In other embodiments, the difference in the residual acetate content of the first and second polyvinyl acetal) resins can be less than about 3, not more than about 2, not more than about 1, or not more than about 0.5 weight percent and the difference in the residual hydroxyl content of the first and second polyvinyl acetal) resins can be at least about 2, at least about 5, at least about 10, at least about 12, at least about 15, at least about 20, or at least about 30 weight percent.
[0049] In various embodiments, the differences in residual hydroxyl and/or residual acetate content of the first and second polyvinyl acetal) resins can be selected to control or provide certain performance properties, such as strength, impact resistance, penetration resistance, processability, or acoustic performance to the final composition, layer, or interlayer. For example, polyvinyl acetal) resins having a higher residual hydroxyl content, usually greater than about 16 weight percent, can facilitate high impact resistance, penetration resistance, and strength to a resin composition or layer, while lower hydroxyl content resins, usually having a residual hydroxyl content of less than 16 weight percent, can improve the acoustic performance of the interlayer or blend.
[0050] Polyvinyl acetal) resins having higher or lower residual hydroxyl contents and/or residual acetate contents may also, when combined with at least one plasticizer, ultimately include different amounts of plasticizer. As a result, layers or domains formed of first and second polyvinyl acetal) resins having different compositions may also have different properties within a single polymer layer or interlayer. Although not wishing to be bound by theory, it is assumed that the compatibility of a given plasticizer with a polyvinyl acetal) resin can depend, at least in part, on the composition of the polymer, and, in particular, on its residual hydroxyl content. Overall, polyvinyl acetal) resins with higher residual hydroxyl contents tend to exhibit a lower compatibility (or capacity) for a given plasticizer as compared to similar resins having a lower residual hydroxyl content. As a result, polyvinyl acetal) resins with higher residual hydroxyl contents tend to be less plasticized and exhibit higher stiffness than similar resins having lower residual hydroxyl contents. Conversely, polyvinyl acetal) resins having lower residual hydroxyl contents may tend to, when plasticized with a given plasticizer, incorporate higher amounts of plasticizer, which may result in a softer polymer layer that exhibits a lower glass transition temperature than a polymer layer including a similar resin having a higher residual hydroxyl content. Depending on the specific resin and plasticizer, these trends could be reversed.
[0051] When two polyvinyl acetal) resins having different levels of residual hydroxyl content are blended with a plasticizer, the plasticizer may partition between the polymer layers or domains, such that more plasticizer can be present in the layer or domain having the lower residual hydroxyl content and less plasticizer may be present in the layer or domain having the higher residual hydroxyl content. Ultimately, a state of equilibrium is achieved between the two resins. The correlation between the residual hydroxyl content of a polyvinyl acetal) resin and plasticizer compatibility/capacity can facilitate addition of a proper amount of plasticizer to the polymer resin. Such a correlation also helps to stably maintain the difference in plasticizer content between two or more resins when the plasticizer would otherwise migrate between the resins.
[0052] In some embodiments, a polymer layer or interlayer can include at least a first polymer layer comprising a first polyvinyl acetal) resin and a first plasticizer, and a second polymer layer, adjacent to the first polymer layer, comprising a second polyvinyl acetal) resin and a second plasticizer. The first and second plasticizer can be the same type of plasticizer, or the first and second plasticizers may be different. In some embodiments, at least one of the first and second plasticizers may also be a blend of two or more plasticizers, which can be the same as or different than one or more other plasticizers. When one of the first and second polyvinyl acetal) resins has a residual hydroxyl content that is at least 2 weight percent higher or lower than the residual hydroxyl content of the other, the difference in plasticizer content between the polymer layers can be at least about 2, at least about 5, at least about 8, at least about 10, at least about 12, or at least about 15 phr. In most embodiments, the polymer layer that includes the resin having a lower hydroxyl content can have the higher plasticizer content. In orderto control or retain other properties of the polymer layer or interlayer, the difference in plasticizer content between the first and second polymer layers may be not more than about 40, not more than about 30, not more than about 25, not more than about 20, or not more than about 17 phr. In other embodiments, the difference in plasticizer content between the first and second polymer layers can be at least about 40, at least about 50, at least about 60, or at least about 70 phr.
[0053] As a result, in some embodiments, wherein the first and second polyvinyl acetal) resins are present in adjacent layers of a multilayer interlayer, the first and second polymer layers can exhibit different glass transition temperatures. Similarly, when the first and second polyvinyl acetal) resins are present in a blend, the domains of one of the first and second polyvinyl acetal) resins can exhibit a different glass transition temperature than the other of the first and second polyvinyl acetal) resins. Glass transition temperature, or Tg, is the temperature that marks the transition from the glass state of the polymer to the rubbery state. The glass transition temperatures of the resins and layers described herein were determined by dynamic mechanical thermal analysis (DMTA). The DMTA measures the storage (elastic) modulus (G') in Pascals, loss (viscous) modulus (G") in Pascals, and the tan delta (G"/G') of the specimen as a function of temperature at a given oscillation frequency and temperature sweep rate. The glass transition temperature is then determined by the position of the tan delta peak on the temperature scale. Glass transition temperatures provided herein were determined at an oscillation frequency of 1 Hz under shear mode and a temperature sweep rate of 3°C/min.
[0054] The difference in the glass transition temperature of the first polymer layer and the second polymer layer, or between various regions of a blended resin or polymer layer, can be at least about 3, at least about 5, at least about 8, at least about 10, at least about 12, at least about 15, at least about 18, at least about 20, at least about 22, or at least about 25°C. One of the first and second polymer layers can have a glass transition temperature of at least about 26, at least about 28, at least about 30, at least about 33, at least about 35°C and/or not more than about 70, not more than about 65, not more than about 60, not more than about 55, not more than about 50°C, or in the range of from about 26 to about 70, about 30 to about 60, about 35 to about 50°C. The other of the first and second polyvinyl acetal) resins can have a glass transition temperature of not more than 25, not more than about 20, not more than about 15, not more than about 10, not more than about 5, not more than about 0, not more than about -5, or not more than about -10°C.
[0055] When the first and second polyvinyl acetal) resins are blended with one another such that domains of one resin are dispersed within the other, such differences in plasticizer content and/or glass transition temperature may also exist between domains of the first and second resins. For example, in some embodiments, a polymer layer or interlayer may include various domains of higher or lower plasticizer content and/or domains having higher or lower glass transition temperatures, as described previously. In some embodiments, at least a portion of the polymer layer or interlayer can have a glass transition temperature of at least about 26, at least about 28, at least about 30, at least about 33, at least about 35°C and/or not more than about 70, not more than about 65, not more than about 60, not more than about 55, not more than about 50°C, or in the range of from about 26 to about 70, about 28 to about 60, about 35 to about 50°C and/or at least a portion of the polymer layer or interlayer can have a glass transition temperature of not more than 25, not more than about 20, not more than about 15, not more than about 10, not more than about 5, not more than about 0°C, not more than about -5°C, or not more than about -10°C.
[0056] One or more resin blends, layers, and interlayers described herein may include various other additives to impart particular properties or features to the interlayer. Such additives can include, but are not limited to, dyes, pigments, stabilizers such as ultraviolet stabilizers, antioxidants, anti-blocking agents, flame retardants, IR absorbers or blockers such as indium tin oxide, antimony tin oxide, lanthanum hexaboride (LaBe) and cesium tungsten oxide, processing aides, flow enhancing additives, lubricants, impact modifiers, nucleating agents, thermal stabilizers, UV absorbers, dispersants, surfactants, chelating agents, coupling agents, adhesives, primers, reinforcement additives, and fillers.
[0057] Additionally, various adhesion control agents ("ACAs") can be used in the interlayers of the present disclosure to control the adhesion of the sheet to glass. In various embodiments, the amount of ACAs present in a resin composition, layer, or interlayer can be at least about 0.003, at least about 0.01, at least about 0.025 and/or not more than about 0.15, not more than about 0.10, or not more than about 0.04 phr, or in the range of from about 0.003 to about 0.15, about 0.01 to about 0.10, or about 0.025 to about 0.04 phr. Suitable ACAs can include, but are not limited to, sodium acetate, potassium acetate, magnesium bis(2-ethyl butyrate), magnesium bis(2-ethylhexanoate), and combinations thereof, as well as the ACAs disclosed in U.S. Patent No. 5,728,472.
[0058] Resins having different compositions and plasticized polymer layers having different properties also tend to exhibit different refractive indices, which can reduce the optical quality of the resulting layer or blend. Although not wishing to be bound by theory, it is believed that such differences in refractive index may cause light that passes through the different polymer layers or domains to be refracted in different directions, which may cause haze in the final product. At times, the absolute value of the difference between the refractive index of the first polyvinyl acetal) resin or layer and the refractive index of the second polyvinyl acetal) resin or layer, measured according to ASTM D542 at a wavelength of 589 nm and 25°C, can exceed 0.010. As a result, these compositions, layers, or interlayers can have a haze value greater than 5 percent and/or a mottle value greater than 3.
[0059] However, in various embodiments of the present invention, compositions, layers, and interlayers comprising a polyvinyl acetal) resin may further include at least one refractive index (Rl) balancing agent for adjusting the refractive index of the composition, layer, or interlayer. In some embodiments, the composition, layer, or interlayer may include at least a first polyvinyl acetal) resin and a second polyvinyl acetal) resin along with at least one Rl balancing agent. In other embodiments, the composition, layer, or interlayer ma include a single polyvinyl acetal) resin along with at least one Rl balancing agent. As discussed above, the Rl balancing agent can be any suitable agent present in a resin or a resin blend, layer, or interlayer, or portion thereof, that increases or reduces the refractive index of at least one resin or layer, which may improve the optical properties of the interlayer as compared to an identical interlayer formed without an Rl balancing agent. In some embodiments, the resin blend, layer, or interlayer may have a haze value of at least 5 percent when formed in the absence of the Rl balancing agent.
[0060] The Rl balancing agent can be in any suitable form and may be physically blended with one or more resins or it can be chemically bonded, or reacted, with at least one resin so that the Rl balancing agent is incorporated into the polymer chain. Examples of Rl balancing agents can include, but are not limited to, liquid Rl additives, solid Rl additives, and residues of at least one aldehyde present in one or more of the polyvinyl acetal) resins. Various embodiments of Rl balancing agents, as well as resin compositions, layers, and interlayers including the same, will now be discussed in detail below.
[0061] The Rl balancing agent may be present in the resin, polymer layer, or interlayer in an amount sufficient to modify the refractive index of polyvinyl acetal) resin, polymer layer, or interlayer. The Rl balancing agent may also be present in the composition, layer, or interlayer in an amount sufficient to modify the refractive index of at least one of the two polyvinyl acetal) resins, thereby minimizing the difference between the refractive indices of two polyvinyl acetal) polymer layers having different refractive indices. The Rl balancing agent may also minimize the difference between the refractive index of one or more polyvinyl acetal) resins and one or more plasticizers within a resin composition, layer, or interlayer. In some embodiments, the Rl balancing agent may be present in an amount sufficient to reduce the absolute value of the difference between the refractive index the first polyvinyl acetal) polymer layer and the refractive index of the second polyvinyl acetal) polymer layer to not more than 0.010, not more than about 0.009, not more than about 0.008, not more than about 0.007, not more than about 0.006, not more than about 0.005, not more than about 0.004, or not more than about 0.003. When a multilayer interlayer includes two or more polymer layers, the Rl balancing agent may be present in one or both layers and can, in some embodiments, be present in one of the layers in a higher amount than in one or more of the other layers.
[0062] In some embodiments, the Rl balancing agent can comprise one or more residues of an aldehyde having a refractive index of at least 1.421, as measured by ASTM D542 at a wavelength of 589 nm and a temperature of 25°C. The Rl balancing aldehyde, which may also be referred to herein as a "high refractive index aldehyde" or "high Rl aldehyde," can have a refractive index of at least about 1.425, at least about 1.450, at least about 1.475, at least about 1.500, at least about 1.510, or at least about 1.515 and/or not more than about 1.675, not more than about 1.650, or not more than about 1.625, or in the range of from about 1.425 to about 1.675, about 1.475 to about 1.650, or about 1.515 to about 1.625. The high Rl aldehyde may be an aromatic aldehyde that includes at least one aromatic ring or group. Examples of aromatic aldehydes can include, but are not limited to, C7 to C30 aromatic aldehydes, Cs to C25 aromatic aldehydes, or Cg to C20 aromatic aldehydes. Specific examples of high Rl aldehydes that can be used as Rl balancing agents in various embodiments of the present invention are listed in Table 1, below. Table 1: Exemplary High Rl Aldehydes
Aldehyde Refractive Index
Hexylcinnamaldehyde 1.517
Benzaldehyde 1.545
Cinnamaldehyde 1.620
4-Chlorobenzaldehyde 1.585
4-t-butylphenylacetaldehyde 1.530
2-phenylpropionaldehyde 1.517
Hydrocinnamaldehyde 1.523
[0063] When the Rl balancing agent includes residues of at least one high Rl aldehyde, at least one of the first and second polyvinyl acetal) resins can include residues of at least one high Rl aldehyde in an amount of at least about 0.5, at least about 1, at least about 5, at least about 10, at least about 15, at least about 20, at least about 25, at least about 30, at least about 35, at least about 40, at least about 45, at least about 50, at least about 55, at least about 60, at least about 65, at least about 70, at least about 75, at least about 80, at least about 85, at least about 90, at least about 95 percent and/or not more than about 99.5, not more than about 99, not more than about 97, not more than about 95, not more than about 90, not more than about 85, not more than about 80, not more than about 75, not more than about 70, not more than about 65, or not more than about 60 weight percent, based on the total weight of aldehyde residues of the first or second polyvinyl acetal) resin. At least one of the first and second polyvinyl acetal) resins can include residues of at least one high Rl aldehyde in an amount in the range of from about 0.5 to about 99.5, about 10 to about 90, about 25 to about 75, or about 40 to about 60 weight percent, based on the total weight of aldehyde residues of the first or second polyvinyl acetal) resin.
[0064] The amount of high Rl aldehyde residues can be determined using a combination of Fourier Transform Infrared Spectroscopy (FT-IR) and Size Exclusion Chromatography (SEC) with UV detection. In particular, FT-IR is used to measure residual hydroxyl content of the resin and SEC is used to determine the amount of high Rl aldehyde residues, with the amount of any other aldehyde residues being determined by the difference. The FT-IR analysis is performed using a Perkin Elmer Spectrum 100 FT-IR Spectrometer (commercially available from Perkin Elmer, Waltham, Massachusetts) with an ATR sampling attachment. The analysis is performed using 8 scans at a 4 cm-1 resolution. Prior to testing, a calibration is generated from several polyvinyl n-butyral) samples of varying residual hydroxyl content which have been dried in a desiccator with silica overnight at room temperature to remove excess moisture. The peak maximum wave number of the hydroxyl stretching band is correlated with the molar vinyl alcohol content of each sample, which was previously determined by ASTM D1396, and the resulting linear curve fits are used to predict molar residual hydroxyl content of the samples being analyzed. These values can be converted to weight percent by calculation after determination of the composition of the polyvinyl acetal) resin using SEC analysis has been completed, as described below.
[0065] The SEC analysis is performed using a Waters 2695 Alliance pump and autosampler with a Waters 410 inline differential refractive index detector and a Waters 2998 PDA inline UV detector (commercially available from Waters Corporation, Milford, Massachusetts) with Dionex Chromeleon v. 6.8 data acquisition software with an extension pack (commercially available from Thermo Fischer Scientific, Sunnyvale, CA). The analysis is performed with a PL Gel Mixed C (5 micron) column and Mixed E (3 micron) columns with an injection volume of 50 microliters at a flow rate of 1.0 mL/minute. Samples are prepared by dissolving between 0.03 and 0.09 grams of resin in 10-15 mL of stabilized tetrahydrofuran and then filtering each through a 0.22 micron PTFE filter. Initial calibrations of the chromatograph are performed using a narrow molecular weight polystyrene standard and a polyvinyl acetal) resin including only residues of the high Rl aldehyde, and subsequent samples were calibrated with a broad molecular weight polystyrene (commercially available as PSBR250K from American Polymer Standard Corporation, Mentor, Ohio).
[0066] In some embodiments, only one of the first and second polyvinyl acetal) resins includes residues of the high Rl aldehyde, while, in other embodiments, both of the resins may include such residues. The refractive index of a resin comprising residues of a high Rl aldehyde can be at least about 1.492, at least about 1.495, at least about 1.500, at least about 1.505, at least about 1.510, or at least about 1.515.
[0067] In various embodiments, at least one of the first and second polyvinyl acetal) resins may also include residues of at least one aldehyde having a refractive index of less than 1.421. Examples of these aldehydes can include, for example, aliphatic aldehydes such as the C4 to Cs aldehydes discussed above. The aldehydes having a refractive index of less than 1.421 can be selected from the group consisting of n-butyraldehyde, iso-butyraldehyde, and 2-ethylhexyl aldehyde.
[0068] When these residues are present, the first and/or second polyvinyl acetal) resin can include at least about 10, at least about 15, at least about 20, at least about 25, at least about 30, at least about 35, at least about 40, at least about 45, at least about 50, at least about 55, at least about 60, at least about 65, at least about 70, at least about 75, at least about 80, at least about 85, at least about 90, at least about 95 percent and/or not more than about 99, not more than about 97, not more than about 95, not more than about 90, not more than about 85, not more than about 80, not more than about 75, not more than about 70, not more than about 65, or not more than about 60 weight percent, of these aldehydes, based on the total weight of aldehyde residues of the first or second polyvinyl acetal) resin.
[0069] The amount of residues of an aldehyde having a refractive index of less than 1.421 are determined using the FT-IR/SEC method described above and then by calculation according to the following formula: 100 weight percent - weight percent residual hydroxyl (from FT-IR)— weight percent of high Rl aldehyde residues (from SEC) - weight percent residual acetate (from FT-IR) = weight percent of residues of aldehyde having refractive index less than 1.421. The first and/or second polyvinyl acetal) resin can include residues of an aldehyde having a refractive index of less than 1.421 in an amount in the range of from about 10 to about 99, about 25 to about 75, or about 40 to about 60 weight percent, based on the total weight of aldehyde residues of the first or second polyvinyl acetal) resin. The refractive index of one of these resins can be less than about 1.492, less than about 1.491, or less than about 1.490, measured as described previously.
[0070] According to some embodiments, one of the first and second polyvinyl acetal) resins primarily includes residues of a high Rl aldehyde, while the other of the first and second polyvinyl acetal) resins primarily includes residues of at least one aldehyde having a refractive index of less than 1.421. As used herein, the term "primarily" means at least 75 weight percent, so that a polyvinyl acetal) resin primarily including residues of a specified aldehyde includes at least 75 weight percent of residues of the specified aldehyde, based on the total weight of aldehyde residues of that resin. The polyvinyl acetal) resin primarily including residues of a high Rl aldehyde can include not more than about 25, not more than about 20, not more than about 15, not more than about 10, not more than about 5, not more than about 2, or not more than about 1 weight percent of residues of other aldehydes having a refractive index less than 1.421, based on the total weight of aldehyde residues of the resin.
[0071] Similarly, the other polyvinyl acetal) resin, which can primarily include residues of an aldehyde having a refractive index of less than 1.421, may comprise not more than about 25, not more than about 20, not more than about 15, not more than about 10, not more than about 5, not more than about 2, or not more than about 1 weight percent of residues of a high Rl aldehyde, based on the total weight of aldehyde residues of the resin, and may include at least about 75, at least about 80, at least about 85, at least about 90, at least about 95, at least about 97, or at least about 99 percent of residues of one or more aldehydes having a refractive index less than 1.421. In some embodiments, the ratio of the resin primarily including residues of the high Rl aldehyde to the other resin or resins in the composition can be at least about 1:99, at least about 5:95, at least about 10:90, at least about 20:80, at least about 25:75, at least about 30:70, at least about 40:60 and/or not more than about 99:1, not more than about 95:5, not more than about 90:10, not more than about 85:15, not more than about 75:25, not more than about 70:30, or not more than about 60:40, or in the range of from about 1:99 to 99:1, about 10:90 to about 90:10, about 25:75 to 75:25, or about 40:60 to 60:40.
[0072] In other embodiments, at least one of the first and second polyvinyl acetal) resins includes residues of a high Rl aldehyde and at least one aldehyde having a refractive index of less than 1.421, thereby forming a "hybrid" resin that includes residues of both high and low Rl aldehydes. According to these embodiments, the amounts of the high Rl aldehyde residues and the residues of aldehydes having a refractive index of less than 1.421, as well as the weight ratios of one to the other, in the hybrid resin can be within the same ranges provided above with respect to the resin blends. When the first or second polyvinyl acetal) resin includes residues of both high Rl and lower Rl aldehydes, the other of the two polyvinyl acetal) resins may also include residues of at least one high Rl aldehyde. Alternatively, the other of the two resins may include little or no high Rl aldehyde residues, such that it includes less than about 10, less than about 5, less than about 2, or less than about 1 weight percent of residues of a high Rl aldehyde, with the balance being residues of an aldehyde having a refractive index of less than 1.421, including, for example, aldehydes selected from the group consisting of n-butyraldehyde, iso-butyraldehyde, 2-ethylhexyl aldehyde, and combinations thereof.
[0073] When the interlayer is a multilayer interlayer, it can include at least one polymer layer having at least a first polyvinyl acetal) resin and another polymer layer comprising at least a second polyvinyl acetal) resin, wherein the difference between the residual hydroxyl content of the first polyvinyl acetal) resin and the second polyvinyl acetal) resin is at least 2 weight percent. One or both of the polyvinyl acetal) resins can include residues of a high Rl aldehyde and one of the polymer layers may have a refractive index that is higher or lower than the other by at least about 0.002, at least about 0.003, at least about 0.004 and/or not more than about 0.010, not more than about 0.009, not more than about 0.008, or not more than about 0.007, or by an amount in the range of from about 0.002 to about 0.010, about 0.003 to about 0.009, or about 0.004 to about 0.007. In some embodiments when the interlayer includes at least three polymer layers, the innermost polymer layer can have the higher refractive index, while in other embodiments, the refractive index of one or both of the outer polymer layers may be higher. In some embodiments, only one of the first and second polyvinyl acetal) resins may include residues of the high Rl aldehyde. In other embodiments, both of the polyvinyl acetal) resins may include residues of at least one high Rl aldehyde, but the resins can still exhibit a difference in refractive index within the ranges provided above.
[0074] One or both of the polyvinyl acetal) resins can include residues of at least one high Rl aldehyde. In some embodiments, when the polyvinyl acetal) resin including such residues has a residual hydroxyl content of not more than, for example, 15 weight percent, the polymer layer including such a resin may have a glass transition temperature of less than 20, not more than about 15, not more than about 10, not more than about 5, not more than about 0, not more than about -5, or not more than about -10°C and a refractive index of at least about 1.465, at least about 1.470, at least about 1.475, at least about 1.480, at least about 1.485, at least about 1.490, at least about 1.495, at least about 1.500, at least about 1.510, at least about 1.520, at least about 1.525, at least about 1.540, at least about 1.550, at least about 1.575, at least about 1.590, at least about 1.600, at least about 1.615, at least about 1.625, or at least about 1.650, each measured as described previously. The plasticizer content of the layer, according to various embodiments, can be at least about 50, at least about 55, at least about 60, at least about 65 phr and/or not more than about 120, not more than about 110, not more than about 90, not more than about 85, not more than about 80, or not more than about 75 phr, or in the range of from about 50 to about 120, about 55 to about 110, about 60 to about 90, or about 65 to about 75 phr.
[0075] When the resin having the residues of a high Rl aldehyde in the multilayer interlayer discussed above has a residual hydroxyl content greater than, for example 16 weight percent, the polymer layer including that resin may have a glass transition temperature of at least about 26, at least about 30, at least about 33, or at least about 35°C, and a refractive index of at least about 1.470, at least about 1.475, at least about 1.480, at least about 1.485, at least about 1.490, at least about 1.495, at least about 1.500, at least about 1.510, at least about 1.520, at least about 1.525, at least about 1.540, at least about 1.550, at least about 1.575, at least about 1.590, at least about 1.600, at least about 1.615, at least about 1.625, or at least about 1.650, each measured as described previously. The plasticizer content of the layer, according to some embodiments, can be less than 50 phr, not more than about 45 phr, not more than about 40 phr, not more than about 30, not more than about 20 phr.
[0076] The refractive index of the entire interlayer can be at least about 1.477, at least about 1.478, at least about 1.480, at least about 1.485, at least about 1.490, at least about at least about 1.495, at least about 1.500, at least about 1.505, at least about 1.510, at least about 1.515, at least about 1.520, at least about 1.540, at least about 1.550, at least about 1.575, at least about 1.580, at least about 1.590, at least about 1.600, at least about 1.610, at least about 1.620, at least about 1.630, at least about 1.640, or at least about 1.650, measured as described previously.
[0077] According to various embodiments of the present invention, the Rl balancing agent can comprise a liquid Rl balancing agent. As used herein, the term "liquid Rl balancing agent" refers to an Rl balancing agent that is liquid at standard conditions of 25°C and 1 atm. In some embodiments, the liquid Rl balancing agent can be, for example, a high Rl plasticizer. As used herein, the term "high Rl plasticizer," refers to a plasticizer having a refractive index of at least 1.460, measured as described previously. The high Rl plasticizers suitable for use as Rl balancing agents can have a refractive index of at least about 1.470, at least about 1.480, at least about 1.490, at least about 1.500, at least about 1.510, at least about 1.520 and/or not more than about 1.600, not more than about 1.575, or not more than about 1.550, measured as discussed above. The refractive index of the high Rl plasticizers may be in the range of from about 1.460 to about 1.600, about 1.470 to about 1.575, about 1.480 to about 1.550, about 1.490 to about 1.525.
[0078] Examples of types or classes of high Rl plasticizers can include, but are not limited to, polyadipates (Rl of about 1.460 to about 1.485); epoxides such as epoxidized soybean oils (Rl of about 1.460 to about 1.480); phthalates and terephthalates (Rl of about 1.480 to about 1.540); benzoates and toluates (Rl of about 1.480 to about 1.550); and other specialty plasticizers (Rl of about 1.490 to about 1.520). Specific examples of suitable Rl plasticizers can include, but are not limited to, dipropylene glycol dibenzoate, tripropylene glycol dibenzoate, polypropylene glycol dibenzoate, isodecyl benzoate, 2-ethylhexyl benzoate, diethylene glycol benzoate, butoxyethyl benzoate, butoxyethyoxyethyl benzoate, butoxyethoxyethoxyethyl benzoate, propylene glycol dibenzoate, 2,2,4-trimethyl-l,3-pentanediol dibenzoate, 2,2,4-trimethyl-l,3-pentanediol benzoate isobutyrate, 1,3-butanediol dibenzoate, diethylene glycol di-o-toluate, triethylene glycol di-o-toluate, dipropylene glycol di-o- toluate, 1,2-octyl dibenzoate, tri-2-ethylhexyl trimellitate, di-2-ethylhexyl terephthalate, bis-phenol A bis(2-ethylhexaonate), di-(butoxyethyl) terephthalate, di- (butoxyethyoxyethyl) terephthalate, and mixtures thereof. The high Rl plasticizer may be selected from dipropylene glycol dibenzoate and tripropylene glycol dibenzoate, and/or 2,2,4-trimethyl-l,3-pentanediol dibenzoate.
[0079] When the polymer layer or interlayer includes a high Rl plasticizer, the plasticizer can be present in the layer alone or it can be blended with one or more additional plasticizers. The other plasticizer or plasticizers may also comprise high Rl plasticizers, or one or more may be a lower Rl plasticizer having a refractive index of less than 1.460. In some embodiments, the lower Rl plasticizer may have a refractive index of less than about 1.450, less than about 1.445, or less than about 1.442 and can be selected from the group listed previously. When a mixture of two or more plasticizers are employed as a Rl balancing agent, the mixture can have a refractive index within one or more of the above ranges.
[0080] When used as an Rl balancing agent in a multilayer interlayer, a high Rl plasticizer may be present in different amounts in two or more of the polymer layers. Similarly, when used as an Rl balancing agent in a resin composition or blended polymer layer, the high Rl plasticizer may be partitioned as described previously, such that polymer layers or domains having a lower residual hydroxyl content may have higher amounts of the high Rl plasticizer. In some embodiments, at least one layer or portion of a polymer layer or interlayer may comprise a high Rl plasticizer as an Rl balancing agent in an amount of at least about 5, at least about 10, at least about 15, at least about 20, at least about 25, at least about 30, at least about 35 and/or not more than about 50, not more than about 45, or not more than about 40 phr. The high Rl plasticizer can be present in the polymer layer or interlayer in an amount in the range of from about 5 to about 50, about 10 to about 45, about 20 to about 40 phr. In some embodiments, one or more other layers or portions can include the high Rl plasticizer in an amount of at least about 50, at least about 55, at least about 60, at least about 65, at least about 70 and/or not more than about 120, not more than about 110, not more than about 100, not more than about 90, or not more than about 75 phr, or in the range of from about 50 to about 120, about 55 to about 110, about 60 to about 90, about 65 to about 75 phr. These amounts may include any other plasticizers present in the composition, including those having a refractive index less than 1.460, or may include only the high Rl plasticizer.
[0081] When a high Rl plasticizer is used as an Rl balancing agent in a multilayer interlayer, the interlayer can include at least one polymer layer having a first polyvinyl acetal) resin and another polymer layer comprising a second polyvinyl acetal) resin, wherein the difference between the residual hydroxyl content of the first polyvinyl acetal) resin and the second polyvinyl acetal) resin is at least 2 weight percent. At least one of the polymer layers can include a high Rl plasticizer in an amount sufficient so that the absolute value of the difference between the refractive index of the polymer layer and the refractive index of the another polymer layer is not more than 0.010. In some embodiments when the interlayer includes at least three polymer layers, the innermost polymer layer can have a higher refractive index, while in other embodiments, the refractive index of one or both of the outer polymer layers may be higher.
[0082] When a high Rl plasticizer is included in a polymer layer that includes at least one polyvinyl acetal) resin having the lower residual hydroxyl content, at least a portion of the polymer layer can have a glass transition temperature of not more than 25, not more than about 20, not more than about 15, not more than about 10, not more than about 5, not more than about 0, not more than about -5, or not more than about -10°C, and the layer can have a refractive index of at least about 1.465, at least about 1.470, at least about 1.475, at least about 1.480, at least about 1.485, at least about 1.490, at least about 1.495, at least about 1.500, at least about 1.510, at least about 1.520, at least about 1.525, at least about 1.540, at least about 1.550, at least about 1.575, at least about 1.590, at least about 1.600, at least about 1.615, at least about 1.625, or at least about 1.650, measured as described previously. The plasticizer content of this layer, in some embodiments, can be at least about 50, at least about 55, at least about 60 phr and/or not more than about 120, not more than about 110, not more than about 90, not more than about 85, not more than about 80, or not more than about 75 phr, or in the range of from about 50 to about 120, about 55 to about 110, about 60 to about 90, or about 60 to about 75 phr.
[0083] When the high Rl plasticizer is present in the polymer layer that comprises the polyvinyl acetal) resin having a higher residual hydroxyl content, at least a portion of the layer can have a glass transition temperature of at least about 26, at least about 30, at least about 33, or at least about 35°C, and the layer can have a refractive index of at least about 1.470, at least about 1.475, at least about 1.480, at least about 1.485, at least about 1.490, at least about 1.495, at least about 1.500, at least about 1.510, at least about 1.520, at least about 1.525, at least about 1.540, at least about 1.550, at least about 1.575, at least about 1.590, at least about 1.600, at least about 1.615, at least about 1.625, or at least about 1.650, measured as described previously. The plasticizer content of this layer, according to some embodiments, can be less than 50 phr, not more than about 45 phr, not more than about 40 phr, not more than about 30, or not more than about 20 phr.
[0084] According to various embodiments of the present invention, the Rl balancing agent may be a solid Rl additive present in one or more layers or portions of a layer or interlayer. As used herein, the term "solid Rl additive" refers to an additive used to adjust the refractive index of a polyvinyl acetal) resin, polymer layer, or interlayer and which is solid at ambient conditions of 25°C and 1 atm. In various embodiments, the solid Rl additive may have a melting point of at least about 27, at least about 30, at least about 35, at least about 40, at least about 45, at least about 50, at least about 55, at least about 60, at least about 75, at least about 80, at least about 85, at least about 90, at least about 95, or at least about 100°C. When employed in a resin blend, layer, or interlayer, the solid Rl additive can be present in an amount sufficient such that the absolute value of the difference between the refractive indices of the first and second polymer layers is not more than about 0.010. The difference between the refractive index of the first and second polymer layers may be greater than 0.010, when formulated into identical polymer layers in the absence of the solid Rl additive.
[0085] In some embodiments, the solid Rl additive can be a high Rl solid additive for increasing the refractive index of at least one polymer layer or interlayer. The refractive index of the high Rl solid additive can be at least about 1.460, at least about 1.465, at least about 1.470, at least about 1.475, at least about 1.480, at least about 1.485, at least about 1.490, at least about 1.495, at least about 1.500, at least about 1.505, at least about 1.510, at least about 1.525, at least about 1.550, at least about 1.575, or at least about 1.600, measured as described previously. In other embodiments, the solid Rl additive may be a Rl lowering solid additive for reducing the refractive index of at least one resin or polymer layer. The Rl lowering solid additive can have a refractive index of less than 1.460, not more than about 1.455, not more than about 1.450, not more than about 1.445, or not more than about 1.440, measured as described previously. Whether higher or lower, the solid Rl additive can have a refractive index that is at least about 0.005, at least about 0.010, at least about 0.050, at least about 0.10 and/or not more than about 0.50, not more than about 0.35, or not more than about 0.20 different than the refractive index of the polyvinyl acetal) resin. The difference in refractive index between the solid Rl additive and the polyvinyl acetal) resin can be in the range of from about 0.005 to about 0.50, about 0.010 to about 0.35, or about 0.050 to about 0.35.
[0086] In various embodiments, the solid Rl additive can be present in a resin composition or interlayer in an amount of at least about 0.5, at least about 1, at least about 1.5, at least about 2, or at least about 5 phr, depending on the specific type of additive and layer or interlayer. The solid Rl additive, whether a high Rl additive or an Rl lowering additive, may comprise a physical solid Rl additive capable of being physically mixed or blended with at least one polyvinyl acetal) resin in a resin composition or layer, or it can be a reactive solid Rl additive, which may react with and become incorporated into the backbone of one or more polyvinyl acetal) resins.
[0087] The solid Rl additive can be used in combination with one or more low Rl plasticizers. Examples of low Rl plasticizers can include, but are not limited to, triethylene glycol di-(2-ethylhexanoate) ("3GEH"), triethylene glycol di-(2- ethylbutyrate), triethylene glycol diheptanoate, tetraethylene glycol diheptanoate, tetraethylene glycol di-(2-ethylhexanoate) ("4GEH"), dihexyl adipate, dioctyl adipate, hexyl cyclohexyladipate, diisononyl adipate, heptylnonyl adipate, di(butoxyethyl) adipate, and bis(2-(2-butoxyethoxy)ethyl) adipate, dibutyl sebacate, dioctyl sebacate, and mixtures thereof. The plasticizer may be selected from the group consisting of triethylene glycol di-(2-ethylhexanoate) and tetraethylene glycol di-(2- ethylhexanoate), or the plasticizer can comprise triethylene glycol di-(2- ethylhexanoate). The solid Rl additive can also be used in combination with one or more high Rl plasticizers mentioned previously.
[0088] When the solid Rl additive is a physical solid Rl additive, it may be combined with one or more polyvinyl acetal) resins or layers in an interlayer. In some embodiments, the physical solid Rl additive may be present in at least one layer or in an interlayer in an amount of at least about 1, at least about 2, at least about 3, at least about 5, at least about 8, at least about 10, at least about 12, at least about 15, at least about 20 and/or not more than about 60, not more than about 55, not more than about 50, not more than about 45, not more than about 40, not more than about 35, not more than about 30, not more than about 25, not more than about 20, or not more than about 15 phr, or in an amount in the range of from about 1 to about 60, about 5 to about 50, or about 10 to about 45 phr. Examples of suitable physical solid high Rl additives can include, but are not limited to, polyadipates, polystyrene having a molecular weight of less than 2500, epoxides, phthalic acid esters, benzoic acid esters, inorganic oxides such as, for example, zirconium oxide, and combinations thereof. Physical solid Rl lowering additives can be selected from the group consisting of halogenated additives, and silicon-containing additives.
[0089] When utilized in a multilayer interlayer, the physical solid Rl additive may be present in one of the polymer layers in a higher amount than one or more other layers. The difference between the amount of the physical solid Rl additive present in one of the polymer layers and the amount of physical solid Rl additive present in another layer, including, for example, an adjacent layer, can be at least about 2, at least about 5, at least about 8, at least about 10 phr and/or not more than about 30, not more than about 25, or not more than about 20 phr, or it can be in the range of from about 2 to about 30, about 5 to about 25, or about 10 to about 20 phr. According to some embodiments, at least one of the layers can include at least about 1, at least about 5, at least about 10, at least about 15 phr and/or not more than about 60, not more than about 55, not more than about 50, not more than about 45 phr of the physical solid Rl additive, or the physical solid Rl additive can be present in an amount in the range of from about 1 to about 60, about 10 to about 50, or about 15 to about 45 phr. In some embodiments, the physical solid Rl additive can be present in one or more layers in an amount of at least about 5, at least about 10, at least about 15, at least about 20 phr and/or not more than about 60, not more than about 55, not more than about 50 phr, or in an amount in the range of from about 5 to about 60, about 15 to about 55, or about 20 to about 50 phr.
[0090] When the multilayer interlayer comprises three or more polymer layers and the solid Rl additive is a solid high Rl additive, the inner, or core, layer or layers can include higher amounts of the physical solid Rl additive than the outer, or skin, layers. However, if the solid Rl additive is a solid Rl lowering additive, the outer skin layers may include higher amounts of the solid Rl additive than the inner core layer. The core layer can include at least about 30, at least about 40, at least about 50, at least about 60, at least about 70, or at least about 80 percent of the total amount of physical solid Rl additive present in the interlayer.
[0091] When the solid Rl additive is a reactive solid Rl additive, it may be reacted with at least one polyvinyl acetal) resin such that at least a portion of the additive is incorporated into the polymer chain. The reactive Rl additive can be an aromatic additive and can comprise, in some embodiments, phthalic anhydrides and phenylalkoxysilanes including, for example, diphenyldimethoxysilane.
[0092] In some embodiments, the reactive Rl additive may be present in one layer of a multilayer interlayer in a higher amount than it is present in one or more other layers of the interlayer. In some embodiments, it may be absent, or substantially absent, from one or more polymer layers. For example, when the interlayer is a multilayer interlayer including at least three polymer layers, the inner core layer may include at least about 0.5, at least about 1, at least about 1.5, at least about 2, at least about 2.5, at least about 3 and/or not more than about 50, not more than about 30, not more than about 20, not more than about 15, not more than about 12, not more than about 10, or not more than about 8 phr of one or more reactive solid Rl additives, or an amount in the range of from about 0.5 to about 20, about 1 to about 12, or about 2 to about 8 phr. The outer skin layer or layers may include not more than about 10, not more than about 5, not more than about 2, not more than about 1, or not more than about 0.5 phr of the reactive solid Rl additive. The core layer can include at least about 65, at least about 75, at least about 85, at least about 95, or at least about 99 percent of the total amount of the reactive Rl additive present in the interlayer.
[0093] When a solid Rl additive is used as an Rl balancing agent in a multilayer interlayer, the interlayer can include at least one polymer layer having a first polyvinyl acetal) resin and another polymer layer comprising a second polyvinyl acetal) resin, wherein the difference between the residual hydroxyl content of the first polyvinyl acetal) resin and the second polyvinyl acetal) resin is at least 2 weight percent. At least one of the polymer layers can include the high Rl additive in an amount sufficient so that the absolute value of the difference between the refractive index of the first polymer layer and the refractive index of the second polymer layer is not more than 0.010. In some embodiments when the interlayer includes at least three polymer layers, the innermost polymer layer can have a higher refractive index, while in other embodiments, the refractive index of one or both of the outer polymer layers may be higher.
[0094] When a solid Rl additive is included in a polymer layer comprising the polyvinyl acetal) resin having the lower residual hydroxyl content, the polymer layer can have a glass transition temperature of not more than 25, not more than about 20, not more than about 15, not more than about 10, not more than about 5, not more than about 0, not more than about -5, or not more than about-10°C, and a refractive index of at least about 1.465, at least about 1.470, at least about 1.475, at least about 1.480, at least about 1.485, at least about 1.495, at least about 1.500, at least about 1.510, at least about 1.520, at least about 1.525, at least about 1.540, at least about 1.550, at least about 1.575, at least about 1.590, at least about 1.600, at least about 1.615, at least about 1.625, or at least about 1.650, each measured as described previously. The plasticizer content of this layer, in some embodiments, can be at least about 50, at least about 55, at least about 60, at least about 65 phr and/or not more than about 120, not more than about 110, not more than about 90, not more than about 85, not more than about 80, or not more than about 75 phr, or in the range of from about 50 to about 120, about 55 to about 110, about 60 to about 90, about 65 to about 75 phr.
[0095] When the solid Rl additive is present in the polymer layer that comprises the polyvinyl acetal) resin having a higher residual hydroxyl content, the layer can have a glass transition temperature of at least about 26, at least about 30, at least about 33, or at least about 35°C. In some embodiments, the layer can have a refractive index of at least about 1.470, at least about 1.475, at least about 1.480, at least about 1.485, at least about 1.490, at least about 1.500, at least about 1.510, at least about 1.520, at least about 1.525, at least about 1.540, at least about 1.550, at least about 1.575, at least about 1.590, at least about 1.600, at least about 1.615, at least about 1.625, or at least about 1.650. The plasticizer content of this layer, according to some embodiments, can be less than 50 phr, not more than about 45 phr, not more than about 40 phr, not more than about 30, or not more than about 20 phr.
[0096] According to some embodiments, the refractive index of the interlayer can be greater than 1.475, at least about 1.480, at least about 1.490, at least about 1.500, at least about 1.510, at least about 1.520, at least about 1.530, at least about 1.540, at least about 1.550, at least about 1.560, at least about 1.570, at least about 1.580, at least about 1.590, at least about 1.600, at least about 1.610, at least about 1.620, at least about 1.630, at least about 1.640, at least about 1.650, at least about 1.660, or at least about 1.670, measured as described above. The interlayer can include one or more of the Rl balancing agents described herein, or one or more other Rl balancing agents not specifically mentioned. The interlayer may be a single layer (or monolithic interlayer), or it may comprise two or more layers adjacent to one another, as discussed herein.
[0097] Resin compositions, layers, and interlayers formulated according to various embodiments of the present invention to include at least two polyvinyl acetal) resins and an Rl balancing agent can exhibit enhanced optical properties without sacrificing other properties such as impact resistance and acoustic performance. As discussed above, due to differences in properties or composition of the resins, such as, for example, residual hydroxyl content, residual acetate content, or aldehyde residues, identical blends of the same resins formulated without the Rl balancing agent may provide compositions, layers, and interlayers with reduced optical performance.
[0098] Clarity is one parameter used to describe the optical performance of compositions, layers, and interlayers described herein and may be determined by measuring haze value or percent. Haze value represents the quantification of light scattered by a sample in contrast to the incident light. In some embodiments, the resin blends, layers, and interlayers described herein may have a haze value of less than 5 percent, less than about 4 percent, less than about 3 percent, less than about 2 percent, less than about 1, or less than about 0.5 percent, as measured in accordance with ASTM D1003-13- Procedure B using llluminant C, at an observer angle of 2 degrees. The test is performed with a spectrophotometer, such as a Hunterlab UltraScan XE instrument (commercially available from Hunter Associates, Reston, VA), on a polymer sample having a thickness of 0.76 mm, which has been laminated between two sheets of clear glass each having a thickness of 2.3 mm (commercially available from Pittsburgh Glass Works of Pennsylvania).
[0099] Additionally, the polymer layers and interlayers described herein may have a mottle value of not more than 3, not more than 2, or not more than 1. Mottle is another measure of optical quality, which is detected as a texture or graininess. Mottle is a visual defect if the level is too high or too severe, thereby causing objectionable visual appearance. Mottle is assessed and categorized by a side-by-side qualitative comparison of shadowgraph projections for a test laminate with a set of standard laminate shadowgraphs that represent a series, or scale, of mottle values ranging from 1 to 4, with 1 representing a standard of low mottle (i.e., a low number of disruptions) and 4 representing a standard of high mottle (i.e., a high number of disruptions). High mottle is generally considered objectionable, particularly in automotive and architectural applications. Optionally, a model laminate having a single layer interlayer with zero mottle (no mottle) is used to facilitate the evaluation in a test laminate that has a mottle rating lower than the scale of the standard set, such as lower than a rating of 1. A test laminate that shows a shadowgraph projection similar to that of a zero-mottle laminate is assessed to have a mottle rating of zero. The test laminate is prepared with two sheets of clear glass each having a thickness of 2.3 mm (commercially available from Pittsburgh Glass Works of Pennsylvania) and an interlayer. The interlayer typically has a random rough surface Rz of about 35 to 40 microns and thickness of 0.76 to 0.86 mm.
[0100] The mottle values provided herein were determined using a Clear Mottle Analyzer (CMA) that includes a xenon arc lamp, a sample holder, a projection screen, and a digital camera. The xenon arc lamp is used to project a shadowgraph of a laminated sample onto the screen and the camera is configured to capture an image of the resulting shadowgraph. The image is then digitally analyzed using computer imaging software and compared to images of previously-captured standard samples to determine the mottle of the sample. A method of measuring mottle using a CMA is described in detail in U.S. Patent Application Publication No. US 2012-0133764.
[0101] Another parameter used to determine the optical performance is transparency, or percent visual transmittance (%TViS), which is measured using a spectrophotometer, such as a HunterLab UltraScan EX, in accordance with ASTM D1003, Procedure B using llluminant C at an observer angle of 2 degrees. The values provided herein were obtained by analyzing a glass laminate samples having an interlayer thickness of about 0.76 mm and a clear glass thickness of 2.3 mm (commercially available from Pittsburgh Glass Works of Pennsylvania). In some embodiments, the polymer layers and interlayers of the present invention can have a percent visual transmittance of at least about 70, at least about 75, at least about 80, at least about 81, at least about 82, at least about 83, at least about 84, at least about 85, at least about 85.5, at least about 86, at least about 86.5, at least about 87, at least about 87.5, at least about 88, or at least about 88.5 percent. More specifically, the polymer layers and interlayers of the present invention have a %TViS of greater than 85 for the interlayers containing only additives of ACAs, UV stabilizers, and antioxidant, or greater than 80% for the interlayers containing additional additives such as pigments, IR absorbers or blockers as mentioned above. Polymer interlayers containing high levels of pigments and/or dyes may have lower % TViS values as desired, such as in mass pigmented or colored polymer interlayers. [0102] I n addition to exhibiting one or more optical properties within the ranges above, the polymer layers and interlayers described herein may also exhibit acoustic properties within a desirable range. In some embodiments, as discussed above, at least a portion of a polymer layer or interlayer may have a glass transition temperature of not more than 25, not more than about 20, not more than about 15, not more than about 10, not more than about 5, not more than about 0, not more than about -5, or not more than about -10°C, which may facilitate acoustic performance of the layer or interlayer. At the same time, at least a portion of the layer or interlayer may have a glass transition temperature of at least about 26, at least about 30, at least about 35°C, which may facilitate impact resistance properties and strength.
[0103] I n some embodiments, a polymer layer or interlayer according to the present invention may have a tan delta value of at least about 0.70. Tan delta is the ratio of the loss modulus (G") in Pascals to the storage modulus (G') in Pascals of a specimen measured by Dynamic Mechanical Thermal Analysis (DMTA). The DMTA is performed with an oscillation frequency of 1 Hz under shear mode and a temperature sweep rate of 3°C/min. The peak value of the G"/G' curve at the glass transition temperature is the tan delta value. Polymer layers or interlayers as described according to various embodiment herein can have a tan delta of at least about 1.0, at least about 1.05, at least about 1.10, at least about 1.25, at least about 1.50, at least about 1.75, at least about 2.0, or at least about 2.25.
[0104] Additionally, the polymer layers and interlayers can have a damping loss factor, or loss factor, of at least about 0.10, at least about 0.15, at least about 0.17, at least about 0.20, at least about 0.25, at least about 0.27, at least about 0.30, at least about 0.33, or at least about 0.35. Loss factor is measured by Mechanical Im pedance Measurement as described in ISO Standard 16940. A polymer sample is laminated between two sheets of clear glass, each having a thickness of 2.3 mm, and is prepared to have a width of 25 mm and a length of 300 mm. The laminated sample is then excited at the center point using a vibration shaker, commercially available from Bruel and Kjaer (Naerum, Netherlands) and an impedance head (Bruel and Kjaer) is used to measure the force required to excite the bar to vibrate and the velocity of the vibration. The resultant transfer function is recorded on a National Instrument data acquisition and analysis system and the loss factor at the first vibration mode is calculated using the half power method. In some embodiments, when the Rl balancing agent is a high Rl plasticizer, the layer or interlayer may have a loss factor greater than 0.25, greater than 0.27, greater than 0.30, or greater than 0.35 at 20°C, while, in other embodiments, when the Rl balancing agent is a solid Rl additive or residues of at least one high Rl aldehyde, the layer or interlayer may have a loss factor of at least about 0.10, at least about 0.15, at least about 0.20, at least about 0.25, or at least about 0.30°C at 20°C.
[0105] Similar to the resin blend of two distinct resins of the first polyvinyl acetal) resin and the second polyvinyl acetal) resin, blending two or more distinct polymer layers or interlayers can often result in the new polymer layer(s) or interlayer(s) having unexpected properties and performance attributes. For example, a polymer layer or interlayer having lower residual hydroxyl content and lower glass transition temperature may be blended with another polymer layer or interlayer having higher residual hydroxyl content and higher glass transition temperature, resulting a new polymer layer or interlayer having soft domains of lower glass transition temperature, which enhances its acoustic performance, and stiff domains of higher glass transition temperature, which imparts enhanced processability, strength, and impact resistance to the polymer layer or interlayer. Other example includes blending a single sheet interlayer and multilayer interlayer, blending two multilayer interlayers, or blending one multilayer interlayer into a polymer layer of another multilayer interlayer. In essence, the effect arising from blending two materials can also be achieved from blending two or more resins, plasticizers, and other additives according to the contents of the materials. As used herein, a "blend resin material" or "blend material" refers to the resin composition, polymer layer or interlayer to be blended into another resin composition, polymer layer or interlayer. In blending two polymer layers or two interlayers, at least one of the two materials to be blended can include the polymer layer or interlayer of the present invention. In other embodiments, both materials can include the polymer layers or interlayers of the present invention.
[0106] According to some embodiments, at least a portion of the resin compositions, layers, or interlayers described herein may comprise another resins, layers, or interlayers. In some embodiments, at least about 0.5, at least about 1, at least about 5, at least about 10, at least about 15, at least about 20, at least about 25, at least about 30, or at least about 50 percent of the total amount of resin in a composition, layer, or interlayer can originate from a blend resin material.
[0107] Often, when the type and/or amount of resins and plasticizers in the blend resin material differ substantially from the type and/or amount of the resin or plasticizer being produced, and into which the blend resin material is being added, the optical performance, as determined by the clarity or haze, of the resulting resin composition, layer, or interlayer that includes the blend resin material may be adversely impacted. According to embodiments of the present invention, polymer layers and interlayers that include higher levels of blend resin material can be produced by utilizing one or more of the Rl balancing agents discussed above.
[0108] When the Rl balancing agent includes a high Rl plasticizer, higher amounts of blend resin materials can be added to a process for producing a resin composition, layer, or interlayer described herein without reducing the clarity or increasing the haze of the final composition, layer, or interlayer. In some embodiments, the composition that includes blend materials can include a first polyvinyl acetal) resin and a second polyvinyl acetal) resin, wherein one of the resins has a residual hydroxyl content that can be at least 2 weight percent lower than the residual hydroxyl content of the other resin. Such a composition may further include at least one high Rl plasticizer having a refractive index of 1.460, and, in some embodiments, more than 3 percent of the combined amount of the first and second polyvinyl acetal) resins present in the composition, layer, or interlayer may have originated from a blend composition, layer, or interlayer. Despite the difference in residual hydroxyl contents of the first and second polyvinyl acetal) resins, the composition that includes more than 0.5 weight percent of blend resin materials may have a haze value of not more than about 5, not more than about 4, not more than about 3, not more than about 2, or not more than about 1, or not more than about 0.5.
[0109] The high Rl plasticizer used as an Rl balancing agent with blend resin compositions can have a refractive index within one or more of the ranges described previously. The high Rl plasticizer may be added during production of the composition, layer, or interlayer along with the blend material and/or at least a portion of the high Rl plasticizer may be present in the blend resin material added to the process. Additionally, one or more other plasticizers may also be present in the resin material being blended and/or in the resin composition, layer, or interlayer being produced, including, for example, those having a refractive index less than about 1.450, less than about 1.445, or less than about 1.442, measured as described previously. In some embodiments, one or more additional high Rl plasticizers may also be present in the blend material and/or in the resin composition, layer, or interlayer into which the materials are being blended.
[0110] The resin composition that includes blended resin material as described above can be used to form layers and interlayers according to various embodiments of the present invention. For example, the resin composition including a blend resin material can be used to form a single monolithic interlayer, or it may be used to form one or more layers of a multilayer interlayer. When used in various layers and interlayers, additional plasticizer may be added such that the total amount of plasticizer present in the polymer layer or interlayer can be within the range described previously. Similarly, the glass transition temperature and refractive indices of polymer layers and interlayers formed from a composition that includes a blend resin material may also be within the ranges provided above. Additionally, polymer layers and interlayers formed from a composition that includes blended materials may also exhibit acoustic properties as described previously and may be included in any of the applications described below.
[0111] According to some embodiments, at least a portion of the resin compositions, layers, or interlayers described herein may comprise one or more recycled resin materials, including, for example, recycled layers or interlayers. As used herein, the term "recycled" means removed from and subsequently returned to a production line. Often, utilizing recycled materials may adversely affect the optical performance of the final composition, layer, or interlayer, as determined by clarity or haze, because of the different compositions and properties of the materials being blended or combined. However, in some embodiments, layers or interlayers as described herein may include at least one recycled resin material, while still exhibiting the same optical and/or acoustic properties as described herein. The type and/or amount of recycle resin material may fall within one or more of the ranges described previously and the layer or interlayer may further include at least one Rl balancing agent. Additionally, the polymer layers and interlayers including recycled resin material may also have optical and/or acoustic performance within one or more of the ranges described below.
[0112] The resin compositions, layers, and interlayers described above may be produced according to any suitable method. In various embodiments, the method for producing these compositions, layers, and interlayers can include providing two or more polyvinyl acetal) resins, blending at least one resin with an Rl balancing agent and, optionally, at least one plasticizer or other additive, to form a blended composition, and forming a layer from the blended composition.
[0113] In some embodiments, the resins provided in the initial steps of the method can be in the form of one or more polyvinyl acetal) resins, while, in other embodiments, one or more resin precursors can also be provided. In some embodiments, when two or more polyvinyl acetal) resins are physically blended, the blending of the two resins can comprise melt blending and may be performed at a temperature of at least about 140, at least about 150, at least about 180, at least about 200, at least about 250°C. In other embodiments, when the polyvinyl acetal) resin components provided include resin precursors, the blending step may include reacting two or more aldehydes with a polyvinyl alcohol to provide a single polyvinyl acetal) resin having two or more aldehyde moieties. Additionally, a portion of the blending step can include blending one or more of the resins with at least one plasticizer and/or with one or more of the Rl balancing agents described previously.
[0114] The resulting blended resins can then be formed into one or more polymer layers according to any suitable method. Exemplary methods of forming polymer layers and interlayers can include, but are not limited to, solution casting, compression molding, injection molding, melt extrusion, melt blowing, and combinations thereof. Multilayer interlayers including two or more polymer layers may also be produced according to any suitable method such as, for example, co- extrusion, blown film, melt blowing, dip coating, solution coating, blade, paddle, air- knife, printing, powder coating, spray coating, and combinations thereof. In various embodiments of the present invention, the layers or interlayers may be formed by extrusion or co-extrusion. In an extrusion process, one or more thermoplastic polymers, plasticizers, and, optionally, at least one additive, including one or more Rl balancing agents as described previously, can be pre-mixed and fed into an extrusion device. Other additives, such as ACAs, colorants, and UV inhibitors, which can be in liquid, powder, or pellet form, may also be used and may be mixed into the thermoplastic polymers or plasticizers prior to entering the extrusion device. These additives can be incorporated into the polymer resin and, by extension, the resultant polymer sheet, thereby enhancing certain properties of the polymer layer or interlayer and its performance in the final multiple layer glass panel or other end product.
[0115] In various embodiments, the thickness, or gauge, of the layers or interlayers can be at least about 10, at least about 15, at least about 20 mils and/or not more than about 100, not more than about 90, not more than about 60, not more than about 50, or not more than about 35 mils, or it can be in the range of from about 10 to about 100, about 15 to about 60, or about 20 to about 35 mils. In millimeters, the thickness of the polymer layers or interlayers can be at least about 0.25, at least about 0.38, at least about 0.51 mm and/or not more than about 2.54, not more than about 2.29, not more than about 1.52, or not more than about 0.89 mm, or in the range of from about 0.25 to about 2.54 mm, about 0.38 to about 1.52 mm, or about 0.51 to about 0.89 mm. In some embodiments, the polymer layers or interlayers can comprise flat polymer layers having substantially the same thickness along the length, or longest dimension, and/or width, or second longest dimension, of the sheet, while, in other embodiments, one or more layers of a multilayer interlayer, for example, can be tapered or can have a wedge-shaped profile, such that the thickness of the interlayer changes along the length and/or width of the sheet, such that one edge of the layer or interlayer has a thickness greater than the other. When the interlayer is a multilayer interlayer, at least one, at least two, or at least three of the layers of the interlayer can comprise at least one tapered zone. When the interlayer is a monolithic interlayer, the polymer sheet can be flat or may include at least one tapered zone. Tapered interlayers may be useful in, for example, heads-up-display (HUD) panels in automotive and aircraft applications.
[0116] Turning now to FIGS. 1 through 8, several embodiments of tapered interlayers according to the present invention are provided. FIG. 1 is a cross-sectional view of an exemplary tapered interlayer that includes a tapered zone of varying thickness. As shown in FIG. 1, the tapered zone has a minimum thickness, Tmin, measured at a first boundary of the tapered zone and a maximum thickness, Tmax, measured at a second boundary of the tapered zone. In certain embodiments, Tmin can be at least about 0.25, at least about 0.40, or at least about 0.60 millimeters (mm) and/or not more than 1.2, not more than about 1.1, or not more than about 1.0 mm. Further, Tmin can be in the range of 0.25 to 1.2 mm, 0.4 to 1.1 mm, or 0.60 to 1.0 mm. In certain embodiments, Tmax can be at least about 0.38, at least about 0.53, or at least about 0.76 mm and/or not more than 2.2, not more than about 2.1, or not more than about 2.0 mm. Further, Tmax can be in the range of 0.38 to 2.2 mm, 0.53 to 2.1 mm, or 0.76 to 2.0 mm. In certain embodiments, the difference between I max anu I min can be at least about 0.13, at least about 0.15, at least about 0.2, at least about 0.25, at least about 0.3, at least about 0.35, at least about 0.4 mm and/or not more than 1.2, not more than about 0.9, not more than about 0.85, not more than about 0.8, not more than about 0.75, not more than about 0.7, not more than about 0.65, or not more than about 0.6 mm. Further, the difference between I max anu I min can be in the range of 0.13 to 1.2 mm, 0.25 to 0.75 mm, or 0.4 to 0.6 mm. In certain embodiments, the distance between the first and second boundaries of the tapered zone (i.e. the "tapered zone width") can be at least about 5, at least about 10, at least about 15, at least about 20, or at least about 30 centimeters (cm) and/or not more than about 200, not more than about 150, not more than about 125, not more than about 100 or not more than about 75 cm. Further, the tapered zone width can be in the range of 5 to 200 cm, 15 to 125 cm, or 30 to 75 cm.
[0117] As shown in FIG. 1, the tapered interlayer includes opposite first and second outer terminal edges. In certain embodiments, the distance between the first and second outer terminal edges (i.e., the "interlayer width") can be at least about 20, at least about 40, or at least about 60 cm and/or not more than about 400, not more than about 200, or not more than about 100 cm. Further the interlayer width can be in the range of 20 to 400 cm, 40 to 200 cm, or 60 to 100 cm. In the embodiment depicted in FIG. 1, the first and second boundaries of the tapered zone are spaced inwardly from the first and second outer terminal edges of the interlayer. In such embodiments, only a portion of the interlayer is tapered. When the tapered zone forms only a portion of the interlayer, the ratio of the interlayer width to the tapered zone width can be at least about 0.05:1, at least about 0.1:1, at least about 0.2:1, at least about 0.3:1, at least about 0.4:1 at least about 0.5:1, at least about 0.6:1, or at least about 0.7:1 and/or not more than about 1:1, not more than about 0.95:1, not more than about 0.9:1, not more than about 0.8:1, or not more than about 0.7:1. Further, the ratio of interlayer width to the tapered zone width can be in the range of 0.05:1 to 1:1 or 0.3:1 to 0.9:1. In an alternative embodiment, discussed below, the entire interlayer is tapered. When the entire interlayer is tapered, the tapered zone width is equal to the interlayer width and the first and second boundaries of the tapered zone are located at the first and second terminal edges, respectively.
[0118] As illustrated in FIG. 1, the tapered zone of the interlayer has a wedge angle, which is defined as the angle formed between a first reference line extending through two points of the interlayer where the first and second tapered zone boundaries intersect a first (upper) surface of the interlayer and a second reference line extending through two points where the first and second tapered zone boundaries intersect a second (lower) surface of the interlayer. In certain embodiments, the wedge angle of the tapered zone can be at least about 0.13, at least about 0.15, at least about 0.2, at least about 0.25, at least about 0.3, at least about 0.35, at least about 0.4 milliradians (mrad) and/or not more than about 1.2, not more than about 1.0, not more than about 0.9, not more than about 0.85, not more than about 0.8, not more than about 0.75, not more than about 0.7, not more than about 0.65, not more than about 0.6, not more than about 0.55, not more than about 0.5, or not more than about 0.45 mrad. Further, the wedge angle of the tapered zone can be in the range of 0.13 to 1.2 mrad, 0.2 to 0.8 mrad, 0.25 to 0.75 mrad, 0.3 to 0.6, or 0.4 to 0.55 mrad.
[0119] When the first and second surfaces of the tapered zone are each planar, the wedge angle of the tapered zone is simply the angle between the first (upper) and second (lower) surfaces. However, as discussed in further detail below, in certain embodiments, the tapered zone can include at least one variable angle zone having a curved thickness profile and a continuously varying wedge angle. Further, in certain embodiments, the tapered zone can include two or more constant angle zones, where the constant angle zones each have a linear thickness profile, but at least two of the constant angle zones have different wedge angles.
[0120] FIGS. 2-7 illustrate various tapered interlayers configured according embodiments of the present invention. FIG. 2 depicts an interlayer 20 that includes a tapered zone 22 extending entirely from a first terminal edge 24a of the interlayer 20 to a second terminal edge 24b of the interlayer 20. In this configuration, the first and second boundaries of the tapered zone are located at the first and second terminal edges 24a, b of the interlayer. The entire tapered zone 22 of the interlayer 20 depicted in FIG. 2 has a constant wedge angle Θ that is simply the angle formed between the first (upper) planar and second (lower) planar surfaces of the interlayer 20.
[0121] FIG. 3 illustrates an interlayer 30 that includes a tapered zone 32 and a flat edge zone 33. The first boundary 35a of the tapered zone 32 is located at the first terminal edge 34a of the interlayer 30, while the second boundary 35b of the tapered zone 32 is located where the tapered zone 32 and the flat edge zone 33 meet. The tapered zone 32 includes a constant angle zone 36 and a variable angle zone 37. The constant angle zone 36 has a linear thickness profile and a constant wedge angle, 9C, while the variable angle zone 37 has a curved thickness profile and a continuously varying wedge angle. The starting wedge angle of the variable angle zone 37 is equal to the constant wedge angle 9C and the ending wedge angle of the variable angle zone 37 is zero. The interlayer 30 depicted in FIG. 3 has a constant wedge angle 9C that is greater than the overall wedge angle of the entire tapered zone 32.
[0122] FIG. 4 illustrates an interlayer 40 that includes a tapered zone 42 located between first and second flat edge zones 43a, b. The first boundary 45a of the tapered zone 42 is located where the tapered zone 42 and the first flat edge zone 43a meet, while the second boundary 45b of the tapered zone 42 is located where the tapered zone 42 and the second flat edge zone 43b meet. The tapered zone 42 includes a constant angle zone 46 located between first and second variable angle zones 47a, b. The first variable angle zone 47a forms a transition zone between the first flat edge zone 43a and the constant angle zone 46. The second variable angle zone 47b forms a transition zone between the second flat edge zone 43b and the constant angle zone 46. The constant angle zone 46 has a linear thickness profile and a constant wedge angle, 9C, while the first and second variable angle zones 47a, b have curved thickness profiles and continuously varying wedge angles. The starting wedge angle of the first variable angle zone 47a is equal to zero and the ending wedge angle of the first variable angle zone 47b is equal to the constant wedge angle 9C. The starting wedge angle of the second variable angle zone 47b is equal to the constant wedge angle 9C and the ending wedge angle of the second variable angle zone 47b is zero. The interlayer 40 depicted in FIG 4 has a constant wedge angle 9C that is greater than the overall wedge angle of the entire tapered zone 42.
[0123] FIG. 5 illustrates an interlayer 50 that includes a tapered zone 52 located between first and second flat edge zones 53a, b. The tapered zone 52 of the interlayer 50 does not include a constant angle zone. Rather, the entire tapered zone 52 of the interlayer 50 is a variable angle zone having a curved thickness profile and a continuously varying wedge angle. As described above, the overall wedge angle, Θ, of the tapered zone 52 is measured as the angle between a first reference line "A" extending through the two points where the first and second boundaries 55a, b of the tapered zone 52 meet the first (upper) surface of the interlayer 50 and a second reference line "B" extending through the two points where the first and second boundaries 55a, b of the tapered zone 52 meet the second (lower) surface of the interlayer 50. However, within the tapered zone 52, the curved thickness profile provides an infinite number of wedge angles, which can be greater than, less than, or equal to the overall wedge angle Θ of the entire tapered zone 52.
[0124] FIG. 6 illustrates an interlayer 60 that does not include any flat end portions. Rather, the tapered zone 62 of the interlayer 60 forms the entire interlayer 60. Thus, the first and second boundaries 65a, b of the tapered zone 60 are located at the first and second terminal edges 64a, b of the interlayer 60. The tapered zone 62 of the interlayer 60 includes first, second, and third constant angle zones 46a, b,c separated by first and second variable angle zones 47a, b. The first, second, and third constant angle zones 46a,b,c each have a linear thickness profile and each have unique first, second, and third constant wedge angles, θ0ι,θ02,θ03, respectively The first variable angle zone 47a acts as a transition zone between the first and second constant angle zones 46a, b. The second variable angle zone 47b acts as a transition zone between the second and third constant angle zones 46b,c. As discussed above, the overall wedge angle, Θ, of the tapered zone 62 is measured as the angle between a first reference line "A" and a second reference line "B." The first constant wedge angle 9ci is less than the overall wedge angle Θ of the tapered zone 62. The second constant wedge angle 9c2 is greater the overall wedge angle Θ of the tapered zone 62. The third constant wedge angle 9c3 is less than the overall wedge angle Θ of the tapered zone 62. The wedge angle of the first variable angle zone 47a continuously increases from the first constant wedge angle 9ci to the second constant wedge angle, 9c2. The wedge angle of the second variable angle zone 47b continuously decreases from the second constant wedge angle 9c2 to the third wedge angle 9c3.
[0125] FIG. 7 illustrates an interlayer 70 that includes a tapered zone 72 located between first and second flat edge zones 73a,b. The first and second boundaries 75a, b of the tapered zone 72 are spaced inwardly from the first and second outer edges 74a, b of the interlayer 70. The tapered zone 72 of the interlayer 70 includes first, second, third, and fourth variable angle zones 77a,b,c,d and first, second, and third constant angle zones 76a, b,c. The first variable angle zone 77a acts as a transition zone between the first flat edge zone 73a and the first constant angle zone 76a. The second variable angle zone 77b acts as a transition zone between the first constant angle zone 76a and the second constant angle zone 76b. The third variable angle zone 77c acts as a transition zone between the second constant angle zone 76b and the third constant angle zone 76c. The fourth variable angle zone 77d acts as a transition zone between the third constant angle zone 76c and the second flat edge zone 73b. The first, second, and third constant angle zones 76a, b,c each have a linear thickness profile and each have unique first, second, and third constant wedge angles, θ0ι,θο2ο3, respectively As discussed above, the first, second, third, and fourth variable angle zones 77a,b,c,d have wedge angles that continuously transition from the wedge angle of the constant angle zone on one side of the variable angle zone 77 to the wedge angle of the constant angle zone on the other side of the variable angle zone 77. [0126] As discussed above, the tapered interlayer can include one or more constant angle tapered zones, each having a width that is less than the overall width of the entire tapered zone and each having a wedge angle that is the same as or different than the overall wedge angle of the entire tapered zone. For example, the tapered zone can include one, two, three, four, five, or more constant angle tapered zones. When multiple constant angle tapered zones are employed, the constant angle tapered zones can be separated from one another by variable angle tapered zones that serve to transition between adjacent constant angle tapered zones.
[0127] In certain embodiments, the width of each constant angle tapered zone can be at least about 2, at least about 5, at least about 10, at least about 15, or at least about 20 cm and/or not more than about 150, not more than about 100, or not more than about 50 cm. In certain embodiments, the ratio of the width of each constant angle tapered zone to the overall width of the entire tapered zone can be at least about 0.1:1, at least about 0.2:1, at least about 0.3:1 or at least about 0.4:1 and/or not more than about 0.9:1, not more than about 0.8:1, not more than about 0.7:1, not more than about 0.6:1, or not more than about 0.5:1.
[0128] In certain embodiments, the wedge angle of each constant angle tapered zone can be at least about 0.13, at least about 0.15, at least about 0.2, at least about 0.25, at least about 0.3, at least about 0.35, at least about 0.4 mrad and/or not more than about 1.2, not more than about 1.0, not more than about 0.9, not more than about 0.85, not more than about 0.8, not more than about 0.75, not more than about 0.7, not more than about 0.65, or not more than about 0.6 mrad. Further, the wedge angle of each constant angle tapered zone can be in the range of 0.13 to 1.2 mrad, 0.25 to 0.75 mrad, or 0.4 to 0.6 mrad. In certain embodiments, the wedge angle of at least one constant angle tapered zone is at least about 0.01, at least about 0.05, at least about 0.1, at least about 0.2, at least about 0.3, or at least about 0.4 mrad greater than the overall wedge angle of the entire tapered zone. In certain embodiments, the wedge angle of at least one constant angle tapered zone is at least about 0.01, at least about 0.05, at least about 0.1, at least about 0.2, at least about 0.3, or at least about 0.4 mrad less than the overall wedge angle of the entire tapered zone. In certain embodiments, the wedge angle of at least one constant angle tapered zone is not more than about 0.4, not more than about 0.3, not more than about 0.2, not more than about 0.1, not more than about 0.05, or not more than about 0.01 mrad greater than the overall wedge angle of the entire tapered zone. In certain embodiments, the wedge angle of at least one constant angle tapered zone is not more than about 0.4, not more than about 0.3, not more than about 0.2, not more than about 0.1, not more than about 0.05, or not more than about 0.01 mrad less than the overall wedge angle of the entire tapered zone.
[0129] FIGS. 8a and 8b illustrate an interlayer 80 that is similar in thickness profile to the interlayer 30 of FIG. 3. The interlayer 80 of FIGS. 8a and 8b is configured for use in a vehicle windshield by fixing the interlayer between two sheets of glass. As depicted in FIG. 8a, the first terminal edge 84a of the interlayer 80 can be located at the bottom of the windshield, while the second terminal edge 84b of the interlayer 80 can be located at the top of the windshield. The tapered zone 82 of the interlayer 80 is positioned in an area of the windshield where a heads-up display is to be located. The tapered zone 82 of interlayer 80 includes a constant angle zone 86 and a variable angle zone 87. As depicted in FIG. 8a, in certain embodiments, the tapered zone 82 extends entirely across the interlayer 80 between a first side edge 88a and a second side edge 88b of the interlayer 80. FIG. 8b, which is similar to FIG. 3, shows the thickness profile of the interlayer 80 between the bottom of the windshield and the top of the windshield.
[0130] Although not illustrated in the drawings, it should be understood that in certain embodiments, the tapered interlayer can be a multilayered interlayer. When the tapered interlayer comprises multiple individual layers, all of the individual layers can be tapered, some of the individual layers can be tapered, or only one of the individual layers can be tapered. Further, in certain embodiments the glass transition temperatures of the individual layers can be different than another. For example, in one embodiment, the interlayer includes a tapered middle layer having a lower glass transition temperature than two tapered outer layers of the interlayer, where the glass transition temperature of one or both of the outer layers exceeds the glass transition temperature of the middle layer by at least about 10, at least about 20, at least about 30, at least about 40, or at least about 50°C.
[0131] In some embodiments, the polymer layers or interlayers can comprise flat polymer layers having substantially the same thickness along the length, or longest dimension, and/or width, or second longest dimension, of the sheet, while, in other embodiments, one or more layers of a multilayer interlayer, for example, can be wedge-shaped or can have a wedge-shaped profile, such that the thickness of the interlayer changes along the length and/or width of the sheet, such that one edge of the layer or interlayer has a thickness greater than the other. When the interlayer is a multilayer interlayer, at least one, at least two, or at least three of the layers of the interlayer can be wedge-shaped. When the interlayer is a monolithic interlayer, the polymer sheet can be flat or wedge shaped. Wedge-shaped interlayers may be useful in, for example, heads-up-display (HUD) panels in automotive and aircraft applications.
[0132] The resin compositions, layers, and interlayers according to embodiments of the present invention may be utilized in a multiple layer panel that comprises a polymer layer or interlayer and at least one rigid substrate. In some embodiments, the multilayer panels include a pair of rigid substrates with the resin interlayer disposed therebetween. The total thickness of the panel, measured as the combined thickness of the substrates and the interlayer, can be at least about 2, at least about 3, at least about 3.5, at least about 4, at least about 4.5, at least about 4.65, at least about 4.75, or at least about 5 mm and/or not more than about 6.5, not more than about 6.25, not more than about 6.0, not more than about 5.75, not more than about 5.5, or not more than about 5 mm. The thickness of one or both substrates may be substantially less than would be expected for a conventional multiple layer panel. For example, in some embodiments, the combined thickness of each of the rigid substrates can be not more than about 4.0, not more than about 3.9, not more than about 3.8, not more than about 3.7, not more than about 3.6, not more than about 3.5, not more than about 3.4 mm.
[0133] Any suitable rigid substrate may be used to form a multiple layer panel, and in some embodiments, the substrates may comprise a material selected from the group consisting of glass, polycarbonate, biaxially oriented PET, copolyesters, acrylic, and combinations thereof. When the rigid substrate includes a polymeric material, the polymeric material may or may not include a hard coat surface layer. In certain embodiments, the rigid substrates may have a refractive index less than the refractive index of the interlayer used to form the multiple layer panel. For example, the refractive index of at least one of the rigid substrates can be not more than about 1.550, not more than about 1.545, not more than about 1.540, not more than about 1.535, not more than about 1.530, or not more than about 1.525, measured as described above. In some embodiments, the refractive index of at least one of the rigid substrates can be at least about 5, at least about 10, at least about 15, at least about 20 percent lower than the refractive index of the interlayer used to form the multiple layer panel. In certain embodiments, the refractive index of one or both substrates can be at least about 0.25 units, at least about 0.50 units, at least about 0.75 units, at least about 1.0 units, at least about 1.1 units, or at least about 1.5 units lower than the refractive index of the interlayer. Alternatively, it can be said that the refractive index of the interlayer is higher than the refractive index of at least one of the substrates by the amounts or percentages described herein.
[0134] Multiple layer panels, configured according to certain embodiments of the present invention, may have an equivalent refractive index that is higher than the refractive index of one or more of the rigid substrates. As used herein, the term "equivalent refractive index" refers to the overall refractive index of a composite material, such as, for example, a multiple layer panel. The equivalent refractive index (neq) of a particular multiple layer panel is calculated according the following equations (l) and (2): tan 6eq = ^
(1)
nA sin θχ = neq sin 9eq
U), wherein i and tj are defined as follows:
(3)
*r =∑T=1 xi =∑T=1 ti Xan 0i (4)
[0135] I n the above equations, Qeq is the equivalent incident angle of the composite, τ is the distance light travels through the entire composite, tj is the total thickness of the composite having m layers, /IA is the refractive index of air, θι is the incident angle of light passing through the air-layer 1 interface, neq is the equivalent refractive index of the composite, t, is the thickness of layer , and Θ, is the incident angle of light passing through layer . The equivalent refractive index of a multiple layer panel as described herein can be at least about 1.490, at least about 1.495, at least about 1.500, at least about 1.505, at least about 1.510, at least about 1.515, at least about 1.520, at least about 1.525, at least about 1.530, at least about 1.535, at least about 1.540, or at least about 1.545.
[0136] I n some embodiments, the multiple layer panel can have an equivalent refractive index that is at least about 0.25, at least about 0.5, at least about 0.75, at least about 1, or at least about 1.5 percent higher than the refractive index of at least one of the substrates used to form the multiple layer interlayer. For example, the panel can have an equivalent refractive index that is at least 0.010, at least about 0.015, at least about 0.020, or at least about 0.025 higher than the refractive index of one or more rigid substrates used to form the panel. In certain embodiments, the equivalent refractive index of a multiple layer panel may be less than the refractive index of the interlayer used to form the panel and can be, for example, at least about 0.5, at least about 1, at least about 1.5, at least about 2, at least about 2.5, at least about 3, at least about 5, or at least about 7 percent lower than the refractive index of the interlayer used to form the multiple layer panel. The difference between the refractive index of the interlayer and the equivalent refractive index of the panel can be at least about 0.010, at least about 0.025, at least about 0.050, at least about 0.10, at least about 0.125, at least about 0.50, or at least about 0.75.
[0137] Multiple layer panels as described herein can be used for a variety of end use applications, including, for example, for automotive windshields and windows, aircraft windshields and windows, panels for various transportation applications such as marine applications, rail applications, etc., structural architectural panels such as windows, doors, stairs, walkways, balusters, decorative architectural panels, weather-resistant panels, such as hurricane glass or tornado glass, ballistic panels, and other similar applications.
[0138] In certain embodiments, multiple layer panels as described herein may exhibit a reduction in interfering double or reflected "ghost" images when, for example, used for projecting a heads-up display (HUD) image onto the windshield of an automobile or aircraft. Typically, ghost images are most problematic when the windshield has a generally uniform thickness profile, due to the differences in position of the projected image when it is reflected off the inside and outside surfaces of the glass. In some embodiments, however, multiple layer panels as described herein can minimize projection of ghost images such that, for example, the panel has a double image separation distance significantly lower than would be exhibited by a conventional panel. [0139] The method of determining double image separation includes providing a multiple layer panel that includes at least a pair of rigid substrates and an interlayer disposed therebetween. The interlayer can include any properties of, or may be, any of the interlayers described herein. In some embodiments, the interlayer may be a tapered interlayer comprising, for example, at least one tapered zone having a wedge angle of at least 0.05 mrad. The substrates may also include one or more properties of the substrates described herein and, in certain embodiments, may comprise glass.
[0140] To measure the double image separation of a given panel, a projection image can be generated by passing light through at least a portion of the panel. In some embodiments, the light passing through the panel includes an image such as, for example, a grid, a line, a shape, or a picture. In some embodiments, the image may be generated by reflecting a thin film transistor display off of a substantially flat mirrored surface, although other suitable methods of generating images may be used. If the multiple layer panel is formed using a tapered interlayer, at least a portion of the light passing though the panel may be passed through at least a portion of the tapered zone. Alternatively, or in addition, the light may pass through one or more other zones of interest along the panel in order to determine the double image separation formed as light projects through those zones.
[0141] Once light has passed through and is reflected off the surfaces of the panel, the projection image can be projected onto a surface and then captured to form a captured image. In some embodiments, the projected image displayed on the surface may include a primary image and a secondary "ghost" image, off-set and slightly overlapping the primary image, as shown in FIG. 10. The projected image may be captured using a digital camera or other suitable device, and the capture may include digitizing the projected image to form a digital projection image comprising a plurality of pixels.
[0142] Once digitized, the captured image can be quantitatively analyzed to form a profile that includes at least one primary image indicator and at least one secondary image indicator. The analyzing may be performed by converting at least a portion of the digital projection image to a vertical image matrix that includes a numerical value representing the intensity of pixels in that portion of the image. A column of the matrix can then be extracted and graphed against pixel number, as shown in FIG. 11, to provide the profile. The primary image indicator of the profile can then be compared with the secondary image indicator of the profile to determine a difference. In some embodiments, the primary image indicator may comprise the higher intensity peaks of the graph, while the secondary image indicator may be the lower intensity peaks. Any suitable difference between the two indicators can be determined and, in some embodiments, can be the difference in position between the two indicators in the profile graph. Based on the difference, the double image separation distance for the portion of the panel being tested can be calculated. A specific use of the above method for determining double image separation distance is described in Example 11.
[0143] Multiple layer panels configured according to embodiments of the present invention may have a significantly lower double image separation distance than conventionally-formed panels. For example, in some embodiments, the double image separation distance of panels as described herein may be at least about 10, at least about 20, at least about 30, at least about 40 percent less than the double image separation distance of panels formed from conventional interlayers such as, for example, those having a refractive index less than 1.480, all other things being equal. The double image separation distance for a given panel may depend, in part, on its specific configuration, including the type and dimensions of its interlayer and substrates. Specific examples of double image separation distances for several inventive and comparative panels are provided in the Examples.
[0144] When laminating the polymer layers or interlayers between two rigid substrates, such as glass, the process can include at least the following steps: (1) assembly of the two substrates and the interlayer; (2) heating the assembly via an IR radiant or convective device for a first, short period of time; (3) passing the assembly into a pressure nip roll for the first de-airing; (4) heating the assembly for a short period of time to about 60°C to about 120°C to give the assembly enough temporary adhesion to seal the edge of the interlayer; (5) passing the assembly into a second pressure nip roll to further seal the edge of the interlayer and allow further handling; and (6) autoclaving the assembly at temperature between 135°C and 150°C and pressures between 150 psig and 200 psig for about 30 to 90 minutes. Other methods for de-airing the interlayer-glass interface, as described according to some embodiments in steps (2) through (5) above include vacuum bag and vacuum ring processes, and both may also be used to form interlayers of the present invention as described herein.
[0145] In some embodiments, the multiple layer panel may include at least one polymer film disposed on the layer or interlayer, forming a multiple layer panel referred to as a "bilayer." In some embodiments, the interlayer utilized in a bilayer may include a multilayer interlayer, while, in other embodiments, a monolithic interlayer may be used. The use of a polymer film in multiple layer panels as described herein may enhance the optical character of the final panel, while also providing other performance improvements, such as infrared absorption. Polymer films differ from polymer layers or interlayers in that the films alone do not provide the necessary penetration resistance and glass retention properties. The polymer film can also be thinner than the sheet, and may have a thickness in the range of from 0.001 to 0.25 mm. Poly(ethylene terephthalate) ("PET") is one example of a material used to form the polymer film.
[0146] The following examples are intended to be illustrative of the present invention in order to teach one of ordinary skill in the art to make and use the invention and are not intended to limit the scope of the invention in any way.
EXAMPLES
[0147] The following Examples describe the preparation of several resin compositions, layers, and interlayers that include various polyvinyl acetal) reins. As described below, several tests performed on many of the compositions, layers, and interlayers were used to evaluate the acoustic and optical properties of several comparative and inventive materials.
Example 1: Preparation of High Refractive Index Polyvinyl acetal) Resins
[0148] Several comparative polyvinyl acetal) resins, referred to as Comparative Resins CR-1 through CR-12 in Table 2 below, were prepared by acetalizing polyvinyl alcohol with one or more aldehydes including n-butyraldehyde (nBuCHO; Rl = 1.377), iso-butyraldehyde (iBuCHO; Rl = 1.374), and 2-ethylhexyl aldehyde (2EHCHO; Rl = 1.414). The composition of the resulting resins were measured using either the ASTM D1396 or FT-IR/SEC method described in detail previously. The refractive index and glass transition temperature (Tg) of several of the resins was also measured according to the methods described previously, and the results are provided in Table 2, below.
Table 2: Properties of Several Comparative Polyvinyl acetal) Resins
Residual Residual Residual Resin
Residual Residual
Polyvinyl Polyvinyl Polyvinyl Refractive
Resin Hydroxyl Acetate
nBuCHO iBuCHO 2EHCHO Index (wt%) (wt%)
(wt%) (wt%) (wt%) (nD25)
C -1 21 1 78 - - 1.491
CR-2 19 1 80 - - 1.490
CR-3 19 1 46 - 34 1.489
CR-4 16 1 83 - - 1.488
CR-5 15 1 39 - 45 1.487
CR-6 13 1 86 - - 1.486
CR-7 12 18 70 - - 1.481
CR-8 12 12 76 - - nd
CR-9 12 10 78 - - 1.483
CR-10 11 1 88 - - 1.485
CR-11 12 1 - 88 - nd
CR-12 13 1 - 86 - nd nd = not determined
[0149] Additionally, several polyvinyl acetal) resins according to embodiments of the present invention were also prepared in a similar manner. These inventive resins, referred to as Disclosed Resins DR-1 through DR-21 in Table 3, were formed by acetalizing polyvinyl alcohol with mixtures of n-butyraldehyde and various high refractive index aldehydes, including benzaldehyde (BzCHO Rl = 1.545), cinnamaldehyde (CCHO; Rl = 1.620), 4-chlorobenzaldehyde (4-CIBzCHO; Rl = 1.5850), 2-phenylpropionaldehyde (2PHPrCHO; Rl =1.517), and hydrocinnamaldehyde (HCCHO; Rl = 1.523). The refractive index of several of the Disclosed Resins was also determined and the results are summarized in Table 3, below. Table 3: Properties of Disclosed Resins
Resin
Residual Residual Aldehyde HCCHO/ CCHO/ 2PhPrCHO/ BzCHO/Bu 4CIBzCHO/
HCCHO/ Refractive
Resin Hydroxyl Acetate Component BuCHO BuCHO BuCHO CHO BuCHO
■BuCHO Index (wt%) (wt%) (wt%) (mol/mol) (mol/mol) (mol/mol) (mol/mol) (mol/mol)
(nD25)
DR-1 11 1 88 5/95 - - 1.496
DR-2 11 1 88 10/90 - - 1.500
DR-3 11 1 88 15/85 - - 1.504
DR-4 11 1 88 20/80 - - 1.510
DR-5 11 1 88 25/75 - - 1.511
DR-6 11 1 88 50/50 - - 1.528
DR-7 11 1 88 100/0 - - 1.552
DR-8 19 1 80 10/90 - - nd
DR-9 19 1 80 25/75 - - nd
DR-10 19 1 80 50/50 - - nd
DR-11 19 1 80 100/0 - - nd
DR-12 12 18 70 25/75 - - nd
DR-13 12 10 78 25/75 - - nd
DR-14 17 1 82 25/75 - - 1.507
DR-15 15 1 84 25/75 - - 1.505
DR-16 14 1 85 25/75 - - 1.503
DR-17 18 1 81 25/75 - - 1.507
DR-18 14 1 85 25/75 - - 1.501
DR-19 20 1 79 - 25/75 - 1.507
DR-20 14 1 85 - 25/75 - 1.509
DR-21 11 1 88 - - 25/75 nd nd = not determined
[0150] As shown in Tables 2 and 3, above, polyvinyl acetal resins comprising residues of at least one high refractive index aldehyde, including those listed above, tend to exhibit higher refractive indices than those comprising residues of aldehydes such as n-butyraldehyde, iso-butyraldehyde, and 2-ethylhexyl aldehyde.
Example 2: Preparation of High Refractive Index Resin Interlayers
[0151] Several Comparative and Disclosed Interlayers were formed by mixing and melt blending several of the Comparative Resins listed in Table 2 and several of the Disclosed Resins listed in Table 3 above, with varying amounts of the plasticizer triethylene glycol bis(2-ethylhexanoate) (3GEH). The composition, refractive index, and glass transition temperature of each of the resulting interlayers, referred to as Comparative Interlayers CL-1 through CL-14 and Disclosed Interlayers DL-1 through DL-26, were measured as described previously, and the results are respectively summarized in Tables 4 and 5, below.
Table 4: Properties of Several Comparative Interlayers
Refractive
Plasticizer Tg
Interlayer Resin Index
(phr) (°C)
(nD25)
CL-1 CR-1 34 1.478 36
CL-2 CR-2 38 1.477 30
CL-3 CR-3 38 1.475 28
CL-4 CR-4 50 1.472 17
CL-5 CR-4 30 1.477 30
CL-6 CR-5 75 1.468 6
CL-7 CR-6 75 1.467 2
CL-8 CR-7 75 1.464 -4
CL-9 CR-8 75 1.466 -3
CL-10 CR-9 75 1.465 -3
CL-11 CR-10 75 1.466 -2
CL-12 CR-10 50 1.47 12
CL-13 CR-11 75 nd nd
CL-14 CR-12 75 nd nd nd = not determined Table 5: Properties of Several Disclosed Interlayers
Sheet
Plasticizer
Refractive Tg
Interlayer Resin content
Index (°C)
(phr)
(nD25)
DL-1 DR-1 75 1.473 1
DL-2 DR-1 50 1.479 12
DL-3 DR-2 75 1.475 0
DL-4 DR-3 75 1.477 0
DL-5 DR-4 75 1.480 1
DL-6 DR-5 75 1.482 1
DL-7 DR-6 75 1.490 2
DL-8 DR-7 75 1.506 3
DL-9 DR-14 75 1.480 12
DL-10 DR-15 75 1.478 11
DL-11 DR-16 75 1.477 7
DL-12 DR-17 75 1.480 22
DL-13 DR-18 75 1.476 12
DL-14 DR-19 75 1.480 17
DL-15 DR-20 75 1.479 12
DL-16 DR-12 75 nd nd
DL-17 DR-13 75 nd nd
DL-18 DR-21 75 nd nd
DL-19 DR-8 38 1.477 30
DL-20 DR-9 38 1.487 nd
DL-21 DR-10 38 1.501 nd
DL-22 DR-11 38 1.525 nd
DL-23 DR-5 38 nd nd
DL-24 DR-5 50 1.488 nd
DL-25 DR-5 60 1.484 2
DL-26 DR-7 38 nd nd
nd = not determined
[0152] As shown in Tables 4 and 5, above, Disclosed Interlayers utilizing higher refractive index Disclosed Resins from Table 3 exhibit higher refractive indices than
Comparative Interlayers formulated with lower refractive index resins, such as the Comparative Resins listed in Table 2. Additionally, as shown by comparison of Disclosed Interlayers DL-1 and DL-2 and DL-6 and DL-23 through DL-25, the amount of plasticizer used to form an interlayer affects both the glass transition temperature and refractive index of the layer, although not necessarily to the same extent for all resins. For example, as shown by the comparison of DL-1 (75 phr 3GEH; DR-1) and DL-2 (50 phr 3GEH; DR-1), reducing the amount of plasticizer by about 33 percent increases the glass transition temperature of the interlayer by 11°C (from 1°C to 12°C), but only increases the refractive index by 0.006 (from 1.473 to 1.479). However, as shown by the comparison of DL-25 (60 phr 3GEH; DR-5) and DL-6 (75 phr of 3GEH; DR-5), reducing the plasticizer content in layers formed by this resin increases the glass transition temperature by only 1°C (from 1°C to 2°C), while increasing the refractive index by 0.004 (from 1.484 to 1.488).
Example 3: Preparation of Interlayers using High Refractive Index Resins
[0153] Several of the Comparative and Disclosed Interlayers formed in Example 2 and respectively summarized in Tables 4 and 5, above, were used to create several Comparative and Disclosed Multilayer Interlayers. Each multilayer interlayer included a pair of outer "skin" layers, having a total thickness of 28 mils, sandwiching an inner "core" layer having a thickness of 5 mils, usually formed of a resin having a lower residual hydroxyl content. The composition and several properties of the interlayers including refractive index, glass transition temperature, mottle, and loss factor, were measured as described above, and the results for the Comparative Multilayer Interlayers (Cl-l to CI-16) and Disclosed Multilayer Interlayers (Dl-l to Dl- 29) are summarized in Tables 6 and 7, below. Table 6: Properties of Several Comparative Multilayer Interlayers
Δ
Refractive
Polymer layer Tg {°C) Refractive Index Refractive Loss
Index of
Interlayer Index Mottle Factor
Interlayer
(Skin- at 20°C
Skin 1 Core Skin 2 Skin 1 Core Skin 2 Skin 1 Core Skin 2 (nD25)
Core)
Cl-l CL-2 CL-7 CL-2 30 2 30 1.477 1.467 1.477 0.010 1.475 4 0.29
CI-2 CL-2 CL-11 CL-2 30 -2 30 1.477 1.466 1.477 0.011 1.475 5 0.33
CI-3 CL-2 CL-8 CL-2 30 -4 30 1.477 1.464 1.477 0.013 1.475 5 nd
CI-4 CL-1 CL-9 CL-1 36 -3 36 1.478 1.466 1.478 0.012 1.477 5 nd
CI-5 CL-1 CL-8 CL-1 36 -4 36 1.478 1.464 1.478 0.014 nd 5 0.36
CI-6 CL-2 CL-9 CL-2 30 -3 30 1.477 1.466 1.477 0.011 nd 5 nd
CI-7 CL-1 CL-11 CL-1 36 -2 36 1.478 1.466 1.478 0.012 1.477 5 0.35
CI-8 CL-2 CL-10 CL-2 30 -3 30 1.477 1.465 1.477 0.012 nd 5 0.31
CI-9 CL-1 CL-7 CL-1 36 2 36 1.478 1.467 1.478 0.011 nd 5 nd
CI-10 CL-1 CL-10 CL-1 36 -3 36 1.478 1.465 1.478 0.013 nd 5 nd
Cl-ll CL-2 CL-13 CL-2 30 nd 30 nd nd nd nd nd > 5 nd
CI-12 CL-2 CL-14 CL-2 30 nd 30 nd nd nd nd nd > 5 nd
CI-13 CL-1 CL-13 CL-1 36 nd 36 nd nd nd nd nd > 5 nd
CI-14 CL-1 CL-14 CL-1 36 nd 36 nd nd nd nd nd > 5 nd
CI-15 CL-2 DL-7 CL-2 30 2 30 1.477 1.490 1.477 -0.013 1.479 > 5 nd
CI-16 CL-2 DL-8 CL-2 30 3 30 1.477 1.506 1.477 -0.029 1.481 > 5 nd nd = not determined
Table 7: Properties of Some Disclosed Multilayer Interlayers
Refractive Index Δ
Polymer layer Tg (°C) Refractive
(nD25) Refractive
Interlayer Index of Mottle
Index
Interlayer
(Skin-Core)
Skin 1 Core Skin 2 Skin 1 Core Skin 2 Skin 1 Core Skin 2
Dl-l CL-2 DL-1 CL-2 30 1 30 1.477 1.473 1.477 0.004 1.476 1
DI-2 CL-2 DL-4 CL-2 30 0 30 1.477 1.477 1.477 0.000 1.477 1
DI-3 CL-5 DL-6 CL-5 30 1 30 1.477 1.482 1.477 -0.005 1.478 nd
DI-4 CL-2 DL-6 CL-2 30 1 30 1.477 1.482 1.477 -0.005 nd < 1
DI-5 CL-1 DL-6 CL-1 36 1 36 1.478 1.482 1.478 -0.004 nd < 1
DI-6 CL-2 DL-3 CL-2 30 0 30 1.477 1.475 1.477 0.002 nd < 1
DI-7 CL-2 DL-5 CL-2 30 1 30 1.477 1.480 1.477 -0.003 nd < 1
DI-8 CL-2 DL-6 CL-1 30 1 36 1.477 1.482 1.478 -0.005 nd < 1
DI-9 CL-2 DL-6 CL-5 30 1 30 1.477 1.482 1.477 -0.005 nd < 1
DI-10 CL-2 DL-16 CL-2 30 nd 30 1.477 nd 1.477 nd nd < 1
Dl-ll CL-2 DL-17 CL-2 30 nd 30 1.477 nd 1.477 nd nd < 1
DI-12 CL-1 DL-16 CL-1 36 nd 36 1.478 nd 1.478 nd nd < 1
DI-13 CL-1 DL-17 CL-1 36 nd 36 1.478 nd 1.478 nd nd < 1
DI-14 CL-2 DL-18 CL-2 30 nd 30 1.477 nd 1.477 nd nd < 1
DI-15 CL-1 DL-18 CL-1 36 nd 36 1.478 nd 1.478 nd nd < 1 nd = not determined
Table 7 (Continued): Properties of Some Disclosed Multilayer Interlayers
Refractive Index
Polymer layer Tg (°C) Δ Refractive Refractive
(nD25)
nterlayer Index Index of Mottle
(Skin-Core) Interlayer
Skin 1 Core Skin 2 Skin 1 Core Skin 2 Skin 1 Core Skin 2
DI-16 DL-19 DL-24 DL-19 30 1 30 1.477 1.488 1.477 -0.005 1.478 < 1
DI-17 CL-2 DL-9 CL-2 30 12 30 1.477 1.480 1.477 -0.003 nd < 1
DI-18 CL-2 DL-10 CL-2 30 11 30 1.477 1.478 1.477 -0.001 nd < 1
DI-19 CL-2 DL-11 CL-2 30 7 30 1.477 1.477 1.477 0.000 nd < 1
DI-20 CL-2 DL-12 CL-2 30 22 30 1.477 1.480 1.477 -0.003 nd < 1
DI-21 CL-2 DL-13 CL-2 30 12 30 1.477 1.476 1.477 0.001 nd < 1
DI-22 CL-2 DL-14 CL-2 30 17 30 1.477 1.480 1.477 -0.003 nd < 1
DI-23 CL-2 DL-15 CL-2 30 12 30 1.477 1.479 1.477 -0.002 nd < 1
DI-24 DL-20 DL-7 DL-20 nd 2 nd 1.487 1.490 1.487 -0.003 nd < 1
DI-25 DL-21 DL-7 DL-21 nd 2 nd 1.501 1.490 1.501 -0.011 nd > 5
DI-26 DL-22 DL-7 DL-22 nd 2 nd 1.525 1.490 1.525 -0.035 nd > 5
DI-27 DL-20 DL-8 DL-20 nd 3 nd 1.487 1.506 1.487 -0.009 nd 3
DI-28 DL-21 DL-8 DL-21 nd 3 nd 1.501 1.506 1.501 -0.005 nd < 1
DI-29 DL-22 DL-8 DL-22 nd 3 nd 1.525 1.506 1.525 -0.019 nd > 5
[0154] As shown in Table 6, above, interlayers formed from skin and core layers having refractive index differences of 0.010 or more exhibited optical defects, as indicated by the mottle values greater than 5. As shown in Table 7, however, interlayers formed from skin and core layers having refractive index differences of less than 0.010 exhibited low mottle values of 1 or less. Additionally, as shown in Table 7, such low mottle values were achievable by interlayers having a core layer with a higher or lower refractive index than the skin layer, as long as the absolute value of the difference between the refractive indices of adjacent layers was less than 0.010. Also as shown in Table 7, interlayers formed from skin a nd core layers both having high Rl aldehyde residues and having refractive index differences of greater than 0.010 exhibited high mottle values of 5 or greater.
Example 4: Stability of Multilayer Interlayers
[0155] Two Comparative Multilayer Interlayers, CI-2 and CI-7, and two Disclosed Multilayer I nterlayers, DI-4 and DI-5, prepared as described in Examples 1-3 above, were tested to determine the relative stability of the interlayers over time. Net plasticizer migration was measured by comparing the glass transition temperatures of each layer at an initial time (t=0) and after the layers have achieved equilibrium. The results are summarized in Table 8, below.
Table 8: Net Plasticizer Migration and Properties of Exemplary Comparative and
Disclosed Interlayers
Δ
Refractive
TG at t=0 TG at Equilibrium
Δ TG CO Index Mottle
Interlayer CO CO (Skin-Core)
Tg Skin Tg Core Tg Skin Tg Core Δ Tg Skin Δ Tg Core
CI-2 36 4.2 36 4.6 0.0 0.4 0.011 > 5
DI-4 36 1.4 36.4 1.4 0.4 0.0 -0.005 < 1
CI-7 42.5 2.2 42.5 1.4 0.0 -0.8 0.012 > 5
DI-5 40.9 0.2 41.7 -1.8 0.8 -2.0 -0.004 < 1 [0156] Disclosed Interlayer DI-4 (as well as Comparative Interlayers CI-2 and CI-7) exhibited minimal changes in the glass transition temperature of both the skin and core layers of the interlayer at equilibrium. This indicates a minor amount of plasticizer migration between the skin and core layers of each of Interlayers CI-2, Cl- 7, and DI-4. Although Comparative Interlayers CI-2 and CI-7 may be relatively stable, both exhibited a mottle value greater than 5, which would be unacceptable for most optical applications. In contrast, the mottle value exhibited by Disclosed Interlayer Dl- 4 was less than 1.
[0157] The slight decrease in glass transition temperature exhibited by Disclosed Interlayer DI-5 at equilibrium indicated that a small amount of plasticizer migrated from the skin layer to the core layer. Such migration could be alleviated by utilizing a smaller amount of plasticizer in the skin layer or a larger amount in the core. Even so, the refractive index of the core layer and the skin layer of Disclosed Interlayer DI-5 differed by only 0.004 and, as a result, the interlayer also exhibited a mottle value less than 1.
Example 5: Blended Polyvinyl acetal) Resins
[0158] Several Comparative and Disclosed Resins, prepared as described in Example 1 above, were mixed and melt-blended together with 38 phr of 3GEH plasticizer to form Comparative Blended Layers CBL-16 and CBL-17 and Disclosed Blended Layers DBL-27 and DBL-28. Comparative Polymer Layer CL-2 is listed in Table 4. Comparative Polymer Layer CL-15 was formulated with Comparative Resin CR-10 and 38 phr of 3GEH, while Disclosed Polymer layers DL-27 and DL-28 were formulated with Disclosed Resins DR-3 and DR-5, respectively, and 38 phr of 3GEH. The haze and percent visual transmittance (TViS) for each blended resin interlayer were measured, along with the haze and percent visual transmittance. The results are provided in Table 9, below. Table 9: Haze and Percent Visual Transmittance of Several Polymer Layers
Layer Composition Property
Plasticizer
Interlayer CR-2 CR-10 DR-3 DR-5
content Haze (%) % Tvis (wt%) (wt%) (wt%) (wt%)
(phr)
CL-2 100 - - 38 0.5 87.7
CL-15 - 100 - 38 0.5 87.8
CBL-16 96 4 - 38 2.1 84.3
CBL-17 89 11 - 38 14.7 80.2
DBL-27 96 4 - 38 0.8 87.8
DBL-28 89 - 11 38 0.6 87.8
DL-27 - 100 - 38 0.5 87.7
DL-28 - - 100 38 0.5 87.8
[0159] As shown in Table 9 above, Comparative Blended Interlayers CBL-16 and CBL-17, which were formed from a blend of Comparative Resins CR-2 and CR-10, exhibited high haze values and lower percent visual transmittance than single polymer layers of Comparative Resin CR-2 (Comparative Layer CL-2) or CR-10 (Comparative Interlayer CL-15). In contrast, Disclosed Blended Interlayers DBL-27 and DBL-28, which were formed from a blend of Comparative Resin CR-2 and a high refractive index Disclosed Resin (Resin DR-3 in Layer DBL-27 or Resin DR-5 in Layer DBL-28), exhibited substantially the same haze and percent visual transmittance as Comparative Interlayer CL-2, which was formulated with Comparative Resin CR-2 alone. Thus, addition of inventive high refractive index resins to a comparative interlayer does not reduce the optical quality of the resulting interlayer.
Example 6: Preparation of Interlayers having High Refractive Index Additives
[0160] Several polyvinyl acetal) resins were prepared by acetalizing polyvinyl alcohol with n-butyraldehyde. The resins, which had different residual hydroxyl contents, were melt blended with varying amounts of a 3GEH plasticizer and used to form various layers of multilayer interlayers. Each interlayer had an inner "core" layer having a thickness of 5 mils sandwiched between two outer "skin" layers, each having a thickness of 14 mils. The polyvinyl butyral) resin used to form the core layers had a hydroxyl content of 11 weight percent and the resin used for the skin layers had a hydroxyl content of 19 weight percent. Both resins had a residual acetate content of about 2 weight percent.
[0161] Comparative Interlayers CI-17 through CI-19 were formed with polymer layers plasticized with 3GEH, which was present in varying amounts in the core and skin layers. In addition to the 3GEH, Disclosed Interlayers DI-30 through Dl- 38 also included varying amounts of two different high refractive index additives, Benzoflex™ 2-45 (diethyleneglycol dibenzoate; commercially available from Eastman Chemical Company, Kingsport, Tennessee) (Additive A-1), which had a melting point of 28°C and a refractive index of 1.542; and Benzoflex™ 352 (1,4-cyclohexane dimethanol dibenzoate; commercially available from Eastman Chemical Company) (Additive A-2), which had a melting point of 118°C and a refractive index of 1.554. The refractive index and glass transition temperatures of each of the layers of Comparative Interlayers CI-17 through CI-19 and Disclosed Interlayers DI-30 through DI-38 were measured and the results are summarized in Table 10 below.
Table 10: Properties of Several Comparative and Disclosed Interlayers
Skin Layers Core Layer
Plasticizer High Rl Plasticizer High Rl Δ
High Rl High Rl
Interlayer Content Additive Total A:P Tg Content Additive Total A:P Tg Refracti
Additive Rl Additive Rl
(P) (A) A+P Ratio (V (P) (A) A+P Ratio (V Index
Type Type
(phr) (phr) (phr) (phr) (Skin-Cor
CI-17 40 - - - 1.476 30 65.0 - - - 1.467 2.9 0.008
CI-18 40 - - - 1.476 30 75.0 - - - 1.466 -2.0 0.010
CI-19 40 - - - 1.476 30 85.0 - - - 1.465 -3.1 0.011
DI-30 20 A-l 20 40 1.0 1.492 29 32.5 A-l 32.5 65 1.0 1.488 4.2 0.004
DI-31 20 A-l 20 40 1.0 1.492 29 37.5 A-l 37.5 75 1.0 1.488 -0.6 0.004
DI-32 20 A-l 20 40 1.0 1.489 29 42.5 A-l 42.5 85 1.0 1.488 -3.3 0.004
DI-33 17.2 A-l 22.8 40 1.3 1.496 30 22.8 A-l 42.2 65 1.9 1.494 5.2 0.002
DI-34 17.2 A-l 22.8 40 1.3 1.496 30 26.2 A-l 48.8 75 1.9 1.494 2.4 0.002
DI-35 17.2 A-l 22.8 40 1.3 1.496 30 29.8 A-l 55.2 85 1.9 1.494 -2.1 0.002
DI-36 20 A-2 20 40 1.0 1.493 34 27.5 A-2 27.5 55 1.0 1.490 15.9 0.003
DI-37 20 A-2 20 40 1.0 1.493 34 35.0 A-2 35.0 70 1.0 1.490 8.4 0.003
DI-38 20 A-2 20 40 1.0 1.493 34 42.5 A-2 42.5 85 1.0 1.491 1.8 0.002
[0162] As shown in Table 10, above, increasing the plasticizer content of the core layer of an interlayer that only included a 3GEH plasticizer reduced the glass transition temperature of the layer, which, ultimately, would have improved its acoustic performance. However, such an increase also widened the difference between the refractive indices of the skin and core layers, thereby reducing the optical quality of the interlayer. As shown by comparison with Disclosed Interlayers DI-30 through DI-38 in Table 10, the refractive index of core layers formulated with an additional high refractive index additive, remained fairly constant with increased plasticizer loading, while still exhibiting a similar reduction in glass transition temperature. The result was an interlayer having core and skin layers with nearly the same refractive index, which greatly reduced optical defects such as mottle. At the same time, the core layer also exhibited a sufficiently low glass transition temperature, indicating that the resin also had acoustic properties.
Example 7: Preparation of Core Layers having Reactive High Refractive Index Additives
[0163] Several polymer layers, used to simulate the inner core layer of a multilayer interlayer, were formed by melt blending a polyvinyl n-butyral resin having a residual hydroxyl content of 11 weight percent and a residual acetate content of about 2 weight percent with varying amounts of 3GEH plasticizer. Comparative Layer CL-16 included 75 phr of 3GEH, while Disclosed Layers DL-29 through DL-31 were formulated with various mixtures of 3GEH and a reactive high refractive index additive (reactive high Rl additive). The reactive high Rl additive used in Disclosed Layers DL- 29 and DL-30 (Additive A) was diphenyldimethoxysilane (commercially available as SID4535.0 from Gelest, Inc., Morrisville, Pennsylvania), and the reactive high Rl additive used in Disclosed Layer DL-31 (Additive B) was phthalic anhydride (commercially available from Sigma Aldrich Co., St. Louis, Missouri). The refractive index of Comparative Layer CL-16 and each of Disclosed Layers DL-29 through DL-31 was measured and the results are provided in Table 11, below. Table 11: Refractive Index of Comparative and Disclosed Core Polymer Layers
Plasticizer Additive A Additive B
Polymer Refractive Index
Content Content Content
Layer (nD25)
(phr) (phr) (phr)
CL-16 75 - - 1.466
DL-29 72 3 - 1.468
DL-30 72 6 - 1.470
DL-31 72 - 3 1.470
[0164] As shown in Table 11, polymer layers formed using 3GEH in combination with one or more reactive high refractive index additives had a higher refractive index than polymer layers formulated with only 3GEH. As a result, when employed as an inner core layer in a multilayer interlayer, the Disclosed Layers DL-29 through DL-31 had a refractive index that more closely matched the refractive index of a skin layer formed of polyvinyl n-butyral (Rl=1.477). As a result, multilayer interlayers formed with Disclosed Layers DL-29 through DL-31 as a core layer exhibit fewer optical defects than multilayer interlayers formed with Comparative Layer CL- 16 as an inner core layer.
Example 8: Various Interlayers with Resin Blends having a High Refractive Index Plasticizer
[0165] Two polyvinyl n-butyral resins, R-l and R-2, were prepared according to the procedure described above in Example 1. Resin R-l had a residual hydroxyl content of 19 weight percent, while resin R-2 had a residual hydroxyl content of 11 weight percent. Both resins had residual acetate contents of 2 weight percent. Several resin blends were prepared that included varying amounts of resins R-l and R-2 in order to simulate various blending rates. The blends were combined with 38 phr of a plasticizer selected from 3GEH (plasticizer P-l; Rl = 1.442), dioctyl phthalate (plasticizer P-2; Rl = 1.485), a blend of 30 weight percent 3GEH and 70 weight percent Benzoflex® 2088, which is commercially available from Eastman Chemical Company, Kingsport, Tennessee, (plasticizer P-3; Rl = 1.506), and nonylphenyl tetraethylene glycol (plasticizer P-4; Rl = 1.500). The resulting plasticized resins were then formed into single sheets that included both resins and the plasticizer. The refractive index, haze, and percent visual transmittance was determined for each sheet and the results are provided in Table 12, below.
Table 12: Properties of Several Resin Blends
Plasticizer P-1 Plasticizer P-2 Plasticizer P-3 Plasticizer P-4
Resin A Resin B
Rl of Haze Tvis Rl of Haze Tvis Rl of Haze Tvis Rl of Haze Tvis {wt %) {wt %)
Interlayer {%) {%) Interlayer {%) {%) Interlayer {%) {%) Interlayer {%) {%)
100 0 1.477 0.4 88.5 1.494 0.4 88.5 1.495 0.3 88.4 1.493 0.3 88.5
98.9 1.1 1.477 0.6 87.9 1.494 0.4 88.6 1.495 0.3 88.8 1.493 0.3 88.7
97.8 2.2 1.476 1.2 87.1 1.498 0.3 88.4 1.495 0.3 88.7 1.493 0.2 88.7
95.6 4.4 1.477 1.9 84.6 1.495 0.4 88.4 1.495 0.3 88.6 1.492 0.4 88.5
91.2 8.8 1.476 5.4 81.7 1.495 0.5 88.3 1.495 0.4 88.5 1.493 0.3 88.6
88.9 11.1 1.476 12.9 80.6 1.494 0.6 88.2 1.495 0.4 88.2 1.492 0.4 88.2
[0166] As shown in Table 12, above, although blended polymer layers formulated with plasticizer P-1 maintained a substantially constant refractive index with increasing amounts of the lower hydroxyl content resin R-2, the optical properties of these resin blends having high levels of R-2 worsened as the amount of R-2 increased. For example, as shown in Table 12, the haze of blends that included more than 1.1 percent of resin R-2 increased, while the percent visual transmittance of these blends decreased from 88.5 percent to 81.7 percent.
[0167] In contrast, the resin blends including more than 2.2 percent of resin R- 2 that were plasticized with higher refractive index plasticizers P-2 through P-4, each exhibited substantially the same haze value and percent visual transmittance as blends having lower amounts of resin R-2. Therefore, it can be concluded that the resin blends utilizing higher refractive index plasticizers, such as plasticizers P-2 through P-4, may permit higher amounts of lower hydroxyl content resins without adversely impacting the optical properties of the final blend.
Example 9: Polyvinyl butyral) Layers including a High Refractive Index Plasticizer
[0168] Several polyvinyl n-butyral) layers were formed by combining and melt blending three different polyvinyl n-butyral) resins (PVB-1 through PVB-3) with different types and amounts of plasticizer. Each of the resins PVB-1 through PVB-3 had a different residual hydroxyl content, ranging from 11 to 20.4 weight percent, and all three resins had a residual vinyl acetate content of 1 weight percent. Comparative Layers CL-17 through CL-19 were formulated with varying amounts of triethylene glycol di-(2-ethylhexanoate) ("3GEH"; Rl=1.442), while Disclosed Layers DL-32 through DL-37 included a mixture of 3GEH with Benzoflex™ 354 (commercially available from Eastman Chemical Company, Kingsport, Tennessee)(RI=1.53). The refractive index of each layer was measured and the results are summarized in Table 13, below. Table 13: Several Poly(vinyl) Butyral Layers with Various Plasticizers
Plasticizer Content
Polymer hydroxy 1 Ratio of Total
3GEH Benzoflex™ Refractive Layer content 3GEH to plasticizer
content 354 Index (wt%) Benzoflex™ content
(phr) (Phr) (nD25)
354 (Phr)
CL-17 19 38 - - 38 1.477
CL-18 19 38 - - 38 1.477
CL-19 11 75 - - 38 1.466
DL-32 20.4 30.1 12.9 30/70 43 1.484
DL-33 20.4 25.8 17.2 40/60 43 1.485
DL-34 20.4 21.5 21.5 50/50 43 1.488
DL-35 11 59.5 25.5 30/70 85 1.479
DL-36 11 51 34 40/60 85 1.481
DL-37 11 42.5 42.5 50/50 85 1.486
[0169] As shown in Table 13, above, polymer layers that included a high refractive index plasticizer exhibited a higher refractive index than those that included only a low refractive index plasticizer.
Example 10: Preparation of Interlayers having High Refractive Index Additives
[0170] Several of the Comparative and Disclosed Interlayers formed in Example 9 and summarized in Table 13, above, were used to create several Comparative and Disclosed Multilayer Interlayers. Each multilayer interlayer included a pair of outer "skin" layers, each having a thickness of 14 mils, sandwiching an inner "core" layer, having a thickness of 5 mils, formed of a resin having a lower residual hydroxyl content. The composition and several properties of the multilayer interlayers, including total plasticizer content, refractive index, glass transition temperature, mottle, and loss factor, were measured as described above, and the results for the Comparative Multilayer Interlayers CI-20 and CI-21 and Disclosed Multilayer Interlayers DI-39 through DI-41 are summarized in Table 14, below. Table 14: Properties of Several Comparative and Disclosed Interlayers
Δ
Total
Skin Skin Refractive Refractive Tg Loss
Interlayer Core plasticizer
Layer Layer Index Index (°C) Mottle Factor
No Layer content
1 2 (Skin- (nD25) at 20°C
(phr) Skin Core
Core)
CI-20 CL-17 CL-18 CL-17 38 0.000 1.477 30 - 0 0.02
CI-21 CL-17 CL-19 CL-17 42.5 0.011 1.475 35 3 5 0.32
DI-39 DL-32 DL-35 DL-32 48 0.005 1.484 38.8 2.6 0.4 0.41
DI-40 DL-33 DL-36 DL-33 48 0.004 1.486 39.6 4.7 0.4 0.39
DI-41 DL-34 DL-37 DL-34 48 0.002 1.488 40.9 8.7 0.4 0.33
[0171] As shown in Table 14 above, interlayers formed from skin and core layers having a refractive index difference greater than 0.010 exhibited more optical defects, as shown by the mottle value of 5. Additionally, Disclosed Interlayers DI-39 through DI-41, which utilized a high refractive index plasticizer, exhibited a higher overall refractive index as compared to Comparative Interlayers CI-20 and CI-21, which only utilized a plasticizer having a refractive index less than 1.460.
Example 11: Measurement of Double Image Separation Distance for Comparative and Disclosed Multiple Layer Panels with Varying Thickness and Wedge Angle
[0172] Several interlayers were formed by combining polyvinyl butyral) resin having a residual hydroxyl content of 18.7 weight percent with 38 phr of the plasticizer triethylene glycol bis(2-ethylhexanoate) (3GEH), and extruding the resulting mixture to form single layer sheets. A flat interlayer sheet, i.e., with no tapered zone, was formed with a uniform thickness of about 30 mils (about 0.76 mm) and was cut to form several comparative interlayers having a wedge angle of 0°.
[0173] Several of the sheets were formed with tapered zones each having a different constant wedge angle, and each sheet was cut to form several tapered monolithic interlayers. The tapered interlayers each had a wedge angle ranging from 0.30 to 0.73 mrad. Each of the interlayer samples was then laminated between pairs of 6 inch by 12 inch glass sheets, with each glass/interlayer/glass multiple layer panel having a thickness of 3.0 mm, 4.32 mm, or 5.0 mm. The specific configuration of each of the Comparative Multiple Layer Panels (CP-1 through CP-3) and Disclosed Multiple Layer Panels (DP-1 through DP-15) are shown in Table 15, below.
Table 15: Double Image Separation of Several Comparative & Disclosed Laminates
Wedge Laminate Double Image
Laminate Angle Thickness Separation
(mrad) (mm) (arc min)
CP-1 0.00 3.0 5.459
CP-2 0.00 4.3 7.389
CP-3 0.00 5.0 8.491
DP-1 0.20 3.0 3.305 Wedge Laminate Double Image
Laminate Angle Thickness Separation
(mrad) (mm) (arc min)
DP-2 0.20 4.3 5.362
DP-3 0.20 5.0 6.527
DP-4 0.30 3.0 2.228
DP-5 0.30 4.3 4.411
DP-6 0.30 5.0 5.576
DP-7 0.41 3.0 1.088
DP-8 0.41 4.3 3.271
DP-9 0.41 5.0 4.436
DP-10 0.50 3.0 -0.618
DP-11 0.50 4.3 1.789
DP-12 0.50 5.0 3.042
DP-13 0.73 3.0 -2.714
DP-14 0.73 4.3 -0.403
DP-15 0.73 5.0 0.888
[0174] Each of the laminates listed in Table 15 was subjected to the double image separation test using the apparatus 100 depicted in FIG. 9. As shown in FIG. 9, test apparatus 100 includes a projector 130, an adjustable mirror 140, and a detector 120. The distance between projector 130 and adjustable mirror 140, shown in FIG. 9 as line A, was 43.8 cm, the distance between adjustable mirror 140 and panel 110, shown in FIG. 9 as line B, was 31.7 cm, and the distance between panel 110 and detector 120, shown in FIG. 9 as line C, was 47 cm. Additionally, the incident angle at which the light from projector 130 hit adjustable mirror 140, shown in FIG. 9 as θι, was 30.11°, and panel 110 was arranged so that the incident angle of the image from mirror 140 onto panel 110, shown in FIG. 9 as θ2, and the light reflected from panel 110 to detector 120, shown as θ2', were each about the same and equal to 24.8°. Finally, as shown in FIG. 9 by θ3, panel 110 was oriented from the vertical by an angle of 30.5°.
[0175] To measure the double image separation distance of panel 110 using apparatus 100 shown in FIG. 9, an image was generated using a standard thin film transistor display and was reflected by a flat surface of mirror 140 to panel 110. The image was reflected off of one or more surfaces of panel 110 and projected to detector 120. The image was then recorded using a digital camera to form a captured image, as shown in FIG. 10, which was then analyzed to form a profile by converting the digital image to a matrix having elements that represent the intensity (grey scale level) of each pixel of the digital image. The matrix was then plotted, column by column, as a function of pixel number, as shown in FIG. 11. The higher intensity peaks shown in FIG. 11 represented the primary image reflected from the panel, while the shorter, less intense peaks corresponded to the secondary or "ghost" image. The separation distance, in pixels, between the primary and secondary peaks was then determined used to calculate the double image separation distance (D) for each panel, in minutes
(arc min), according to the following equation:
peak separation (pixels)
D =— i- — - - X3427.75
Virtual Image distance (mm)
[0176] Using the above-described procedure, the double image separation distance for each of the Comparative Panels (CP-1 through CP-3) and each of the Disclosed Panels (DP-1 through DP-15) was measured, and the results are provided in Table 15, above. The results are also summarized graphically in FIG. 12.
[0177] Additionally, several additional Comparative Multiple Layer Panels (CP- 4 through CP-8) and Disclosed Multiple Layer Panels (DP-16 through DP-29) were constructed in a similar manner as described above, but with varying thicknesses at several different wedge angles. The above-described double image separation test was then performed on each of the Comparative Panels CP-4 through CP-8 and Disclosed Panels DP-16 through DP-29, and the results are provided in Table 16, below. FIG. 13 shows the double image separation distance as a function of wedge angle for Comparative Panels CP-4 through CP-8 and Disclosed Panels DP-16 through DP-29 at varying glass configurations. Table 16: Double Image Separation of Several Comparative and Disclosed
Laminates
Wedge Laminate Double Image
Laminate Angle Thickness Separation
(mrad) (mm) (arc min)
CP-4 0.0 2.16 3.97
CP-5 0.0 3.06 5.45
CP-6 0.0 3.97 6.83
CP-7 0.0 4.66 7.96
CP-8 0.0 5.36 9.02
DP-16 0.20 3.19 3.49
DP-17 0.20 4.07 4.82
DP-18 0.20 5.45 7.06
DP-19 0.41 3.39 0.55
DP-20 0.41 4.12 2.88
DP-21 0.41 5.47 4.44
DP-22 0.50 4.16 1.22
DP-23 0.50 4.64 2.39
DP-24 0.50 2.20 -2.10
DP-25 0.50 5.44 3.43
DP-26 0.73 2.30 -4.27
DP-27 0.73 3.20 -2.59
DP-28 0.73 3.90 -0.53
DP-29 0.73 4.60 -0.04
Example 12: Determination of Equivalent Refractive Index (neq) for Several Comparative and Disclosed Multiple Layer Panels
[0178] The equivalent refractive index, ne£?, of a Comparative Multiple Layer
Panel and a Disclosed Multiple Layer Panel are determined in the following example.
A Comparative Panel (CP-A) is formed by laminating a PVB interlayer having a uniform thickness of 0.76 mm and a refractive index of 1.475 between glass panels, one of which has a thickness of 1.6 mm and the other of which has a thickness of 2.3 mm.
The glass panels each have a refractive index of 1.52, measured according to ASTM
D542 at a wavelength of 589 nm and 25°C. At an incident angle (θ2) of 60°, the equivalent refractive index of the Comparative Panel is determined, according to the above equations (1) through (4), to be 1.512. [0179] Similarly, a Disclosed Multiple Layer Panel (DP-B) is formed by laminating another PVB interlayer having a uniform thickness of 0.76 mm between two glass panels, each panel having the same thickness as the panels used to form the Comparative Multiple Layer Panel. However, the PVB interlayer used to form the Disclosed Multiple Layer Panel (DP-B) has a refractive index of 1.65. Using the formulas above, the equivalent refractive index of the Disclosed Multiple Layer Panel is calculated to be 1.540. This Disclosed Multiple Layer Panel DP-B may represent the practical maximum (or practical limit) of equivalent refractive index achievable in some cases. The results are summarized in Table 17, below.
Table 17: Refractive Index Properties of Interlayers (at incident angle of 60°)
Example 13: Effect of Refractive Index on Double Image Separation for Various Laminates
[0180] Several glass/air/glass laminates were formed to simulate multiple layer panels having different equivalent refractive indices. Each laminate was constructed by spacing several glass sheets of varying thickness apart from one another using appropriately-sized metal shims in order to create and maintain air gaps between the glass sheets. The overall thickness of the resulting glass/air/glass laminates was maintained at between 4 and 5 mm, and the equivalent refractive index for each was calculated according to Formulas (1) through (4), above. The specific configuration and values for the parameters of Form ulas (1) through (4), above, for two exemplary panels, AGL-1 and AGL-2, are summarized in respective Tables 18 and 19, below. Table 18: Configuration and Equivalent Refractive Index Parameters for AGL-1
Thickness
Layer Material
(mm) ni n2 Q2 X (mm)
Layer 1 Air 1 65.20
Layer 2 Glass 0.7 1 65.20 1.52 36.67 0.521217
Layer 3 Air 3.6 1.52 36.67 1.00 65.20 7.791114
Layer 4 Glass 0.7 1 65.20 1.52 36.67 0.521217
Layer 5 Air 1.52 36.67 1.00 65.20
Equivalent 5 1.04 60.49 8.833547
Table 19: Configuration and Equivalent Refractive Index Parameters for AGL-2
Thickness
Layer Material
(mm) ni n2 X (mm)
Layer 1 Air 1 65.20
Layer 2 Glass 2.3 1 65.20 1.52 36.67 1.712569
Layer 3 Air 0.4 1.52 36.67 1.00 65.20 0.865679
Layer 4 Glass 2.3 1 65.20 1.52 36.67 1.712569
Layer 5 Air 1.52 36.67 1.00 65.20
Equivalent 5 1.39 40.63 4.290818
[0181] Each of the glass/air/glass panels formed as described above was then subjected to a double image separation test similar to the one described in Example 11 above using the apparatus shown in FIG. 9, except that the captured image formed when analyzing these panels included three double images, instead of one, due to the large difference between the refractive indices of glass and air. For this analysis, the separation between the primary image and the last double image were analyzed when determining the double image separation distance for each panel. The results of these analyses are summarized graphically in FIG. 14.
[0182] While the invention has been disclosed in conjunction with a description of certain embodiments, including those that are currently believed to be the preferred embodiments, the detailed description is intended to be illustrative and should not be understood to limit the scope of the present disclosure. As would be understood by one of ordinary skill in the art, embodiments other than those described in detail herein are encompassed by the present invention. Modifications and variations of the described embodiments may be made without departing from the spirit and scope of the invention
[0183] It will further be understood that any of the ranges, values, or characteristics given for any single component of the present disclosure can be used interchangeably with any ranges, values or characteristics given for any of the other components of the disclosure, where compatible, to form an embodiment having defined values for each of the components, as given herein throughout. For example, an interlayer can be formed comprising polyvinyl butyral) having a residual hydroxyl content in any of the ranges given in addition to comprising a plasticizers in any of the ranges given to form many permutations that are within the scope of the present disclosure, but that would be cumbersome to list. Further, ranges provided for a genus or a category, such as phthalates or benzoates, can also be applied to species within the genus or members of the category, such as dioctyl terephthalate, unless otherwise noted.

Claims

CLAIMS What is claimed is
1. A tapered interlayer comprising at least one polymer layer comprising a polyvinyl acetal) resin and at least one plasticizer, wherein said polymer layer has a refractive index of at least 1.480, and wherein said interlayer comprises a tapered zone having an overall wedge angle of not more than 0.85 mrad.
2. The interlayer of claim 1, wherein said tapered zone has an overall wedge angle of less than 0.55 mrad and wherein said polymer layer has a refractive index of at least 1.500.
3. The interlayer of claim 1, wherein said interlayer is a monolithic interlayer.
4. The interlayer of claim 1, wherein said interlayer is a multiple layer interlayer comprising said polymer layer and another polymer layer adjacent to said polymer layer, wherein the difference between the glass transition temperature of said polymer layer and the glass transition temperature of said another polymer layer is at least 3°C.
5. The interlayer of claim 4, wherein said another polymer layer comprises a second polyvinyl acetal) resin and at least one plasticizer, wherein the difference between the residual hydroxyl content of said polyvinyl acetal) resin in said polymer layer and the residual hydroxyl content of said second polyvinyl acetal) resin in said another polymer layer is at least 2 weight percent.
6. The interlayer of claim 1, wherein said tapered zone comprises at least one variable angle zone having a curved thickness profile and a continuously varying wedge angle.
7. The interlayer of claim 1, wherein said tapered zone comprises at least one constant angle zone having a linear thickness profile and a constant wedge angle.
8. A multiple layer panel comprising a pair of rigid substrates and the interlayer of claim 1, wherein said interlayer is disposed between said pair of rigid substrates and wherein said rigid substrates have a combined thickness of less than 4.0 mm.
9. A multiple layer panel comprising:
a pair of rigid substrates; and
an interlayer disposed between said substrates, wherein said interlayer comprises a tapered zone having an overall wedge angle of less than 0.85 mrad, wherein the equivalent refractive index of said multiple layer panel is at least 0.010 higher than the refractive index of each of said rigid substrates.
10. The panel of claim 9, wherein the equivalent refractive index of said multiple layer panel is at least 1.500.
11. The panel of claim 9, wherein the refractive index of each of said substrates is at least 20 percent lower than the refractive index of said interlayer.
12. The panel of claim 9, wherein the refractive index of said interlayer is at least about 1.600.
13. The panel of claim 9, wherein said tapered zone has an overall wedge angle of less than 0.55 mrad.
14. The panel of claim 9, wherein said interlayer comprises at least one polymer layer comprising a polyvinyl acetal) resin and at least one plasticizer, wherein said combined thickness of each of said rigid substrates is not more than 4.0 mm.
15. The panel of claim 14, wherein said interlayer comprises a multiple layer interlayer comprising two or more polymer layers each comprising a polyvinyl acetal) resin and at least one plasticizer, wherein said interlayer comprises at least two glass transition temperatures, wherein the difference between said two glass transition temperatures is at least about 3°C.
16. A multiple layer panel comprising
a pair of rigid substrates; and
a tapered interlayer disposed between said substrates, wherein said tapered interlayer comprises at least one polymeric resin,
wherein the refractive index of said interlayer is at least 5 percent higher than the refractive index of each of said rigid substrates.
17. The panel of claim 16, wherein said tapered comprises a tapered zone having a wedge angle of not more than 0.85 mrad and wherein said interlayer comprises at least one polymer layer having a refractive index of at least about 1.480.
18. The panel of claim 16, wherein said panel has an equivalent refractive index higher than said refractive index of each of said rigid substrates.
19. The panel of claim 16, wherein said interlayer is a multiple layer interlayer comprising at least a first polymer layer and a second polymer layer adjacent to said first polymer layer, wherein first polymer layer comprises a first polyvinyl acetal) resin and at least one plasticizer and said second polymer layer comprises a second polyvinyl acetal) resin and at least one plasticizer, wherein the difference between the glass transition temperature of said first polymer layer and the glass transition temperature of said second polymer layer is at least 3°C, and wherein the difference between the residual hydroxyl content of said first polyvinyl acetal) resin and the residual hydroxyl content of said second polyvinyl acetal) resin is at least 2 weight percent.
20. The panel of claim 16, wherein said interlayer has a minimum thickness in the range of from about 0.25 to about 1.2 mm and a maximum thickness in the range of from about 0.38 to about 2.2 mm, wherein the difference between the minimum thickness of said interlayer and the maximum thickness of said interlayer is at least about 0.13 mm, and wherein the combined thickness of each of said rigid substrates is less than about 4.0 mm.
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