WO2016094204A1 - Compositions de résine poly(acétal de vinyle), couches et couches intermédiaires présentant des propriétés améliorées - Google Patents

Compositions de résine poly(acétal de vinyle), couches et couches intermédiaires présentant des propriétés améliorées Download PDF

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Publication number
WO2016094204A1
WO2016094204A1 PCT/US2015/063877 US2015063877W WO2016094204A1 WO 2016094204 A1 WO2016094204 A1 WO 2016094204A1 US 2015063877 W US2015063877 W US 2015063877W WO 2016094204 A1 WO2016094204 A1 WO 2016094204A1
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Prior art keywords
resin
polyvinyl acetal
composition
value
residues
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PCT/US2015/063877
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English (en)
Inventor
Yinong Ma
Nandan U. UKIDWE
Aristotelis Karagiannis
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Solutia Inc.
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Publication date
Priority claimed from US14/562,884 external-priority patent/US9758662B2/en
Priority claimed from US14/563,077 external-priority patent/US9926431B2/en
Application filed by Solutia Inc. filed Critical Solutia Inc.
Publication of WO2016094204A1 publication Critical patent/WO2016094204A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered 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
    • B32B17/10—Layered 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
    • B32B17/10005—Layered 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
    • B32B17/1055—Layered 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
    • B32B17/10761—Layered 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 containing vinyl acetal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/10—Properties of the layers or laminate having particular acoustical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/418—Refractive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/58—Cuttability
    • B32B2307/581—Resistant to cut
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/12—Photovoltaic modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2607/00—Walls, panels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

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.
  • UV ultraviolet
  • IR infrared
  • Polyvinyl acetal) resins typically include acetate pendant groups, hydroxyl pendant groups, and aldehyde pendant groups, such as n- butyraldehyde groups for a PVB resin, that are present along the vinyl polymer backbone. Properties of polyvinyl acetal) resins are determined, in part, by the relative amount of hydroxyl, acetate, and aldehyde groups and/or by the type and amount of plasticizer added to the resin. Therefore, selection of certain resin compositions and combination of those resins with various types and amount of plasticizers, can provide resin compositions, layers, and interlayers having different properties.
  • PVB resin compositions having high residual hydroxyl contents and low plasticizer contents tend to have higher glass transition temperatures, which make such resins desirable in safety performance applications.
  • PVB resin compositions having lower residual hydroxyl contents and higher amounts of plasticizer may exhibit good vibration and sound dampening properties, but typically have limited, if any, impact resistance over a broad temperature range.
  • compositions, layers, and interlayers including such resins which can be employed in several end uses, including in safety glass and as polymeric laminates.
  • One embodiment of the present invention concerns a resin composition
  • a resin composition comprising a first polyfvinyl acetal) resin component having a first value, A, for a selected resin property, wherein the first polyfvinyl acetal) resin component is present in the composition in an amount of Y weight percent; and a second polyvinyl acetal) resin component having a second value, B, for the selected resin property, wherein the second polyvinyl acetal) resin component is present in the composition in an amount of Z weight percent, wherein the resin composition has an actual composition value, C, for the selected resin property, wherein the actual composition value, C, is not equal to a value within 5 percent of the calculated value, C, determined by the following equation:
  • Another embodiment of the present invention concerns a method for making an interlayer, the method comprising the steps of identifying a target value for at least one resin layer property, wherein the resin layer property is selected from the group consisting of glass transition temperature, refractive index, viscosity, tan delta, impact resistance, melt flow, and combinations thereof; blending a first polyvinyl acetal) resin or precursor thereto and a second polyvinyl acetal) resin or precursor thereto to provide a blended resin composition; and forming a resin layer from the blended resin composition, wherein the resin layer has a value for the resin layer property that is within 5 percent of the target value for the resin layer property identified.
  • DESCRIPTION OF THE DRAWINGS DESCRIPTION OF THE DRAWINGS
  • FIG. 1 is a graph depicting the tan delta of several plasticized polyvinyl acetal) resins described in Example 1 , over a temperature range of 30°C to 1 10°C;
  • FIG. 2 is a graph depicting the tan delta of several plasticized polyvinyl acetal) resins described in Example 3, over temperature range of - 30 to 60 °C;
  • FIG. 3 is a graph depicting the refractive index of several polyvinyl acetal) resins described in Example 4 as a function of plasticizer content;
  • FIG. 4 is a graph depicting the cloud point of two polyvinyl acetal) resins described in Example 8 as a function of residual hydroxyl content;
  • FIG. 5 is a graph depicting the tan delta of several plasticized resin compositions described in Example 9 over a temperature range of -20 °C to 30 °C;
  • FIG. 6a is a graph depicting the glass transition temperature of several plasticized resins described in Example 10 as a function of plasticizer loading.
  • FIG. 6b is a graph depicting the tan delta of the resin compositions described in Example 10 and shown in FIG. 6a as a function of glass transition temperature.
  • the present invention relates to polymer resin compositions, layers, and interlayers that include at least one polyvinyl acetal) resin that exhibits different properties than a conventional polyvinyl n-butyral) (PVB) resin, but that can be used in many of the same applications as PVB, including, for example, safety glass applications.
  • Compositions, layers, and interlayers according to various embodiments of the present invention may have different glass transition temperatures, different refractive indices, and/or different viscosities than comparable polyvinyl acetal) resins that only include residues of n-butyraldehyde.
  • the resins, compositions, layers, and interlayers described herein may also exhibit enhanced optical, mechanical, and/or acoustic performance.
  • compositions, layers, and interlayers having optimized properties according to various embodiments of the present invention are also described herein.
  • polymer resin composition and “resin composition” refer to compositions that include one or more polymer resins.
  • Polymer compositions may optionally include other components, such as plasticizers and/or other additives.
  • plasticizers and/or other additives.
  • polymer resin 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, resin layers may include one or more additional additives.
  • 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 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 that are coextruded, laminated, or otherwise coupled to one another.
  • Resin compositions, layers, and interlayers according to various embodiments of the present invention can include at least one polyvinyl acetal) resin.
  • Polyvinyl acetal) resins can be formed by aqueous or solvent-based acetalization of polyvinyl alcohol) with one or more aldehydes in the presence of an acid catalyst. The resulting resin can then be
  • the total amount of residual aldehyde groups, or residues, present in the resulting polyvinyl acetal) resin can be at least about 50, at least about 60, at least about 70, at least about 75, at least about 80, at least about 85, at least about 90, at least about 92 weight percent, as measured by ASTM D-1396.
  • 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 comprising residual hydroxyl or acetate groups, which will be discussed in further detail below.
  • polyvinyl acetal) resin is a polyvinyl n-butyral) (PVB) resin
  • PVB polyvinyl n-butyral
  • a polyvinyl n-butyral) resin may comprise less than 10, not more than about 5, not more than about 2, not more than about 1 , or not more than about 0.5 weight percent of residues of an aldehyde other than n-butyraldehyde, based on the total weight of aldehyde residues of that resin.
  • compositions, layers, and interlayers according to
  • embodiments of the present invention can include at least one polyvinyl acetal) resin that comprises at least about 10 weight percent of residues of an aldehyde other than n-butyraldehyde.
  • the polyvinyl acetal) resin may include at least about 15, at least about 20, at least about 30, at least about 40, at least about 50, at least about 60, at least about 70, at least about 80, at least about 90, at least about 95, or at least about 99 weight percent of residues of an aldehyde other than n-butyraldehyde, based on the total weight of aldehyde residues of the polyvinyl acetal) resin.
  • This resin may also include 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 n- butyraldehyde, based on the total weight of aldehyde residues of the polyvinyl acetal) resin.
  • the polyvinyl acetal) resin includes residues of one or more aldehydes other than n-butyraldehyde
  • any suitable aldehyde can be used.
  • the aldehyde other than n-butyraldehyde can comprise, for example, an aldehyde having between 3 and 12 carbon atoms per molecule (i.e., a C 3 to C-
  • the aldehyde can include 8 or fewer carbon atoms per molecule, 6 or fewer carbon atoms per molecule, or 4 or fewer carbon atoms per molecule. In other embodiments, the aldehyde can have more than 4 carbon atoms per molecule, more than 5 carbon atoms per molecular, or more than 6 carbon atoms per molecule.
  • the aldehyde other than n-butyraldehyde may be an aliphatic aldehyde and can be either a branched or a straight chain molecule.
  • suitable aldehydes other than n-butyraldehyde can include, but are not limited to, i-butyraldehyde, 2-methylvaleraldehyde, n-hexyl aldehyde, 2-ethylhexyl aldehyde, n-octyl aldehyde, and combinations thereof.
  • the aldehyde other than n-butyraldehyde can be selected from the group consisting of i-butyraldehyde, 2-methylbutyraldehyde, 2-ethylhexyl aldehyde, and combinations thereof, while, in some embodiments, the aldehyde other than n-butyraldehyde can be selected from the group consisting of i-butyraldehyde, 2-ethylhexyl aldehyde, and combinations thereof.
  • the resin composition, layer, or interlayer may also include a polyvinyl acetal) resin comprising residues of n-butyraldehyde.
  • these residues of n- butyraldehyde may be present in the same resin having residues of an aldehyde other than n-butyraldehyde, thereby forming a single "hybrid" resin with multiple aldehyde residues.
  • the n-butyraldehyde residues may be present on a second polyvinyl acetal) resin physically blended with the first polyvinyl acetal) resin that includes residues of an aldehyde other than n-butyraldehyde, and the blend can be present in the composition, layer, or interlayer.
  • an equivalent single hybrid polyvinyl acetal) resin also exists that may be substituted for the blend with similar results.
  • the residues of the aldehyde other than n-butyraldehyde and the residues of n-butyraldehyde may each be present in the resin in an amount of at least about 1 , at least about 2, 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, or at least about 45 percent, based on the total weight of the aldehyde residues of the single resin.
  • the combined amount of these two residues can comprise at least about 40, at least about 50, at least about 60, at least about 70, at least about 80, or at least about 90 percent of the total weight of the aldehyde residues of the resin.
  • the ratio, by weight, of residues of the aldehyde other than n-butyraldehyde to the n-butyraldehyde residues can be at least about 1 :99, at least about 5:95, at least about 10:90, at least about 15:85, 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, not more than about 60:40, or in the range of from about 1 :99 to about 99:1 , about 5:95 to about 95:5, about 10:90 to about 90:10, about 15:
  • each of the polyvinyl acetal) resins may be present in the composition, layer, or interlayer in an amount of at least about 1 , at least about 2, 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 total weight of the resins in the composition.
  • the combined amount of the first and second polyvinyl acetal) resins can make up at least about 40, at least about 50, at least about 60, at least about 70, at least about 80, or at least about 90 percent of the total weight of the resins in the composition, layer, or interlayer.
  • the ratio, by weight, of the first polyvinyl acetal) resin to the second polyvinyl acetal) resin can be in the range of from about 1 :99 to 99:1 , about 5:95 to 95:5, about 10:90 to 90:10, about 15:85 to 85:15, about 25:75 to 75:25, about 30:70 to 70:30, or about 40:60 to 60:40.
  • the first polyvinyl acetal) resin which can include residues of an aldehyde other than n-butyraldehyde, can be present in the composition, layer, or interlayer in an amount of at least about 1 , at least about 5, at least about 10, at least about 15, at least about 25, at least about 30, or at least about 40 weight percent, based on the combined weight of the first and second resins.
  • the polyvinyl acetal) resins described herein may also include residual hydroxyl and/or residual acetate groups.
  • residual hydroxyl content and “residual acetate content” refer to the amount of polyvinyl hydroxyl and polyvinyl 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.
  • one or more of the polyvinyl acetal) resins present in a composition, layer, or interlayer may 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 23, not more than about 22, not more than about 21 .5, not more than about 21 , not more than about 20.5, not more than about 20, not more than about 19.5, not more than about 19, not more than about 18.7 weight percent, measured as described previously.
  • the residual hydroxyl content can be 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 20, or about 19.5 to about 21 weight percent.
  • At least one polyvinyl acetal) resin can have a residual hydroxyl content of at least about 8, at least about 8.5, at least about 9, at least about 9.5 weight percent and/or not more than about 13, not more than about 12.5, not more than about 12, not more than about 1 1 .5, not more than about 1 1 , 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 13, about 9 to about 12, or about 9.5 to about 1 1 .5 weight percent.
  • one or more of the resins can have a residual hydroxyl content different from the residual hydroxyl content of one or more of the other resins.
  • a resin composition, layer, or interlayer includes a first polyvinyl acetal) resin and a second polyvinyl acetal) resin
  • at least one of the resins can have a residual hydroxyl content that is at least 2 weight percent different than the other.
  • One or both resins can include residues of an aldehyde other than n- butyraldehyde as described previously.
  • weight percent refers to a difference between two given weight percentages, calculated by subtracting one number from the other number.
  • a polyvinyl acetal) resin having a residual hydroxyl content of 12 weight percent and a polyvinyl acetal) resin having a residual hydroxyl content of 14 weight percent have a weight percent difference of 2.
  • the residual hydroxyl content of one polyvinyl acetal) resin can be at least about 3, at least about 4, at least about 6, or at least about 8 weight percent higher or lower than the residual hydroxyl content of another.
  • the difference between the residual hydroxyl content of one of the polyvinyl acetal) resins and the residual hydroxyl content of another of the polyvinyl acetal) resins in the compositions, layers, and interlayers described herein can be at least about 10, at least about 12, at least about 15, at least about 20, or at least about 30 weight percent.
  • the difference in residual acetate contents between two of the resins can be at least about at least about 2, at least about 4, at least about 6, at least about 8, at least about 10, at least about 12 and/or not more than about 30, not more than about 20, not more than about 15, or not more than about 10 weight percent, or the difference can be in the range of from about 2 to about 30, about 4 to about 20, about 6 to about 15, or about 8 to about 10 weight percent.
  • At least one of the polyvinyl acetal) resins described herein can 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 previously.
  • at least another of the polyvinyl acetal) resins may have a residual acetate content of at least about 8, at least about 10, at least about 12, at least about 14, at least about 16, at least about 18, or at least about 20 weight percent.
  • the first and second polyvinyl acetal) resins may be blended such that one of the first and second polyvinyl acetal) resins is dispersed within the other of the first and second polyvinyl acetal) 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 42, at least about 45, at least about 50, at least about 55, at least about 60, at least about 65, at least about 70 parts per hundred parts of resin (phr) and/or not more than about 120, not more than about 1 10, 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
  • 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 the 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.
  • the plasticizer may be present in an amount of at least about 42, at least about 45, at least about 50, at least about 55, at least about 60, at least about 65, or at least about 70 phr, while, in some embodiments, the plasticizer may be present in an amount of not more than about 50, not more than about 45, not more than about 42, not more than about 40, not more than about 38, not more than about 35, not more than about 30, not more than about 30, not more than about 25, not more than about 20, not more than about 17, not more than about 15, not more than about 12, or not more than about 10 phr.
  • 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”),
  • the plasticizer may be selected from the group consisting of triethylene glycol di- (2-ethylhexanoate), tetraethylene glycol di-(2-ethylhexanoate), and
  • At least two plasticizers may be present in the compositions, layers, and interlayers described herein, with one of the plasticizers enhancing the compatibility of one or more other
  • the refractive index, measured according to ASTM D542 at a wavelength of 589 nm and 25 °C, of one or all plasticizers in the composition can be at least about 1 .440, at least about 1 .442, at least about 1 .445 and/or not more than about 1 .500, not more than about 1 .475, not more than about 1 .460, not more than about 1 .455, or not more than about 1 .450, or in the range of from about 1 .440 to about 1 .500, about 1 .442 to about 1 .475, about 1 .445 to about 1 .460.
  • One or more resin compositions, 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 (LaB 6 ) 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, 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 (LaB
  • 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, residual 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.
  • the differences may 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 can facilitate increased 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 13 weight percent, can improve the acoustic performance of the interlayer or blend.
  • 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.
  • 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 resin layer that exhibits a lower glass transition temperature than a similar resin having a higher residual hydroxyl content.
  • plasticizer Depending on the specific resin and plasticizer, however, these trends could be reversed.
  • the plasticizer may partition between the resin 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.
  • the resin layer or interlayer when the resin layer or interlayer includes at least a first resin layer comprising a first polyvinyl acetal) resin and a first plasticizer, and a second resin layer, adjacent to the first resin layer, comprising a second polyvinyl acetal) resin and a second plasticizer, the resin layers may have different plasticizer contents.
  • the difference in plasticizer content between the resin 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 resin 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 resin layers may be not more than about 30, not more than about 25, not more than about 20, or not more than about 17 phr.
  • the first and second resin layers can exhibit different glass transition temperatures.
  • Glass transition temperature or T g
  • 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 (DTMA).
  • the DTMA measures the storage (elastic) modulus (G') in Pascals, loss (viscous) modulus (G") in Pascals, and the tan delta (G7G') of the specimen as a function of temperature at a given frequency and temperature sweep rate.
  • the glass transition temperature was then determined by the position of the tan delta peak on the temperature scale.
  • Glass transition temperatures provided herein were determined at a frequency of 1 Hz and a sweep rate of 3°C/min.
  • the difference in the glass transition temperature of the first resin layer and the glass transition temperature of the second resin 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 resin layers can have a glass transition temperature of at least about 25, at least about 27, at least about 30, at least about 33, at least about 35, at least about 37 °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 25 to about 70, about 27 to about 60, about 35 to about 50.
  • the other of the first and second polyvinyl acetal) resins can have a glass transition temperature of less 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 2, not more than about 1 , not more than about 0, not more than about -1 , not more than about -2°C.
  • resin compositions, layers, and interlayers as described herein that include at least one polyvinyl acetal) resin having residues of an aldehyde other than n- butyraldehyde may exhibit different properties, such as, for example, glass transition temperature, refractive index, and tan delta, as compared to similar resin compositions, layers, and interlayers formed using conventional polyvinyl n-butyral) resins.
  • polyvinyl acetal) resins including residues of aldehydes other than n-butyraldehyde may have a different molecular weight than a comparable polyvinyl n-butyral) resin.
  • the term "comparable polyvinyl n-butyral) resin” refers to a polyvinyl acetal) resin having the same residual acetal, residual hydroxyl, and acetate content as a given polyvinyl acetal) resin, but that includes an acetal component including only residues of n-butyraldehyde.
  • the polyvinyl acetal) resin that includes residues of an aldehyde other than n-butyraldehyde can have a molecular weight that is at least about 5, at least about 10, at least about 15, or at least about 20 percent higher or lower than the molecular weight of a comparable polyvinyl n- butyral) resin.
  • the molecular weight of the polyvinyl acetal) resin including residues of an aldehyde other than n-butyraldehyde can be lower than a comparable polyvinyl n-butyral) resin.
  • the molecular weight of polyvinyl acetal) resins comprising residues of an aldehyde other than n-butyraldehyde may be at least about 10,000, at least about 15,000, at least about 20,000, at least about 25,000 and/or not more than about
  • 250,000 not more than about 200,000, not more than about 150,000, not more than about 100,000, or not more than about, or less than about, 50,000 Daltons, or in the range of from about 10,000 to about 250,000, about 15,000 to about 200,000, about 20,000 to about 150,000, or about 25,000 to about 50,000 Daltons.
  • a polyvinyl n-butyral (PVB) resin may have a molecular weight of at least about 50,000, at least about 70,000, at least about 80,000, at least about 90,000, 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, not more than about 425,000, or not more than about 325,000 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 the weight average molecular weight (M w ).
  • the molecular weight of the PVB resin can be in the range of from about 50,000 to about 600,000, about
  • polyvinyl acetal) resin having residues of an aldehyde other than n-butyraldehyde can have higher compatibility with a plasticizer than a comparable polyvinyl n-butyral) resin.
  • Higher compatibility of a polyvinyl acetal) resin in a given plasticizer can be measured as the cloud point of the resin in that plasticizer.
  • cloud point refers to the temperature at which a dissolved solid is no longer completely soluble in a liquid. Cloud point is measured by mixing 0.05 grams of resin with 1 .95 grams of a plasticizer at room temperature and then heating the mixture in a silicone oil bath under continuous stirring conditions until the resin is completely dissolved and the solution is clear. The heating is then stopped and the temperature continuously monitored. The temperature at which the solution begins to cloud, which indicates
  • polyvinyl acetal) resins that include residues of an aldehyde other than n-butyraldehyde can have a lower cloud point than a comparable polyvinyl n-butyral) resin in one or more plasticizers. For these plasticizers, this indicates higher compatibility with the plasticizer than a comparable polyvinyl n-butyral) resin.
  • the polyvinyl acetal) resin comprising residues of an aldehyde other than n- butyraldehyde can have a cloud point temperature that is at least about 1 , at least about 2, at least about 5, or at least about 10°C lower than the cloud point temperature of a comparable polyvinyl n-butyral) resin in a given plasticizer.
  • the plasticizer can be one or more of those listed above.
  • polyvinyl acetal) resins comprising residues of an aldehyde other than n-butyraldehyde may have a lower viscosity than a comparable polyvinyl n-butyral) resin.
  • the viscosity of a polyvinyl acetal) resin comprising residues of an aldehyde other than n-butyraldehyde can be at least about 5, at least about 10, at least about 15, or at least about 20 percent lower than the viscosity of a
  • the viscosity of a polyvinyl acetal) resin comprising residues of an aldehyde other than n-butyraldehyde can be at least about 5, at least about 10, at least about 15, at least about 20, or at least about 30 centipoise (cps) lower than the viscosity of a comparable polyvinyl n-butyral) resin.
  • a polyvinyl acetal) resin comprising residues of an aldehyde other than n-butyraldehyde may also have a glass transition temperature that is different than the glass transition temperature of a comparable polyvinyl butyral) resin.
  • the glass transition temperature of the polyvinyl acetal) resin including residues of an aldehyde other than n-butyraldehyde can be at least about 5, at least about 10, at least about 15, at least about 20, or at least about 25 percent higher or lower than the glass transition temperature of a comparable polyvinyl n-butyral) resin.
  • the glass transition temperature of the polyvinyl acetal) resin comprising residues of an aldehyde other than n-butyraldehyde 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 5, at least about 6, at least about 10, or at least about 12°C higher or lower than the glass transition temperature of a comparable polyvinyl n- butyral) resin.
  • the polyvinyl acetal) resin including residues of an aldehyde other than n-butyraldehyde may have a glass transition temperature of not more than about 83, not more than about 82, not more than about 80, not more than about 75, not more than about 70, not more than about 65, not more than about 60, or not more than about 55 °C, while in other embodiments, the glass transition temperature of the polyvinyl acetal) resin comprising residues of an aldehyde other than n-butyraldehyde can be at least about 80, at least about 82, at least about 83, at least about 84, at least about 85, or at least about 86 °C, measured as described previously.
  • polyvinyl acetal) resins When two or more polyvinyl acetal) resins are present in a composition, layer, or interlayer, the difference in glass transition temperature between one of the resins and at least one or more other resins can be at least about 2, at least about 5, at least about 10, or at least about 15°C.
  • polyvinyl acetal) resins comprising residues of an aldehyde other than n-butyraldehyde may also have a refractive index different than a comparable polyvinyl n-butyral) resin. Refractive index was measured according to ASTM D542 at a wavelength of 589 nm and 25 °C.
  • the refractive index of a polyvinyl acetal) resin comprising residues of an aldehyde other than n-butyraldehyde can be at least about 0.001 , at least about 0.002, at least about 0.003, at least about 0.004, at least about 0.005 and/or not more than about 0.010, not more than about 0.007, or not more than about 0.006 higher or lower than the refractive index of a comparable polyvinyl butyral) resin, or the difference can be in the range of from about 0.001 to about 0.010, about 0.002 to about 0.007, or about 0.003 to about 0.006.
  • the refractive index of the polyvinyl acetal) resin comprising residues of an aldehyde other than n-butyraldehyde can be at least about 1 .480, at least about 1 .481 , at least about 1 .482, at least about 1 .483, or at least about 1 .484.
  • the refractive index of the polyvinyl acetal) resin including residues of an aldehyde other than n- butyraldehyde can be not more than about 1 .490, not more than about 1 .489, not more than about 1 .488, not more than about 1 .487, not more than about 1 .486, not more than about 1 .485, not more than about 1 .484, not more than about 1 .483, not more than about 1 .482, not more than about 1 .481 , or not more than about 1 .480.
  • the refractive index of the polyvinyl acetal) resin comprising residues of an aldehyde other than n-butyraldehyde can be in the range of from about 1 .480 to about 1 .490, about 1 .482 to about 1 .489, or about 1 .483 to about 1 .488.
  • polyvinyl acetal resins comprising residues of an aldehyde other than n-butyraldehyde may, in some
  • polyvinyl acetal) resin component refers either to an individual polyfvinyl acetal) resin present in a blend of resins or to an acetal moiety present on a single polyfvinyl acetal) resin.
  • a blend of first and second polyfvinyl acetal) resin components may not only exhibit properties different than each individual component, but may also exhibit properties unexpected for the combination.
  • a resin composition may comprise a first polyvinyl acetal) resin component and a second polyvinyl acetal) resin component.
  • the second polyvinyl acetal) resin component can have a second value B, for the same selected resin property.
  • the values, A and B, for the selected resin property correspond to the values for that property exhibited by a polyvinyl acetal) resin including only residues of that aldehyde.
  • the value, A, for the selected resin property for the first polyvinyl acetal) resin component would be the value of that property for a polyvinyl acetal) resin including only residues of i-butyraldehyde.
  • the selected resin property can be any measurable property of a polyvinyl acetal) resin. Examples of resin properties can include, but are not limited to, glass transition temperature, tan delta, refractive index, viscosity, melt flow, impact resistance, and others. In some embodiments, the resin property can be selected from the group consisting of glass transition temperature, tan delta, refractive index, and viscosity.
  • the resin composition which includes the first and second polyvinyl acetal) resin components, which may be present in the composition in respective amounts of Y and Z weight percent, can have an actual value, C, for the selected resin property that is not equal to a value within about 15, within about 10, or within about 5 percent of the calculated value, C, calculated by equation (1 ), below.
  • the actual value, C, of the selected resin property for the resin composition can be closer to the value, A, of the selected resin property of the first polyfvinyl acetal) resin component such that the absolute value of the difference between A and C is less than the absolute value of the difference between C and B.
  • the actual value, C, of the selected resin property can be closer to the value, B, of the selected resin property of the second polyfvinyl acetal) resin component such that the absolute value of the difference between B and C is less than the absolute value of the difference between C and A.
  • first and second polyvinyl acetal) resin components can have respective first and second values, R and S, for another resin property and the resin composition may have a value, T, for the other property.
  • At least one resin property may have an actual composition value that falls within about 15, within about 10, within about 5, within about 2, or may equal the calculated value, T, determined by equation (2), above.
  • the values for R, S, and T may be substantially the same, such that each value is within about 15, within about 10, or within about 5 percent of each of the others.
  • the first and second polyvinyl acetal) resin components and the resin composition may include one or more other properties that fall within one of the ranges described previously.
  • the first polyvinyl acetal) resin component, second polyvinyl acetal) resin component, and/or resin composition may have values for other resin properties, including glass transition temperature and viscosity, that fall within one or more of the ranges provided previously.
  • a resin layer or interlayer includes at least one polyvinyl acetal) resin including residues of an aldehyde other than n- butyraldehyde
  • the layer or interlayer may also exhibit unexpected or enhanced properties, as compared to a comparable resin layer formed from a polyvinyl n-butyral) resin and a plasticizer of the same type and in the same amount.
  • the term "comparable polyvinyl n-butyral) resin layer” refers to a resin layer formed using a comparable polyvinyl n-butyral) resin, as defined previously, and a plasticizer of the same type and in the same amount as a given layer.
  • a resin layer that includes at least one polyvinyl acetal) resin having residues of an aldehyde other than n-butyraldehyde can have a different glass transition temperature than a comparable polyvinyl n-butyral) resin layer.
  • the glass transition temperature of a resin layer including a polyvinyl acetal) resin having residues of an aldehyde other than n-butyraldehyde can be at least about 0.25, at least about 0.50, at least about 1 , at least about 1 .5, at least about 2, at least about 3, at least about 4, or at least about 5°C higher or lower than the glass transition temperature of a comparable polyvinyl n-butyral) resin layer.
  • the glass transition temperature of the resin layer that comprises a polyvinyl acetal) resin having residues of an aldehyde other than n-butyraldehyde can be at least about 25, at least about 30, at least about 35, or at least about 37°C, while, in some embodiments, it may be less 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, not more than about 1 , not more than about 0, not more than about -1 , not more than about - 2°C, measured as described previously.
  • the resin layer may have a high glass transition temperature, such as, for example a glass transition temperature of greater than about 46 °C.
  • Such a resin layer which may also be used as a single-layer interlayer or may be combined with one or more other layers to form a dual-layer interlayer or a multilayer interlayer comprising three or more layers, may be used in applications requiring high levels of impact resistance or strength.
  • such an interlayer may be formed by combining at least one polyvinyl acetal) resin comprising at least 10 weight percent of residues of an aldehyde other than n-butyraldehyde and a plasticizer.
  • the plasticizer may be present in the composition in an amount to provide the resin layer with a glass transition temperature greater than 46 °C such as, for example, an amount of at least about 1 , at least about 2, at least about 5 phr and/or not more than about 30, not more than about 25, not more than about 20 phr, not more than about 15 phr, or not more than about 10 phr, or an amount in the range of from about 1 to about 30, about 2 to about 25, about 5 to about 15, about 5 to about 30, or about 5 to about 20 phr.
  • the glass transition temperature of the layer or interlayer can be at least about 30, at least about 37, at least about 40, at least about 46, at least about 48, at least about 50, at least about 52, at least about 54, at least about 55, at least about 60, at least about 65, or at least about 70 °C.
  • such layers and interlayers may be utilized in a multiple layer panel with at least one rigid substrate, examples of which are provided below.
  • the rigid substrate may be any transparent, rigid substrate.
  • the rigid substrate may be a glass substrate, such as, for example, a glass substrate may be selected from the group consisting of flat glass, float glass, warped glass, wavy glass, tempered glass, heat-strengthened glass, bent glass, chemically tempered glass, and combinations thereof.
  • the glass substrate may be selected from the group consisting of warped glass, wavy glass, tempered glass, heat-strengthened glass, bent glass, and combinations thereof. Additional embodiments of multiple layer panels, including one or more different types of rigid substrates will be discussed in detail shortly.
  • Resin layers that include at least one polyvinyl acetal) resin including residues of an aldehyde other than n-butyraldehyde can also exhibit enhanced optical properties such as, for example, refractive index.
  • the refractive index of a resin layer including at least one polyvinyl acetal) resin including residues of an aldehyde other than n- butyraldehyde can be at least about 0.001 , at least about 0.002, at least about 0.003, at least about 0.004, at least about 0.005 and/or not more than about 0.010, not more than about 0.007, or not more than about 0.006 higher or lower than the refractive index of a comparable polyvinyl n-butyral) resin layer.
  • the difference between the refractive index of a resin layer including at least one polyvinyl acetal) resin including residues of an aldehyde other than n-butyraldehyde and the refractive index of a comparable polyvinyl n-butyral) resin layer can be in the range of from 0.001 to about 0.010, about 0.002 to about 0.007, or about 0.003 to about 0.006.
  • the refractive index of the resin layer that includes at least one polyvinyl acetal) resin having residues of an aldehyde other than n-butyraldehyde can be at least about 1 .470, at least about 1 .471 , at least about 1 .472, at least about 1 .473, at least about 1 .474, at least about 1 .475, at least about 1 .476, at least about 1 .477, at least about 1 .480 and/or not more than about 1 .490, not more than about 1 .489, not more than about 1 .488, not more than about 1 .487, not more than about 1 .486, not more than about 1 .485, not more than about 1 .484, not more than about 1 .483, not more than about 1 .482, not more than about 1 .481 , not more than about 1 .480, or not more than about 1 .479, or not more than about 1 .470, at least about 1
  • the refractive index of the resin layer having residues of an aldehyde other than n-butyraldehyde can be in the range of from about 1 .470 to about 1 .490, about 1 .572 to about 1 .488, about 1 .475 to about 1 .486, about 1 .477 to about 1 .485, about 1 .480 to about 1 .484.
  • the resin layer including at least one polyvinyl acetal) resin having residues of an aldehyde other than n- butyraldehyde may also exhibit enhanced acoustic properties, such as, for example, an improved tan delta as compared to a comparable polyvinyl n- butyral) resin layer.
  • 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 DTMA 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 G7G' curve at the glass transition temperature is the tan delta value. Higher tan delta values are indicative of higher damping, which can translate to better sound dampening, or acoustic, performance.
  • the tan delta of the resin layer including at least one polyvinyl acetal) resin having residues of an aldehyde other than n-butyraldehyde can be at least about 1 , at least about 2, at least about 3, at least about 4, at least about 5, at least about 10, at least about 15, or at least about 20 percent higher than the tan delta of a comparable polyvinyl n-butyral) resin.
  • the tan delta of the resin layer comprising the polyvinyl acetal) resin including residues of an aldehyde other than n- butyraldehyde can be at least about 0.70, at least about 1 .0, at least about 1 .05, at least about 1 .10, at least about 1 .15, at least about 1 .20, at least about 1 .25, at least about 1 .30, at least about 1 .35, or at least about 1 .40, measured as described previously.
  • the resin layer or interlayer includes at least a first polyvinyl acetal) resin component and a second polyvinyl acetal) resin component along with at least one plasticizer
  • one or more properties of the layer or interlayer can be different than expected.
  • the resin layer which may include x phr of a plasticizer along with Y weight percent of a first polyvinyl acetal) resin component and Z weight percent of a second polyvinyl acetal) resin component, may also have an actual value, D, for at least one resin layer property that is not equal to the calculated value, D', determined by equation (3) below.
  • E is the value of the selected layer property for a resin layer formed from a resin including only the first polyvinyl acetal) resin component and phr of the plasticizer and F is the value of the selected resin layer property for a resin layer formed from a resin including only the second polyvinyl acetal) resin component and phr of the plasticizer.
  • Examples of resin layer properties can include, but are not limited to, glass transition temperature, refractive index, and tan delta. Values for these properties may fall within the ranges provided above. Additionally, the amount of plasticizer present in the resin composition can fall within any of the ranges above.
  • the resin layer may also have at least one other actual resin layer value that is not equal to a value within about 15, within about 1 0, or within about 5 percent of the calculated value, D', determined by equation (3) above and/or may have at least one other actual resin layer value that falls within about 1 5, within about 1 0, within about 5, within about 2, or is equal to the calculated value D' determined by equation (3) above.
  • E and F may both have a value within about 15, within about 1 0, or within about 5 percent of the actual resin layer value D.
  • a method of making a polymer interlayer comprises selecting and blending at least a first polyvinyl acetal) resin or precursor thereto, and a second polyvinyl acetal) resin or precursor thereto, in order to provide a blended resin composition, layer, or interlayer having desirable final properties.
  • the method can include the step of identifying at least one resin layer property, including, for example, one or more properties selected from the group consisting of glass transition temperature, refractive index, viscosity, tan delta, impact resistance, melt flow, and combinations thereof.
  • the target value for one or more resin layer properties can fall within at least one of the ranges provided previously.
  • the method may also include the step of selecting and blending at least a first polyvinyl acetal) resin component and a second polyvinyl acetal) resin component to provide a blended resin composition.
  • the type and amount of the first and second polyvinyl acetal) resin, or precursors thereto, can be any of those described herein and, in some embodiments, may be any of those described herein.
  • the blending can comprise a melt blending step and may be performed at a temperature of at least about 150, at least about 200, at least about 250 °C .
  • the blending step may include mixing a first and a second aldehyde and using the mixed aldehyde to form a blended resin.
  • the aldehydes can be mixed prior to forming the resin, such that a mixed aldehyde is reacted with the polyvinyl alcohol).
  • at least a portion of the blending of the aldehydes may take place during acetalization.
  • the formation of the blended resin may be carried out as described previously. Thereafter, at least one resin layer may be formed using the blended resin, optionally combined with one or more plasticizers of types and in amounts as discussed previously.
  • the types and/or amounts of the first and second polyvinyl acetal) resin components, or precursors thereto, may be selected in order to achieve a value for the selected resin layer property that is within about 20, within about 10, within about 5, or within about 2 percent of the target value identified previously.
  • the blending may be performed to produce a blended resin with a lower glass transition temperature than a comparable polyvinyl n-butyral) resin so that less plasticizer is required to achieve a given glass transition temperature or certain acoustic property for the final layer.
  • the blending may be performed to produce a blended resin having a higher or lower refractive index than a comparable polyvinyl n- butyral) resin in order to minimize dilution by a lower refractive index additive or to minimize the difference between the refractive indices of two resin layers.
  • a blended resin having a higher or lower refractive index than a comparable polyvinyl n- butyral) resin in order to minimize dilution by a lower refractive index additive or to minimize the difference between the refractive indices of two resin layers.
  • Other applications or uses for blending the polyvinyl acetal) resins, or precursors thereto, are also possible and may be utilized according to various embodiments of the present invention.
  • the resulting blended resins can then be formed into one or more resin 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 resin 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
  • 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 e.g., colorants
  • UV inhibitors e.g., UV inhibitors
  • 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 resin 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 interlayers may also exhibit one or more improved or enhanced properties.
  • the interlayers can comprise single, or monolithic, interlayers, or dual-layer interlayers having a pair of adjacent resin layers.
  • the interlayers can include three or more resin layers with at least a first, second, and third resin layer, with the second resin layer sandwiched between the first and third.
  • adjacent resin layers can comprise different polyvinyl acetal) resins, and can have one or more properties that differ from each other.
  • the polyvinyl acetal) resins present in adjacent layers may have different residual hydroxyl and/or acetal contents that differ from each other by an amount within the ranges provided above.
  • adjacent resin layers may have different glass transition temperatures, such as, for example, glass transition temperatures that differ from one another by 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.
  • the difference between the refractive index of the adjacent layers may be minimized by, for example, utilizing at least one polyvinyl acetal) resin comprising residues of an aldehyde other than n- butyraldehyde.
  • the absolute value of the difference between refractive indices between adjacent resin layers, of which at least one includes a polyvinyl acetal) resin comprising residues of an aldehyde other than n-butyraldehyde can be not more than about 0.010.
  • the absolute value of the difference in the refractive indices between such layers can be 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, not more than about 0.003, or not more than about 0.002.
  • interlayers according to various embodiments of the present invention exhibit optimized or enhanced optical properties.
  • 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 D1003-61 (reapproved 1977) - Procedure A using llluminant C, at an observer angle of 2 degrees. The test is performed with a hazemeter, such as a Model D25 Hazemeter
  • % T V i S percent visual transmittance
  • the resin compositions, layers, and interlayers of the present invention can have a percent visual transmittance of 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 resin layers and interlayers described herein may also exhibit acoustic properties within a desirable range.
  • the resin 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
  • the resin compositions, layers, and interlayers according to embodiments of the present invention may be utilized in a multiple layer panel that comprises a resin layer or interlayer and at least one rigid substrate.
  • Any suitable rigid substrate may be used and in some embodiments may be selected from the group consisting of glass, polycarbonate, biaxially oriented PET, copolyesters, acrylic, and combinations thereof.
  • the rigid substrate includes glass
  • the glass can be selected from the group listed previously.
  • the rigid substrate includes a polymeric material
  • the polymeric material may or may not include a hard coat surface layer.
  • the multilayer panels include a pair of rigid substrates with the resin interlayer disposed therebetween. The panels 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 combinations thereof.
  • 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
  • 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 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)
  • acetalizing polyvinyl alcohol with several different aldehydes having acetal chain lengths from 4 to 8 carbon atoms.
  • Each resin was prepared by first dispersing polyvinyl alcohol) powder in water in a 5-L glass reactor at ambient temperature. The resulting slurry was then heated to a temperature greater than 90 °C to dissolve the polyvinyl alcohol) and the resulting solution was then cooled to ambient temperature. Upon addition of an aldehyde and an acid catalyst, polyvinyl acetal) polymer precipitated within a few minutes. The resulting mixture was held for several hours in order to achieve the target conversion of the polyvinyl alcohol) and, if necessary, the reaction mixture was heated to speed the conversion.
  • n-butyraldehyde nBuCHO
  • i-butyraldehyde iBuCHO
  • 2-methylbutyraldehyde 2MeBuCHO
  • 2-methylvaleraldehyde 2MeValCHO
  • 2-ethylhexanaldehyde 2EHCHO
  • FIG. 1 provides a graphical representation of the tan delta of several of the resins listed in Table 1 as a function of temperature.
  • polyvinyl acetal resins can be produced that have similar refractive indices and residual hydroxyl contents, but different glass transition temperatures. Additionally, as shown in Table 1 , polyvinyl acetal) resins having similar refractive indices may have
  • Table 4 lists several combinations of high and low glass transition temperature resins shown in Table 3a and 3b above suitable as respective skin and core layers in multilayer interlayers.
  • a Comparative Interlayer, CI-1 included a resin layer having a high glass transition temperature polyvinyl n-butyral) resin (R-1 ) adjacent to a resin layer having a low glass transition temperature polyvinyl n-butyral) resin (R-2).
  • R-1 high glass transition temperature polyvinyl n-butyral
  • R-2 low glass transition temperature polyvinyl n-butyral
  • Disclosed Interlayers DI-1 through DI-5 had a maximum difference in refractive index of 0.006 (DI-1 and DI-2), with a difference as low as 0.002 (DI-5).
  • Disclosed Interlayers DI-1 through DI-5 had a smaller difference in refractive index than Comparative Interlayer CI-1 , which translated to fewer optical defects in the final laminated product.
  • Disclosed Interlayers DI-1 through DI-5 had similar differences in glass transition temperature between the skin and core layers as Comparative Interlayer CI-1 , and, as a result, the Disclosed Interlayers retain the strength and acoustic properties of Comparative Interlayer CI-1 , while exhibiting improved optical qualities.
  • Example 4 Properties of Mixed Polyvinyl acetal) Resins
  • Two polyvinyl acetal) resins, R-10 and R-1 1 were formed as described in Example 1 , above, using n-butyraldehyde and i- butyraldehyde, respectively.
  • the resulting polyvinyl n-butyral) (PVB) resin (R-10) and polyvinyl i-butyral) (PViB) resin (R-1 1 ) were then divided into several portions and melt blended with varying amounts of 3GEH.
  • An additional polyvinyl acetal) resin (R-12) was formed by mixing and melt blending 50 weight percent of polyvinyl n-butyral) resin R-10 and 50 weight percent of polyvinyl i-butyral) resin R-1 1 .
  • Mixed resin R-12 was also divided into several portions and combined with varying amounts of 3GEH. The refractive index of each plasticized resin sample was measured and the results, shown as a function of plasticizer content, are depicted graphically in FIG. 3.
  • polyvinyl i-butyral) resin R-1 1 exhibited the lowest refractive index of the three resins tested and, unlike the other two resins, it maintained a substantially constant refractive index up to a plasticizer loading of about 20 phr. Additionally, as shown in FIG. 3, none of the resins exhibited a strictly linear relationship between plasticizer loading and refractive index. For each plasticizer loading, blended resin R-12 had a refractive index between the refractive indices of its component resins, although the value was not an arithmetic average of the two.
  • Another mixed polyvinyl acetal) resin (R-13) was formed in a similar manner as described in Example 1 , above, but with a mixed aldehyde that included equal weights of i-butyraldehyde and n-butyraldehyde.
  • the resulting hybrid resin R-13 had an acetal component that included moieties of both i-butyraldehyde and n-butyraldehyde and exhibited a similar trend in refractive index as a function of plasticizer loading as the physically blended resin R-12.
  • PVB Polyvinyl n-butyral
  • PV2EH polyvinyl 2-ethylhexanal
  • resins such as PVB and PV2EH can be formulated into a mixed polyvinyl acetal) resin that exhibits different glass transition temperatures over a wide blending range, but that have substantially the same refractive index.
  • a polyvinyl n-butyral) resin (R-33) was prepared by acetalizing a 98 to 98.8 percent hydrolyzed polyvinyl alcohol) (PVOH) with n- butyraldehyde (BuCHO) according to the procedure described in Example 1 , above.
  • the PVOH had a viscosity between 28 and 32 cps, measured in 4 percent water at 20 °C.
  • a polyvinyl i-butyral resin) (R-34) was prepared under exactly the same conditions, but with i-butyraldehyde (iBuCHO).
  • polyfvinyl i-butyral resins R- 34 and R-36 exhibited a lower viscosity than the polyfvinyl n-butyral) resins R- 33 and R-35 prepared with the same polyfvinyl alcohol) under identical conditions. Additionally, the polyvinyl i-butyral) resin (R-34) exhibited a higher glass transition temperature than its comparable polyvinyl n-butyral) resin (R-33, even when plasticized with 38 phr of 3GEH.
  • Example 7 Preparation of High Glass Transition Temperature Resins
  • Several polyvinyl acetal) resins were formulated according to the procedure described above in Example 1 .
  • Three of the resins were formulated using i-butyraldehyde (R-38 through R-40) and one was formed with n-butyraldehyde (R-37).
  • R-38 through R-40 i-butyraldehyde
  • R-37 n-butyraldehyde
  • Each of the resins was combined with a different amount of 3GEH plasticizer and formed into sheets. The glass transition temperature of each sheet was determined and the results are summarized in Table 9, below.
  • the polyvinyl i-butyral) resin R-38 achieves a higher glass transition temperature than the polyvinyl n-butyral) resin R-37. Additionally, lower levels of plasticizer in the polyvinyl i-butyral) resins R-38 through R-40 results in increased glass transition temperature, which provides these resins with increased impact and penetration resistance.
  • Example 8 Plasticizer Compatibility of Polyvinyl acetal) Resin Layers
  • the tan delta of resin R-42 was also nearly 18 percent higher than the tan delta of resin R-41 , which included the same type and amount of plasticizer, but had a higher residual hydroxyl content than resin R- 42.
  • Example 10 Tan Delta and Glass Transition Temperature of Polyvinyl acetal) Resins
  • Two polyvinyl acetal) resins R-45 and R-46 were prepared according to the procedure described in Example 1 . Both were prepared under identical conditions and both had residual hydroxyl contents of approximately 9.1 weight percent. However, resin R-45 was a polyvinyl i- butyral) resin, formed using i-butyraldehyde, and resin R-46 was a polyvinyl n-butyral), formed using n-butyraldehyde. Resin R-46 was mixed and melt blended with 3GEH plasticizer to produce a plasticized resin having a glass transition temperature of 2.23 °C.
  • resins such as resin R-45, that include residues of aldehydes other than n-butyraldehyde, require higher plasticizer loadings and exhibit higher glass transition temperatures than similar resins that only include residues of n-butyraldehyde.
  • 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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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des compositions de résine, des couches et des couches intermédiaires comprenant une résine poly(acétal de vinyle) qui comprend des résidus d'un aldéhyde autre que le n-butyraldéhyde. Ces compositions, couches et couches intermédiaires peuvent présenter des propriétés améliorées ou optimisées par rapport à celles formulées avec des résines poly(butyral de vinyle) comparables.
PCT/US2015/063877 2014-12-08 2015-12-04 Compositions de résine poly(acétal de vinyle), couches et couches intermédiaires présentant des propriétés améliorées WO2016094204A1 (fr)

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US14/563,077 US9926431B2 (en) 2014-12-08 2014-12-08 Poly(vinyl acetal) resin compositions, layers and interlayers having enhanced properties
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Citations (6)

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Publication number Priority date Publication date Assignee Title
US5290660A (en) * 1993-04-23 1994-03-01 Minnesota Mining And Manufacturing Company Dye permeable polymer interlayers
US20040065229A1 (en) * 2001-01-09 2004-04-08 Bernd Papenfuhs Plasticizer-containing polyvinylbutyrals, method for producing the same and the use thereof, especially for producing films for use in laminated safety glasses
US20080268270A1 (en) * 2007-04-30 2008-10-30 Wenjie Chen High impact polymer interlayers
US20130022824A1 (en) * 2011-07-22 2013-01-24 Kuraray Europe Gmbh High-Strength Film Laminates Having Layers Of Plasticizer-Containing Polyvinyl (N)Acetal and Plasticizer-Containing Polyvinyl (Iso)Acetal
US20140138580A1 (en) * 2011-07-27 2014-05-22 Fujifilm Corporation Compound, haze-lowering agent, liquid crystal composition, polymer material, and film
US20140364550A1 (en) * 2013-06-10 2014-12-11 Solutia Inc. Polymer interlayers comprising a blend of two or more resins

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5290660A (en) * 1993-04-23 1994-03-01 Minnesota Mining And Manufacturing Company Dye permeable polymer interlayers
US20040065229A1 (en) * 2001-01-09 2004-04-08 Bernd Papenfuhs Plasticizer-containing polyvinylbutyrals, method for producing the same and the use thereof, especially for producing films for use in laminated safety glasses
US20080268270A1 (en) * 2007-04-30 2008-10-30 Wenjie Chen High impact polymer interlayers
US20130022824A1 (en) * 2011-07-22 2013-01-24 Kuraray Europe Gmbh High-Strength Film Laminates Having Layers Of Plasticizer-Containing Polyvinyl (N)Acetal and Plasticizer-Containing Polyvinyl (Iso)Acetal
US20140138580A1 (en) * 2011-07-27 2014-05-22 Fujifilm Corporation Compound, haze-lowering agent, liquid crystal composition, polymer material, and film
US20140364550A1 (en) * 2013-06-10 2014-12-11 Solutia Inc. Polymer interlayers comprising a blend of two or more resins

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