Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • 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
  • B32B17/10614—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 comprising particles for purposes other than dyeing
  • B32B17/10623—Whitening agents reflecting visible light
• • 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
  • B32B17/10651—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 comprising colorants, e.g. dyes or pigments
• • 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
  • B32B17/10743—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 acrylate (co)polymers or salts thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
• • E—FIXED CONSTRUCTIONS
  • E04—BUILDING
  • E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
  • E04C2/00—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels
  • E04C2/54—Slab-like translucent elements
• • 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
  • B32B2250/03—3 layers
• • 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
  • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
• • 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
  • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
  • B32B2264/10—Inorganic particles
  • B32B2264/102—Oxide or hydroxide
• • 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
  • B32B2307/414—Translucent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2227—Oxides; Hydroxides of metals of aluminium

Definitions

• the invention is directed to translucent white polymer compositions.
• the compositions include a pigment and a polymeric resin that is an ionomer of an ethylene acid copolymer.
• Alumina trihydrate (ATH) is one preferred pigment.
• Alumina is another preferred pigment.
• the translucent white polymer compositions are useful in various articles, such as molded articles.
• the translucent white polymer compositions are particularly useful as interlayers in glass laminates, including safety glass laminates and structural glass laminates.
• Architects and designers often use frosted glass to allow light into a space while affording privacy to those within the space.
• Sand blasting and acid etching are two ways to produce frosted glass from smooth, transparent glass lites. Frosted glass is difficult to clean and maintain, however.
• sand blasting and acid etching are not medically or environmentally friendly processes, because of their many waste products, and because of the risk of burns from handling acids and silicosis from inhaling the dust that results from sand blasting.
• laminated glass with a diffuse translucent interlayer was developed. The interlayer provides the desired optical properties, and it may be laminated between smooth glass lites that are easy to clean and maintain. Often, the diffuse translucent interlayers are based on polyvinyl butyral compositions.
• Translucent white polyvinyl butyral compositions are commercially available from every major manufacturer of polyvinyl butyral. Typically, the optical properties of these compositions feature light transmission (LT) of approximately 65%; clarity of approximately 15 to 30%; and haze of 95% or higher.
• the commercially available polyvinyl butyral compositions include calcium carbonate as a diffusing agent.
• interlayer sheets having a thickness or caliper of 0.76 mm contain approximately 2.5 wt % of calcium carbonate having a particle size of around 3.5 microns.
• ionomeric interlayers such as DuPontTM SentryGlas® are required.
• These structural applications include architectural features, such as stairs, balconies and balustrades, and windows and skylights that are vulnerable to damage caused by severe weather or physical attack, for example.
• a variety of articles made from ionomers are used in our daily life. These articles may be made by injection molding processes, for example, and include items such as containers, caps or stoppers, trays, medical devices or instruments, handles, knobs, push buttons, panels, console boxes, footwear components, figurines or other decorative articles, and intermediate articles such as pre-forms or parisons.
• DuPontTM Surlyn® is one type of ionomeric material that has been used in fabricating these and other articles, because Surlyn®'s physical and optical properties are superior to those of many thermoplastic materials.
• optical properties associated with etched, ground or frosted glass may also be considered desirable in these everyday articles.
• a translucent white polymer composition having characteristics similar to those of Surlyn® will provide the articles with the desired appearance and physical properties.
• the use of a suitable translucent white polymer composition will obviate the need to tool special molds or to treat the articles' surfaces with solvents or abrasives in order to obtain the desired appearance of frosted glass.
• calcium carbonate is a diffusing agent commonly used in commercially available translucent polyvinyl butyral compositions.
• suitable ionomeric resins When calcium carbonate is compounded into suitable ionomeric resins, however, significant foaming is frequently observed, due to the gas produced by the chemical reaction between the ionomer and the calcium carbonate.
• titanium dioxide Another commonly used whitening agent is titanium dioxide.
• the average particle size of titanium dioxide is too small to achieve the desired optical effects, however, whether the glass laminate includes a polyvinyl butyral interlayer or an ionomeric interlayer. More specifically, adding titanium dioxide to the interlayer reduces its light transmission but not its clarity. Therefore, the key design function of providing privacy is not achieved.
• pigments with relatively low indices of refraction comparable to that of calcium carbonate are available.
• silica, alumina, talc, clay, vermiculite, glass fibers, barium sulfate, alumina trihydrate (ATH), alumina (Al 2 O 3 ), magnesium oxide (periclase), beryllium aluminate, calcium sulfate, zinc phosphate tetrahydrate and mullite have been used as fillers in ionomeric compositions.
• alumina trihydrate (ATH) has been compounded into ionomers at high loadings of approximately 65 parts ATH to 100 parts resin to achieve fire retardancy. Handbook of Fillers for Plastics Harry S.
• a translucent white polymer composition suitable for use in various articles having a frosted appearance.
• the translucent white polymer composition is particularly suitable for use as an interlayer in a glass laminate, for example a safety glass laminate or a structural glass laminate.
• the translucent white polymer composition comprises a pigment and a polymeric resin that comprises an ionomer of an ethylene acid copolymer.
• Alumina trihydrate is one preferred pigment.
• Alumina is another preferred pigment.
• articles such as glass laminates comprising the translucent white polymer composition and methods of making the translucent white polymer composition and the articles.
• the terms “comprises,” “comprising,” “includes,” “including,” “containing,” “characterized by,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
• a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
• compositions, a process, a structure, or a portion of a composition, a process, or a structure is described herein using an open-ended term such as “comprising,” unless otherwise stated the description also includes an embodiment that “consists essentially of” or “consists of” the elements of the composition, the process, the structure, or the portion of the composition, the process, or the structure.
• the conjunction “or” refers to an inclusive or and not to an exclusive or.
• the condition “A or B” is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
• Exclusive “or” is designated herein by terms such as “either A or B” and “one of A or B”, for example.
• ranges set forth herein include their endpoints unless expressly stated otherwise.
• an amount, concentration, or other value or parameter is given as a range, one or more preferred ranges or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether such pairs are separately disclosed.
• the scope of the invention is not limited to the specific values recited when defining a range.
• alkyl group refers to saturated hydrocarbon groups that have from 1 to 8 carbon atoms having one substituent and that may be branched or unbranched.
• alkylene refers to a saturated hydrocarbon having two substituents, such as methylene, ethylene or propylene.
• copolymer refers to polymers comprising copolymerized units resulting from copolymerization of two or more comonomers.
• a copolymer may be described herein with reference to its constituent comonomers or to the amounts of its constituent comonomers, for example “a copolymer comprising ethylene and 18 weight % of acrylic acid”, or a similar description.
• Such a description may be considered informal in that it does not refer to the comonomers as copolymerized units; in that it does not include a conventional nomenclature for the copolymer, for example International Union of Pure and Applied Chemistry (IUPAC) nomenclature; in that it does not use product-by-process terminology; or for another reason.
• IUPAC International Union of Pure and Applied Chemistry
• a description of a copolymer with reference to its constituent comonomers or to the amounts of its constituent comonomers means that the copolymer contains copolymerized units (in the specified amounts when specified) of the specified comonomers.
• copolymer is not the product of a reaction mixture containing given comonomers in given amounts, unless expressly stated in limited circumstances to be such.
• copolymer may refer to polymers that consist essentially of copolymerized units of two different monomers (a dipolymer), or that consist essentially of more than two different monomers (a terpolymer consisting essentially of three different comonomers, a tetrapolymer consisting essentially of four different comonomers, etc.).
• acid copolymer refers to a polymer comprising copolymerized units of an ⁇ -olefin, an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid, and optionally other suitable comonomer(s), such as an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid ester.
• ionomer refers to a polymer that is produced by partially or fully neutralizing an acid copolymer as described above.
• laminate refers to a structure having at least two layers that are adhered or bonded firmly to each other, optionally using heat, vacuum or positive pressure.
• the layers may be adhered to each other directly or indirectly. “Directly” means that there is no additional material, such as an interlayer or an adhesive layer, between the two layers, and “indirectly” means that there is additional material between the two layers.
• glass laminate refers to a layered structure including a polymeric interlayer.
• the structure also includes one or more glass sheets.
• the layers of the glass laminate are adhered or bonded to each other so that the glass laminate retains its integrity under self-supporting conditions.
• safety glass laminate refers to a glass laminate that has the properties that are traditionally associated with safety glass, for example, one or more of high clarity, good adhesion to glass so that shattered fragments are retained by the interlayer, and resistance to penetration or puncturing by a mass travelling at velocities resulting from acceleration due to gravity at a height of about 3 meters.
• structural glass laminate refers to a subset of safety glass laminates that have superior properties, for example, being able to resist penetration or puncturing by a mass travelling at ballistic speeds, or having an interlayer that is able to maintain its structural integrity without support from an intact sheet of glass.
• the terms “transmission” and “light transmission” and the abbreviation “LT” are synonymous and used interchangeably herein.
• the transmission of a material is the percentage of the total amount of light in the incident beam with which the material is illuminated (“input light”) that travels through the material and, upon exiting the material, travels in a direction that has a vector component in the direction of the incident beam.
• the amount of transmitted light is reduced, compared to the total amount of input light, by the amount of light, if any, that is reflected, absorbed, and scattered backwards by the measured material. Transmission is measured according to ASTM Method No. D1003 (2000) using a HazeGard Plus hazemeter, available from BYK-Gardner USA of Columbia, Md.
• haze refers to the percentage of transmitted light which in passing through a material deviates from the incident beam by greater than 2.5 degrees. Haze is measured according to ASTM Method No. D1003 (20000) using a Hazegard Plus hazemeter.
• Clarity is related to the percentage of transmitted light which in passing through a material deviates from the incident beam; however, the angle of the deviation is less than 2.5 degrees. Clarity is also measured using a Hazegard Plus hazemeter.
• specular transmitted light light that is not scattered (its angle of deviation equals zero degrees, also referred to as “specular transmitted light”) is not included in the amount of low-angle scattered light.
• a high degree of clarity means that a small amount of light is scattered.
• clarity as a percentage is defined as 100(1 ⁇ (amount of low-angle scattered light)/(total amount of transmitted light)).
• the total amount of transmitted light is the sum of the specular transmitted light, the high-angle scattered light (haze) and the low-angle scattered light.
• L* refers to the axes of a three-dimensional system for reporting color values.
• “L*a*b*” values are measured according to CIE Publication 15.2 (1986) using a HunterLab Ultrascan XE spectrophotometer, available from HunterLab of Reston, Va.
• a translucent white polymer composition that comprises a pigment and a polymeric resin.
• the polymeric resin comprises an ionomer of an ethylene acid copolymer.
• Suitable pigments include alumina trihydrate (ATH), alumina (Al 2 O 3 ), magnesium oxide (periclase), beryllium aluminate, calcium sulfate, zinc phosphate tetrahydrate and mullite either alone or in combination with other white pigments such as TiO 2 .
• Suitable pigments have an index of refraction of about 1.5 to about 2.8, preferably about 1.5 to about 1.8.
• Suitable pigment particles are able to scatter visible light. Consequently, the minimum average size of the suitable pigment particles is of the same order of magnitude as the wavelength of visible light, that is, about 380 to 720 nm. Because the appearance of the translucent white polymer composition is desirably uniform and similar to that of frosted glass, the individual pigment particles should not be visible to the naked eye. Consequently, the maximum median size (d50) of suitable pigment particles is about 0.2 mm. Preferably, the median particle size (d50) of the pigment is from about 1 micron to about 4 microns; more preferably from about 1.5 to about 3.0 microns, and still more preferably about 1.5 microns.
• the aspect ratio of the pigment particles is close to 1; stated alternatively, the pigment particles are preferably approximately regularly polyhedral to spherical in shape. More preferably, the aspect ratio of the particles is in the range of 1.00 ⁇ 0.75; 1.00 ⁇ 0.50; 1.00 ⁇ 0.25; 1.00 ⁇ 0.10; or 1.00 ⁇ 0.05.
• pigments examples include alumina trihydrate, alumina, talc, titanium dioxide, barium sulfate, silica, some clays, and combinations of two or more of these pigments.
• Alumina and combinations of alumina with other pigments are preferred. More preferred are alumina trihydrate (Al(OH) 3 ; CAS No. 8064-00-4) and combinations of alumina trihydrate with other pigments, such as for example titanium dioxide.
• the pigment consists essentially of alumina or of alumina trihydrate.
• alumina trihydrate (ATH) as used herein is synonymous and interchangeable with the terms aluminum (III) hydroxide, hydrated alumina, aluminum trihydrate, trihydrated alumina, and trihydroxy aluminum.
• the translucent white polymer composition also includes a polymeric resin that comprises an ethylene acid copolymer, an ionomer of an ethylene acid copolymer, and combinations thereof.
• a polymeric resin that comprises an ethylene acid copolymer, an ionomer of an ethylene acid copolymer, and combinations thereof.
• Suitable ethylene acid copolymers and ionomers are described in U.S. Pat. No. 7,641,965, issued to Bennison et al., for example.
• the ethylene acid copolymer comprises copolymerized units of an ⁇ -olefin having from 2 to 10 carbon atoms and about 8 to about 30 wt %, preferably about 15 to about 30 wt %, more preferably about 20 to about 30 wt %, yet more preferably about 20 to about 25 wt %, or still more preferably about 21 to about 23 wt % of copolymerized units of an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid having 3 to 8 carbon atoms.
• the weight percentage is based on the total weight of the ethylene acid copolymer.
• the ⁇ -olefin comprises ethylene; more preferably, the ⁇ -olefin consists essentially of ethylene.
• the ⁇ , ⁇ -ethylenically unsaturated carboxylic acid comprises acrylic acid, methacrylic acid, or a combination of acrylic acid and methacrylic acid. More preferably, the ⁇ , ⁇ -ethylenically unsaturated carboxylic acid consists essentially of acrylic acid, methacrylic acid, or a combination of acrylic acid and methacrylic acid.
• the ethylene acid copolymers may further comprise copolymerized units of other comonomer(s), such as unsaturated carboxylic acids having 2 to 10, or preferably 3 to 8 carbon atoms or derivatives thereof.
• Suitable acid derivatives include acid anhydrides, amides, and esters.
• Esters are preferred derivatives.
• the esters are ⁇ , ⁇ -ethylenically unsaturated carboxylic acid ester comonomers and include, but are not limited to, methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate and combinations thereof.
• the ethylene acid copolymers may be synthesized by any suitable polymerization process.
• the ethylene acid copolymers may be polymerized as described in U.S. Pat. Nos. 3,404,134; 5,028,674; 6,500,888; and 6,518,365.
• the ethylene acid copolymer has a melt index (MI) of about 60 g/10 min or less, more preferably about 45 g/10 min or less, yet more preferably about 30 g/10 min or less, or yet more preferably about 25 g/10 min or less, or still more preferably about 10 g/10 min or less, as measured by ASTM method D1238 at 190° C. and 2.16 kg.
• MI melt index
• ethylene acid copolymer resins are commercially available from E.I. du Pont de Nemours and Company of Wilmington, Del. (“DuPont”), under the trademark Nucrel®.
• the translucent white polymer composition includes a polymeric resin that comprises an ionomer of an ethylene acid copolymer or a mixture of these ionomers.
• a polymeric resin that comprises an ionomer of an ethylene acid copolymer or a mixture of these ionomers.
• at least a portion of the carboxylic acid moieties of the ethylene acid copolymers is neutralized to form carboxylate groups.
• carboxylate groups Preferably about 5 to about 90%, more preferably about 10 to about 50%, yet more preferably about 20 to about 50%, or still more preferably about 20 to about 35% of the carboxylic acid groups are neutralized, based on the total carboxylic acid content of the ethylene acid copolymers.
• An example of a suitable procedure for neutralizing the ethylene acid copolymers is also described in U.S. Pat. No. 3,404,134.
• the ionomers comprise cations as counterions to the carboxylate anions.
• Suitable cations include any positively charged species that is stable under the conditions in which the ionomer composition is synthesized, processed and used.
• the cations are metal cations that may be monovalent, divalent, trivalent or multivalent. Combinations of two or more cations that may have different valencies, for example mixtures of Na + and Zn 2+ or mixtures of NH 4 + and K + , are also suitable.
• the cations are more preferably monovalent or divalent metal ions.
• the metal ions are selected from the group consisting of ions of sodium, lithium, magnesium, zinc, and potassium and combinations of two or more thereof.
• the metal ions are selected from the group consisting of ions of sodium, ions of zinc and combinations thereof. Still more preferably, the metal ions comprise or consist essentially of sodium ions.
• the ionomer preferably has a MI of about 10 g/10 min or less, more preferably about 5 g/10 min or less, or still more preferably about 3 g/10 min or less, about 1.0 g/10 min or less, about 0.5 g/10 min or less, about 0.2 g/10 min or less, or about 0.1 g/10 min or less, as measured by ASTM method D1238 at 190° C. and 2.16 kg.
• the ionomer also preferably has a flexural modulus greater than about 40,000 psi (276 MPa), more preferably greater than about 50,000 psi (345 MPa), or still more preferably greater than about 60,000 psi (414 MPa), as measured by ASTM method D790 (Procedure A).
• ionomeric resins are commercially available from DuPont, under the trademarks Surlyn® resins and SentryGlas® interlayer sheets.
• the amount of the pigment in the translucent white polymer composition is determined by the level necessary to achieve the desired optical properties, including transmittance, haze, clarity, and color. Of necessity, the amount of pigment required to attain the desired optical properties varies with the thickness of the portion of translucent white polymer composition whose properties are being measured. In addition, if one pigment is substituted for another, then different levels of the two pigments may be required to attain a desirable balance of optical properties. Variations between pigments, such as different particle sizes, aspect ratios or indices of refraction, have an effect on their optical properties in polymer blends.
• the translucent white polymer composition may contain about 1.0 to about 10.0 wt % of the pigment and about 99 to about 90 wt % of the polymeric resin, based on the total weight of the translucent white polymer composition.
• the translucent white polymer compositions may further comprise any other suitable additive(s) that are known in the art.
• additives may include, but are not limited to, plasticizers, processing aides, flow enhancing additives, lubricants, pigments, dyes, flame retardants, impact modifiers, nucleating agents, antiblocking agents (e.g., silica), UV stabilizers, dispersants, surfactants, chelating agents, coupling agents, adhesives, primers, reinforcement additives (e.g., glass fiber), other fillers that do not affect the optical properties of the translucent white polymer composition, and the like.
• Suitable additives, additive levels, and methods of incorporating the additives into the ionomer compositions may be found in the Kirk - Othmer Encyclopedia of Chemical Technology, 5th Edition, John Wiley & Sons (New Jersey, 2004).
• the total amount of these additives is less than 5 wt %, less than 3 wt %, less than 2 wt %, less than 1 wt %, or less than 0.5 wt %, based on the total weight of the translucent white polymer composition.
• the amount of each of these additives, if present is preferably less than 10 wt %, less than 5 wt %, less than 3 wt %, less than 2 wt %, less than 1 wt %, less than 0.5 wt %, less than less than 0.2 wt %, or less than 0.1 wt %, based on the total weight of the translucent white polymer composition.
• the translucent white polymer compositions may contain, but preferably do not contain, additives for effecting and controlling cross-linking, such as organic peroxides, inhibitors and initiators.
• additives for effecting and controlling cross-linking such as organic peroxides, inhibitors and initiators.
• additives for effecting and controlling cross-linking such as organic peroxides, inhibitors and initiators.
• thermal stabilizers such as thermal stabilizers, UV absorbers, hindered amine light stabilizers (HALS), and silane coupling agents.
• HALS hindered amine light stabilizers
• the translucent white polymer composition has highly desirable optical properties, similar to those of etched or frosted glass, in which a high percentage of the incident light is transmitted, and yet the transmitted image has a low definition. Thus, privacy and efficient use of ambient light are maintained.
• the first set results in a translucent white polymer composition that has a balance of properties in which the transmission is slightly lower (56 to 75%), the level of haze is high, and the level of clarity is low (10 to 30%). This property set sacrifices a significant percentage of the incoming light to scattering; however, a good level of privacy is provided by the low definition of the transmitted image.
• the second set results in a translucent white polymer composition that has a balance of properties in which the transmission (80 to 90%), haze (75 to 85%) and clarity (70 to 86%) are all relatively high.
• the values for Property Set A and Property Set B are independent of the thickness of the sample of translucent white polymer composition through which the image is transmitted.
• the amount of ATH having a median particle size of 1.5 to 4.5 microns is about 3.0 wt %.
• the amount of ATH having a median particle size of 1.5 to 4.5 microns is about 6.25 wt %.
• the amount of ATH having a median particle size of 1.5 to 4.5 microns is about 1.0 wt %.
• the amount of ATH having a median particle size of 1.5 to 4.5 microns is about 2.0 wt %.
• transmission is approximately proportional to the amount of pigment to the layer thickness.
• Clarity generally decreases as a well-behaved linear or quadratic function of pigment level, in a defined region spanning about 10 percentage points of clarity. Haze is high and relatively constant, once the desired transmission and clarity levels have been achieved.
• the translucent white polymer composition may be made by any suitable process, such as melt mixing.
• High-shear melt-mixing is preferred.
• Suitable high shear mixing equipment includes static mixers, rubber mills, Brabender mixers, Buss kneaders, single screw extruders, twin screw extruders, heated or unheated two-roll mills, and the like. Additional examples of suitable compounding processes and conditions may also be found in the Kirk - Othmer Encyclopedia and the Modern Plastics Encyclopedia , McGraw-Hill (New York, 1995).
• the translucent white polymer composition may be formed into a number of articles, including without limitation films, sheets, and molded articles.
• the molded articles may be prepared by any conventional molding process, such as compression molding, injection molding, extrusion molding, blow molding, injection blow molding, injection stretch blow molding, extrusion blow molding and the like.
• Articles may also be formed by combinations of two or more of these processes, such as for example when a core formed by compression molding is overmolded by injection molding.
• Information about these fabrication methods may be found in reference texts such as, for example, the Kirk Othmer Encyclopedia, the Modern Plastics Encyclopedia , McGraw-Hill (New York, 1995) or the Wiley Encyclopedia of Packaging Technology, 2d edition, A. L. Brody and K. S. Marsh, Eds., Wiley-Interscience (Hoboken, 1997).
• the article comprising the translucent white polymer composition described herein is an injection molded article having a minimum thickness (i.e, the thickness at the smallest dimension of the article) of at least about 1 mm.
• the injection molded article may have a thickness of about 1 mm to 100 mm, or 2 mm to 100 mm, or 3 to about 100 mm, or about 3 to about 50 mm, or about 5 to about 35 mm.
• the article is an injection molded article in the form of a multi-layer structure, such as an over-molded article.
• At least one layer of the multi-layer structure comprises or consists essentially of the translucent white polymer composition described above and that layer has a minimum thickness of at least about 1 mm.
• the at least one layer of the multi-layer article has a thickness of about 1 mm to 100 mm, or 2 mm to 100 mm, or about 3 to about 100 mm, or about 3 to about 50 mm, or about 5 to about 35 mm.
• the article is an injection molded article in the form of a sheet, a container (e.g., a bottle or a bowl), a cap or stopper (e.g. for a container), a tray, a medical device or instrument (e.g., an automated or portable defibrillator unit), a handle, a knob, a push button, a decorative article, a panel, a console box, or a footwear component (e.g., a heel counter, a toe puff, or a sole).
• the article comprises or consists essentially of the translucent white polymer composition.
• the article is an injection molded intermediate article for use in further shaping processes.
• the article may be a pre-form or a parison suitable for use in a blow molding process to form a container (e.g., a cosmetic container).
• the injection molded intermediate article may be in the form of a multi-layer structure such as the one described above, and it may therefore produce a container having a multi-layer wall structure.
• the article comprises or consists essentially of the translucent white polymer composition.
• Injection molding is a well-known molding process.
• the article described herein When the article described herein is in the form of an injection molded article, it may be produced by any suitable injection molding process.
• Suitable injection molding processes include, for example, co-injection molding and over-molding. These processes are sometimes also referred to as two-shot or multi-shot molding processes.
• the translucent white polymer composition may be used as the substrate material, the over-mold material or both.
• the translucent white polymer composition described herein may be over-molded on a glass, plastic or metal container.
• the translucent white polymer composition may be over-molded on other articles (such as household items, medical devices or instruments, electronic devices, automobile parts, architectural structures, sporting goods, etc.) to form a soft touch and/or protective overcoating.
• the melt index of the composition is preferably from 0.1 g/10 min or 0.75 g/10 min or 5 g/10 min up to about 35 g/10 min, as determined in accordance with ASTM D1238 at 190° C. and 2.16 kg.
• the composition preferably comprises an ionomer having zinc cations.
• the overmolding material comprises the translucent white polymer composition
• the composition preferably comprises an ionomer and the ionomer may comprise any suitable cation.
• the ionomer's precursor acid copolymer preferably has a melt index of 200 to 500 g/10 min, as determined in accordance with ASTM D1238 at 190° C. and 2.16 kg.
• the ionomer preferably has a melt index of from about 0.1 to about 2.0 g/10 min or from about 0.1 to about 35 g/10 min, as determined in accordance with ASTM D1238 at 190° C. and 2.16 kg. More specifically, when the substrate comprises the ionomer, the ionomer preferably has a melt index of about 0.5 to about 4 g/10 min. When the overmolding material comprises the ionomer, however, the ionomer preferably has a melt index of from 0.1 g/10 min or 0.75 g/10 min or 4 g/10 min or 5 g/10 min up to about 35 g/10 min.
• the translucent white polymer composition may be molded at a melt temperature of about 120° C. to about 250° C., or about 130° C. to about 210° C. In general, slow to moderate fill rates with pressures of about 69 to about 110 MPa may be used.
• the mold temperatures may be in the range of about 5° C. to about 50° C., preferably 5° C. to 20° C., and more preferably 5° C. to 15° C.
• Films and sheets comprising the translucent white polymer composition may be made by any suitable process.
• the terms “film” and “sheet”, as used herein, refer to substantially planar, continuous articles.
• the term “continuous”, as used in this context, means that the film or sheet has a length of at least about 3 m, at least about 10 m, at least about 50 m, at least about 100 m, or at least about 250 m.
• the sheeting has an aspect ratio, that is, a ratio of length to width, of at least 5, at least 10, at least 25, at least 50, at least 75 or at least 100.
• a film has a thickness of about 10 mils (0.25 mm), or less; preferably about 0.5 mils (0.012 mm) to about 10 mils (0.25 mm); more preferably about 1 mil (0.025 mm) to about 5 mils (0.13 mm).
• a sheet has a thickness of greater than about 10 mils (0.25 mm); preferably greater than about 15 mils (0.38 mm); more preferably greater than about 30 mils (0.75 mm); and still more preferably, greater than about 60 mils (1.50 mm), 90 mils (2.25 mm), or 120 mils (3.00 mm).
• the descriptions herein pertain equally to films and to sheets, unless otherwise limited in specific instances. For convenience, however, only one of these terms may be used in a given context.
• the sheets may be formed through dipcoating, solution casting, compression molding, injection molding, lamination, melt extrusion, blown film, extrusion coating, tandem extrusion coating, or any other suitable procedure.
• the sheets are formed by a melt extrusion, melt coextrusion, melt extrusion coating, or tandem melt extrusion coating process.
• the sheets comprising the translucent white polymer composition may have a smooth or rough surface on one or both sides.
• the sheets Preferably, the sheets have rough surfaces on both sides to facilitate the deaeration during the lamination process.
• Rough surfaces may be produced by conventional processes such as mechanical embossing.
• the as-extruded sheet may be passed over a specially prepared surface of a die roll positioned in close proximity to the exit of the die. This die roll imparts the desired surface characteristics to one side of the molten polymer.
• the surface of such a textured roll has minute peaks and valleys
• the still-impressionable polymer sheet cast on the textured roll will have a rough surface on the side that is in contact with the roll.
• the rough surface generally conforms respectively to the valleys and peaks of the roll surface.
• Textured rolls are described in, e.g., U.S. Pat. No. 4,035,549 and U.S. Patent Application Publication No. 2003-0124296.
• glass laminates comprising an interlayer of the translucent white polymer composition.
• Suitable translucent white polymer compositions for use as interlayers in glass laminates are characterized by the desirable optical properties described above.
• the glass laminates are safety glass laminates.
• Suitable translucent white polymer compositions for use as interlayers in safety glass laminates have physical properties including good adhesion to glass, high strength, and post-breakage structural performance, such as good puncture resistance.
• the adhesion of an interlayer to glass may be measured by the pummel test or by 90° peel adhesion. The experimental methods are described in detail in the Examples, below.
• the pummel adhesion rating of an interlayer that is suitable for use in a safety glass laminate is greater than 6 pummel units.
• the 90° peel adhesion of an interlayer that is suitable for use in a safety glass laminate is greater than 2.0 N/mm.
• the modulus of the interlayer may be measured by dynamic mechanical analysis using a TA Instruments Q800 DMA available from TA Instruments, New Castle, Del. via ASTM 4065 at 1 Hz frequency and over the temperature range of ⁇ 150 to 100° C.
• the modulus of a material that is suitable for use as an interlayer in a structural glass laminate is about 20 to about 60 kpsi.
• the modulus of a material that is suitable for use as an interlayer in a safety glass laminate may be somewhat lower.
• Tensile properties are also correlated with good post breakage structural performance. Tensile properties such as strength and elongation at break may be measured according to ASTM D882. The experimental method is also described in the Examples, below. In general, materials that are suitable for use as an interlayer in a structural glass laminate have a strength of about 20 to about 40 MPa and an elongation of break of about 200 to about 400%. The strength and elongation at break of a material that is suitable for use as an interlayer in a safety glass laminate may be somewhat lower.
• Structures of glass laminates that may suitably include a translucent white interlayer include, without limitation, the structures that are described in detail in U.S. Patent Appln. PubIn. No. 2007/0228341.
• the translucent white interlayer may be substituted for any polymeric interlayer described therein.
• the most common laminates are glass/interlayer/glass laminates. When the translucent white interlayer is used, these laminates provide the optical properties of frosted glass together with the ease of cleaning associated with smooth glass surfaces and preferably the superior mechanical properties associated with safety glass having an ionomeric interlayer.
• interlayer/polyester film and glass/interlayer/polyester film/interlayer/glass, wherein the two interlayers may be the same or different, for example one pigmented and one unpigmented, or one ionomeric and one based on polyvinyl butyral or ethylene vinyl acetate.
• the interlayer(s) are preferably ionomeric and preferably have a total thickness of at least 62 mil.
• the desired optical properties of the glass laminate are defined by the translucent white polymer composition, as the other layers of the glass laminate may be water white, such as for example smooth, clear, colorless glass or an unpigmented polymeric interlayer.
• the translucent white polymer composition may be water white, such as for example smooth, clear, colorless glass or an unpigmented polymeric interlayer.
• Those of skill in the art are capable of combining the optical properties of the translucent white polymer composition and those of other components of the glass laminates to provide the desired effects.
• glass laminates that are both frosted and tinted may be obtained by tinting the translucent white polymer composition, by using tinted glass, or by including a tinted PET film in the laminate structure.
• a decorative glass laminate in which a frosted effect is combined with a printed image may be produced, for example, by combining a printed PET film in a laminate with an interlayer of the translucent white polymer composition; by combining an interlayer of the translucent white polymer composition in a laminate with a printed interlayer to form a laminate such as those available from DuPont under the trademark SentryGlas® ExpressionsTM decorative glass; or by forming a laminate from an interlayer of the translucent white polymer composition onto which an image has been printed directly.
• An image against a frosted background is produced when the image is viewed against a background of the translucent white polymer composition interlayer.
• a laminate displaying a sharp image together with a misty image is produced when one image viewed against the background of the translucent white polymer composition interlayer and one image viewed through the translucent white polymer composition interlayer.
• Glass laminates comprising the translucent white polymer composition may be made by any suitable process.
• glass laminates are made by autoclave lamination processes, such as those described in U.S. Pat. No. 7,763,360 and in U.S. Patent Appln. PubIn. No. 2007/0228341.
• Non-autoclave lamination processes may also be used, however.
• suitable non-autoclave lamination processes are also described in U.S. Pat. No. 7,763,360 and in U.S. Patent Appln. PubIn. No. 2007/0228341.
• the amount of pigment in the translucent white polymer composition described herein is believed to be too small to require significant changes to the lamination process, relative to an unpigmented interlayer that is otherwise of the same composition. It is believed, however, that one of ordinary skill in the art will be able to make any adjustments to the lamination process that may be required. For example, if the thermal conductivity of the translucent white interlayer is increased relative to that of the unpigmented interlayer, reasonable adjustments to the process include decreasing the lamination temperature or the cycle time.
• the float glass was clear annealed float glass having a thickness of 2.3 mm, available from PPG Industries, Inc., of Pittsburgh, Pa. (“PPG”).
• the ionomer was derived from a copolymer of ethylene with methacrylic acid (22 wt %, based on the copolymer weight).
• the copolymer of ethylene with methacrylic acid had a melt index prior to neutralization of 1.8 g/10 min (ASTM D1238; 190 C, 2.16 kg).
• the ionomer's neutralization level was 1.6% or 15%, and the cation was sodium.
• the alumina trihydrate (Al(OH) 3 or ATH) was grade BSI 3400 , obtained from Brenntag Specialties, Inc., of Philadelphia, Pa.
• the alumina (Al 2 O 3 ) had a particle size of 3 microns and was obtained from Pace Technologies of Arlington, Ariz.
• the glass laminates described below were produced by stacking the individual layers of the laminate in order to form a pre-press assembly.
• the pre-press assembly is heated at 120° C. for 1 hour under vacuum and then processed in an air autoclave at 135° C./200 psig for 30 min hold time to provide the glass laminate.
• the laminates for pummel adhesion testing were prepared by placing the ionomer sheeting between two lites of float glass. The “tin” side of the float glass lites was in contact with the ionomer. This pre-press assembly was laminated according to the standard procedure. The laminate was conditioned at 23 to 25° C. for a minimum of 2 hours prior to pummel adhesion testing. The conditioned laminate was held at a 45° angle on a support table and struck by hand with a 454 g (1 lb) hammer to pulverize the top layer of float glass over an area of about 3 by 4 inches. The pulverized glass that was not adhered to the interlayer was removed. The area of the interlayer that was bare of remaining adhered glass was evaluated visually and rated according to the standards set forth in the Table, below.
• the laminates for 90° peel adhesion testing were prepared by laminating the ionomer sheeting to a single lite of float glass. The “tin” side of the float glass lite was in contact with the ionomer.
• This pre-press assembly was laminated according to the standard procedures, then conditioned at room temperature (23 to 25° C.) for at least 24 h.
• the conditioned laminate was subjected to a 90° peel test using an Instron Model 5500R tensile tester, available from Instron, a business segment of Illinois Tool Works of Glenview, Ill. Instron Worldwide headquarters is at Norwood, Mass.
• the tensile tester was equipped with a 50 lb load cell and the crosshead speed was 25.4 mm/min.
• Tensile properties were measured according to ASTM D882 using an Instron Model 1122 mechanical testing apparatus. The films were conditioned at room temperature (23° C. ⁇ 2° C.) and 50% relative humidity prior to testing.
• Butacite® Translucent White polyvinyl butyral sheeting having a caliper of 0.76 mm was laminated between two lites of float glass.
• the ionomer and Ti-Pure® R105 titanium dioxide (0.027 wt % loading; available from DuPont) were fed into a 1.5 inch single screw extruder (Model DS-15H, available from Davis-Standard, LLC, of Pawcatuck, Conn.) to produce a sheet having a caliper of 0.63 mm.
• the extruder temperature conditions were as follows:
• Zone 1 128° C. Zone 2 149° C. Zone 3 180° C. Zone 4 180° C. Die 180° C. This sheeting was laminated between two lites of float glass.
• the ionomer was compounded with Al(OH) 3 and extruded into sheeting under the extruder conditions that are set forth above in Comparative Example 2.
• the sheeting had a caliper of 0.63 mm.
• the loading of Al(OH) 3 in each sheet is a weight percentage, based on the total weight of the translucent white polymer composition, and is set forth in Table 1. A portion of each sheet was laminated between two lites of float glass.
• the ionomer was extruded as a trilayer sheeting wherein the outermost layers were clear and the inner layer contained Al(OH) 3 (6.25%).
• the total sheeting caliper was 1.59 mm; the thickness of the translucent white layer was 0.63 mm and the thickness of each of the two clear outer layers was 0.48 mm.
• the three layers were produced by three extruders that were associated with a Killion horizontal three-layer stack having 14-inch rolls.
• the white layer was produced by the Model DS-15H extruder; one clear layer was produced by an HPE-150 side extruder, and the second clear layer was produced by a DS-15 side extruder.
• the Killion equipment and the two side extruders are available from Davis-Standard, LLC.
• the trilayer sheeting was laminated between two lites of float glass.
• the ionomer was compounded with alumina (Al 2 O 3 ) and extruded as sheeting under the extruder conditions that are set forth above in Comparative Example 2.
• the loadings are given in Table 1.
• the sheeting caliper was 0.63 mm.
• the sheeting was laminated between two lites of float glass.
• the ionomer was compounded with Al(OH) 3 and extruded into sheeting having a caliper of 0.63 mm under the conditions described in Comparative Example 2. Two layers of the sheeting were plied together to form an interlayer with a total thickness of 1.26 mm. The plied sheeting was laminated between two lites of float glass according to the standard procedure.
• the results for Examples 15 and 16, set forth in Table 1, are similar to those obtained in Examples 7 and 6, respectively.
• the ionomer was compounded with Al(OH) 3 (6.25%) and extruded into sheeting having a caliper of 0.63 mm under the conditions described in Comparative Example 2. A layer of this sheeting was plied with a layer of clear sheeting. The ionomer was the same in both layers, and the caliper of the clear sheeting was 0.96 mm. The plied sheeting was laminated between two lites of float glass according to the standard procedure. The results, set forth in Table 1, are similar to those obtained in Example 7.
• the ionomer was compounded with the alumina (Al 2 O 3 , 1.15%) and extruded into sheeting having a caliper of 0.89 mm under the conditions described in Comparative Example 2.
• the sheeting also contained Tinuvin® 328 (0.17%), available from the BASF Corporation of Florham Park, N.J., as a UV absorber.
• the sheeting was laminated between two lites of float glass according to the standard procedure. The results are shown in Table 1.
• the adhesion properties of the translucent white ionomers were measured by pummel adhesion and by 90° peel adhesion tests, as described in the Standard Procedures, above.
• the ionomer was compounded with ATH (for Examples 19 and 20) and extruded into sheeting having a caliper of 0.63 mm under the conditions described in Comparative Example 2.
• the tensile properties of the translucent white ionomers were measured according to the standard procedure set forth above.
• the ionomer was compounded with ATH (for Examples 26 to 30) or Al 2 O 3 (for Examples 32 to 35) and extruded into sheeting under the conditions described in Comparative Example 2.
• the results, which are set forth in Table 3, demonstrate that the translucent white polymer composition maintains tensile strength and elongation at break at values sufficient to enable the translucent white polymer composition to act as an interlayer in a functioning safety glass laminate.

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