WO2013040096A1 - Compositions à faible perlescence - Google Patents

Compositions à faible perlescence Download PDF

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Publication number
WO2013040096A1
WO2013040096A1 PCT/US2012/054947 US2012054947W WO2013040096A1 WO 2013040096 A1 WO2013040096 A1 WO 2013040096A1 US 2012054947 W US2012054947 W US 2012054947W WO 2013040096 A1 WO2013040096 A1 WO 2013040096A1
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WIPO (PCT)
Prior art keywords
composition
preform
poly
melt
temperature
Prior art date
Application number
PCT/US2012/054947
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English (en)
Inventor
David Voisin
Andre Rannard Cotterlaz
Original Assignee
E. I. Du Pont De Nemours And Company
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Application filed by E. I. Du Pont De Nemours And Company filed Critical E. I. Du Pont De Nemours And Company
Publication of WO2013040096A1 publication Critical patent/WO2013040096A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00—Indexing scheme relating to blow-moulding
    • B29C2949/07—Preforms or parisons characterised by their configuration
    • B29C2949/0715—Preforms or parisons characterised by their configuration the preform having one end closed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
    • B29C49/06—Injection blow-moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/08—Biaxial stretching during blow-moulding
    • B29C49/10—Biaxial stretching during blow-moulding using mechanical means for prestretching
    • 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

Definitions

  • the present invention relates to compositions for preparing shaped articles such as bottles using polyester pellet blend and melt extruded blend compositions comprising poly(trimethylene terephthalate) and polyethylene terephthalate, as well as the use thereof.
  • PET poly(ethylene terephthalate)
  • a common package currently made from PET is an injection- stretch-blow-molded (ISBM) bottle, jar or other container.
  • ISBM injection- stretch-blow-molded
  • the polymer resin is heated to the molten form in an extruder and then injection-molded in a mold to provide a "preform" or parison.
  • the preform is then heated and stretched or expanded by application of air pressure to its final shape.
  • ISBM injection-stretch-blow-molding
  • bottles displaying pearlescence can be used to package opaque or strongly colored liquids, such as lemonades, milk or red wine, a bottle displaying pearlescence cannot be used to contain drinking water, since the pearlescence is easily detected upon visual inspection, and turns off prospective customers.
  • the present invention provides for a process or method for reducing pearlescence in shaped articles, comprising the steps of preparing a thermoplastic composition; heating the composition to a melt; molding the melt into a substantially tubular hollow perform; bringing the preform to a temperature between the glass transition temperature and the temperature of crystallization from the glass or cold crystallization of the composition; and stretching the preform in the axial direction, radial direction or combination thereof; wherein the composition comprises from 85 percent to 97 weight percent of a poly(ethylene terephthalate) and from 3 to 15 weight percent of a poly(trimethylene terephthalate), based on the total weight of the composition; wherein the composition does not contain a crystallization accelerator or nucleating agent; wherein the preform has one closed end and one open end; and wherein the stretching is optionally carried out by application of air pressure, mechanical pressure to the interior of the perform, or both to provide a shaped article.
  • FIGURE 1 shows a perspective drawing of the lower portion of an injection blow molded bottle.
  • Homopolymer means a polymer containing many repeat units of one kind.
  • a 3GT homopolymer means a polymer substantially derived from the polymerization of 1 ,3-propanediol with terephthalic acid, or alternatively, derived from the ester-forming equivalents thereof (e.g., any reactants such as dimethyl terephthalate which may be polymerized to ultimately provide a polymer of
  • Copolymer refers to polymers comprising repeat units of two or more different kinds.
  • a 3GT copolymer means any polymer comprising (or derived from) at least about 70 mole percent trimethylene terephthalate and the remainder of the polymer being derived from monomers other than terephthalic acid and 1 ,3-propanediol (or their ester forming equivalents).
  • compositions useful in the process for reducing pearlescence according to the present invention may compositions comprising of from 3 to 15 weight percent, preferably of from 3 to 10 weight percent, and more preferably of from 3 to 8 weight percent of 3GT or poly(trimethylene terephthalate), based on the total weight of the composition, while the remaining weight percent may be of PET or poly(ethylene terephthalate).
  • Polyester polymers are well known to one skilled in the art and may include any condensation polymerization products derived from, by esterification or transesterification, an alcohol and a dicarboxylic acid including ester thereof.
  • Alcohols include glycols having 2 to about 10 carbon atoms such as ethylene glycol, propylene glycol, butylene glycol, methoxypolyalkylene glycol, neopentyl glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, diethylene glycol,
  • Dicarboxylic acids include terephthalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, isophthalic acid, 1 ,10- decanedicarboxylic acid, phthalic acid, dodecanedioic acid, the ester- forming equivalents (e.g., diesters such as dimethylterephthalate), or combinations of two or more thereof.
  • Polyethylene terephthalate is a polyester prepared by the
  • the PET may be a PET homopolymer or a copolymer that preferably contains 70 percent or more of poly(ethylene terephthalate) in mole percentage, or blends thereof. These may be modified with up to 30 mol percent of polyesters made from other diols or diacids.
  • Poly(trimethylene terephthalate) is a polyester that may be prepared by the condensation polymerization of 1 ,3-propanediol and terephthalic acid.
  • a 3GT may also be prepared from 1 ,3-propane diol and dimethylterephthalate (DMT), for example, in a two-vessel process using an organotitanate catalyst, e.g., tetraisopropyl titanate catalyst, TYZOR TPT (E. I. du Pont de Nemours and Company (DuPont), Wilmington, Del.).
  • organotitanate catalyst e.g., tetraisopropyl titanate catalyst, TYZOR TPT (E. I. du Pont de Nemours and Company (DuPont), Wilmington, Del.).
  • Molten DMT is added to 1 ,3-propanediol and the catalyst at about 185°C in a transesterification vessel, and the temperature is increased to 210°C while methanol is removed.
  • the resulting intermediate is transferred to a polycondensation vessel where the pressure is reduced to one millibar (10.2 kg/cm 2 ) and the temperature is increased to 255°C.
  • the pressure is increased and the polymer may be extruded, cooled and cut into pellets.
  • the 3GT may be a homopolymer or a copolymer that preferably contains 70 percent or more of 3GT in mole percentage, or blends thereof. These may be modified with up to 30 mol percent of polyesters made from other diols or diacids.
  • the most preferred resin is 3GT homopolymer.
  • diols include ethylene glycol, 1 ,4-butanediol, 1 ,2-propanediol, diethylene glycol, triethylene glycol, 1 ,3-butanediol, 1 ,5-pentanediol, 1 ,6- hexanediol, 1 ,2-, 1 ,3- and 1 ,4-cyclohexane dimethanol (CHDM), the longer chain diols and polyols made by the reaction product of diols or polyols with alkylene oxides, or combinations of two or more thereof.
  • CHDM cyclohexane dimethanol
  • polyesters and processes for making them are well known to one skilled in the art, further description is omitted herein for the interest of brevity.
  • Intrinsic viscosity is a measure of the capability of a polymer in solution to enhance the viscosity of the solution. IV may be measured according to ASTM D2857.95. For example, a Viscotek Forced Flow Viscometer model Y-900 may be used and the polymers dissolved in 50/50 w/w trifluoroacetic acid/methylene chloride at a 0.4percent (wt/vol) concentration and tested at 19 C°. Intrinsic viscosity typically increases with increasing polymer molecular weight, but is also dependent on the type of macromolecule, its shape or conformation, and the solvent it is measured in. Because 3GT and PET polymers have different shapes, 3GT has higher IV than PET for a given molecular weight. For example, 3GT with IV of about 1 .0 corresponds to PET with IV of about 0.7.
  • Differential Scanning Calorimetry may be used to determine glass transition temperature (T g ), temperature of crystallization from the glass or cold crystallization (T cg or T cc ), crystallization from the melt, and melting point (T m ).
  • T g glass transition temperature
  • T cg or T cc cold crystallization
  • T m melting point
  • compositions may additionally comprise small amounts of optional materials commonly used and well known in the polymer art.
  • materials include conventional additives used in polymeric materials including plasticizers, stabilizers including viscosity stabilizers and hydrolytic stabilizers, primary and secondary antioxidants such as for example IRGANOX 1010, ultraviolet ray absorbers and stabilizers, antistatic agents, dyes, pigments or other coloring agents, fire-retardants, lubricants, processing aids, slip additives, antiblock agents such as silica or talc, release agents, and/or mixtures thereof.
  • Additional optional additives may include inorganic fillers; acid copolymer waxes, such as for example Honeywell wax AC540; T1O2, which is used as a whitening agent; optical brighteners; surfactants; and other components known in the art to be useful additives. These additives are described in the Kirk Othmer Encyclopedia of Chemical Technology.
  • antioxidants e.g., hindered phenols
  • Hindered phenols may include 1 ,3,5-trimethyl-2,4,6-tris-(3,5-di-tert-butyl-4- hydroxybenzyl)-benzene; pentaerythrityl tetrakis-3(3,5-di-tert-butyl-4- hydroxyphenyl)-propionate; n-octadecyl-3(3,5-di-tert-butyl-4- hydroxyphenyl)-propionate; 4,4'-methylenebis-(2,6-tert-butyl-phenol); 4,4'- thiobis-(8-tert-butyl-o-cresol); 2,6-di-n-tert-butylphenol; 6-(4- hydroxyphenoxy)-2,4-bis(n-octyl-thio)-1 ,3,5 trioxide
  • antioxidant of note is bis-(2,4-di-t-butylphenyl)pentaerythritol diphosphite, CAS Number 26741 -53-7, available under the tradename ULTRANOX 626 from Chemtura.
  • additive(s) may be present in the compositions in quantities that are generally from 0.01 to 15 weight percent, preferably from 0.01 to 10 weight percent, so long as they do not detract from the basic and novel characteristics of the composition and do not significantly adversely affect the performance of the composition, i.e. the reduction of pearlescence (the weight percentages of such additives are not included in the total weight percentages of the compositions as defined above in the Summary of the Invention). Many such additives may be present in amounts from 0.01 to 5 weight percent.
  • additives into the compositions may be carried out by any known process, for example, by dry blending, by extruding a mixture of the various constituents, by the conventional masterbatch technique, or the like.
  • compositions disclosed do not contain crystallization
  • compositions are used in preparing injection molded preforms, which desirably comprise amorphous polymer compositions to allow for orientation in a subsequent blowing step (see below). Accordingly, use of crystallization accelerators that promote crystallization is undesirable. In addition, crystallization accelerators may reduce transparency and/or clarity of the shaped articles.
  • the process or method comprises preparing a thermoplastic composition as disclosed above.
  • the composition may be prepared by blending the components by any means known to one skilled in the art, e.g., dry blending/mixing, extrusion, co-extrusion, to produce the composition.
  • the composition may be a pellet blend or melt extruded blend.
  • the composition may be prepared by a combination of heating and mixing (melt-mixing or melt-blending).
  • the component materials may be mixed to be substantially dispersed or homogeneous using a melt-mixer such as a single or twin-screw extruder, blender, Buss Kneader, double helix Atlantic mixer, Banbury mixer, roll mixer, etc., to give a resin composition.
  • a portion of the component materials may be mixed in a melt-mixer, and the rest of the component materials subsequently added and further melt-mixed until substantially dispersed or homogeneous.
  • a salt and pepper blend of the components may be made and the components may then be melt-blended in an extruder.
  • the components may be fed to the extruder separately and melt-blended.
  • the blended composition may be further processed.
  • the composition may be processed into pellets by a combination of extruding the melt into a strand, cutting the strand and cooling. Cooling may be effected by exposure to cool air or water.
  • a Gala underwater pelletizing system may be used to pelletize the extrudates into small pellet size.
  • the blended composition may be passed directly from the extruder into an injection molding apparatus as a melt.
  • the first and second steps of the process may be
  • a preform or parison is a substantially tubular hollow article having a closed end and an open end having relatively thick walls that is adapted for subsequent blow molding into a finally desired container form.
  • the preform may be produced with the necks of the bottle, including threads or other means for attaching as closure (the "finish") on one end.
  • Injection molding of preforms for later blow molding into container configurations may include some balancing of factors (See, e.g., Blow Molding Handbook, by Rosato and Rosato, Hanser Publishers, New York, N.Y., 1988). See also U.S. Pat. Nos. 5,914,138, 6,596,213, 5,914,138, and 6,596,213.
  • Injection molding a bottle preform may be conducted by
  • the mold includes a first cavity extending inwardly from an outer surface of the mold to an inner end, an article formation cavity, and a gate connecting the first cavity to the article formation cavity.
  • the gate defines an inlet orifice in the inner end of the first cavity, and an outlet orifice that opens into the article formation cavity.
  • the article formation cavity typically may be cylindrical (but other profiles are contemplated) with an axially centered projection at the end opposite the gate.
  • the molten material flows through the gate into the cavity, filling the cavity.
  • the molding may provide an article that is substantially a tube with an "open" end and a "closed” end encompassing a hollow volume.
  • the open end may provide the neck of the bottle and the closed end may provide the base of the bottle after subsequent blow molding.
  • the molding may be such that various flanges and protrusions at the open end provide strengthening ribs and/or closure means, for example screw threads, for a cap.
  • Parison programming to change wall thickness and die shaping to adjust wall distribution, mainly for non-round containers, may be used to modify the resultant parison for improved blow molding performance.
  • Transporting the material extends from a melt source to the vicinity of the inlet orifice of the gate and includes an elongated bushing residing at least partially within the first cavity.
  • This bushing defines an elongated, axial passageway therethrough that terminates at a discharge orifice.
  • a "gate area”, therefore, is defined by the assembled mold and bushing between the discharge orifice of the bushing and the outlet orifice of the gate. Ideally, this gate area is the portion of the system/apparatus in which the transition of the material from the molten phase present in the "runnerless" injection apparatus to the glassy phase of the completed article occurs during the time period between sequential "shots" of material.
  • the melt may flow from the discharge orifice of the bushing, through the gap between the discharge orifice of the bushing and the inlet of the gate, through the gate, and into the article formation cavity of the mold.
  • the preform mold is ideally maintained at a temperature below the minimum T g of the polymer resin, which enables the polymer to be quenched in the amorphous phase.
  • the majority of each shot cools quickly to its glassy state in the article formation cavity of mold. This results in the preform having low crystallinity levels (i.e., an article made up of substantially amorphous material) because the material temperature does not remain within its characteristic crystallization range for any appreciable length of time.
  • injection pressure may be maintained on the melt for between about 1 and 5 seconds in order to assure that the melt is appropriately packed into the article formation cavity of the mold. Thereafter, the injection pressure on the melt is released, and the article may be allowed to cool in the mold for about 10 to 20 seconds.
  • the temperature of the melt material may transition in the gate area of the system/apparatus during the time interval between successive material "shots" between its molten phase temperature and its glassy (rigid) phase temperature in a controlled manner.
  • the preforms and final shaped articles prepared from the preforms may comprise materials other than the polyester blend, such as layers of polymeric material other than the polyester blend.
  • Various additives as generally practiced in the art may be present in the respective layers including the presence of tie layers and the like, provided their presence does not substantially alter the properties of the article.
  • additives including antioxidants and thermal stabilizers, ultraviolet light stabilizers, pigments and dyes, fillers, anti-slip agents, plasticizers, other processing aids, and the like may be employed in the layers other than the polyester blend layer.
  • preforms may be prepared by coinjection molding wherein two melt streams are injected into a mold in such a way that one polymeric material (for example, the more expensive and/or more functional material) is on the exterior of the article while another polymer is in the interior.
  • one polymeric material for example, the more expensive and/or more functional material
  • the molten materials may be injected into the mold from an annular die such that they form a laminar flow of concentric layers.
  • the inside layer and the outside layer comprise the polyester blend composition and the interior layer (a layer in which both faces of the layer are in contact with another layer) comprises a different material such as, for example, a barrier material.
  • the molten materials are introduced into the mold such that the material for the outside layer and the inside layer enter the mold cavity before the material for the interior layer enters.
  • the material for the outside and inside layer forms a leading edge of the laminar flow through the cavity.
  • the three layers enter the mold cavity in a three-layer concentric laminar flow.
  • Positioning of the various layers in a cross-section of the preform may be adjusted by controlling relative volumetric flow rates of the inside and outside layers to enable relative shifting of the position of the core, and also the relative thickness of the inside and outside layers in the molded articles (see U.S. Patent 6,596,213).
  • Molding of three materials to form a four-layer or five-layer object may include a plastic container comprising two interior layers (one layer selected for its gas barrier or gas scavenger properties, and the other layer for its UV protection or for some other property such as a structural layer or a recycled layer).
  • an additional interior structural layer may be between these interior layers.
  • the leading edge of gas barrier and/or gas scavenger property may preferably be such that one of the two interior layers is uniform in its penetration around the circumference of the molded object. This uniform penetration may be achieved by starting the flow of this one interior layer before starting the flow of the second interior layer, so that the leading edge of this first- flowing interior layer starts on the zero gradient of the velocity profile.
  • each of the interior layers may be chosen to enhance the properties of the final molded object.
  • the chosen position of the gas scavenger layer may be the innermost interior layer to reduce the permeation rate of gas through the outer layers of the container into the scavenger, and to increase the rate of gas scavenging from the contents of the container.
  • Such a position may extend the shelf life of the container contents if the purpose of the scavenger layer is to absorb gas permeating from the atmosphere exterior to the container.
  • the position of outermost interior layer may enhance the performance of a humidity-sensitive gas barrier layer, by moving the barrier layer away from the 100 percent relative humidity of the contents of a beverage that is to fill the container to a position in the wall that is closer to the lower relative humidity of the atmosphere surrounding the container.
  • Injection molded preforms may include mostly amorphous material to allow the preform to be blow-molded into a desired shape easily and with a minimum of reheating and avoiding the formation of undesirable cracks or haziness in the finished article/preform caused by the presence of excessive crystallized material therein.
  • the preform may be reheated and biaxially expanded by axial stretching and radial stretching in a blow molding operation (as described below), usually in a shaped mold so that it assumes the desired configuration.
  • the neck region is unaffected by the blow molding operation while the bottom and particularly the walls of the preform are stretched and thinned.
  • the resulting thickness of the exterior layers and the interior layers may provide sufficient strength and barrier properties to allow the bottle to contain and protect the product packaged within.
  • Biaxial orientation provides enhanced physical properties such as higher mechanical strength and rigidity, clarity
  • thermoplastic materials may be the temperature range between T g and T cc or T cg .
  • 3GT has a relatively narrow processing window.
  • Blends of 3GT and PET provide a broader processing window by shifting the crystallization temperature from glass to a higher temperature region.
  • compositions may be used to produce dimensionally-stable ISBM bottles with shrinkage in height and diameter that are statistically equivalent to the control, higher-T g PET copolymer resin and do not display the pearlescence found in PET copolymer or homopolymer ISBM bottles, especially at overall stretch ratios in excess of 15.
  • the bottles manufactured according to the process of the present invention display haze values below 1 .5, or of from 1 .5 to 0.1 , even at overall stretch ratios in excess of 15, in contrast to bottles consisting purely of poly(ethylene terephthalate).
  • compositions wherein the T g is from about 45 to about 90°C and the T cg is from about 70°C to about 150°C, as determined by differential scanning calorimetry by heating from room temperature to 280°C using a heating rate of 10°C/min, holding at 280°C for two minutes, cooling to below room temperature, and then reheating from room temperature to 280°C.
  • compositions wherein the T g is from about 45 to about 80°C. and the T cg is from about 70 to about 130, and compositions wherein the T g is from about 65 to about 80°C and the Ten is from about 90 to about 150.
  • the preforms are heated (for example, using infrared heaters) above their T g , then blown using high pressure air into the final desired shape.
  • the blowing operation is conducted in the absence of a mold cavity that defines a predetermined volume (free-blowing).
  • the blowing operation is performed using metal blow molds having an inner volume equal to the size and shape of the desired article.
  • the blowing operation may also be performed using a core rod.
  • the core rod may stabilize the preform in the proper orientation in the mold cavity and may be used to help heat the preform as it is blown.
  • the preform optionally may also be stretched axially (lengthwise) with a core rod as part of the process.
  • a representative process for producing an article such as container or bottle includes (i) preparing a composition as disclosed herein; (ii) injection molding or extrusion molding a closed-end hollow preform; (iii) (re)heating the preform to the blow molding temperature, such as about 5°C to about 30°C lower than, or about 10°C to 20°C above, the glass transition temperature range of the preform material; (iv) stretching the preform axially in the blow mold by means of a stretch rod; and (v) simultaneously with the axial stretching, introducing compressed air into the preform so as to biaxially expand the preform outwardly against the walls of the blow mold so that it assumes the desired
  • the molding temperature for the composition containing a poly(trimethylene terephthalate) can be carried out at about 15°C to about 30°C lower than the molding temperature of a polyester composition comprising no poly(trimethylene terephthalate). Also, molding can be carried out at a pressure about 10 psi to about 25 psi lower than the pressure necessary to blow mold the composition
  • preforms are injection molded, stored for a short period of time (for example 1 to 4 days) at a temperature below the T g of the composition, and blown into containers using a reheat-blow (RHB) machine. Because of the relatively high cost of molding and RHB equipment, this is the best technique for producing high-volume items such as carbonated beverage bottles.
  • RHB reheat-blow
  • the shaped articles may comprise materials other than the polyester blend, such as layers of polymeric material other than the polyester blend, or nonpolymeric substrates.
  • articles may be prepared by coinjection molding as described above wherein multiple melt streams are injected into a mold in such a way that one polymer is on the exterior of the article while at least one additional layer is in the interior.
  • Vials, bottles, jars and other containers comprising the modified polyester composition may be prepared, for example by injection-stretch- blow-molding.
  • Bottle and/or jar sizes may range from under 2-ounce to 128-ounce capacity or larger.
  • containers are generally described herein as bottles, other containers such as vials, jars, drums and fuel tanks may be prepared as described herein from the
  • compositions described herein Larger capacity containers such as drums or kegs may be similarly prepared, as are smaller vials, bottles and other containers.
  • the present process or method is particularly suitable to reduce pearlescence in shaped articles having one or more corners or salient angles or edges, such as for example in bottles having triangular, square, rectangular or polygonal shapes, since the edges of a bottle are the parts experiencing the most important amount of stretching.
  • the article disclosed above has reduced heat deformation or shrinkage, as compared to an article made from 3GT or a composition comprising more than 50 weight percent 3GT, when the article is aged at high temperature of about 30 to about 55°C or about 35 to about 45°C and at a high relative humidity of from about 60 to about 100, about 70 to about 100, or about 80 to about 95 percent.
  • the article is a heat stable article where the article is substantially the same as an article made from PET in heat deformation or shrinkage.
  • Poly(ethylene terephthalate) is commercially obtainable from M&G under the trademark CLEARTUF P76.
  • Poly(trimethylene terephthalate) is commercially obtainable from E. I. du Pont de Nemours and Company under the trademark BIOMAX PTT 1002.
  • compositions 1 to 6 having varying percentages of poly(trimethylene terephthalate) and poly(ethylene terephthalate), were prepared.
  • Composition 1 consisted of pure polyethylene terephthalate.
  • Composition 2 consisted of 3 weight percent of poly(trimethylene terephthalate) and 97 weight percent of poly(ethylene terephthalate).
  • Composition 3 consisted of 5 weight percent of poly(trimethylene terephthalate) and 95 weight percent of poly(ethylene terephthalate).
  • Composition 4 consisted of 7 weight percent of poly(trimethylene terephthalate) and 93 weight percent of poly(ethylene terephthalate).
  • Composition 5 consisted of 15 weight percent of poly(trimethylene terephthalate) and 85 weight percent of poly(ethylene terephthalate).
  • Composition 6 consisted of 27 weight percent of poly(trimethylene terephthalate) and 73 weight percent of poly(ethylene terephthalate).
  • compositions 1 to 6 were melt blended, pelletized and then dried for a minimum of 8 hours at 160°C.
  • the compositions 1 to 6 were heated to a melt at 280 °C for 150 seconds and were then injected for 3 seconds into a mold under a pressure of 800 bar. After the injection of molten composition filled up the mold cavity, the mold was cooled within 30 seconds to a temperature of 60 °C and the solidified parisons were then ejected from the mold. The parisons were then allowed to cool to ambient storage temperature and each had a weight of 80 g.
  • sample bottles 1 , 2, 3, 4, 5 and 6 each having a volume of 6 liters and made with compositions 1 , 2, 3, 5 and 6 respectively, by first applying a preblow pressure of 7 bar and then a high pressure of 30 bar.
  • the overall stretch ratio is defined as the product of the length stretch ratio and the hoop stretch ratio.
  • the length stretch ratio is defined as the length of the middle contour line of the injection stretch blow molded sample bottle, divided by the length of the middle contour line of the parison and characterizes the lengthwise stretch along the central axis of the parison into the stretch blow molded bottle.
  • the middle contour line is equidistant to the inner and outer contour lines and characterizes a contour line unaffected by localized variations in wall thickness.
  • the hoop stretch ratio is defined as the middle radius of the injection stretch blow molded sample bottle, divided by the middle radius of the parison and characterizes the increase in diameter of the parison when stretch blow molded into a bottle.
  • the middle radius is equidistant to the inner and outer radius characterizes a radius unaffected by localized variations in wall thickness.
  • the overall stretch ratio can be computed for 3 directions, the directions being front-to-back, side-to-side and diagonal.
  • the contour lines measured are defined by the intersection between the surface of the parison or bottle and a plane passing through the central axis of the parison or bottle and which is perpendicular to the front and back faces of the bottle.
  • the contour lines measured are defined by the intersection between the surface of the parison or bottle and a plane passing through the central axis of the parison or bottle and which is perpendicular to the side faces of the bottle.
  • the contour lines measured are defined by the intersection between the surface of the parison or bottle and a plane which passes through the central axis of the parison or bottle and through opposed rims of the bottle or parison.
  • compositions 1 to 6 were then tested for pearlescence according to ASTM D1003 (Procedure B) using a Minolta M3600D spectrometer.
  • pearlescence can be correlated to the haze (more haze means more pearlescence). Haze was measured according to ASTM D1003
  • Table 1 the haze values are shown for samples cut out from the bottommost sidewall of 6 liter sample bottles obtained by stretch blow molding of parisons made with compositions 1 , 2, 3, 4, 5 and 6

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)

Abstract

L'invention concerne un procédé de réduction de la perlescence de bouteilles de poly(éthylène téréphtalate) moulées par injection-soufflage avec étirage, comprenant la préparation d'un mélange fondu constitué de 85 pour cent à 97 pour cent en poids d'un poly(éthylène téréphtalate) et de 3 à 15 pour cent en poids d'un poly(triméthylène téréphtalate) et le moulage par injection-soufflage avec étirage de bouteilles à partir dudit mélange.
PCT/US2012/054947 2011-09-12 2012-09-12 Compositions à faible perlescence WO2013040096A1 (fr)

Applications Claiming Priority (2)

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US201161533393P 2011-09-12 2011-09-12
US61/533,393 2011-09-12

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WO2013040096A1 true WO2013040096A1 (fr) 2013-03-21

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019041205A1 (fr) 2017-08-31 2019-03-07 The Procter & Gamble Company Articles rigides comprenant un coin bien défini

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5914138A (en) 1996-09-27 1999-06-22 Kortec, Inc. Apparatus for throttle-valving control for the co-extrusion of plastic materials as interior core streams encased by outer and inner streams for molding and the like
JP2002097353A (ja) * 2000-09-25 2002-04-02 Teijin Ltd 樹脂組成物およびその製造方法
US6596213B2 (en) 2001-04-06 2003-07-22 Kortec, Inc. Method of molding multi-layer polymer plastic articles with control of relative shifting of the core layer
US20100044928A1 (en) * 2008-08-22 2010-02-25 E. I. Du Pont De Nemours And Company Process for Shaped Articles from Polyester Blends

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5914138A (en) 1996-09-27 1999-06-22 Kortec, Inc. Apparatus for throttle-valving control for the co-extrusion of plastic materials as interior core streams encased by outer and inner streams for molding and the like
JP2002097353A (ja) * 2000-09-25 2002-04-02 Teijin Ltd 樹脂組成物およびその製造方法
US6596213B2 (en) 2001-04-06 2003-07-22 Kortec, Inc. Method of molding multi-layer polymer plastic articles with control of relative shifting of the core layer
US20100044928A1 (en) * 2008-08-22 2010-02-25 E. I. Du Pont De Nemours And Company Process for Shaped Articles from Polyester Blends

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Blow Molding Handbook, by Rosato and Rosato", 1988, HANSER PUBLISHERS
DATABASE WPI Week 200265, Derwent World Patents Index; AN 2002-601738, XP002686643 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019041205A1 (fr) 2017-08-31 2019-03-07 The Procter & Gamble Company Articles rigides comprenant un coin bien défini

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