WO1999026771A1 - Procede de fabrication d'emballages de polyester ayant des proprietes ameliorees - Google Patents

Procede de fabrication d'emballages de polyester ayant des proprietes ameliorees Download PDF

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Publication number
WO1999026771A1
WO1999026771A1 PCT/US1998/024685 US9824685W WO9926771A1 WO 1999026771 A1 WO1999026771 A1 WO 1999026771A1 US 9824685 W US9824685 W US 9824685W WO 9926771 A1 WO9926771 A1 WO 9926771A1
Authority
WO
WIPO (PCT)
Prior art keywords
container
crystallinity
inside surface
molecular weight
diol
Prior art date
Application number
PCT/US1998/024685
Other languages
English (en)
Inventor
Mark Edward Stewart
David Dunlap Cornell
Original Assignee
Eastman Chemical Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eastman Chemical Company filed Critical Eastman Chemical Company
Priority to AU16999/99A priority Critical patent/AU1699999A/en
Priority to EP98961743A priority patent/EP1032491A1/fr
Publication of WO1999026771A1 publication Critical patent/WO1999026771A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • 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
    • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/0009—After-treatment of articles without altering their shape; Apparatus therefor using liquids, e.g. solvents, swelling agents
    • 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
    • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/0063—After-treatment of articles without altering their shape; Apparatus therefor for changing crystallisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/712—Containers; Packaging elements or accessories, Packages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the invention concerns a method for forming a container with improved properties, particularly barrier to gases. More particularly, the invention relates to blow molding a polyester container which incorporates hydrolyzing and crystallizing at least a portion of the container's interior surface.
  • Rigid containers made from polyesters such as poly(ethylene terephthalate) and its copolymers (PET) are widely used to package food, beverage and other products.
  • PET poly(ethylene terephthalate) and its copolymers
  • their application is limited by the fact that gases are absorbed into and permeate through the polymer.
  • low permeability is necessary to prevent packaged components, such as carbon dioxide in a carbonated drink, from escaping through the PET container wall. This loss of carbon dioxide from carbonated beverages results in the drink being "flat”. This loss is more pronounced for small packages due to their higher surface to volume ratio.
  • PET is not commonly used for soft drink packages below about 16 fluid ounces in size. Oxygen is also transported through PET. This limits the use of PET packages for oxygen sensitive products such as beer, fruit juices and tomato-based products.
  • polyester transport properties limit their use is in packaging of water.
  • Acetaldehyde a by-product of melt processing of PET caused by the thermal degradation of the PET, diffuses from PET into the water over time.
  • Acetaldehyde in very low concentrations will affect the taste of the water.
  • U.S. patent no. 5,342,558 discloses a "double blow" processes where an amorphous PET preform having a body and a neck sections have dimensions greater than the dimensions of the final PET container to be formed.
  • the body of the intermediate container are heated under specified conditions to rapidly shrink the body, to form a contracted body.
  • the neck section is then heated to effect crystallization.
  • the neck section is then slowly cooled while heating the contracted intermediate body.
  • the heated contracted body of the intermediate container is then blow molded in a second mold to its final shape and dimensions.
  • U.S. patent no. 5,730,914 Another method for increasing the barrier properties of a PET container is described in U.S. patent no. 5,730,914 where a PET bottle preform is preheated to soften the PET. A stretch rod is inserted through the top of the preform to stretches the preform axially until the preform is the length of the final product. The preform is expanded using compressed ambient air, and is molded against the walls of the mold. The air is vented, and dry nitrogen at a temperature below -50° C is injected into the molded preform to purge and cool the molded preform while maintaining pressure of at least 520 kPag.
  • the molded preform is held against the mold for a predetermined time, during which the outer and inner surfaces of the molded preform are annealed, and the molded preform transforms into the final product.
  • the present invention provides a method for increasing the crystallinity of at least a portion of a thermoplastic container.
  • the method includes the steps of hydrolyzing at least a portion of an inside surface of the container so that a portion of the inside surface has a lower molecular weight, M n relative to the remainder of the container and crystallizing at least a portion of the inside surface.
  • M n molecular weight
  • the crystallinity of the inside surface of the container is greater than about 30 percent.
  • Another aspect of the invention is for a thermoplastic container having a crystallinity of the inside surface greater than about 30 percent.
  • the inside surface of the container is at least partially hydrolyzed and then crystallized to produce a container having an inside surface with a greater crystallinity relative to the remainder of the container.
  • the polyester component of the present invention is a polyethylene terephthalate (PET) or polyethylene naphthalate (PEN) resin. Copolyesters and blends of PET, PEN and polyamides may also be used.
  • the polyester resin of the present invention contains repeat units from at least 80 mole percent of a first dicarboxylic acid selected from terephthalic acid, 2,6-naphthalene- dicarboxlic acid and mixtures thereof and at least 80% ethylene glycol, based on 100 mole percent dicarboxylic acid and 100 mole percent diol.
  • the dicarboxylic acid component of the polyester may optionally be modified with up to about 20 mole percent of one or more different dicarboxylic acids other than terephthalic acid or suitable synthetic equivalents such as dimethyl terephthalate.
  • Such additional dicarboxylic acids include aromatic dicarboxylic acids preferably having 8 to 14 carbon atoms, aliphatic and hetero dicarboxylic acids preferably having 4 to 12 carbon atoms, or cycloaliphatic dicarboxylic acids preferably having 8 to 12 carbon atoms.
  • dicarboxylic acids to be included with terephthalic acid are: phthalic acid, isophthalic acid, isomers of naphthalenedicarboxylic acid other than the 2,6-isomer, cyclohexanedicarboxylic acid, cyclohexanediacetic acid, diphenyl-4,4'-dicarboxylic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, diglycotic acid, 1-3-phenylene dioxydiacetic acid and the like. Polyesters may be prepared from two or more of the above dicarboxylic acids.
  • polyester component may optionally be modified with up to about 20 mole percent, of one or more different diols other than ethylene glycol.
  • additional diols include cycloaliphatic diols preferably having 6 to 20 carbon atoms or aliphatic diols preferably having 3 to 20 carbon atoms.
  • the diols may further contain hetero carbon atoms.
  • diols to be included with ethylene glycol are: diethylene glycol, triethylene glycol, 1 ,4-cyclohexanedimethanol, propane- 1,3-diol, butane- 1,2-diol, pentane-l,5-diol, hexane-l,6-diol, 3-methylpentanediol-(2,4), 2-methylpentanediol-(l,4), 2,2,4-trimethylpentane-diol-(l,3), 2-ethylhexanediol- (1,3), 2,2-diethylpropane-diol-(l,3), hexanediol-(l,3), l,4-di-(hydroxyethoxy)-benzene, 2,2-bis-(4-hydroxy-cyclohexyl)-propane, 2,4-dihydroxy- 1,1,3, 3-tetramethyl- cycl
  • the polyethylene terephthalate resin may also contain small amounts of trifunctional or tetrafunctional comonomers such as trimellitic anhydride, trimethylolpropane, pyromellitic dianhydride, pentaerythritol, and other polyester forming polyacids or polyols generally known in the art.
  • trifunctional or tetrafunctional comonomers such as trimellitic anhydride, trimethylolpropane, pyromellitic dianhydride, pentaerythritol, and other polyester forming polyacids or polyols generally known in the art.
  • PET polyesters comprise at least about 85 mole % and more preferably about 90 mole% of said first dicarboxylic acid and about 85 mole % and more preferably about 90 mole% ethylene glycol residues.
  • Polyethylene terephthalate based polyesters of the present invention can be prepared by conventional polycondensation procedures well-known in the art. Such processes include direct condensation of the dicarboxylic acid(s) with the diol(s) or by ester interchange using a dialkyl dicarboxylate. For example, a dialkyl terephthalate such as dimethyl terephthalate is ester interchanged with the diol(s) at elevated temperatures in the presence of a catalyst.
  • the polyesters may also be subjected to solid state polymerization methods.
  • PEN and PEN-T copolymers and blends may also be prepared by well known polycondensation procedures.
  • compositions of the present invention can be added to the compositions of the present invention to enhance the performance properties of the polyesters.
  • crystallization aids for example, crystallization aids, impact modifiers, surface lubricants, denesting agents, stabilizers, antioxidants, ultraviolet light absorbing agents, metal deactivators, colorants, nucleating agents, fillers, reheat aids, acetaldehyde reducing agents and the like can be included. All of these additives and many others and their use are well known in the art and do not require extensive discussion. Therefore, only a limited number will be referred to, it being understood that any of these compounds can be used so long as they do not hinder the present invention from accomplishing its objects.
  • a polyester bottle having improved barrier properties can be produced by increasing the crystallinity of the inside surface of the container.
  • the crystallinity of the inside surface may be determined by using methods known to those skilled in the art. Such methods include, but are not limited to, x-ray defractions, differential scanning calorimetry and refractive index.
  • polyesters are formed into preforms using any method known to one skilled in the art.
  • Equipment for making preforms by injection molding is readily available from Husky, Nissei, Aoki and others.
  • the preforms are heated to an appropriate blowing temperature, based on its composition, predetermined size, shape and the like.
  • the blow molding temperature is greater than about glass transition temperature, but below about the onset of crystallization of the polyester being used.
  • this temperature is generally in the range of about 90°C and about 130°C.
  • Suitable pressurized fluids include, but are not limited to air, nitrogen, steam, any inert gas, CO2 and the like. Air is most commonly used. Generally inflation takes place in a mold of the desired size and shape.
  • At least a portion of the inside surface area is hydrolyzed so as to lower the molecular weight, M n , of at least a portion of the inside surface area of the preform.
  • Hydrolysis of the inside surface area of the polyester can be effected at any time, i.e., before expansion, during expansion, or subsequent to expansion.
  • the polyester can be hydrolyzed using methods known to those skilled in the art and include, contacting the inside surface with one or more, either alone or in combination, hydrolyzing agents, such as, steam, a lower alkyl alcohol, a diol, an acid and/or a base, with steam being preferred and super heated steam being more preferred.
  • Suitable lower alkyl alcohols include, C ⁇ -C ⁇ 2 alcohols with C ⁇ -C 8 alcohols being preferred and C ⁇ -C 4 being more preferred.
  • Non- limiting examples of preferred lower alkyl alcohols include methanol, ethanol, n-propanol and isoropanol.
  • Suitable diols include ethane diol; propane diol; ethylene glycol; diethylene glycol; propylene glycol; 2-ethylhexane-l,3-diol; 3-methylpentane-2,4-diol; 2- methylpentane-2,4-diol, 2,2,4-trimethylpentane-l,3-diol; 2,2-diethylprop.ane-l,3-diol; butane- 1,4-diol; hexane-2,5-diol; propane- 1,3-diol and butane-l,3-diol.
  • Suitable acids and bases include, but are not limited to, acetic acid, hydrochloric acid, and sodium hydroxide.
  • the hydrolyzing agent is a generally recognized as safe food additive as defined in 21 CFR, the disclosure of which is incorporated herein by reference, or would meet the definition as a generally recognized as safe food additive.
  • the inside surface of the polyester container desirably has from about 10% to 100%) of the surface contacted with one or more of the above hydrolyzing agents. Preferably, from about 25%> to 100% of the inside surface is contacted with the hydrolyzing agent and more preferably greater than about 50% of the inside surface is contacted with the hydrolyzing agent.
  • the molecular weight of at least a portion of the hydrolyzed polyester is lowered by at least about 20 %, preferably, by at least about 30%, and more preferably by at least about 50% so that the hydrolyzed polyester has a molecular weight of from about 1000 to about 15,000 and preferably from about 1000 to about 10,000.
  • a preform contacted (either before expansion, during expansion or after the final dimensions have been achieved) with a hydrolysis agent produces a thin film of polyester having a lower molecular weight than the untreated polyester. Surprisingly, subsequent crystalization of the lower molecular weight polyester results in a container having improved barrier properties. While the preform is in the mold, the interior of the container is treated with the hydrolysis agent. Although not wishing to be bound by any theory, it is believed that the containers should be in contact with the mold during this step to produce optimum properties.
  • the hydrolysis agent should be at a pressure which is at least about the pressure of the fluids which are used in stage blow molding where the hydrolysis agent is introduced.
  • typical steam pressures include those between about 100 to about 600 lbs.
  • the hydrolysis agent may be introduced concurrently with the pressurized fluid (which is at about 600 lbs) or sequentially, i.e., after stretching, which could be as a pressure, below about 600 lbs, to as low as about 100 lbs.
  • Conventional processes sometimes use pulsed pressurized fluids and the hydrolysis agent of this invention may be introduced in a continuous, staged or pulsed phase, either at or slightly above the pressures which are conventionally used at that stage.
  • the total contact time (either continuous or the aggregation of pulses or stages) may be up to about 5 seconds, and preferably from about 0J second to about 5 seconds. It should be appreciated that higher pressure or temperature, and more acidic or basic hydrolysis agents may require shorter contact times.
  • the method of the invention further includes crystallizing at least a portion of the inside surface area of the container.
  • Method for crystallizing a polyester are well known in the art and include introducing or subjecting the container to sufficient energy to overcome the energy of crystallization.
  • the interior of the containers may also be irradiated to effect crystallization.
  • Suitable radiation sources include any source which is capable of starting crystallization of the container interior surface. Suitable radiation sources include electromagnetic radiation having a wavelength of from about 300 nanometers ( ⁇ ) to about 1 cm and preferably 700 nm - 2000 nm. Examples of suitable sources of irradiation include electron beam, electron plasma, high intensity visible light, lasers, infrared light, microwave and the like.
  • the irradiation time is of a limited duration sufficiently so that only a thin layer of crystallized polyester is generated.
  • Exposure time to the radiation source will vary depending on the type and intensity of the radiation source selected. Generally exposure times of less than about 20 seconds, and preferably from about 0.2 seconds to about 10 seconds are contemplated.
  • the process of the present invention produces a polyester container having a thin interior layer having high crystallinity.
  • the crystalline layer provides containers of the present invention with significantly improved barrier and resistance to sorption over conventional non-treated polyester containers.
  • the method of the invention produces a polyester container having an inside surface with a crystallinity greater than about 30 %>, preferably, greater than about 40%, more preferably greater than about 50% and most preferably greater than about 60%.
  • thermoplastic container and preferably, a polyester container having an inside surface with a crystallinity greater than the remainder of the container.
  • the crystallinity of the inside surface is desirably greater than about 30 %, preferably, greater than about 40%, more preferably greater than about 50% and most preferably greater than about 60%.
  • the increased crystallinity of the inside of the container is achieved using the method of the invention as described above.

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  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)

Abstract

L'invention concerne un procédé permettant d'améliorer la cristallinité d'un conteneur thermoplastique (par exemple, en polyester), et plus particulièrement d'une bouteille en polyéthylène téréphtalate (PET), ou en polyéthylène naphtalate (PEN), ou à base d'un mélange des deux. On hydrolyse au moins une partie de la surface interne de la bouteille pour réduire le poids moléculaire, Mn, du polyester par rapport au reste de la bouteille, et on cristallise au moins une partie de ladite surface. Il est souhaitable que cette surface ait une cristalllinité supérieure à environ 30 %. On obtient donc un conteneur thermoplastique à surface interne dont la cristalllinité est supérieure à celle du reste du conteneur, la cristallinité intérieure étant augmentée grâce au procédé décrit.
PCT/US1998/024685 1997-11-21 1998-11-20 Procede de fabrication d'emballages de polyester ayant des proprietes ameliorees WO1999026771A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU16999/99A AU1699999A (en) 1997-11-21 1998-11-20 Method for production of polyester packages with improved properties
EP98961743A EP1032491A1 (fr) 1997-11-21 1998-11-20 Procede de fabrication d'emballages de polyester ayant des proprietes ameliorees

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US6633097P 1997-11-21 1997-11-21
US60/066,330 1997-11-21
US19729898A 1998-11-20 1998-11-20
US09/197,298 1998-11-20

Publications (1)

Publication Number Publication Date
WO1999026771A1 true WO1999026771A1 (fr) 1999-06-03

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Application Number Title Priority Date Filing Date
PCT/US1998/024685 WO1999026771A1 (fr) 1997-11-21 1998-11-20 Procede de fabrication d'emballages de polyester ayant des proprietes ameliorees

Country Status (2)

Country Link
EP (1) EP1032491A1 (fr)
WO (1) WO1999026771A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001034370A1 (fr) * 1999-11-09 2001-05-17 Schmalbach-Lubeca Ag Procede de moulage par soufflage et machine pour produire des recipients pasteurisables
WO2014183812A1 (fr) * 2013-05-16 2014-11-20 Equipolymers Gmbh Procédé de fabrication d'une bouteille en pet ayant une résistance améliorée à la fissuration sous contrainte environnementale
WO2015090424A1 (fr) * 2013-12-19 2015-06-25 Equipolymers Gmbh Pet résistant à la fissuration sous contrainte et fabrication associée

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2856638A (en) * 1954-07-20 1958-10-21 Eastman Kodak Co Process for the after-treatment of polymeric articles
US3546332A (en) * 1967-12-26 1970-12-08 Union Carbide Corp Surface crystallization of poly(2,2,4,4-tetramethylcyclobutanediol - 1,3)carbonates
US3716606A (en) * 1969-07-21 1973-02-13 Kemp Prod Ltd Method of stabilizing thermo-plastic containers
JPS5466967A (en) * 1977-11-08 1979-05-29 Yoshino Kogyosho Co Ltd Method of preventing whitening or crazing of extention blow molding bottle made of saturated polyester
JPS5544871A (en) * 1978-09-28 1980-03-29 Mitsubishi Plastics Ind Ltd Thermal setting method for a hollow body
US4260567A (en) * 1979-02-26 1981-04-07 Standard Oil Company (Indiana) Shrinkage reduction of blow molded oriented pet bottle
JPS59129125A (ja) * 1983-01-17 1984-07-25 Nippon Ester Co Ltd 熱可塑性ポリエステル容器の製造方法
US4764323A (en) * 1985-11-19 1988-08-16 Cobarr S.P.A. Method of treating hollow articles, in particular polyethylene terephthalate preforms
US5039467A (en) * 1989-07-25 1991-08-13 Hoechst Celanese Corporation Process for producing zero pilling polyester
US5650204A (en) * 1993-09-16 1997-07-22 Mitsui Petrochemical Industries, Ltd. Polyester bottle and method of removing adsorbates on the bottle

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2856638A (en) * 1954-07-20 1958-10-21 Eastman Kodak Co Process for the after-treatment of polymeric articles
US3546332A (en) * 1967-12-26 1970-12-08 Union Carbide Corp Surface crystallization of poly(2,2,4,4-tetramethylcyclobutanediol - 1,3)carbonates
US3716606A (en) * 1969-07-21 1973-02-13 Kemp Prod Ltd Method of stabilizing thermo-plastic containers
JPS5466967A (en) * 1977-11-08 1979-05-29 Yoshino Kogyosho Co Ltd Method of preventing whitening or crazing of extention blow molding bottle made of saturated polyester
JPS5544871A (en) * 1978-09-28 1980-03-29 Mitsubishi Plastics Ind Ltd Thermal setting method for a hollow body
US4260567A (en) * 1979-02-26 1981-04-07 Standard Oil Company (Indiana) Shrinkage reduction of blow molded oriented pet bottle
JPS59129125A (ja) * 1983-01-17 1984-07-25 Nippon Ester Co Ltd 熱可塑性ポリエステル容器の製造方法
US4764323A (en) * 1985-11-19 1988-08-16 Cobarr S.P.A. Method of treating hollow articles, in particular polyethylene terephthalate preforms
US5039467A (en) * 1989-07-25 1991-08-13 Hoechst Celanese Corporation Process for producing zero pilling polyester
US5650204A (en) * 1993-09-16 1997-07-22 Mitsui Petrochemical Industries, Ltd. Polyester bottle and method of removing adsorbates on the bottle

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001034370A1 (fr) * 1999-11-09 2001-05-17 Schmalbach-Lubeca Ag Procede de moulage par soufflage et machine pour produire des recipients pasteurisables
WO2014183812A1 (fr) * 2013-05-16 2014-11-20 Equipolymers Gmbh Procédé de fabrication d'une bouteille en pet ayant une résistance améliorée à la fissuration sous contrainte environnementale
WO2014183791A1 (fr) * 2013-05-16 2014-11-20 Equipolymers Gmbh Procédé de fabrication d'une bouteille en pet présentant une résistance améliorée à la fissuration sous contrainte dans un environnement donné
WO2015090424A1 (fr) * 2013-12-19 2015-06-25 Equipolymers Gmbh Pet résistant à la fissuration sous contrainte et fabrication associée

Also Published As

Publication number Publication date
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