Source: https://patents.google.com/patent/US4512948A/en
Timestamp: 2019-08-24 01:56:43
Document Index: 122866353

Matched Legal Cases: ['Application No. 146', 'Application No. 77', 'Application No. 21', 'Application No. 78', 'Application No. 78', 'Application No. 41']

US4512948A - Method for making poly(ethylene terephthalate) article - Google Patents
Method for making poly(ethylene terephthalate) article Download PDF
US4512948A
US4512948A US06/354,473 US35447382A US4512948A US 4512948 A US4512948 A US 4512948A US 35447382 A US35447382 A US 35447382A US 4512948 A US4512948 A US 4512948A
US06/354,473
1982-03-03 Application filed by Owens Illinois Inc filed Critical Owens Illinois Inc
1982-03-03 Priority to US06/354,476 priority Critical patent/US4419151A/en
1982-12-20 Assigned to OWENS-ILLINOIS, INC. reassignment OWENS-ILLINOIS, INC. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: JABARIN, SALEH A.
1983-01-20 Priority claimed from CA000419874A external-priority patent/CA1197961A/en
1983-12-02 Priority claimed from US06/557,566 external-priority patent/US4476170A/en
1985-04-23 Publication of US4512948A publication Critical patent/US4512948A/en
Disclosed is a process of making an oriented and heat set blow molded bottle of poly(ethylene terephthalate) so that the bottles resulting from the process have a density over 1.3860 cc./gm. and an onset-of-shrinkage temperature over 80° C. In the process preform preheated to a temperature suitable for orientation is biaxially stretched in a blow mold and then while the hollow article walls are still in contact with the blow mold walls, the article is raised to a higher heat setting temperature in the range of 200°-250° C. (except for the neck) thus heat setting the bottle, and while the article is still at a shrinkage resisting pressure exceeding atmospheric cooling the article to a temperature at which it maintains its shape when not pressurized but not below 100° C. It is also particularly disclosed that this cooling step can be done outside the mold. In a special embodiment of the invention where the cooling step is effected outside the mold, the cooling under the shrinkage resisting pressure is below 100° C., even down to room temperature and lower, before the shrinkage resisting pressure is released from the hollow article.
It is stated in Collins that the heat setting temperature used is that normally encountered in heat setting of oriented films or fibers made from the given plastic material. It is not stated, however, what heat setting temperatures are "normal" for making oriented films or fibers from poly(ethylene terephthalate). See Collins, infra. However, for this plastic it is disclosed in Collins that the mold is preferably maintained at 130° to 220° C.
It is disclosed in Collins that after heat setting, the container should be cooled down to a temperature, for instance, below about 60° C. In one example of Collins, the heat setting temperature of the mold is 200° C. and in the other, it is 140° C.
In unexamined Japanese Patent Application No. 146,175, laid open Nov. 15, 1980, containers are stretch blow molded under conditions to biaxially orient the polyester molecules. It is explained that as a result of the stretch blow molding, the residual strain was large and that when heated subsequent to the molding, the residual strain was released, causing deformation of the container. To solve this problem, the reference recommends heat setting the containers after blow molding. It is also recommended that the heat setting temperature in unstretched areas such as the neck be held to 95°-125° C. so that hazing will not occur in these areas. Other areas are heat set at a higher temperature. It is recommended that the heat setting of the highly strained areas of the container be in the range from 125° C. to 235° C. However, quenching of the heat set container at 100° C. or above is not disclosed.
Unexamined Japanese Patent Application No. 77,672, laid open June 21, 1979, is similar except that it is not taught to heat set unoriented parts at a lower temperature than other parts. The highest temperature disclosed for heat setting is 130° C. and in the only specific example the oriented blow molded bottle is heat set by contacting with the hot blow mold kept at 130° C. and then lowering the mold temperature to 100° C. to prevent bottle deformation when the bottle is discharged from the mold. In this reference, it is stated that hazing occurs when higher heat setting mold temperatures are used. The reference does not disclose the present method or the novel products of the present invention.
In unexamined Japanese Patent Application No. 21,463, laid open Feb. 17, 1979, a blown poly(ethylene terephthalate) bottle was heat set by heating the bottle to 140° C. while still within the blow mold.
In unexamined Japanese Patent Application No. 78,267, laid open June 11, 1978, there is disclosed stretch blow molding a thermoplastic resin, in the example specifically poly(ethylene terephthalate) to make a hollow article, and while the article is still in the mold to introduce hot gases for purposes of heat setting. In the example, the hot gas is at 180° C. The example does not disclose cooling the heat set article before removal from the mold, but the description of the drawing does describe this as an alternative treatment, using normal temperature compressed gas to cool the molded piece.
In unexamined Japanese Patent Application No. 78,268, laid open June 11, 1978, a stretch blow molded hollow body, including those made from poly(ethylene terephthalate) is heat set by introducing hot gas under pressure into the interior of the bottle while in the mold. After the heat setting, normal temperature gas can be optionally blown into the article to cool the article before removal from the mold, or the heat set body can simply be exhausted to atmospheric. In an example, the heated gas for heat setting is at 200° C. In the specific example, no cooling before removal from the mold was disclosed. Again, the heating includes heating of the neck portion of the bottle.
In unexamined Japanese Patent Application No. 41,973, laid open Apr. 3, 1979, it is disclosed to heat set stretch blow molded containers, including those made from poly(ethylene terephthalate) by heating the blown containers at a high temperature and then rapidly cooling them to room temperature. Heat treatment can be within the mold while under pressure and the heating can be by means of a hot mold. It is disclosed that the heat treatment should be such that the density of the bottle body following the heat treatment is no greater than 1.40 gms./cc. In the example given, steam at 179° C. is used for heating the mold in the heating step.
Scarlett U.S. Pat. No. 2,823,421 discloses heat setting of PET films using heat setting temperatures of 150°-250° C. after orientation stretching. This patent does not state, however, what "normal" PET film heat setting temperatures are. It does disclose that for a film stretched three times in each direction that a heat setting temperature of 200° C. is preferred by Scarlett.
German Pat. No. 2,540,930 discloses heat setting of hollow articles. The blank or parison is blow molded at 70°-140° C. and then cooled in the mold to below 70° C. Thereafter, the bottle can be reheated to heat setting temperature in that mold or in a different mold. The heat setting temperature is said to be over 140° C. or higher. In the disclosed process the entire bottle including the neck is heated in the heat setting step to the same temperature and the neck of the bottle crystallizes to an opaque state.
In Brady et al. U.S. Pat. No. 4,233,022 a bottle oriented by blow molding PET at 75°-100° C. is heat set. Heat setting is accomplished in a hot mold at a suitable heat setting temperature; examples of such temperatures are given as 150° to 220° C. The patent features controlling different zones of the bottle at different temperatures, so that all the sidewall of the bottle is at the maximum heat setting temperatures being used, but the finish or neck, for instance, is actually cooled to prevent crystallization thereof. In this patent after the heat setting step, it is stated that the bottle is cooled to a self-sustaining condition.
In one embodiment the present process features biaxially orienting a parison preheated to orientation temperature, by inflating in a blow mold which has been preheated to the higher, heat setting temperature and holding the bottle or other hollow article against the mold wall for the short time necessary to effect heat setting. The process of the present invention also features thereafter cooling the heat set hollow article or bottle while under pressure but not below 100° C. and then exhausting the pressure in the bottle to essentially atmospheric or ambient pressure before further cooling of the article below 100° C. takes place.
For instance, Collins U.S. Pat. No. 4,039,641 specifically discloses cooling to below 60° C. and in one specific example cools to 40° C., before releasing the gas pressure.
Ordinarily, when a PET bottle is blown in a blow mold, it is cooled to quite a low temperature, a temperature very much below the temperature at which the bottle would be self-sustaining, in fact much below the temperature at which the bottle will shrink at all when the pressure is released. According to an important feature of the present invention, I cool the heat set bottle, while still under pressure preventing shrinkage, to a temperature which will allow the volume of the hollow article to shrink no more than 6 percent, preferably 5 percent, when the pressure is removed and allowed to cool to room temperature, but no lower than 100° C., before releasing the pressure to equalize it with the ambient atmosphere. I have discovered that cooling under pressure, i.e. when not allowing shrinkage, below 100° C. progressively reduces the onset-of-shrinkage temperature even when the final room temperature volume remains the same and does not decrease with decreasing "quench" temperature. Thus, referring to the tables described hereafter, it will be seen that the volume remains essentially constant for quench temperatures of 90° C. and below but that the onset-of-shrinkage temperature becomes progressively lower. It has also been found that the trend continues above 100° C. quench temperature, i.e. that the onset-of-shrinkage temperature increases as the quench temperature increases above 100° C.
(2) while said article is still under pressure sufficient to maintain its essential size and shape, heating to a higher temperature in the range 200° to 250° C. the portions thereof that it is desired to crystallize, thereby increasing the density of such portions, and
(3) while said article is still under a pressure sufficient to maintain its essential size and shape, cooling said article to a temperature at which it maintains its shape even without internal pressure above atmospheric but not below 100° C., and
(2) while said parison is still at said first temperature range expanding said parison into contact and conformance with the blow mold walls by inflation with a gas under pressure to make a hollow blown article, said stretching and expanding under the resulting strain conditions resulting in biaxial orientation and concomitant partial crystallization, and then while the article walls are still inflated in contact with said mold walls, raising the temperature of the article to a higher second temperature in the range 200° to 250° C., except for the neck or finish portion of said article which is kept at a low temperature such that crystallization is minimized or eliminated so that the neck or finish portion remains transparent; this temperature is usually in the range of 40°- 125° C., more usually 40°-80° C., but any non-crystallizing temperature of 125° C. or below can be used,
(4) and while said hollow article is still at a shrinkage-resisting pressure exceeding atmospheric, cooling said article to a temperature at which it maintains its shape when not pressurized but not below 100° C., and
According to another aspect of the present invention, there is provided new a product which is the product of the foregoing process: a transparent hollow article of poly(ethylene terephthalate) having an inherent viscosity of at least 0.6 dl./gm., the body portion of said article being biaxially oriented and heat set and having a density over 1.3860 gm./cc. and an onset-of-shrinkage temperature of over 80° C.
In a preferred embodiment of the present process the heat setting second temperature is in the range of 225° to 250° C. The product of this preferred process is a transparent hollow article of poly(ethylene terephthalate) having an inherent viscosity of at least 0.6 dl./gm., the body portion of said article being biaxially oriented and heat set and having a density over 1.3930 gm./cc. and an onset-of-shrinkage temperature of over 105° C.
In the drawings 23 and 24 are thermocouples positioned as shown and 1/8 inch from the mold cavity wall. In extensive testing, it was shown that the temperature varied only about 4° to 5° F. between the two thermocouples with the hottest temperature being at 23 near the bottom of the bottle.
For comparison or control purposes, a bottle was blown identically to the others except that it was blown into a cold mold and cooled to 23° C. Thus, the control had no heat setting but was only biaxially oriented and not heat set, during the course of which its density increased to 1.3634 gms./cc. Its onset-of-shrinkage temperature was 46° C.
The bottles in the examples represented by the data in Tables 1 and 2 were made from injection molded parisons having the general shape shown in FIG. 1. They were 7.2 inches long with a wall thickness of 145-150 mils and weighed 26 gms. The parisons were preheated to about 190° F. (outside surface 190° F., inside surface 188° F.). The parison at this temperature was enclosed in the split halves of the blow mold, one-half of which is shown in FIG. 1. Then the stretch rod 22 was pushed against the bottom of the parison for 0.15 second before the blow pressure air was applied at 100 psig for 0.5 second, after which it was increased to 300 psig, and the stretch rod was maintained in the position shown on FIG. 2 for 2 seconds and was then retracted. At all times cold water circulated through lower mold section 6 and neck ring 4 so that the unexpanded neck was kept cold. The blown bottle is of course blown against the blow mold wall, which is maintained at the heat setting temperature shown in Table 1 or 2 for the time shown in the table. After this time, cold oil was circulated to replace the hot oil for the length of time needed to lower the temperature to the quench temperature shown in the tables. Once this temperature was reached, the bottle was exhausted to atmospheric and the mold was opened. The bottles are thereafter allowed to cool, eventually to room temperature, without internal pressure.
TABLE 1______________________________________Heat                    Volume       OnsetSetting  Quench    Density.sup.(1)                       2 min..sup. (2)                              24 hrs.                                    Temp.°C.Sec.    Temp. °C.                  gm./cc.                         cubic centimeters                                     °C.______________________________________250  30      148       1.4013250  120     148       1.4022240  6       180       1.3980 497.9  497.4240  6       170       1.3980 501.9  501.6240  6       160       1.3980 506.2  506.1 184240  6       150       1.3980 509.3  509.2240  6       130       1.3978 513.9  514   172240  6       120       1.3978 516.1  515.9 168240  6       110       1.3978 518.5  518.4 --240  6       100       1.3965 519.4  519.7 154240  6       90        1.3970 520.8  520.9 143240  6       80        1.3986 521.7  521.7 139240  6       80        1.3982 none.sup.(3)                                521.8 --240  6       60        1.3982 521.8  522.1 132230  6       170       1.3950 493.1  493.6 --230  6       160       1.3950 499.5  498.8 168230  6       150       1.3950 504.1  503.8 --230  6       140       1.3950 509.0  508.6230  6       129       1.3950 512    511.6 148230  6       124       1.3947 514.1  513.7 138230  6       100       1.3947 520.7  519.8 120230  6       85        1.3945 521.1  520.6 113230  6       75        1.3945 521.4  520.9 104230  6       60        1.3950 521.8  521.8  88______________________________________ .sup.(1) at midsidewall .sup.(2) overflow volume measured by filling with room temperature water minutes after opening mold. .sup.(3) allowed to cool 24 hours in air without filling with water until then.
TABLE 2__________________________________________________________________________Heat              VolumeSetting  Quench        Density.sup.(1)             2 min..sup.(2)                  24 hrs.                      Onset°C.   Sec.  Temp. °C.        gm./cc.             cubic centimeters                      Temp. °C.__________________________________________________________________________220   6   160   1.3912             Deformed220   6   150   1.3928             500.9                  500.7220   6   140   1.3910             502.9                  502.9220   6   135   1.3912             506.0                  505.8                      114220   6   120   1.3914             513.9                  513.6                      108220   6   110   1.3918             517.5                  517.4                      100220   6   100   1.3918             519.8                  519.5                      94220   6   90    1.3923             520.5                  520.5                      88220   6   80    1.3919             521.2                  521.4                      83220   6   60    1.3922             521.5                  521.5                      76200   6   140   1.3867             Deformed200   6   130   1.3867             496.5                  495.7                      102200   6   115   1.3868             513.0                  513.0                      95200   6   100   1.3877             519.9                  519.8                      84200   6   90    1.3870             519.9                  520.0                      80200   6   80    1.3860             520.8                  520.4                      78200   6   60    1.3872             521.0                  520.8                      74130   6   100   1.3702             509  508.4                      74    (Deformed)130   120 100   1.3744             512.2                  511.7                      74    (Deformed)__________________________________________________________________________ .sup.(1) at midsidewall .sup.(2) overflow volume measured by filling with room temperature water minutes after opening mold? .sup.(3) allowed to cool 24 hours in air without filling with water until then.
The bottles made at 250° C. heat setting temperature were made of 0.9 inherent viscosity PET.
Carbon dioxide barrier properties of containers were determined by a gas chromatographic method. Containers were placed in a test fixture in which carbon dioxide gas at one atmosphere absolute was established and maintained at the outside surface and dry nitrogen gas at one atmosphere absolute at the inside surface. Carbon dioxide permeates through the wall from the outside to the inside of the container. The nitrogen gas inside the container was periodically sampled for permeated carbon dioxide with a gas chromatograph. The rate of carbon dioxide permeation was determined from the rate of increase of CO2 concentration in the nitrogen gas inside the container. The system was calibrated by using an assayed calibrting gas of CO2 in nitrogen supplied by Matheson Gas Products. Carbon dioxide test gas was moisturized to 50-100% relative humidity in the test fixture by evaporation of water from several sponges. Test temperature was controlled by placing the entire apparatus in a closed room which was controlled at 73°±2° F.
A method employing a Hersch coulometric detector was used to determine oxygen barrier properties of containers. The apparatus is similar to an Oxtran 100 Permeation Analyzer manufactured by Modern Controls, Elk River, Minn. A test fixture was used to establish oxygen and nitrogen gases at one atmosphere absolute at the outside and inside surfaces of the container respectively. Oxygen surrounding the outside surface was continuously replaced by a flowing gas stream which was vented to the atmospheric environment. The nitrogen gas inside the container was also a flowing system and served as a sweep gas. Oxygen permeated through the wall from the outside to the inside of the container where it was picked up by the nitrogen sweep gas and carried to the coulometric detector for measurement and venting to atmosphere. The output of the detector is directly proportional to the amount of oxygen it receives and calibration is computed from well established laws of electrochemistry. Both oxygen and nitrogen gases were moisturized by bubbling through tubes of water prior to entering the test fixture. Test temperature was controlled by placing the apparatus in a closed room which was maintained at 73°±2° F.
The results in the following Table 3 are for nominal one-half liter bottles made from parisons each weighing about 25.85 grams and made as described for the bottles in connnection with Tables 1 and 2. The control bottles were merely blown under orientation conditions as before described and quenched to near room temperature without heat setting while the heat set bottles were heat set at 241° C. as indicated.
TABLE 3______________________________________                        CarbonHeat-Set   Quench    Oxygen     DioxideTemper- Temper-   Permeation Permeation                                 Densityature °C.   ature °C.             (cc/day atm)                        (cc/day atm)                                 gms./cc.______________________________________control           0.126      0.830    1.3630control           0.128      0.760    1.3630control           0.125      --control           0.125      --average           0.126      0.795241     147       0.093      0.498    1.3996241     148       0.087      --241     147       0.089      0.499    1.4000241     147       0.090      --average           0.090      0.498Average Improvement         29%        37%______________________________________
In an especially advantageous embodiment of the process of the invention the heat set hollow article is removed from the mold at heat-setting temperature and is cooled outside of the heat setting mold to the temperature of 100° C. or higher before designated prior to equalizing the internal pressure of the hollow article with the ambient atmosphere. After heat setting the pressure is reduced to a pressure which maintains its volume about the same as when within the mold, the mold is opened, and the bottle is cooled without confinement in a mold. This cooling can simply be air cooling in the room temperature air. When the desired quench temperature of 100° C. or higher is reached, the internal pressure is then released before further cooling. This specific process offers the shortest cycle time since no blow mold time is spent for quenching; it also results in the greatest energy savings since the blow mold can be kept at constant temperature.
TABLE 4______________________________________    QuenchHeat Setting    Press    Temp.   Density                            Volume  Onset°C.Sec.    Psig     °C.                       gms./cc.                              ccs.    Temp.______________________________________230  6       23       170   1.3950 491     163230  6       23       115   1.3950 515     127______________________________________
If one modifies this last embodiment of my invention--wherein the hollow article is removed under some pressure from the mold at heat setting temperature--so that the article outside the heat setting mold is allowed to cool under shrinkage-resisting pressure to below 100° C., as low as room temperature, e.g. 20° C., or even lower, the maximum benefit of higher onset-of-shrinkage temperatures is not realized, but the advantages of minimum cycle time and the energy savings still obtain. Accordingly, the invention includes this special embodiment; usually one cools to below 80° C., often below 70° C., before exhausting the air or other gas from the hollow article.
Thus, in many instances the higher onset-of-shrinkage temperature obtained when cooling to no lower than 100° C. before releasing the shrinkage resisting pressure, as in the principal embodiment of the invention, is not necessary for the particular end use of the hollow article.
To illustrate this last embodiment, a bottle was made in the same manner as in the 230° C. bottles summarized in Table 4 except that the heat setting temperature was 240° C. and the pressure was 17 psig and this pressure was not released until the bottle had cooled to about 70° C. in the ambient atmosphere. Its density was 1.3975 gms./cc., the bottle volume was 520.5 cc. and the onset-of-shrinkage temperature was 149° C.
When inherent viscosity is referred to herein, it is the viscosity as measured in a 60/40 weight ratio phenol/tetrachloroethane solution at 25° C. Density was determined by the method described in ASTM 1505, entitled "Density Gradient Technique".
1. A method for making a high density, partially crystalline, biaxially oriented, heat set, polyethylene terephthalate hollow container, the container having a body with oriented sidewalls, the method comprising the steps of:
A. providing by blow molding a hollow article with oriented sidewalls,
B. while the article is still under a shrinkage reducing pressure, increasing the density of the oriented sidewalls to at least about 1.391 g/cc by heating the sidewalls to a heat setting temperature equivalent to a temperature of about 220° C. to 250° C. to provide the density of at least about 1.391 g/cc,
C. quenching the sidewalls while still under a shrinkage reducing pressure to provide the article with a shrinkage of less than about 5% of the volume and an onset of shrinkage temperature of at least about 105° C., the quenching being done at a temperature equivalent to that of about room temperature to 180° C. at a high heat setting temperature of 240° C., about 85° to 160° C. for a heat setting temperature of about 230° C., and about 120° C. to 150° C. for a lower heat setting temperature of about 220° C.
2. A method as defined in claim 1 in which the heat setting temperature is about 225° C. to 250° C. and the increased density of the sidewalls is above about 1.393 g/cc.
3. A method as defined in claim 1 in which the heat setting temperature is about 230° C. and the quenching temperature is about 100° C.
4. A method as defined in claim 1 in which the heat setting temperature is about 240° C. and the quenching temperature is about room temperature to 180° C.
5. A method as defined in claim 1 in which the heat setting temperature is about 230° C. and the quenching temperature is about 85° C. to 160° C.
6. A method as defined in claim 1 in which the heat setting temperature is about 220° C. and the quenching temperature is about 120° C. to 150° C.
7. A method of making a high density, partially crystalline, biaxially oriented, heat set, hollow poly(ethylene terephthalate) plastic article comprising
(1) enclosing a tubular parison of said poly(ethylene terephthalate), having a closed end and an open end destined to form the neck or finish of the hollow article, within a blow mold which parison is at a first temperature range, which first temperature range is conducive to orientation during stretching;
(2) while said parison is still at said first temperature range expanding said parison into contact and conformance with the blow mold walls by inflation with a gas under pressure to make a hollow blown article with oriented sidewalls, said stretching and expanding under the resulting strain conditions resulting in biaxial orientation and concomitant partial crystallization, and then while the article walls are still inflated in contact with said mold walls;
(3) increasing the density of the oriented sidewalls to at least about 1.391 g/cc by raising the temperature of the article to a heat setting temperature in the range of about 220° to 250° C. to provide the density of at least about 1.391 g/cc, except for the neck or finish portion of said article which is kept at a low temperature such that crystallization is minimized or eliminated so that the neck or finish portion remains transparent, wherein the heating in said heat setting temperature range heat sets the body of said article by causing further crystallization thereof as indicated by density increase;
(4) reducing the pressure to a pressure above atmospheric that will maintain said hollow article at essentially the same volume and resist shrinkage and then opening the mold;
(5) and while said hollow article is still at a shrinkage-resisting pressure exceeding atmospheric, cooling said article to a quenching temperature sufficient to provide an onset of shrinkage temperature of at least about 105° C. and a volume shrinkage of less than about 5%, the quenching temperature being equivalent to about room temperature to 180° C. for a 240° C. heat setting temperature and about 85° C. to 160° C. for a heat setting temperature of about 230° C., and about 120° C. to 150° C. for a heat setting temperature of about 220° C., and
(6) thereafter reducing the gas pressure within said article to essentially ambient pressure.
US06/354,473 1981-03-11 1982-03-03 Method for making poly(ethylene terephthalate) article Expired - Lifetime US4512948A (en)
US06/354,476 US4419151A (en) 1981-03-11 1982-03-03 Crystal and germanium modification and process for its preparation
CA000419874A CA1197961A (en) 1982-03-03 1983-01-20 Poly(ethylene terephthalate) articles and method
NZ20310083A NZ203100A (en) 1982-03-03 1983-01-26 Blow moulding then heat setting poly(ethylene terephthalate)articles
ZA83909A ZA8300909B (en) 1982-03-03 1983-02-10 Poly(ethylene terephthalate)articles and method
MX19628683A MX164068B (en) 1982-03-03 1983-02-15 Hollow container transparent poly (ethylene terephthalate) and method for making
AU11809/83A AU537534B2 (en) 1982-03-03 1983-02-24 Blow moulding then heatsetting in same mould at higher temp
GB08305375A GB2117697B (en) 1982-03-03 1983-02-25 Heat setting poly(ethylene terephthalate) articles
FR8303277A FR2522580B1 (en) 1982-03-03 1983-02-28 poly products (ethylene-terephthalate) and method for making
BR8301013A BR8301013A (en) 1982-03-03 1983-03-02 Process for forming a hollow plastic article of ethylene terephthalate and article thus formed
BE0/210255A BE896077A (en) 1982-03-03 1983-03-03 poly objects (ethylene terephthalate) and method for making the
DE19833307549 DE3307549C2 (en) 1982-03-03 1983-03-03
JP3389183A JPS58162321A (en) 1982-03-03 1983-03-03 Poly ( ethylene terephthalate ) article and its manufacture
US06/557,566 US4476170A (en) 1982-03-03 1983-12-02 Poly(ethylene terephthalate) articles and method
JP31544687A JPH0443776B2 (en) 1982-03-03 1987-12-15
US06/557,566 Division US4476170A (en) 1982-03-03 1983-12-02 Poly(ethylene terephthalate) articles and method
US4512948A true US4512948A (en) 1985-04-23
ID=23393493
US06/354,473 Expired - Lifetime US4512948A (en) 1981-03-11 1982-03-03 Method for making poly(ethylene terephthalate) article
US (1) US4512948A (en)
FR2567066A1 (en) * 1984-07-05 1986-01-10 Petainer Sa Process for manufacturing a container
EP0200564A2 (en) * 1985-05-03 1986-11-05 Continental Pet Technologies, Inc. Method for producing a hot fillable, collapse resistant polyester container without the need to utilize set process techniques and/or non-conventional container geometries
FR2604118A1 (en) * 1986-09-22 1988-03-25 Owens Illinois Plastic Prod Method and apparatus for manufacturing a hollow container by partially crystalline plastics material thermo-FIXED biaxially oriented
FR2606328A1 (en) * 1986-11-10 1988-05-13 Owens Illinois Plastic Prod multilayer articles thermoset, biaxially oriented, and method of manufacture
US5631054A (en) * 1992-04-30 1997-05-20 Kao Corporation Polyester container and process for producing the same
JP2010528900A (en) * 2007-06-07 2010-08-26 シデル パーティシペイションズ Method of manufacturing a container that allows to improve the mechanical strength
1982-03-03 US US06/354,473 patent/US4512948A/en not_active Expired - Lifetime
EP0511720A1 (en) * 1985-05-03 1992-11-04 Continental Pet Technologies, Inc. Method for producing a hot fillable, collapse resistant polyester container
EP0200564A3 (en) * 1985-05-03 1989-10-18 Continental Pet Technologies, Inc. Method for producing a hot fillable, collapse resistant polyester container without the need to utilize set process techniques and/or non-conventional container geometries
GB2197254A (en) * 1986-11-10 1988-05-18 Owens Illinois Plastic Prod Multilayer biaxially oriented heatset articles and method of making
GB2197254B (en) * 1986-11-10 1990-08-22 Owens Illinois Plastic Prod Multilayer biaxially oriented heatset articles and method of making
EP2152495B1 (en) * 2007-06-07 2016-01-06 Sidel Participations Method and machine for making containers allowing for the improvement of the mechanical strength thereof
US20100237528A1 (en) * 2007-06-07 2010-09-23 Sidel Participations Method for making vessels for improving the mechanical strength thereof
EP0739823B1 (en) 2000-01-12 Self-standing container having excellent heat resistance and pressure resistance and method of producing the same
EP0737621B1 (en) 2002-01-23 Blow moulded bottle and use thereof
EP0552813A2 (en) 1993-07-28 Process for producing polyester resin foam
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:JABARIN, SALEH A.;REEL/FRAME:004068/0266