CN1018353B - Bottles and methods for making thereof - Google Patents
Bottles and methods for making thereofInfo
- Publication number
- CN1018353B CN1018353B CN 90100832 CN90100832A CN1018353B CN 1018353 B CN1018353 B CN 1018353B CN 90100832 CN90100832 CN 90100832 CN 90100832 A CN90100832 A CN 90100832A CN 1018353 B CN1018353 B CN 1018353B
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- bottle
- jar
- centimetre
- neck
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Abstract
The present invention relates to a bottle (can) made of polyethylene naphthalate resin and formed by stretching a preform so that the stretch index defined as follows be 130 cm or more, wherein gas barrier properties are improved greatly. Stretching index = inner volume (excepting cap stopper part) of stretched bottle/inner volume (excepting cap stopper part) of unstretched preform X1/f f = inner surface area (excepting inner surface area of cap stopper part) of stretched bottle/inner volume (excepting volume of cap stopper part) of stretched bottle (cm<-1>).
Description
The present invention relates to PEN (Polyethylene naphthalate) resin bottle (jar) and manufacture method thereof, particularly relate to PEN resin bottle (jar) and manufacture method thereof with good gas sealing ability, resistance to effect of heat and diaphaneity.
Glass has been widely used as the material of various containers, as the container of splendid attire seasonings, oils, juice, carbonated drink, beer, sake, cosmetics, washer solvent and unclassified stores.Yet, generally to reclaim with recirculation after glass container uses and use, because they need higher manufacturing cost.Moreover glass container is too heavy so that need higher cost of transportation, and frangible need be handled with care.
In order to solve these problems of glass container, recently, the use of various plastic container develops rapidly to replace glass container.As material, the type and the application target of content depended in the use of various plastics.For instance, polyethylene terephthalate and PEN are used to do the container of juice, soft drink, carbonated drink, seasonings, washer solvent, cosmetics and unclassified stores, because they have mechanical strength, resistance to effect of heat, the gentle sealed nature of diaphaneity preferably.In the superincumbent usage, the container of the blowing of perfusion juice, soft drink and carbonated drink requires sterilization and requires at high temperature to pour into contents, so they need be made with the resin with the good heat resistance that can stand high-temperature perfusion.Moreover the container of this blowing requires that diaphaneity and shape stability are preferably arranged, and makes the less generation diffusion of container inner volume.
Usually the known bottle of being made by polyethylene terephthalate or PEN (jar) has higher gas tightness and resistance to effect of heat, but wishes to further develop by also have bottle (jar) that more excellent transparency and stable on heating synthetic resin are made except that good air-tightness.
In order to obtain the synthetic resin bottle (jar) that not only has better air-tightness but also have better resistance to effect of heat and diaphaneity, the present inventor had once done various effort, and find to be significantly improved by bottle (jar) its gas tightness of PEN resin manufacture, the tensile figure that wherein limits below can satisfy specified conditions, has therefore finished first invention.
The present inventor finds that also bottle (jar) its air-tightness of being made by the PEN resin can strengthen greatly, wherein to the permeability P of the carbon dioxide that limits below
cBe not more than a particular value, and the mean thickness constant T of the bottle centre portion that limits below simultaneously
cBe not more than a particular value, therefore reached second invention.
Moreover, the present inventor finds that its gas tightness of oriented bottle (jar) of being made by the PEN resin is very good and resistance to effect of heat is also good, wherein the PEN resin of the drawn of bottle centre portion shows peak value on the ad-hoc location of X-ray interference strength distribution curve, has set up the 3rd invention thus.
Simultaneously, by the bottle (jar) of PEN resin making or the film of being made by the PEN resin all is known, for example, in Japan special permission notification number 49-22945, describe to some extent, but do not have the such character that limits by the present invention by known bottle (jar) and the film that PEN is made, and can not obtain the PEN resin bottle (jar) that gas tightness is improved, unless possess the such character that limits just like the present invention.
According to the special proposition of premises the present invention, thus, main purpose of the present invention provides a kind of bottle (jar) and manufacture method thereof of being made by the PEN resin with very superior gas tightness and good heat resistance and diaphaneity.
First kind of Bottle ﹠ Can according to the present invention made by the PEN resin, and it is to come moulding by the method for this resin of high elongation, so the tensile figure that limits below should be 130 centimetres or bigger.
Not tensile figure=(inner volume of drawn bottle (not comprising neck))/(inner volume (not comprising neck) of parison before stretching) * 1/ (f)
F=(internal surface area of drawn bottle (not comprising neck))/(inner volume of drawn bottle (not comprising neck)) (centimetre
-1)
The manufacture method of first kind of bottle of the present invention (jar) includes from the PEN resin-shaped and becomes the parison step, and blowing and stretching parison step, so that the tensile figure that limits above should be 130 centimetres or bigger.
Make by the PEN resin according to second kind of bottle of the present invention (jar), wherein to the permeability P of the carbon dioxide that limits below
cBe 0.13 centimetre centimetre/day barometric pressure or lower, and at the mean thickness constant tc or 0.2 or lower of the centre portion of the bottle that does not comprise neck.They are limited by following formula:
P
c＝p×f
[wherein p represent whole bottle to the permeability of carbon dioxide (centimetre
3/ day barometric pressure), f=S/V(centimetre
-1), S represents the internal surface area (internal surface area that does not comprise neck) of drawn bottle, V is the inner volume (volume that does not comprise neck) of drawn bottle]
tc＝t×f×10
[wherein t is that the qualification of f is as above identical at the mean thickness (millimeter) of the bottle of the centre portion that does not comprise neck.]
The third bottle (jar) according to the present invention is made by the PEN resin, its X-ray interference strength distribution curve is on lip-deep a plurality of points of bottle centre portion (middle body), the maxim that in the β angle is two scopes of 0 ° ± 20 ° and 90 ° ± 20 °, all has itself, its factor of probability is at least 80% or bigger, being 90% or bigger preferably, is 95% or bigger better.
Fig. 1 is the schematic illustration of this bottle (jar), Fig. 2 is the lip-deep X-ray of the centre portion interference strength distribution curve by the bottle (jar) of PEN making of the present invention, and Fig. 3 is the lip-deep X-ray of the bottle centre portion utmost point figure according to the bottle (jar) of PEN making of the present invention.
Number designation is: 1. bottle (jar), 2. neck is 3. gone up shoulder, 4. bottle 5. descends shoulder, 6. bottle at the bottom of.
Bottle of the present invention (tank) and manufacture method thereof are described in more detail in down.
In the present invention, form bottle (tank) with the PEN resin. The PEN resin is required to contain 60 % by mole or more some more, be preferably 80 % by mole or more some more, be 90 % by mole or more some more 2 better, 6-naphthalene dimethyl ester glycol ester unit, it derives from 2,6-naphthalenedicarboxylic acid and ethylene glycol, but can comprise the construction unit that is less than 40 % by mole be different from-NDA glycol ester.
These are different from 2, the construction unit of 6-(ethylene naphthalate) derives from aromatic dicarboxilic acid, comprise terephthalic acids, isophthalic acid, 2, the 7-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, biphenyl-4,4 '-dicarboxylic acids, 4,4 '-diphenyl ether dicarboxylic acids, diphenyl sulphone (DPS) dicarboxylic acids, 4,4 '-biphenoxyl ethane dicarboxylic acids and dibromo terephthalic acids; Ester family dicarboxylic acids comprises adipic acid, azelaic acid, decanedioic acid and decane dicarboxylic acid; The alicyclic ring dicarboxylic acids comprises alkane dicarboxylic acids, hexahydro terephthalic acids in Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid, the ring; Hydroxycarboxylic acid comprises glycolic acid (glycolic), right-hydroxybenzoic acid, to the monohydroxy ethoxybenzoic acid; Propane diols, trimethylene glycol (1,3-PD), diethylene glycol (DEG), BDO, 1,5-pentanediol, 1,6-hexylene glycol, 1,10-decanediol, neopentyl glycol, right-Xylene glycol, 1,4-CHDM, bisphenol-A, P, P-two phenoxy group sulfones, 1, two (β-hydroxy ethoxy) benzene, 2 of 4-, 2 '-two (right-β-the hydroxy ethoxy phenyl) propane, poly-(alkylidene) glycol, right-phenylene two (dimethyl siloxane), and glycerine (glycerine).
In addition, the used PEN resin of the present invention can contain a small amount of for example 2 % by mole or less construction unit, and they derive from polyfunctional compound such as benzenetricarboxylic acid, trimethylolethane, trimethylolpropane, Pehanorm and pentaerythrite.
Also have, the used PEN resin of the present invention can contain a small amount of for example 2 % by mole or less construction unit, they derive from monofunctional compound such as benzoylbenzoic acid, diphenyl sulphone (DPS)-carboxylic acid, stearic acid, methoxy poly (ethylene glycol) and phenoxy group polyethylene glycol.
This PEN resin is actually linear structure, and it can be confirmed that by the following fact namely PEN is dissolvable in water in the o-chlorophenol.
The inherent viscosity [η] that PEN is measured in 25 ℃ adjacent monochlorphenol requires in the scope of 0.2～1.1 deciliter/gram, is 0.3～0.9 deciliter/gram preferably, is 0.4～0.8 deciliter/gram better.
Here the measurement of the inherent viscosity of PEN is undertaken by laxative remedy. Just, PEN is dissolved in the o-chlorophenol that concentration is/100 milliliters of 1 grams, adopts Ubbelodhe (Ubbellohde) capillary viscometer at 25 ℃ of lower these solution viscosities of measuring. Then, add gradually o-chlorophenol, the data that the solution viscosity of measurement under low concentration obtains are used for the calculation by extrapolation when 0% concentration, determine thus inherent viscosity [η].
The heating crystallization temperature (Tc) of PEN is to measure under 10 ℃/minute with differential scanning calorimetry (DSC) (DSC) at heating rate when temperature improves, and is generally 150 ℃ or higher; Being preferably 160～230 ℃, is 170～220 ℃ best.
Here, the heating crystallization temperature (Tc) of PEN is measured by laxative remedy.
About 10 milligrams PEN thin slice is taken from about 5 mmhg pressures, under about 140 ℃ of temperature through about 5 hours Or the middle body of the PEN thin slice of longer time drying, it is enclosed within nitrogen in the aluminum pot used of dress liquid, and uses the differential scanning calorimetry (DSC) of the DSC-2 model of being made by Perkin Elmer, it is measured. By the temperature that raises fast from room temperature, allow test specimen 290 ℃ of lower meltings, and kept 10 minutes. Then it is cooled to room temperature. After this peak temperature that records the heat release temperature rise when temperature rises with 10 ℃/minute speed is again got makes heating crystallization temperature (Tc).
This PEN can prepare by known method.
To the used PEN of the present invention, can to a certain degree add the various additives that make an addition to usually in the polyester, as heat stabilizer, aging stabilizer, antistatic additive, lubricant, mold release, pigment dispersing agent, pigment and dyestuff etc., otherwise will lose purpose of the present invention.
Make by the PEN resin according to first kind of bottle of the present invention (jar), and moulding by the high elongation parison, so the tensile figure that limits below should be 130 centimetres or bigger, is 140～220 centimetres preferably, is 150～200 centimetres better.
Not tensile figure=(inner volume of drawn bottle (not comprising neck))/(inner volume (not comprising neck) of parison before stretching) * 1/ (f)
F=(internal surface area of drawn bottle (not comprising neck))/(inner volume of drawn bottle (not comprising neck)) (centimetre
-1)
Referring now to Fig. 1, explain the tensile figure of first kind of bottle of the present invention (jar).As shown in Figure 1, bottle (jar) 1 of the present invention includes bottleneck 2, last shoulder 3, bottle 4, following shoulder 5 and the bottle end 6.
When making this bottle (jar) 1, need with parison 7, it is represented by dotted lines in Fig. 1.
The inner volume of this oriented bottle (jar) is restricted to the inner volume of the oriented bottle (jar) 1 that does not comprise bottleneck portion 2, in detail, it means the inner volume of the bottle (jar) below the carrier ring 8, in more detail, is meant the inner volume of the bottle (jar) below solid line 9.
The inner volume of parison of not stretching is meant the inner volume of the parison 7 that does not comprise bottleneck 2 parts, and perhaps in detail, it refers to the inner volume of the parison 7 below carrier ring 8, in more detail, is meant the inner volume of the bottle (jar) below solid line 9.
The internal surface area of drawn bottle (jar) is meant the internal surface area of the drawn bottle (jar) 1 that does not comprise bottleneck portion, perhaps in detail, it is meant the internal surface area of the drawn bottle (jar) below carrier ring 8, and in more detail, it refers to the internal surface area of the bottle (jar) below solid line 9.
The internal surface area S(of drawn bottle (jar) does not comprise the internal surface area of neck) can measure by little split plot design, its step is that bottle (jar) is divided into some small parts, record its inner surface configuration with three-dimensional measuring apparatus, and area that will this small part carries out integration.Here, when drawn bottle (jar) when being in simple shape, internal surface area can by suppose this bottle be cylindrical and the upper and lower of bottle both be all hemispheric method and obtain its approximate value.
The inner volume (not comprising neck volume) that the tensile figure of this drawn bottle (jar) can be by trying to achieve drawn bottle (jar) and the inner volume (not comprising neck volume) of unstretched bottle (jar) and and the internal surface area of described drawn bottle (jar) come together to calculate.The inner volume of bottle (jar) can wherein can easily be measured by liquid (as water) poured into.The unit of f value and tensile figure is respectively centimetre
-1With centimetre.
In according to first kind of bottle of the present invention (jar), the thickness of bottle is identical with known bottle (jar), is generally 0.1～0.5 millimeter, is preferably 0.2～0.4 millimeter.
After the method for making above-mentioned first kind of bottle (jar) is illustrated in.
At first, make parison by above-mentioned PEN resin by known method commonly used.
This parison can be made by known method, but in the present invention, preferably must be shorter than the length of known parison with the length adjustment of parison, because the rate of extension of this parison is than the height in the known method.If need, also make the diameter of parison smaller possibly than the diameter of parison commonly used.
In the present invention, above-mentioned this bottle (jar) parison is blow molded and is molded into bottle (jar).
At this moment, ground carries out blowing, so the tensile figure of the gained bottle (jar) of afore mentioned rules should be 130 centimetres or bigger, is 140～220 centimetres preferably, is 150～200 centimetres better.
The blow temperatures of parison requires to be adjusted to 110～150 ℃, is 120～150 ℃ preferably, is 125～145 ℃ better.
As stated above, the tensile figure that promptly limits above is 130 centimetres or big, and the bottle (jar) that derives from this high elongation of PEN resin has very good vapor seal character, for instance, compare with general commercial available polyethylene terephthalate bottle (jar), to carbon dioxide (CO
2) air-tightness for high approximately 20 times, to oxygen (O
2) air-tightness for high approximately 7 times.Even be that the PEN resin bottle (jar) of 95 centimetres of drawns is compared with tensile figure that this specification sheets limits, according to this bottle according to the present invention (jar) to carbon dioxide (CO
2) air-tightness can improve 3 times, to oxygen (O
2) air-tightness can improve 2 times.
Another kind of bottle (jar) its resistance to effect of heat of the present invention also is better (T
gBe about 120 ℃), also its diaphaneity and mechanical strength are also very good.
Second kind of bottle of the present invention (jar) is illustrated in down.Second kind of bottle (jar) is to come resin to make by as above this PEN, wherein to the permeability P of the carbon dioxide that limits below
cIt is 0.13 centimetre
3Centimetre/day barometric pressure or lower is 0.12 centimetre preferably
3Centimetre/day barometric pressure or lower is 0.10 centimetre better
3Centimetre/day barometric pressure or lower, and, at the mean thickness constant t of the centre portion (middle body) of the bottle that does not comprise neck
c(it is defined to down) is 0.2 or lower, is preferably 0.18 or lower.
P
c＝P×f
[wherein P represent whole bottle (jar) to the permeability of carbon dioxide (centimetre
3/ day barometric pressure), f=S/V(centimetre
-1), S represents the internal surface area (internal surface area that does not comprise neck) of drawn bottle (jar), V is the inner volume (volume that does not comprise neck) of drawn bottle (jar)].
t
c＝t×f×10
[wherein t is the mean thickness (millimeter) that does not comprise the bottle centre portion of neck, and f limits as above identical].
This PEN resin bottle (jar) is to permeability P(centimetre of carbon dioxide
3/ day barometric pressure) measures by laxative remedy.Dry ice is encapsulated in the bottle (jar) that the blowing of drawn makes, and the volume of adjusting dry ice then makes the internal pressure of bottle (jar) should be about 5 kilograms per centimeter under 23 ℃
2, will this bottle (jar) be positioned in 23 ℃, the thermostatic chamber of 50% relative humidity, measure bottle (jar) weight over time.After encapsulation the 7th day to the 21st day every day carbon dioxide average permeation volume [be converted to 1 barometric pressure, the carbon dioxide 23 ℃ the time volume (centimetre
3)] be (barometric pressure) divided by the interior pressure after the just encapsulation dry ice, calculate its permeability thus.In test, adopt 3 Bottle ﹠ Cans to make sample, and determine its aviation value thus.
The inner volume V of drawn bottle (jar) and internal surface area S can measure by above-mentioned same method.
The mean thickness t(millimeter that does not comprise the bottle centre portion of neck) can obtain like this, the middle body that is about to bottle is divided into 4 parts, measures the thickness (millimeter) of 4 points, and calculates its mean thickness.
By the air-tightness of thickness correction, it is measured is usefulness for referencial use, and it is the carbon dioxide permeability Pd(CO by general employing
2) and oxygen permeability Pd(O
2) estimate.For this purpose, take from the carbon dioxide permeability Pd(CO of some coupons that thickness is 300～450 microns bottle centre portion
2) measurement, can adopt carbon dioxide permeability measurement mechanism Permatrarc-IV that American Modern Heat ﹠ Control Pty Ltd. [Modern Control(U.S.A)] makes under the condition of 23 ℃ and 0% relative humidity, to carry out, and take from the oxygen permeability Pb(O of some coupons that thickness is 300～400 microns bottle centre portion with the Permatran method
2) measurement, the measurement mechanism that can adopt the Oxtran model 100 that American Modern Heat ﹠ Control Pty Ltd. [Modern Control(U.S.A)] makes carries out under the condition of 23 ℃ and 0% relative humidity with the Oxtran method.
After the manufacture method of second kind of bottle of the present invention (jar) is illustrated in order.The available same quadrat method as first kind of bottle of the present invention (jar) of this bottle (jar) is made, be the resinous parison of blowing PEN and it is stretched, so the tensile figure of above-mentioned qualification should be 130 centimetres or bigger, being 140-220 centimetre preferably, is 150-200 centimetre better.
Such second kind of bottle (jar) according to the present invention has extraordinary vapor seal character, for example, compares with practising normal commercial available polyethylene terephthalate bottle (jar), to carbon dioxide (CO
2) air-tightness be about 20 times of the latter, to oxygen (O
2) air-tightness be 7 times of the latter.
The third bottle (jar) according to the present invention is described in down, the third bottle (jar) is to make by the PEN resin that stretches above-mentioned, and it demonstrates, in the β angle is two scopes of 0 ° ± 20 ° and 90 ° ± 20 °, maxim own is being arranged all on the X-ray interference strength distribution curve that a plurality of points on the circumference of bottle centre portion are marked and drawed, its factor of probability is at least 80% or higher, being 90% preferably, is 95% or higher better.
The method of measurement that X-ray interference strength on the circumference of the resinous drawn bottle of PEN middle part distributes is illustrated in down.
The centre portion of the bottle 4 of this drawn bottle (jar) 1 shown in Figure 1 is cut, take a plurality of samples (2 centimetres of 2 cm x) from the circumference of centre part, be generally 5 or more some more, be preferably 5-10 sample, it is fixed on the specimen holder of X-ray fiber sample additional device.Here, the centre portion of bottle represents to comprise mid point part of solid line 9 following bottle (jar) height that among Fig. 1 draw in bottleneck 2 lower ends.
The X-ray interference strength of measuring this sample distributes.Sample is measured the intensity distributions than X-ray diffraction peak value round the normal rotation of specimen surface, and measuring condition is as follows:
X-ray diffractometer: RU300 is made by Rigaku Denki
Target; CU target (point is burnt)
Voltage, electric current: 50 kilovolts, 300 milliamperes
Annex: fiber sample additional device
Slit system: 1 millimeter Φ of collimator
1.9 millimeters of length to the slit
1.8 millimeters of transverse slots
The α angle: 30 °, static
2θ 15.4°
θ: 7.7 °, static
β angle speed of rotation: 8 °/minute
The β angle limits as follows:
When the circumferencial direction of the bottle angle during in alignment with horizontal direction is counted as 0 °, and the angle when the aligned perpendicular direction is counted as 90 °.
Taking from thus, the X-ray interference strength distribution curve of the sample of the centre portion of gained bottle is shown among Fig. 2.No matter whether can discern any maxim own in X-ray interference strength distribution curve, it can be determined by laxative remedy.At first make a tangent line in its bottom, this place's strength distribution curve represents to have its minimum, and it is defined as baseline.Be defined as I from the height of second nadir between the baseline to 0 °-360 °
bThen, respectively two of comfortable 0 ° ± 20 and 180 ° ± 20 two scopes peaked smaller values itself are defined as I
0, and be defined as I deriving from two of 90 ° ± 20 ° and 270 ± 20 ° scopes peaked smaller values itself respectively
90At this moment, if I
o/ I
bAnd I
90/ I
bThe both is 1.1 or higher, is 1.5 or higher preferably, and just can judge has an own maxim to exist.
According to the third bottle (jar) by the PEN resin manufacture of the present invention, it shows: in the X-ray interference strength distribution curve on the circumference of bottle centre portion on a plurality of points, the maxim that itself is all arranged in the β angle is two scopes of 0 ° ± 20 ° and 90 ° ± 20 °, its factor of probability is at least 80% or higher, being 90% or higher preferably, is 95% or higher better.
In contrast, usually the PEN resin bottle (jar) that known minuent stretches then shows: in the X-ray interference strength distribution curve on the circumference of the drawn bottle centre portion that last method is measured on a plurality of points, the maxim that itself is all arranged in the B angle is 0 ° ± 20 ° and two scopes of 90 ° ± 20, its factor of probability only is less than 80%, is generally less than 60%.
Secondly, taking out a diameter from the circumference of drawn bottle middle part is 34 millimeters sample, and it is fixed on the sample holder of utmost point figure survey meter, measures the utmost point figure on ° (010) face of 2 θ=15.4 thus.
Utmost point figure measures under the following conditions:
(1) instrument: model RU300, Rigaku Denki company makes the Cu target, and point is burnt
50 kilovolts in voltage, electric current, 300 milliamperes
Annex: full automaticity utmost point figure measurement mechanism
(2) sample: take out diameter around point to be measured and be 34 millimeters test piece and be fixed on the clamper.
(3) measuring condition:
Slit system
D, S, O, 1R, S1S, S4Ni light filter use limited slit in bounce technique.
The condition entry of utmost point sample additional device:
Model (1): 1 continuous scanning
Model (2): ring-type circulation
α begins: 0
α stops: 40
α begins: 40
α stops: 90
α stepping: 10
β begins: 0
β stops: 360
β speed: 360
Measure: the bounce technique of Decker method+Suhulz
Peak value 2 θ=15.4 °
B、G2θ＝20.0°
No γ vibration
The example at the X-ray utmost point figure of the sample of bottle middle part that obtains thus is shown in Fig. 3.In this X-ray utmost point figure, the utmost point presents on all points from the B angle 0 °, and 90 °, 180 ° and 270 have dispersion slightly, the prompting of this kind situation constitute bottle PEN strand vertically and circumferencial direction be slightly offset.Yet this to depart from the bottle according to the third drawn of the present invention be in ± 20 ° scope in (jar).
The manufacture method of this third bottle (jar) of the invention described above is illustrated in down.This bottle (jar) is available to be made as the same method of first kind of bottle of the present invention (jar), stretch by the parison of PEN resin and with it by blowing, so the tensile figure that limits above should be 130 centimetres or bigger, being 140-220 centimetre preferably, is 150-200 centimetre better.
According to this third bottle (jar) of the present invention, have extraordinary vapor seal character, for instance, compare with common commercial available polyethylene terephthalate bottle (jar), to carbon dioxide (CO
2) gas tightness be about 20 times of the latter, to oxygen (O
2) air-tightness be 7 times of the latter.
Have largely improvedly according to bottle of the present invention (jar), and have good resistance to effect of heat, diaphaneity and mechanical strength oxygen or carbon-dioxide vapor seal character.
Now the present invention is described, but certainly, the present invention is not limited by these embodiment by some following embodiment.
Embodiment 1
To derive from 2, the PEN resin of 6-binaphthalene dicarboxylic acid and ethylene glycol (having following physical property) is molded into bottle (jar) parison by the M-100A type injection machine of being made by Meiki Seisakusho company.This moment, its forming temperature was 270-290 ℃.
The PEN resin:
Inherent viscosity [η]: 0.6 deciliter/gram
Heating crystallization point (T
c): 180 ℃
Next step is molded into biaxially oriented bottle (jar) by the LB-01 type blow moulding machine of being made by Corpoplast company thus obtained parison.This moment, its draft temperature was 130-140 ℃.
The inner volume of the parison of La Shening (not comprising neck) is not 19 centimetres
3, and the inner volume of the drawn bottle (jar) (not comprising neck) of gained is 1469 centimetres
3
The internal surface area of drawn bottle (jar) (internal surface area that does not comprise neck) is 678 centimetres
2
Therefore, this tensile figure is calculated as follows:
Tensile figure=1469/19 * 1/0.46=168
Measurement to the carbon dioxide permeability is as follows: with dry ice be packaged in drawn blowing the bottle (jar) in after, the adjusting dry ice volume so that its internal pressure under 23 ℃ should be about 5 kilograms per centimeter
2Measure the variation of process in time of its weight, bottle (jar) is positioned in the thermostatic chamber of 23 ℃ of temperature and 50% relative humidity, will from encapsulate afterwards the 7th day to the every day of the 21st day gained average carbon dioxide permeation volume [convert 1 barometric pressure to, the volume of 23 ℃ carbon dioxide (centimetre
3)] divided by the internal pressure (barometric pressure) behind the firm encapsulation dry ice.In test, adopt 3 bottles (jar) to make sample, and determine its aviation value thus.
Air-tightness by thickness correction can be passed through carbon dioxide permeability Pd(CO
2) and oxygen permeability Pd(O
2) estimate.For this purpose, take from thickness and be the measurement of carbon dioxide permeability of some coupons of the bottle centre portion of 300-450 micron, can carry out under the condition of 23 ℃ of temperature and 0% relative humidity with the Permatran method by using the Permatrarc-IV type carbon dioxide permeability measurement mechanism of making by American Modern Heat ﹠ Control Pty Ltd. [Modern Control(U.S.A.)].Take from thickness and be the oxygen permeability Pd(O of some coupons of the bottle centre portion of 300-400 micron
2) measurement, can carry out under the condition of 23 ℃ of temperature and 0% relative humidity with the Oxtran method by the device that uses the Oxtran model of making by American Modern Heat ﹠ Control Pty Ltd. [Modern Control(U.S.A.)] 100.
As for diaphaneity, can extract bottle, the mist degree of test specimen can be measured by using the NDH-20D type mist degree analyzer of being made by Nihon Denshoku company, with the test method that accords with ASTM D1003, test 3 times, diaphaneity is judged with its aviation value.
Its data are shown in Table 1.
Comparative example 1
Repeat to do identical test, just changed the tensile figure to 95 centimetre of bottle as embodiment 1.
The data of gained are shown in Table 1.
Comparative example 2
Repeat to do identical test, just replace PEN with polyethylene terephthalate as embodiment 1.
Its test data is shown in Table 1.
Embodiment 2
Cut off the centre portion of the bottle that in embodiment 1, obtains, take out 5 samples from this centre portion at certain intervals, and the usefulness of making measured X-ray interference strength distribution curve is provided.
Measurement is the I of the each point of 0 ° ± 20 ° or 180 ° ± 20 ° and 90 ° ± 20 ° or 270 ° ± 20 ° at the β angle
0And I
90Calculate I more respectively
0/ I
bAnd I
90/ I
b
Its data are shown in Table 2.
The β angle has the departing from of point of maxim own to use Φ from 0 ° to identification
0Represent; The β angle has the departing from of point of maxim own to use Φ from 90 ° to identification
90Represent; It the results are shown in table 2.
The X-ray interference strength distribution curve of measurement point 3 and X-ray utmost point figure are shown among Fig. 2 and Fig. 3 in the table 2.
Comparative example 3
On the bottle of gained, measure its X-ray interference strength distribution curve by embodiment 2 with quadrat method in comparative example 1, it the results are shown in the table 3.
Table 2
The bottle 12345 of embodiment 2
I
0/I
b1.49 6.17 2.69 1.18 1.43
I
90/I
b5.17 13.7 7.31 2.95 4.93
φ0 1.6 2.4 2.4 4.8 3.2
φ90 7.6 4.4 3.2 11.5 4.0
Numeral 1 to 5 expression measurement point near title
Table 3
The bottle 12345 of comparative example 3
I
0/I
b1.1 2.5 3.5 - -
I
90/I
b1.5 2.9 3.5 - -
φ0 7.2 0.8 6.4 14.4 4
φ90 15.2 10.4 13.6 - -
-: the maxim that does not have itself
Claims (12)
1, a kind of bottle of making by the PEN resin (jar), it makes by the high elongation parison, and it is characterized in that making it is 130 centimetres or higher as the tensile figure that limits below:
Tensile figure=(inner volume of drawn bottle (not comprising neck))/(inner volume (not comprising neck) of parison before stretching) * (l)/(f)
F=(internal surface area of drawn bottle (not comprising neck))/(inner volume of drawn bottle (not comprising neck)) (centimetre
-1)
The permeability P that limits below to carbon dioxide
cIt is 0.13 centimetre
3Centimetre/day barometric pressure or lower;
P
c=P×f，
[wherein P represent whole bottle to the permeability of carbon dioxide (centimetre
3/ day barometric pressure), f=S/V (centimetre
-1), S represents the internal surface area (internal surface area that does not comprise neck) of drawn bottle, V is the inner volume (volume that does not comprise neck) of drawn bottle]
And, at the mean thickness constant t of the bottle centre portion that does not comprise neck
c, its qualification is as follows, is 0.2 or lower;
t
c=t×f×10
[wherein t is that the qualification of f is with last identical at the mean thickness (millimeter) of the bottle of the centre portion that does not comprise neck];
X-ray interference strength distribution curve on a plurality of points on the surface of bottle centre portion all is maxims that itself is arranged in the β angle is 0 ° ± 20 ° and 90 ° ± 20 ° two scopes, and its factor of probability is at least 80% or bigger.
2, bottle as claimed in claim 1 (jar) is characterized in that its tensile figure is 140-220 centimetre.
3, bottle as claimed in claim 1 (jar) is characterized in that P
c(to CO
2Permeability) be 0.1 centimetre
3Centimetre/day barometric pressure or lower.
4, bottle as claimed in claim 1 (jar) is characterized in that t
c(mean thickness constant) is 0.18 or lower.
5, bottle as claimed in claim 1 (jar) is characterized in that at the β angle being that two scopes of 0 ° ± 20 ° and 90 ° ± 20 ° find that all maxim own is arranged, and its factor of probability is 90% or bigger.
6, bottle as claimed in claim 1 (jar) is characterized in that the PEN resin contains 2,6-(ethylene naphthalate) unit, and it derives from 2, and 6-naphthalenedicarboxylic acid and ethylene glycol, its content are 60 moles of % or bigger.
7, a kind of method of making bottle (jar), the step that comprises is: become parison by the PEN resin-shaped, and with this parison blowing so that the tensile figure of following qualification is 130 centimetres or bigger:
Not tensile figure=(inner volume of drawn bottle (not comprising neck))/(inner volume (not comprising neck) of parison before stretching) * 1/ (f)
F=(internal surface area of drawn bottle (not comprising neck))/(inner volume of drawn bottle (not comprising neck)) (centimetre
-1)
It is characterized in that the permeability P that limits below to carbon dioxide
cIt is 0.13 centimetre
3Centimetre/day barometric pressure or lower;
P
c＝P×f，
[wherein P represent whole bottle to the permeability of carbon dioxide (centimetre
3/ day barometric pressure), f=S/V(centimetre
-1), S represents the internal surface area (internal surface area that does not comprise neck) of drawn bottle, V is the inner volume (volume that does not comprise neck) of drawn bottle]
And, at the mean thickness constant t of the bottle centre portion that does not comprise neck
c, its qualification is as follows, is 0.2 or lower;
t
c＝t×f×10
[wherein t is that the qualification of f is with last identical at the mean thickness (millimeter) of the bottle of the centre portion that does not comprise neck];
X-ray interference strength distribution curve on a plurality of points on the surface of bottle centre portion all is maxims that itself is arranged in the β angle is 0 ° ± 20 ° and 90 ° ± 20 ° two scopes, and its factor of probability is at least 80% or bigger.
8, the method for making bottle (jar) as claimed in claim 7 is characterized in that this parison by high elongation, so that its tensile figure is 140-220 centimetre.
9, the method for making bottle (jar) as claimed in claim 7 is characterized in that P
c(to CO
2Permeability) be 0.1 centimetre
3Centimetre/day barometric pressure.
10, the method for making bottle (jar) as claimed in claim 7 is characterized in that t
c(mean thickness constant) is 0.18 or lower.
11, the method for making bottle (jar) as claimed in claim 7 is characterized in that at the β angle being that two scopes of 0 ° ± 20 ° and 90 ° ± 20 ° find that all maxim own is arranged, and its factor of probability is 90% or bigger.
12, the method for making bottle (jar) as claimed in claim 7 is characterized in that the PEN resin contains 2,6-(ethylene naphthalate) unit, and it derives from 2, and 6-naphthalenedicarboxylic acid and ethylene glycol, its content are 60 moles of % or bigger.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3784589A JP2625195B2 (en) | 1989-02-17 | 1989-02-17 | Bottle and manufacturing method thereof |
| JP37845/1989 | 1989-02-17 | ||
| JP37846/89 | 1989-02-17 | ||
| JP37845/89 | 1989-02-17 | ||
| JP4386989A JP2690058B2 (en) | 1989-02-23 | 1989-02-23 | Bottle |
| JP43869/89 | 1989-02-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1044925A CN1044925A (en) | 1990-08-29 |
| CN1018353B true CN1018353B (en) | 1992-09-23 |
Family
ID=26376997
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90100832 Expired CN1018353B (en) | 1989-02-17 | 1990-02-17 | Bottles and methods for making thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1018353B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6004638A (en) * | 1995-03-09 | 1999-12-21 | Mitsui Chemicals, Inc. | Bottle from polyester composition and process for producing the same |
| CN102039666A (en) * | 2009-10-18 | 2011-05-04 | 刘伟民 | Manufacture method, product and manufacture equipment of blow molding container with stable output |
| US8313003B2 (en) | 2010-02-04 | 2012-11-20 | Crown Packaging Technology, Inc. | Can manufacture |
| CA2787546C (en) | 2010-02-04 | 2018-03-13 | Crown Packaging Technology, Inc. | Can manufacture |
| EP2558228A1 (en) | 2010-04-12 | 2013-02-20 | Crown Packaging Technology, Inc. | Can manufacture |
| AR087892A1 (en) | 2011-09-16 | 2014-04-23 | Ball Corp | ALUMINUM ALLOY, PROCESS TO MANUFACTURE A CONTAINER FROM A TARUGO AND METHOD TO FORM THE TARUGO |
| CA2908181C (en) | 2013-04-09 | 2018-02-20 | Ball Corporation | Aluminum impact extruded bottle with threaded neck made from recycled aluminum and enhanced alloys |
| US20180044155A1 (en) | 2016-08-12 | 2018-02-15 | Ball Corporation | Apparatus and Methods of Capping Metallic Bottles |
| EP4219780A1 (en) | 2016-12-30 | 2023-08-02 | Ball Corporation | Aluminum alloy for impact extruded containers and method of making the same |
| MX2019009745A (en) | 2017-02-16 | 2020-02-07 | Ball Corp | Apparatus and methods of forming and applying roll-on pilfer proof closures on the threaded neck of metal containers. |
| US11185909B2 (en) | 2017-09-15 | 2021-11-30 | Ball Corporation | System and method of forming a metallic closure for a threaded container |
-
1990
- 1990-02-17 CN CN 90100832 patent/CN1018353B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN1044925A (en) | 1990-08-29 |
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| GR02 | Examined patent application | ||
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| GR01 | Patent grant | ||
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Free format text: CORRECT: PATENTEE; FROM: MITSUI SEKIYU K.K.K. TO: MITSUI CHEMICALS, INC. |
|
| CP01 | Change in the name or title of a patent holder |
Patentee after: Mitsui Chemical Industry Co., Ltd. Patentee before: Mitsui Petrochemical Industries, Ltd. |
|
| C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
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