TW210976B - Multi-layer refillable container having higher wash temperature and redvced product flavor carryover, preform and method of forming same - Google Patents

Abstract

A multi-layer plastic container, particularly suited for returnable and refillable PET carbonated beverage bottles, having an inner core layer of high copolymer polyester material which resists hazing in the preform injection stage and lower copolymer inner and outer layers which achieve greater surface crystallization in the sidewall during the stretch blow expansion stage. The container can withstand 20 refill cycles at a higher caustic wash temperature of 65xC and exhibits 20% reduced flavor carryover from one product to another. Preferably, the container includes inner and outer layers of no more than 2% copolymer and 20 to 28% crystallinity and the core layer has from 4 to 6% copolymer and 14 to 20% crystallinity.

Description

The Ministry of Economic Affairs, the Central Bureau of the Ministry of Economic Affairs only works to eliminate «· Cooperative Society Print Μ 4UOQ7〇_ V. Description of the invention (l) The present invention is about the exchange of heavy plastic containers. Recyclable and reusable, since the growth of mainland PET. These recycling and recycling and reprocessing devices in Europe, Central and South America can enter markets that are legally prohibited and exclusive. The goal is to endure countless times. Generally speaking, it is considered economically feasible to repeat more than 20 cycles. Return to the pollutant inspection, product retail base, and ⑸ from back to the bottling plant. Its recycling / heavy commercial viability. Package 1. The degree of clarity is clearly checked; 2. The entire container 3. Amendments to the alkaline washing on May 10 | The container is a novel and useful improvement, especially a multilayer that can withstand higher washing temperatures and reduce the smell of the product. After the introduction of the PET Carbonate Soft Cone (CSD) bottle by the city technology company in 1987, the world's heavy / heavy bottle has been commercialized, sweeping most of it, and has now moved to the Far East market. Sex bottles can reduce the existing waste plastic bottle related. In addition, heavy-duty bottles allow safe and lightweight plastics to use non-recyclable packaging. Previously, glass bottles were used to produce heavy-duty bottles, which have the necessary physical characteristics, recycling, and can be produced economically. The plastic bottle must be at least 10 times or better, or the circuit should still maintain its function and aesthetic characteristics. The square path includes: ⑴ the empty bottle is washed with hot alkaline solution, and then ⑵ filling / capping, ⑶ storage, ⑷Distribution to wholesale and consumer purchase, use, and storage of empty bottles, the final ring as shown in Figure 1% sex containers must present a number of key standards in order to achieve content: transparency (transparency), which can be used visually on the production line Dimensional stability in life; and resistance to stress cracking and leaking. The first note item of the back Λ Ben · " installed η line book paper standard side use a Η family sample standard (CHS) T4 execution (210x297 ;; :) 81. 7. 20.000 sheets (11> Ministry of Economic Affairs + Printed by the central government and printed by the employee ’s cooperative _ V. Description of the invention (2) Known commercial ethylene phthalate 1,4-cyclohexane dimethyl The prototype wall type used in this bottle is 2 to 2.5 Times η 6 Read the precautions first and then know this A £ Install the larger chick (ie 0.5 substance content is acceptable. It is not advisable to have a known value of more than 20 in order to smell the product smell product (for example, in the ring, The taste of the infiltrated product is high in washing temperature, so the life expectancy is at least weight-reducing. The following is up to the standard level, type thickness-0.7. In the case of excessive injection, commercialization, commercialization, and secondary washing temperature can communicate. For some, it is necessary to mention the formation of 0 between 5 times of the weight range. The simultaneous dimension container of the present invention is composed of a single layer of 5% comonomer, such as dicarboxylic acid (ΙΡΑ), blown in 5-7 «« The spectrum may be formed from the recyclable / heavy CSD (PET) of a single consumption bottle, containing 3-alcohol (CHDM) or isoparaben. The required PET surface provides the resistance required for abuse »〇»), in order to prevent the prototyping and turbidity in the long-term molding method of the bottle, because it hinders the visual inspection of the CSD container during the washing temperature journey back to the production line. Into the side wall of the bottle, within two products (such as water to increase effective sterilization and / or food, such as fruit juices and cattle high recovery bottles) On the journey of washing, it is better to exchange the odor of the product over 10. The above extension ratio is 6-10: 1, high wall thickness, copolymerization, that is, turbidity. The volume of the bottle is larger. The stability of the average bottle size is visual. Crystallization, yield / heavy process .60eC, which proves that it is necessary to change ° C or above in the commercial market, and the same odor components will be used in the subsequent water), that is, it will reduce the time required to wash the milk. The temperature is 60 ° C or 20 times. The purpose is to reduce the first type of filling when the container is feasible and follow the second type. It needs to be mentioned, and the process, and by the present invention, provides a multi-layered container to improve the crystallinity of the surface side wall to maintain a high level of transparency (clear ), So special 2 paper ft scales are used in a S home furniture (CNS) T4 standard (210x297 male 4) 81 · 7. 20.000 sheets (II) Λ 6 Π 6 21097ο V. Description of the invention (3) applies to Recyclable / heavy urn bottle. The service life of the container is at least 5 heavy gang cycles in size, preferably at least 10 or rings, and exposed to a wash temperature of 60 ° C and above, preferably at least about Ό and above, Resistant to stress cracks and leaks caused by flushing. This is achieved by providing a prototype with multiple layers of side walls, including the first copolymer polyester, and the other layer is the second polyester, the copolymer is the first. Preferably, the core layer is formed from a high copolymer polyester, between the low copolymer layer and the outer layer. The high copolymer core prevents turbidity of the inner core) and cools more slowly during the injection process to preserve the overall capacity and testability. The outer (inner and outer) layers are not easy to crystallize during the injection process. It is made of a copolymer polyester with higher elongation or strain-induced crystallization, thus providing improved resistance to emu-induced stress and reduced odor exchange within the blown container. The core layer typically includes about 50-80% of the thickness of the side walls, which is preferably. The crystallinity percentage of the inner layer and the outer layer is about 20 — while the core layer is about 4-20%. It can be stabilized across 20 repetition cycles of 65 ° C or about 70. One layer is the first polyester and the inner crystallization of the less polyester (the clearness of the turbidity is faster, which is more homopolymer or lower turtle). The cracked surface is in the range of 60-70% 28%, rh first KI ίίϊ back to the opposite-Note Sun% wood binding line Ministry of Economic Affairs, Central Bureau of Standards = 5 Gongxiaoyang cooperatives printed in the preferred specific example, using the metered Sequential co-injection method to produce two-material three-layer PET prototype, first injection of homopolymer or low copolymer, that is, the total weight of copolymer content of 0-2%, to form the inner layer and the outer layer, followed by the second Secondary injection of high copolymer, that is, copolymer content of 4 to 6% of the total weight, forms the core layer. This can achieve a strain-induced surface crystallinity level of about 22-26% in the side wall of the container, resulting in a typical prototype plane extension ratio of 8 _10: 1, the crystallinity percentage is much higher and the core layer of the copolymer is lower. In short, compared with the single-layer known recyclable / heavy CSD bottle, this container can be used at a relatively high temperature (65 l ~ 3 ~ this paper Law ruler Λ side use middle a Η home standard 』MCNS) T4 gauge (210X297 public; it) 81. 7. 20.000 ^ (1!) 21097ο V. Description of the invention (4) and above) Washing, showing reduced odor exchange (improved by 20% or more), without significant loss of container performance. The improvement of the resistance to turbidity and stress cracking when the temperature is increased makes the container of the present invention particularly suitable as a hot-filled container. The heat setting technology can also be used to further increase the surface crystallinity level to 30% or more. The above and other features of the present invention will be more apparent from the following detailed description and examples shown in the accompanying drawings. Figure 1 is a schematic diagram of a typical cycle or circuit that must be traversed by a recyclable / heavy container; Figure 2 is a schematic elevation view of a 1.5-liter PET carbon dioxide gas bottle partly broken away in the present invention, along various positions of the bottle , Indicating that the high copolymer core layer has different crystallinity levels compared to the inner and outer layers of the low copolymer; Figure 3 is an enlarged view of the part along the line 3-3 of Figure 2, detailing the center core of the high copolymer PET Layer, and the inner and outer layers of the low copolymer PET; Figure 4 is a schematic cross-sectional view through the injection of the cavity, showing the way the polyester resin material is introduced into the cavity to form the prototype of the present invention;工 消 " Cooperative printed 3i (please read back and forth and write this page) Figure 5 is a partially enlarged schematic diagram showing the way the first low copolymer material is injected into the bottom of the mold cavity. The surface of the cold mold wall is cooled to form the inner and outer layers of the prototype; Figure 6 is a partially enlarged schematic diagram showing that the second high copolymer material is injected into the bottom of the mold cavity to form the core layer, resulting in the first and The tunnel flow of the second material forms a prototype; Figure 7 shows the system The container of the present invention is an enlarged sectional view of a multilayer with the prototype;

A This paper is used in the margin of the standard a Η 家 炫 毕 (CNS) TM «m (21〇x29 / 公;« :) 81. 7. 20,000 sheets (II) Employee consumption of the Central Bureau of Economic Development of the Ministry of Economic Affairs «· Cooperative cooperative printing 32 .

2109 ^ AG ______ η 6______ V. Description of the invention (5). Figure 8 is a partially enlarged view showing the cross-sectional view of the base of the container made from the prototype of Figure 7; Figure 9 is a partial fracture of the specific example of the modification of the prototype The top view, with a third injection material at the base section of the prototype, instead of the core material, can be a low copolymer material similar to the inner layer and the outer layer; Figure 10 is a partially enlarged view showing the prototype of Figure 9 A sectional view of the base of the container. " Referring now to the drawings, especially Figure 1, the recyclable / heavy container must withstand countless cycles, and still maintain its aesthetic and functional characteristics. The test procedure to simulate this cycle is as follows. The classic commercial emu washing solution in each container is prepared from 3.5% by weight sodium hydroxide and tap water. The lotion is maintained at a relatively high temperature, typically about 60 ° C, and at least about 65 according to the present invention. (: Better, and at least about 7 (TC is particularly preferred. Immerse the bottle in the wash solution for 15 minutes to simulate the time / temperature conditions of a commercial bottle wash system. After the wash solution is taken out, rinse the bottle with tap water and then Filled with carbonated water at 4 · 0 ± 0.2 atmospheric pressure (to simulate the pressure of carbonic acid soft feed), covered and placed in a convection oven at 38 ° C with 50% relative humidity for 24 hours. Select this elevated oven temperature , Designed to simulate a longer period of commercial storage at lower ambient temperatures. After being removed from the oven, the container is emptied and then circulated again through the same weight until it is damaged. Damage means that any cracks pass through the bottle wall, causing leakage and Pressure loss. Volume shrinkage is measured by comparing the internal volume of the container (based on the liquid volume that can be stored at room temperature) before and after each heavy cycle. The container of the present invention is resistant to washing at a temperature of 65 ° C or above At least 5 times, preferably at least 10 or 20 times such heavy cycle, without damage, the capacity change does not exceed about 1.5% 5 ~ This paper is used in the edge of a S Jia Yu Bi (CNS) TM regulations (210X297 Dragon) 81. 7. 20,000ik (||) (Please KJiftlrlr first Note for u ¾ this page) Pack · 210976 A 6 Π 6 V. Description of the invention (6). The gas chromatography mass spectrometry measured the container to reduce the product odor exchange by at least 20% compared to the known commercial CSD bottles. Fig. 2 shows a PET carbonated gas bottle made according to the present invention. The bottle 10 is a core body with an open upper end, a neck (not shown in the figure), and a sealed bottom vertical wall 13 including an upper oblique shoulder 14 Line or center line CL is defined) There is a central flow channel portion 20, an inner concave arch or recess 22, the bottle is placed against this, and gradually radiates to the side wall 16. The multilayered side wall of the bottle 10 has a small scale. Figure 3 shows The side wall of the carcass 16 is broken and the inner layer 32 and the outer layer 34 of the low copolymer are about 13.2 inches (335 liters t 92 coffee tall). The thickness of the core layer 30 is about 0.015 — each thickness is about 0.003 — 0.006 inches, and the root is made of 1.5 liters. The integral blow-molded 12 is processed into a male thread 18. Neck and bottom, and cylindrical carcass. The overall bottom is the incense part 22, the lowest continuous increase outside the bottom 26, is not specific as the second collection / reinforcement biaxial guide vacant to accommodate the screw cap room is substantially 16 (by the bottle & benzine type bottom, ring part Or convex edge for smooth transition as shown in the figure, pay attention to because of vt first reading-Item% This π is printed by the Ministry of Economic Affairs + Central Standards Bureau Cooperative Society 5i, and the plane extension ratio is about 10: 1. The plane extension is average The ratio of the thickness of the side wall of the bottle. The bulk density bottle is better than the flat extension. The ring extension is 3 _ 3.6: 1 and has a high copolymer core layer 30. In a specific example, 1.5 g, (most Width) The diameter of the inner layer 32 and the outer layer 34 is about 3.6 inches (0.024 inches in diameter). The thickness of the sidewall of the prototype is about 0.230 inches. The stretch ratio is based on the average thickness of the sidewall of the prototype. The thickness of the polyester is about 0.5 ~ 2.0 liters. 1, 8-10: 1 is better, and the shaft extension is 2-3: 1. This provides the container side wall with the required abuse resistance, while the prototype side wall has the required visual transparency. Side wall thickness and selected extension ratio , Depending on the size of the characteristic bottle, internal pressure (for example, beer is 2.0 atm, and soft food is 4 atm ~ 6 ^, wood paper side with the scales in a Η house standard half (CHS) TM Imitating (210x297 well; IT)

HI. 7. 20.00〇ikOD The Ministry of Economic Affairs, Bureau of Standards, Beta Engineering Cooperative Cooperative Printed 3i Λ 6 21-0 ^-V. Description of the invention (7), and the processing characteristics of special materials (eg determined by intrinsic viscosity) different. The crystallinity achieved across the side walls of the container is shown in Figure 2. The percentage of crystallinity is determined according to ASTM 1505 as follows: Crystallinity% = [(ds — da) / (dc-da)] X 100 where ds = sample density, g / cm3, da = 0% crystallinity of the amorphous film ( For PET, it is 1.333 g / CTi3), and dc = the crystal density calculated from the unit lattice parameter (for PET, it is 1.45 5 g / CTi3). As shown in Figure 2, the neck 12 crosses the core layer. The inner and outer layers have very low crystallinity (0-2%) because this part of the bottle does not substantially swell. The swelling is smaller than the carcass section 16 as a sloping shoulder 丨 4, and the crystallinity caused by 15-17% strain in the core layer, and the crystallinity caused by 22-24% strain in the inner layer and the outer layer. In the highly extended carcass section 16, the core layer is 16-18% strain-induced crystallinity, and the inner and outer layers are 22-25%. The thicker section of the runner 20 and the bottom recess 22 which is less swellable are again crystallinity caused by 0-2% strain in the core layer and the inner and outer layers. In the flange region 24, the core layer produces 4-8% strain to cause crystallinity, while the inner and outer layers are 16-18%. In addition, different degrees of crystallinity can be achieved by heating (heat-induced), or crystallization caused by combined strain and heat. In general, strain-induced crystallinity tends to be substantially uniform across the thickness of a particular layer, while thermally-induced crystallinity can show a gradient across walls. In the present invention, a high level of crystallinity on the surface of a single sidewall is sufficient, although, typically, a crystallinity of substantially a certain average level can be achieved across layers. The blower container should be substantially transparent based on the aforementioned percentage of crystallinity. Another measure of transparency is the percentage of turbidity (%) of the emitted light through the wall, fixed (please refer to wl-ift first. ^ Please pay attention to the items and write this page hard). Binding. Thread a Sleepy family "quasi (CNS) executive (210> < 297 public;«: > 81. 7. 20.000 sheets (II) printed by the Ministry of Economic Affairs, Bureau of Standards, β-consumer cooperative cooperative 3i V. Description of invention (8 ) The meaning is as follows: HT = [Yd + (Yd + Ys)] X 100. where Yd is the diffused light transmitted by the sample and Ys is the reflected light transmitted by the sample. The transmission values of the diffused and reflected light are in accordance with the ASTM method D 1003 measurement 'Use any standard colorimeter, such as Model D25D3P manufactured by Hunterlab, Inc. The (turbid wall) turbidity percentage of heavy tanks should be less than about 15%, preferably less than about 10%, and lower Preferably it is about 5%. The high copolymer PET forming the core layer 30 preferably contains about 4-6% of the total weight of comonomers, such as 1,4-cyclohexanedimethanol (CHDM) and / or isophthalic acid ( IPA). The inner layer 32 and the outer layer 34 are made of low copolymer PET, preferably containing about 0-2% of the total weight of comonomers, such as CHDM and / or IPA. These materials are in Kingsport, Tennessee, USA Are available from Eastman Chemical Company and Goodyear Tire & Rubber Company in Akron, Oregon. Co-monomers (eg, CHDM instead of diol part, or IPA instead of acid part) intermittent PET polymer architecture (ie acid Rotating unit with glycol) reduces the molecular crystallization rate. The comonomer is the most effective when forming a part of the framework, but it can also form a branched copolymer. __ The bottle is best injected through a two-stage prototype and subsequent reheat It is made by blowing. Generally speaking, the part of the bottle (at moderate temperature) that is stretched shows the maximum amount of crystallinity across the side wall. In addition, the copolymer has varying degrees of multi-layer side wall (see Figure 3), resulting in crystallization The degree of change in the high copolymer core layer 30 shows that the lower crystallinity of the copolymer inner layer 32 and the outer layer 34 is low. Because increasing the copolymer content at a specified temperature will reduce the molecular crystallization rate. A measure of the crystallization rate is from Differential Scanning Calorimeter (DSC) obtained ~ 8 ~ (please read the back first. 5- 江 意 闺 项 #Item write a wooden page) installed-_ line CNS) TM specifications (2 丨 0X297cm) 81. 7. 20.000 sheets (II) Ministry of Economic Affairs Bureau of Standards 3: Cooperate with Industrial Consumers to produce 010975 _____- V. Description of the invention (9) Crystallization curve, measure ΔΤ, ie ΔΤ = Tie — Τρ, where Τρ is the crystallization peak temperature, 'is the initial crystallization temperature (start) , And Tie is the initial temperature extrapolated from the tangent to the base cross at the high temperature side of the exothermic peak. This technique is detailed in HN Beck and HD Ledbetter, J. Appl. Polym. Sci., _ ^, 2131 (1965 ), And 3 & 1611 VIII. ≫ 531411: "Resin and manufacturing process parametric variables affect the crystallization of PET prototypes", BEV-PAK, 1992 The 16th International Ryder Conference on Packaging Materials, March 23, 1992 — On the 25th, from the 6th to the 11th, the full text is listed here. The amount of ΔΤ is a function of the overall crystallization rate. The smaller the ΔT, the greater the crystallization rate. For PET, high copolymers are generally regarded as AT (measured at a cooling rate of 5. (: / min, measured from 300 ° C to below Tg (80 ° C)) at 21.5. (: And above, and low The copolymer is below 21.5 ° C. The ΔT difference between the high and low copolymer layers of the present invention is at least about 20%, for example, the high copolymer ΔT is about 24, and the low copolymer ΔT is about 20. The prototype used for blowing bottles is essentially It is amorphous, meaning to PET about 10% crystallinity, preferably not more than about 5% crystallinity, and preferably not more than about 2% crystallinity. In addition, the substantially amorphous or transparent nature of the prototype is Determination of the percentage of turbidity. The percentage of turbidity across the prototype wall should not exceed about 20%, preferably not more than about 10%, and preferably not more than about 5%. In essence, the amorphous prototype expands, in the container: The side walls produce alignment and crystallization. Any conventional technology that can involve the expansion of the prototype, such as emptiness or press molding, expands the prototype into a container. The two known methods are the integrated injection blow method and the two-stage prototype Injection and subsequent hot air blowing. The expansion step should be at the molecular alignment temperature of the polyester material used Within the scope of the paper, the paper is used in the edge of a Η family sample (CNS) T4 regulation «5 (210X297 public; Jt) 8 丨 7.7. 20,000 sheets (II) (please read the back of the words, pay attention to the city, Xiang Sun (This page is written on the crucible). Installation-Line · 21097ο Λ 6 η 6 5. Description of the invention (10) OK. Generally speaking, the thermoplastic that can be oriented is higher than the glass transition temperature (narrow temperature range of the polymer) to just below the polymerization .According to the actual situation, the orientation of the container row, called the molecular alignment temperature range conversion temperature, the material is too hard, no. When the temperature rises, the processability is much closer to the formation of the so-called sphere. The molecular alignment range is typically about 20 to 65 ° F (11 to 36 ° C), which is good. Typical amorphous PET polymerizations extend within a narrow range of just below or extend too close to the glass equipment. Limit to reach or connect because the transition temperature of the over-shaped polyester material glass to 22 ° C) is about 168 T) to about 205

The material is in a glass state. The melting temperature of the compound is formed. The reason is that the law is improved in knowledge, but it is really agglomerated. For materials that are substantially higher than polyester materials, about 30 to 40, the glass circumference is about 195 " F

The temperature of the sub-alignment temperature is narrower. When the temperature is the upper temperature of the process, the glass temperature of the amorphous material is ° F (17 conversion temperature C 91 ° C. Read the back first and pay attention to the items. Printed by the Ministry of Health, Ministry of Health, and Employee Consultation Cooperatives (76 ° C) * ° F (% · <:) ° It is better to cool to room temperature again, then within. Reheat the bottom inside the open end of the prototype Therefore, the medium is extended through the rod, and it is controlled according to the sign and wall thickness. The extension of the normal temperature range in the general orientation will place the prototype model and extend the inside of the prototype through hole or tool. The air blowing method expands and extends the drawing side wall axis around the rod into the surface. In the initial integrated manufacturing method, the hot injection prototype is reheated into the alignment temperature range gas assembly before the use of the previous step, in which the extension rod moves At the end of the prototype, the blow mold of the inner cavity is extended toward the inner cavity, and at the same time or in sequence, the blow is allowed to enter the inside of the prototype, and the radial extension of the prototype is based on the shape of the blow container and the relative size of the completed container. , The hot shot is partly quenched,利 10〜 This paper is used for the standard SB family ttlMCNS) Ή regulations (2 丨 0x297 g; ":) 81.7. 20.000 < k (ll) 2 2 Printed by Beigongxiao Cooperative Society, Bureau of Standards, Ministry of Economic Affairs 31 V. Description of the invention (11) Before expanding with appropriate blowing similar to the aforementioned or the combined extension / blowing device, allow it to be balanced within the range of the alignment temperature. Figures 4 to 6 show the metering sequential co-injection device to manufacture the multilayer prototype of the present invention. This device is essentially US Patent No. 4,710,118, granted by Krishnakumar et al. On December 1, 1987, and is incorporated herein by reference. As shown in FIG. 4, the injection mold unit 40 includes an outer mold cavity 42, a neck ring 44 forming a neck, and a core 46. The neck ring 44 and the core 46 close the upper end of the mold cavity 42 and the lower end is provided with an opening 48 to receive the nozzle-like end 50 of the rotary valve member 52 of the extruder in a sealed relationship. The valve member 52 is installed in the valve block 54 in a sealed relationship, in which a first passage 56 is formed to receive a conventional nozzle 60 of plasticizer or an injection die. The passage 56 opens radially to the rotary valve member 52, the latter having a through passage 62 with one end ending in a general radial passage 64, which can be aligned with the passage 56. Also associated with the valve block 54 is a second material consumer 66, which contains a consumer piston 68, and a flow passage 70 from there to the valve block 54. The valve block 54 has a radial passage 72 which is axially aligned with and communicates with the passage 70. The valve member 52 has another passage 74 that generally extends radially from the passage 62 and is spaced circumferentially from the passage 64 so that when the passage 64 is aligned with the passage 56, the passage 74 is separated from the passage 72. Turning the valve member 52, the channel 64 is moved out of communication with the channel 56, and the channel 74 is moved into communication with the channel 72. Therefore, it is possible to select the first supply device (injection die) 60 or the second supply device 66 to supply the material. According to a preferred embodiment, the material supplied by the first supply device 60 is a low copolymer PET for inner and outer layers. The material supplied by the anvil of the second supply device is a high-copolymer PET for the core layer. Referring to FIG. 5, it can be seen that the pre-selected amount of the first low copolymer resin 76 may be ~ 11 ~ The BH home «^ (CNS) T4 regulation (2 丨 0X297 public;« :) 81. 7. 20 · 000 sheets (Π) (please read ift back first and pay attention to Lu Xiangsun's hardship page) Installed · Line-* '· Ministry of Economic Affairs, Pentagon Bureau of the Ministry of Economic Affairs Bei Gongxiao ft. · Cooperative Printed 52. V. Inventions Explanation (12) When it is injected into the bottom of the cavity 42, and when it flows through the cavity, the mold unit 40 including the core 46 is colder in temperature, and the resin 76 will solidify, forming the outer surface inner layer 78 and the outer layer of the first material 80. As shown briefly in Figure 6, the high copolymer core material 86 is then injected into the mold cavity. It can be seen that the core material 86 flows through the cavity defined between the two layers 78, 80 in a tunnel manner while pushing the previously injected material 76 forward. The internal core material cools slowly because it does not touch the colder mold wall, but because the core layer has a higher copolymer content, it can resist turbidity. Referring to FIG. 7, the prototype 110 is formed as described above, and includes a high copolymer core layer 130, a continuous low copolymer inner layer 132, and a low copolymer outer layer 134, except for a portion extending through the outer layer in the runner region 120 The core material is continuous. The prototype 110 includes an upper neck 112, a sloping shoulder forming section 114 of increasing thickness from top to bottom, a carcass forming section 116 having a uniform wall thickness, and a bottom forming section 118, including a larger upper portion than the carcass section 116, and Adjacent to the lower portion 119 of the flow channel area 120 of reduced thickness. The prototype with better cross-section is contained in U.S. Patent No. 5066528 granted to Krishnakumar et al. On November 19, 1991, and is fully incorporated in Shenmei. The core layer 130 of the carcass section 116 is approximately twice the thickness of each inner layer 132 and outer layer 134, forming a preferably 1.5 liter bottle with the aforementioned wall thickness. As shown in FIG. 8, the air blowing container has a champagne bottle-shaped bottom section 150, and includes a flow channel portion 152, an inner concave portion 154, a flange 156, and an outer portion 158. The thickness of the core layer 160 and the inner layer 162 and the outer layer 164 vary along the bottom, depending on the relative amount of extension of the specific bottom, but generally speaking, the wall thickness gradually decreases as it leaves the flow channel region 152 in the radial direction. 12 (please read the first -ift and note the item #write this page) 装 · ^ •-This paper is used in the edge of the sheep a B Jiayu standard (CNS) ΤΊ 执 格 (210x297 公 *) 81. 7 . 20.000 sheets (II) A 6 n 6 2109 ^ V. Description of the invention (13) FIG. 9 shows a modified specific example of the bottom forming section 218, in which the third injection of the low-copolymer material is the bottom forming At least a portion 236 of the segment is preferably injected into the lower bottom 219 of reduced wall thickness because it is thinner, cools faster, and is less turbid. The low copolymer segment 236 replaces the core material 230, preferably the same material as the inner layer 232 and the outer layer 234, so in the aforementioned co-injection method, before the start of the next prototype, the nozzle clears the high copolymer to avoid the next copolymer In the mold, any high copolymer is injected into the inner and outer layers. As shown in FIG. 10, the champagne-shaped container bottom 250 blown from the prototype of FIG. 9 includes a flow channel portion 252, an inner concave portion 254, a flange 256, and an outer bottom portion 258. The bottom spanning wall includes an inner layer 262 and an outer layer 264, and a core layer 260. The core layer 260 is at least partially replaced by oligomers in the section 266 spanning the flow channel and the recessed area. The thermoplastic polymer material used in the present invention is preferably based on polyalkylene terephthalate (e.g. ethylene glycol) (PET). PET polymers are generally made of terephthalic acid or its ester-forming derivatives, and ethylene glycol or its ester-forming derivatives, including repeating ethylene terephthalate groups of the following formula: (Please read first Please pay attention to Zao item # item write this page)

T

Printed by C5 Gongxiaozuo Cooperative of the Central Bureau of Economic Affairs of the Ministry of Economic Affairs. 32. The present invention contemplates the use of polyethylene terephthalate copolymers with a small amount, such as about 10% by weight of ethylene terephthalate units. , Replaced by compatible monomer units, where the diol portion of the monomer is changed to aliphatic or cycloaliphatic diols, such as cyclohexanedimethanol, propylene glycol, polybutylene glycol, hexanediol, Dodecanediol, diethylene glycol, polyethylene glycol, polypropylene di ~ 13 ~ 81. 7. 20.000 sheets (II) ft scale of this paper xiao sang a S home sample Bi (CNS) ΤΊ executive (210 乂297 degrees) Λ 6 η 6 21〇 ^ ° V. Description of the invention (w) Alcohol, propylene glycol 1,3, butanediol ~ 1,4, and neopentyl glycol, biphenol, and other aromatic diols Classes, such as hydrazone, and 2,2-bis (4, one / 7-hydroxyethoxyphenyl) propane. The dicarboxylic acid moieties that can be substituted in the monomer unit include, for example, aromatic diacids, such as Isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenoxyethane dicarboxylic acid, dibenzoic acid, and aliphatic or cycloaliphatic dicarboxylic acids, such as hexyl Acids, sebacic acid, azelaic acid, decane dicarboxylic acid and cyclohexane dicarboxylic acid. In addition, various multi-functional compounds, such as trimethylolpropane, pentaerythritol, trimellitic acid and benzene are three Acid, which can be copolymerized with polyethylene terephthalate, the amount of which can be less than about 2% by weight. The polyethylene terephthalate usable in the present invention may also contain other compatible additives and ingredients. Performance characteristics, such as no adverse effects on the taste or other properties of the packaged products. Examples of such ingredients include heat stabilizers, light stabilizers, dyes, pigments, plasticizers, base materials, antioxidants, lubricants, extruded Auxiliaries, residual monomer purification agents, etc. Intrinsic viscosity (I.V.) affects the processability of the polyester resin. The starting material used in the manufacture of the container of the present invention can use an intrinsic viscosity of about 0.55 to about 1.04, preferably about 0.55 to 0.85 Of polyethylene terephthalate. The intrinsic viscosity is in accordance with ASTM D-2857 procedures, using 0.0050 ± 0.0002 g / me polymer in a 30 ° C solvent (including melting point 0. <: o-chlorophenol) Measurement. Intrinsic viscosity (IV) is determined by the following formula set:

IV = (βn (VsoZn / VsoZ)) / C where: VsoZn is the solution viscosity, in any unit, Vso / is the solvent viscosity, in the same unit, 14 paper Λ scale, 18 B home ttUMCNS) T4 «5 (210X297 Public; tt) (please pay attention to wllft first-^ item #write this page)

T% Ministry of Economic Affairs, Central Standards Bureau, Bei Gong Consumer Cooperation Du Yin 31 81. 7. 20.000¾ (II) 2109'Vo Ministry of Economic Affairs Central Standards and Employee Consultation Cooperatives printed 51 V. Description of invention (15) C is for every 100 ml In the production of polymerized heavy-duty polyester urn bottles for solutions, the United States granted Krishnakimer et al. On February 16, 1988 to Collette on February 16, 1988 and the Krishfiakumar number granted on November 19, 1991, both of which are listed here. Enter Shenmei. As mentioned above, the plastic container of the present invention is made of PET). However, in other thermoplastic poly-invented multilayer containers, the first layer is more resistant to crystallization caused by heat injection, and the second layer achieves higher strain and / or heat-induced surface crystallization. In addition to the core layer of the preferred embodiment, other layers are provided. Different base materials can be used. Substantially hemispherical bottom wall, with a plurality of downward holding feet, and horizontal bars between the legs (the bottom wall thickness, prototype and bottle shape, all due to special final invention materials, containers are available Other pressurized or non-alcoholic, fruit juice or milk, or other non-distilled materials such as turbidity resistance and improved resistance at elevated temperatures are used in Collette et al. September 5, 1989, the full text of which is listed in Shenmei. Container 180-185 T (product charging temperature) psi (filling pressure on the line) without substance. Therefore, although the present invention has a number of preferred concentrations of ~ 15 ~ the number of grams of other important factors, contained in the 1982 US patent No. 4334627, National Patent No. 4725464, U.S. Patent No. 5066528, etc. The polyterephthalate resin can also be heat treated or similarly blown or crystallized afterwards to provide, inner and outer layers, such as foot extension legs , To the most part). The product varies, and the product is still pressurized. The stress cracking property of the present invention, the approved U.S. patent must typically be energy spectrum, and the positive internal pressure deformation. Specific examples, such as formate (in the cost process, in addition to the higher degree of expansion stage, can be added, with the following branch materials, wall installation costs, such as beer benefits, examples can be particularly suitable for 4863046 Temperature rises to 2 — 5 Picture and 1 above? First read the back and lack of attention #% This ·> Install rr line private paper ft scale side use S® Home Standard (CNS) T4 regulation (2 丨 0x297 ; Jt) 8K 7. 20,000ik (il) Λ 6 B6 2l〇SsV〇 Fifth, the description of the invention (16) stated that the basic structure, material, container structure and container formation method can be changed without violating the original The spirit and scope of the invention application. First read in Contrary Notes • 4 Fill% This rr is installed by the Ministry of Economic Affairs, the Central Bureau of Economics and Trade, Pinggong Porridge Cooperative, and Du Yinyu. 16 This paper is for standard use. (CNS) T4 regulation (2 丨 0X297 male; ":) 81. 7. 20.000ΪΜΙΙ)

Claims (1)

Qing H Gong Ye Ben ———— Sixth, apply for a patent I Jie-, the main body ... Ethylene formate, with 4 to 6% of the inner layer and the outer layer, which is polyparaben and at least 20% crystallinity, of which It can withstand 20 times of heavy cycle, and reduce 2. If the patent application is the first cause. 3. If the percentage of the crystallinity of the second layer of the patent application range is heated 4. If the listener of the patent application range from 1 0.5 to 0.7. 5. If the scope of the patent application is the fourth stretch ratio 7-11: 1 expansion. A7, Saikou: 2 丨 'B7 C7 May 10, 82 • Correct »} Ά 5. 1 /, I D7 container, including the integrated body formed by the expansion of the multi-layer prototype, there are substantially transparent multi-layer The side wall, including the core layer is poly-p-phenylene dimer and 14 to ethylene acid ester, the container is in the product residual gas item, the item item, the styling and then the item item, 20% crystallinity, and there is no More than 2% copolymerization ash washing temperature of 60 ° C above 20%. The degree of crystallinity is the strain of which the inner layer and the outer layer of the side wall are at least 30%. The wall thickness of the side wall is the container of the item, and the side wall is extended by a plane (please read the precautions on the back and then fill out this page). Installed • Printed • Printed by the Beigong Consumer Cooperative of the Central Bureau of Economics and Trade 6. For example, in the container of claim 1 or 4, the core layer accounts for 50 to 80% of the thickness of the side wall. 7. If the container of the first item of the patent application scope, where the container can withstand the specified heavy cycle, the maximum capacity deviation ± 1.5%. 8. If the container of item 1 of the patent application is applied, the container is a pressurized container. 9. If the container of claim 1 is applied for, the container is a thermal container. 10. For the container of item 1 of the patent application scope, where the turbidity percentage of the side wall does not exceed 15%. 17 The standard of this paper applies to China National Standard (CNS) & F4 specifications (210x297 mm). Line. 〇A7 B7 C7 D7 VI. Patent application model ffl II. A method of making a container, including the following steps: Provide substantially non- The prototype of crystal injection molding, with multiple side walls, including 4 to 6% copolymer of polyethylene terephthalate, and inner and outer layers of polyethylene terephthalate, no more than 2 % Copolymer, expands the prototype to form the body of the container, with a substantially transparent multilayer side wall, expands with a plane extension ratio of 7 ~ 11: 1, so that the inner and outer layers of the side wall have at least 20% crystallinity, and the core Layers with μ% to 20% crystallinity. 12 The method as claimed in item 11 of the patent application, in which the side wall of the container is heated to further raise the percentage of crystallinity of the inner and outer layers. 13. The method as claimed in item 12 of the patent application, in which the inner and outer layers of the side wall of the container are expanded and heated to a crystallinity percentage of at least 30%. 14. For example, if the method of patent application scope item 11 is adopted, the container is a heavy carbon dioxide gas container. 15. A method of forming a multi-layer container, including: providing the first material of polyethylene terephthalate, with 4 to 6% copolymer, and the second material of polyethylene terephthalate, with or without More than 2% copolymer; at elevated temperature to form a substantially amorphous multilayer prototype, with an inner layer of the first material, and at least one outer surface layer of the second material, wherein the prototype is cooled from the outer surface, and the first of the outer surface layer The material is resistant to crystallization caused by heat; the prototype is expanded to form a guided substantially transparent multilayer container. Based on the different crystallization rate of the material, it has a higher degree of crystallization than the inner layer and the outer layer. ～ 18〜 This paper is used in National B (CNS) T4 specifications (210x297mm) for the free use of paper size (please read the notes on the back of K1 first and then fill in two pages). Installed. * Ordered by Jinghu Department Printed by the quasi-bureau Beigongxiao Cooperative Society 91 I A7 B7 C7 210074 --- 21- Liu's patent application Fan Ji 16.-A prototype for forming a substantially transparent biaxial guide container, including substantially amorphous injection molding Components with multiple side walls, a core layer containing polyethylene terephthalate, with 4 to 6% copolymer, and inner and outer layers of polyethylene terephthalate, with no more than 2% copolymer . 17. As in the prototype of patent application scope item 16, where the core layer accounts for 50 to 80% of the thickness of the side wall. 18. For example, in the prototype of the scope of patent application item 16, where the percentage of turbidity of the side wall does not exceed 20%. 19. A method for making a prototype to form a substantially transparent biaxially guided container. This method includes the following steps: injection molding a prototype that is substantially amorphous and transparent, has three layers of side walls, and includes polyethylene terephthalate The inner core layer of diester, with 4 to 6% copolymer, and the outer inner layer and outer layer of polyethylene terephthalate, with no more than 2% copolymer, and cooling the prototype surface to make the core layer resistant Muddy. (Please read the precautions on the back and then write this page) k. • Ordered · Printed by the Employee Consumer Cooperative of the Bureau of Standards, Ministry of Economic Affairs. Line · ~ 19 ~ This paper standard is used in a B home standard (CNS) T4 specification (2 丨 0X297mm)