TW490477B - Improved rigid polymeric beverage bottles with improved resistance to permeant elution - Google Patents

Abstract

Carbonated beverages can have a substantially reduced concentration of water soluble materials derived from biaxially oriented thermoformed beverage containers. Such containers can comprise a permeant barrier and an active trap for water soluble materials that can be removed from the thermoplastic by extraction into the carbonated beverage. The improved container material comprises a blow molded thermoplastic polyester web comprising a compatible modified cyclodextrin material having pendent moieties or substituents that render the cyclodextrin material compatible with the container thermoplastic. The cyclodextrin material, after it is added to the polymer material, acts as a barrier and to trap extractable materials as they permeate through the thermoplastic polyester. The cyclodextrin molecule has a large center cavity having properties that increase the likelihood that organic molecules will be absorbed and trapped in the center pore. The resulting polyester is substantially resistant to any extraction of soluble materials from the polyester material by the carbonated beverage.

Description

Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 490477 A7 B7 V. Description of the Invention (1) The field of the invention The present invention relates to a beverage bottle which contains a single layer of hard thermoplastic, and at least one of the two or more containers contains a The amount of substituted or modified cyclodextrin can prevent the permeate from passing, or the soluble substance can be washed from the thermoplastic into the contents of the liquid container. The present invention also relates to a biaxially oriented thermoformed polyolefin or poly-thermoplastic beverage container which resists permeate movement or passes into the beverage and which is resistant to the extraction or washing of soluble substances from the polyester sheet into the beverage. Inventing the Heat Rigid or semi-rigid hot plastic beverage containers have been known for many years. An example of such a container is a high-density polyethylene milk bottle which has a capacity of one quart, one gallon, or other general size. These containers typically include high density polyethylene. High-density polyethylene is made using ethylene flow qirongle-nata catalysts in a liquid or ammonia phase process. Other vinyl polymers can also be used to formulate these beverage containers, including polymers made from monomers including ethylene, propylene, butene, butadiene, styrene, and others. These materials often contain small concentrations of residual monomers, impurities in the olefin feed, catalyst residues, and other impurities. Such containers are typically blow molded from preforms into finished bottles or containers using general thermoforming techniques. A biaxially stretch blow molded thermoformed polyester beverage container is disclosed in 148! -Noff (Ed) Modern Plastics, Encyclopedia, Vol. 16, No. 10A, P. (84) pp. 192-194. These beverage containers are typically made of polyester material. These polyesters often use diols such as ethylene glycol, 1,4-butanediol, 1,4-cyclohexanediol, and other diols with organic diacids. This paper is sized to the Chinese National Standard (CNS) A4 ( 210X 297mm) —5 _ (Please read the notes on the back before filling this page)

Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 490477 A7 B7 V. Description of the invention (2) Produced by a copolymer such as terephthalic acid, 2,6-dicarboxylic acid, etc. A condensation / polymerization reaction occurs in a thermally driven reaction between a dicarboxylic acid, or its dimethyl ester and a diol substance, in which water or methanol is released as a by-product of the M reaction leaving a high molecular weight polyester substance. Typically, a monolithic polyester is injection blow molded into a steel core rod to form a prepreg containing the polyester. The prepreg is guided into a blow molding machine where the polyester is heated and blow molded into the proper shape and volume for use in beverage containers. The preform may be a single-layer material or a double-layer or multi-layer preform. Their prepregs can form double or multilayer bottles. Thermoplastic polyesters are high molecular weight materials, but can contain a wide variety of relatively low molecular weight compounds, substantially less than 500 grams per person. These compounds can be scooped into the beverage contained in the container. These beverage extractables typically include impurities in the diol or diacid feed stream used to make the polyester. In addition, these extractables may include degradation by-products of polymerization, preform molding processes, or thermoforming blow molding processes. Furthermore, the extractable substance may contain residual diesters, glycols or diacid substances including methanol, ethylene glycol, terephthalic acid, dimethyl terephthalate, 2,6-dicarboxylic acid, and esters or ethers thereof. . It may also contain relatively low molecular weight oligomeric linear or cyclic diesters, triesters or higher esters formed by the reaction of one mole of ethylene glycol with one mole of terephthalic acid. These relatively low molecular oligomers may be Diols that include two or more humoral ears combined with two or more diacids of their ears. Schiono, Journal of Polymer Science * ο I ymfir Chemistry Edition, Vo 1.17, pp. 4123-4127 (1979), John Wiley & Sons, Inc. discusses the separation and identification of PET impurities including poly (ethylene terephthalate) oligomers using permeation chromatography. This paper size applies to Chinese National Standard (CNS) A4 specification (210 × 297 mm) -6-(Please read the precautions on the back before filling this page)

， 1T 490477 A7 B7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the Invention (3) Bar11 et a 1., " Supercritical Fluid Extraction and Chromatography for the Determination of Oligomers and Poly (ethylene terephthalate) Films ", Analytical Chemistry, Vol. 63, No. 20, October 15, 1991, PP. 237 2377, discusses the use of experimental supercritical fluid procedures to separate and identify oligomer impurities from polyethylene terephthalate membranes. Contains these When soluble / extractable beverages are consumed by the public, in some cases, the taste is reduced due to the presence of extractable compounds. Extractable compounds may add or interfere with the aroma speciality or odor characteristics of beverage substances. In addition, there are some substantial concerns about the toxicity or carcinogenicity of any organic substance that can be extracted into beverages consumed by humans. The technology of the composition used in the manufacture of beverage containers is rich and varied. Most of them This technology is related to coated and uncoated polyolefin containers and coated and uncoated polyester, which reduce This technology also relates to the manufacturing method and bottle shape and bottom configuration. Deaf et al., US Patent No. 5,330, 808 mentions the addition of fluoroelastomers to polyolefin bottles. Μ introduces a glossy surface on the bottle., 丨 3 丨 〇1 丨 6131., U.S. Patent No. 5,350,788 refers to a method for reducing the odor in recycled plastic. Vi si oli et a 1. Reveals the use of nitrogen compounds including multi-e Alkylimines and polyethylenimines act as odor scavengers in polyethylene materials containing a large proportion of recycled polymers. Wyeth et al., U.S. Patent No. 3,733,309 shows a blow molding machine that can form a layer on the Polyester blown in a blow mold. Add 1 eman, US Patent No. 4,127,633 mentions polyethylene terephthalate pre (please read the precautions on the back before filling this page)

Remarks · This paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) 490477 Printed by A7 B7, Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (4) Molding material, which has been heated and used polyisocyanate Vinyl chloride copolymer latex coatings form a vapor or gas barrier. Hal ek et a 1., U.S. Patent No. 4,223,128 refers to a method for preparing polyethylene terephthalate that can be used in beverage containers. 8〇 [11 ^ 1 ^ 16131., U.S. Patent No. 4,335,089 mentions a method for preparing a center thermo-glue molded article in a biaxially stretched bottle using biaxial drawing and blow molding techniques. The preform is blow-molded and maintained in contact with the hot wall of the mold at least partially to reduce the internal residual stress in the preform. The prepreg may be cooled to a suitable size in a second blow molding operation. 631 ^ 1 (161: 31., U.S. Patent No. 4,463,121 refers to a polyethylene terephthalate / polyolefin compound with increased impact resistance, high temperature dimensional stability, and improved mold release. Ryder, U.S. Patent No. 4,473,515 refers to an improved injection blow molding apparatus and method. In this method, a hot thermoplastic material is used to form a parison or a preform on a cooling stick. The preform is cooled It is then turned to the blow molding position. The parison is then stretched, biaxially oriented, cooled, and removed from the device. Nilsson, U.S. Patent No. 4,381,277 mentions a method for manufacturing a preform including laminating thermoplastic molds. Method of thermoplastic container. The preform has a thermoplastic layer and a barrier layer, which fully transform from the preformed shape and form a container. Jakobsen et al., US Patent No. 4,374,878 mentions a method of manufacturing with M Tubular preform of a container. The preform is transformed into a bottle. Motill, U.S. Patent No. 4,368,825; Howard Jr., U.S. Patent No. 4,850,494; 1 & ", U.S. Patent No. 4,342,398; 86〇1 (, US patent No. 4,780,257; 1 (43111 ^ 1〇11 ^ "61 冱 1, U.S. Patent No. 4,334,627; 5" (161'6131., U.S. Patent No. 4) This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm ) (Please read the notes on the back before filling this page)

1T 490477 A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs V. Invention Note (5) 4,318,489; and 1 (1 * 丨 3} 11 ^ 1 < 1! 11 ^ 1 * 6131., US Patent No. 4 No. 108,324 each refers to a plastic container or bottle having a better shape or self-supporting bottom configuration. Hirata, U.S. Patent No. 4,370,368 refers to a plastic bottle made of monomers containing vinylidene chloride and propylene. And other vinyl-based thermoplastics have improved oxygen, moisture, or water vapor barrier properties. The bottle can be placed in a bottle mold by pouring water latex, drying the pouring latex, or using water before the bottle is formed Latex coating is made from preforms. 1 (1) 1 ^ 1 ^ 3 0131., U.S. Patent No. 4,459,400 refers to a poly (ester-ester amine) composition that can be used in a variety of applications including packaging materials. 8 & 1 ^} ^ 3 »1 丨 6131. US Patent No. 4,393,106 refers to a laminated or plastic container and a method of manufacturing the container. The laminate includes a moldable plastic material within a coating Smith et el., U.S. Patent No. 4,482,586 mentions good oxygen and dioxide Barrier properties, multilayer polyester objects containing polyisophthalate polymers. Wal 1 es, U.S. Pat. Nos. 3,740,258 and 4,165,914 mention that plastic containers can be improved by sulfonating plastics against organic substances and gases For example, the barrier properties of oxygen passage. In addition, we know that polyesters have been developed and formulated to have high explosion resistance. M resists the pressure of carbonated beverages on the container wall. Furthermore, some specific investigations have been performed to improve the polyester. Material resistance to stress cracking during manufacturing, filling and storage. Beverage manufacturers have been searching for improved barrier materials for a long time. For the most part, this research effort is directed towards carbon dioxide (C02) Barrier, oxygen (〇2) barrier and water vapor (H2〇) barrier. More recently, the original bottle is manufactured in accordance with China National Standard (CNS) A4 specification (210X297 mm) _ g-(Please read the back first (Notes for filling in this page)

Order 490477 Α7 Β7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (6) The vendor has significantly increased sensitivity to resin extractables or beverage solubles contained in the resin or container. This research is to use a polymer coating or polymer laminate made of a polymer with lower penetration to improve the body plastic K and reduce its penetration. However, we do not know of any attempt to introduce effective complex compounds into the bulk polymer resin or polyester resin of the beverage container to improve the barrier properties or capture water-soluble substances to prevent their extraction or washing. within. Even with this specific technology, there is still a substantial need to develop a biaxially stretched thermoplastic polymer material for beverage containers that reduces the coke texture to extractable substances in beverages intended for human consumption. Contains permeate. Brief description of the invention I have found that the polymer or beverage bottle is preferably a polyolefin or polyester biaxially stretched polymer or beverage container having improved barrier or capture properties. In particular, the resistance to the extraction of soluble substances from the bulk polymer can be improved without any significant clarification, reduction in processability or structural properties, by modifying the modified cyclodextrin or phase Capacitive cyclodextrin derivatives are obtained by incorporating or coating polymer materials in beverage containers. We have found that cyclodextrin substances can increase the barrier properties of polymeric materials via the internal hydrophobic spaces that trap permeates within the dextrin molecules. Furthermore, any small molecule or oligomer impurities contained in the container plastic that can be extracted by the beverage can also be trapped in the cyclodextrin before the impurities can be moved into the beverage. In this technique, cyclodextrin material can be added, dispersed or suspended in the bulk polymer used to make plastic bottles. The cyclodextrin can be added and suspended (please read the precautions on the back before filling out this page)

、 1Τ -4— n J— This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) 490477 V. Description of the invention (7) Floating or dispersed in the second thermoplastic layer, which can be used for thermal plastic The materials are co-extruded to form a bottle. Finally, the cyclodextrin material can be used in an aqueous or solvent-based liquid coating material and added to the bottle during the pre-forming phase or in the fully formed bottle phase. Preferred containers include high-density polyethylene milk containers and PET / polypropylene double-layer bottles or containers. The preferred cyclodextrin material is used in the form of a compatible derivative of cyclodextrin. Insufficient compatibility of cyclodextrin molecules without compatible substituents in the bulk polymer material leads to the formation of transparent and useful wells or cap layers in packaging materials. The compatible cyclodextrin derivative is substantially free of a compound containing a complex. For the purposes of the present invention, the term "substantially free of complexes" means that the amount of cyclodextrin material dispersed in the bulk polymer contains a large proportion of polymer impurities, permeates or other inclusions that are not contained within the cyclodextrin molecule Compounds of cyclodextrin. Cyclodextrin compounds are typically added and incorporated into the bulk polymer without any inclusion compounds. However, some compounding may occur during manufacturing. Their recombination may occur when polymer impurities and degrading substances become contained compounds in the cyclodextrin intercalation complex. A preferred cyclodextrin is a derivative of a cyclodextrin having at least one substituent bonded to a cyclodextrin molecule compatible with the bulk polymer. Cyclodextrins are cyclodextrin molecules with six or more glucose moiety in the molecule. Preferably, the cyclodextrin is α-cyclodextrin (a-CD), cold cyclodextrin (Ling-CD), and 5-cyclodextrin (δ-CD) or a mixture thereof. We have found that derivatization of cyclodextrin molecules can lead to improved blending in thermoplastic bulk polymers without losing the clarity, processability, or construction or packaging properties of the bulk polymer. The substituents on the cyclodextrin molecule have been selected to have a size compatible with the polymer. The paper is suitable for China® House Standard Feng (CNS) Λ4 specification (210 × 297 mm) -11-(Please read the notes on the back before filling This page

1T 490477 Consumption Cooperation with Employees of the China Standards and Quarantine Bureau of the Ministry of Economic Affairs, printed by A7 B7i, Invention Description (8) The composition, structure, and polarity M indeed make the cyclodextrin have sufficient compatibility in the polymer material . In addition, I found that derivatized cyclodextrins can be blended into thermoplastic polymers and formed into semi-rigid or rigid containers using traditional thermoplastic blow molding / thermoforming manufacturing techniques. Finally, we have found that the cyclodextrin materials used in the various parts of the present invention can be used to form their thermoplastic beverage containers without any substantial impairment of the structural properties. The first part of the present invention comprises nine pellets of a thermoplastic polymer, which has a large proportion of a polyester material for thermoplastic beverages, which has a sufficient amount of cyclodextrin material therein to improve barrier properties and serve as a trap for polymer impurities. The second part of the present invention includes a thermoplastic beverage container comprising a thermoplastic polyester having a large proportion of a polymer material and a small but effective amount of a cyclodextrin substance M to improve barrier properties and serve as a trap for polymer impurities. The third part of the invention comprises a beverage container comprising a large proportion of a constructed thermoplastic polymer having a second laminate layer comprising a thermoplastic polymer and an effective amount of a cyclodextrin substance M to improve the barrier properties of the beverage container And as a well for polymer impurities contained in the layered structure of beverage containers. The last part of the invention comprises a beverage container comprising a thermoplastic construction having an internal coating, the coating including a film forming material having an effective amount of a cyclodextrin substance which can provide and improve barrier properties or serve as a beverage container Wells containing impurities. Brief Description of the Drawings Figure 1 is a function representation of the size of a cyclodextrin molecule without derivatization. Its central core includes a hydrophilic space or volume inside the cyclodextrin molecule that can serve as a site for absorbing permeate or impurities. 〇 (, / 3, and 7 cyclodextrin are shown. This paper size applies the Chinese National Standard (CNS) Α4 size (210X 297 mm) (Please read the precautions on the back before filling out this page) Order 4. I Λ I---li _ A7 B7 i 'Description of the invention (9) Figure 2 is an isometric view of a two-liter polyester bottle. It has a second layer on a thermoplastic. It is derived from a polymer and an effective amount of cyclodextrin. Inventors_ Detailed discussion We have found that useful engineering thermoplastic polymer resins can be modified for use in applications including packaged beverages. We have found that the polymers modified with cyclodextrin materials have improved barrier properties and Reduced tendency to release polymer residues by extraction into the main beverage liquid. The general engineering plastic polyester material that can be used in the present invention is the condensation / polymerization product of a diacid and a polyol. The product is preferably aromatic Group of compound diacids such as phthalic acid or naphthoic acid. The main diacid returned in the polymer of the present invention is terephthalic acid (1,4-benzenedicarboxylic acid) or 2,6-naphthalenedicarboxylic acid. However, it is also possible Μ uses other phthalic acids and forbidden dicarboxylic acids such as phthalic acid, 1, 7- Dicarboxylic acids, etc. Polyesters are typically referred to as araliphatic or aromatic depending on the diol being copolymerized. For example, Polyethylene Terephthalate Chemical Abstract No. 25038-59-9 (PET) Poly (butylene terephthalate) Chemical Abstract No. 24968-12-5 (PBT) and related polymers are called araliphatic polyesters. Poly (diester A-phthalate) is called aromatic Polyester resin or polyacrylate resin. PET, PBT and poly (ethylene-2,6-non-dicarboxylic acid ester resin) (PEN> are the largest aromatic aliphatic products. Other aromatic aliphatic products include Eastman Kodak's Kodar® resin is a PET resin modified with isocyanate and dimethylcyclohexane. Polyacrylate resin is a lower volume special resin for high temperature (HDT) end use. Better Polyethylene terephthalate is typically made by transesterifying dimethyl terephthalate with ethylene glycol or 1,4-butanediol in the presence of trace metal ion catalysts Paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the notes on the back before filling this page),? Τ Ministry of Economy Printed by the Central Consumers ’Cooperatives 4.ϋ —ϋ MJe— — ^ ϋ —J ^ i · -13-^ U477 Α7 Β7 The printed statement of inventions produced by the Central Consumers’ Cooperatives of the Ministry of Economic Affairs (ί) Methanol by-products are collected overhead and extruded from the reactor in a continuous process. The product PET resin has an inherent viscosity (η) of about 0.72-0.85 kg / g. Bottle-grade PET resin is often inert during manufacturing. Heating M under ambient air promotes further polymerization in the resin. Polyester bottles are typically manufactured via injection blow molding. Two manufacturing techniques are generally used. In one method, a preform is made using injection molding technology. It has a preform shape, has a neck and a screw cap portion of the bottle, has approximately useful dimensions but the body of the preform is substantially smaller than the final shape. Single-component or double-layer prepregs can be used. This prepreg is then placed in a blow molding machine, heated and blown into the proper shape. Alternatively, resin can be injection blow molded onto a steel core rod. The neck of the bottle is formed with a suitably shaped receiving envelope (cap) and the resin is used around the temperature-conditioned rod for the blow molding step. The resin-added rod is introduced into a mold and the resin is blown away from the rod To the mold wall. The resin comes into contact with the mold while cooling into the transparent bottle. After the finished bottle is shot, the rod is moved to the injection molding station. This procedure is advantageous for single cylindrical bottles, but it cannot be used to introduce complex shapes such as handles into the bottle. The most commonly used machines include a four-segment device that injects resin, blows the resin into the proper shape, peels the formed container from the rod, and conditions the core rod before repeating the procedure. These containers are typically associated with It is manufactured together with the shell fitting part of the screw neck of the metal screw cap. The bottom of the bottle typically has a flap wheel design such as a four-lobed wheel or a five-lobed wheel design M to make the bottle stable and upright. In addition, there may be The molded bottle with a hemispherical bottom M adhesive is adhered to the polyethylene or polypropylene bottom cut piece to provide placement stability. Dextrin The paper size applies to the Chinese national standard (CNS) Α4 specification (210X 297mm) · -14-(Please read the precautions on the back before filling out this page) —--- Order 1--1 ϋ-i # 1 ί —4 — · 490477 A7 B7 V. Description of the invention (11) The thermoplastic film member of the present invention contains modified or substituted cyclodextrin which has a chain side body or a substituent group which can make the cyclodextrin material compatible with the thermoplastic polyester polymer For the purposes of the present invention, compatibility means that the essence can be evenly dispersed into the melt-polymerized JiL, retains the ability to capture or compound infiltrates or polymer impurities, and can stay in the polymer without Will substantially reduce the barrier properties or container formation characteristics of polymer films. Compatibility can be measured by measuring polymer characteristics such as tensile strength, tear resistance, etc., permeability or penetration rate of permeate, surface smoothness, clarification The degree of compatibility is determined by M. Qualitative compatibility screening can be obtained by preparing small batches (100 g-1 kg of thermoplastic and substituted cyclodextrin). The blended material is extruded at the manufacturing temperature to form Linear, strip-shaped extrudate with a diameter of about 1 to 5 mm. Incompatible cyclodextrin The substance cannot be uniformly dispersed in the melt and can be immediately seen in the transparent molten polymer when it is extruded from the extrusion head. We found that incompatible cyclodextrin would degrade at the extrusion temperature and The characteristic "burning flour". Odor is produced in the extrudate. In addition, we found that incompatible cyclodextrin may cause substantial melt failure in the extrudate that can be visually inspected. Finally, the extrudate can be cut into small pieces Block, cross-sectioned and examined with an optical microscope and found clearly incompatible incompatible cyclodextrins in the thermoplastic matrix. Cyclodextrins contain at least 5, preferably 6 値 via alpha (144) bonds Linked cyclic oligosaccharides of grape piperanose. Although cyclodextrins containing up to 12 «glucose residues are known, the three most commonly used are those with 6, 7, and 8 residues Identicals (α-cyclodextrin, / 3-cyclodextrin and 7-cyclodextrin). Cyclodextrins are made by highly selective enzyme synthesis. They often include 6, 7, or 8 glucose monomers, configured as donut rings, and the paper size is applicable to China National Standard (CNS) A4 specifications (210X297 mm) (Please read the precautions on the back before filling out this page ) Order printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A— im 1 ^ 1 mu tmmTt 490477 '... 87. 9. 1 7'] A? B7 V. Description of the invention (12) Also called α, / 3 or 7 ring Dextrin (see Figure 1). The specific coupling of glucose monomers makes cyclodextrin a rigid, frusto-conical molecular structure with a hollow interior with a specific volume. This internal cavity is lipophilic when compared to the outside, that is, it can attract hydrocarbons (hydrophobic in aqueous systems). It is an important structural feature of cyclodextrin and can provide the ability to compound molecules (such as Compound to aromatics, alcohols, halides and hydrogen halides, carboxylic acids and their esters, etc.). The compound to be compounded must meet the size criteria for at least partially fitting into the cavity of the cyclodextrin leading to inclusion complexes. Cyclodextrin typical properties a -CD β -CD β -CD Degree of polymerization (η = 0 6 7 8 Molecular size (A) Inner diameter 5.7 7.8 9.5 Outer diameter 13.7 15.3 16.9 Height 7.0 7.0 7.0 Specific rotation [[X] 2 5 +150.5 +162.5 +177.4 Blue-yellow-yellow iodine complex Color water solubility at 25 ° C (g / 100 ml) Distilled water 14.50 1.85 23.20 The oligosaccharide ring forms a ring, like a truncated cone. Each glucose residue The first hydroxyl group is located in the narrow section of the ring body. The second grape piperanose paper applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) according to the standard (read the precautions on the back before filling in this page)

-16-490477 i_ _I__ Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs

Α7 Β7 Description of invention (13) The hydroxyl group is located at the wide end. The inside of the ring is hydrophobic because it contains methylene (-ch2-) and ether groups (-0- >. The parent cyclodextrin molecule, and useful derivatives, can be expressed by the following formula (cyclocarbon M convention (Numbers are shown), in which the vacant bond represents the rest of the cyclic molecule: the first hydroxyl group and the second hydroxyl group in the formula 1 ^ and 112 are the first or second hydroxyl group shown respectively. The cyclodextrin molecule has a The first hydroxyl group at position 6 and the second hydroxyl group at positions 2 and 3 are used for reaction with chemical reagents. Because of the geometry of the cyclodextrin molecule and the chemistry of the substituents on the ring, all hydroxyl groups do not react the same However, under careful and effective reaction conditions, cyclodextrin molecules can be reacted to obtain derivatized molecules in which all hydroxyl groups are derivatized with a single substituent class. Their substituents are fully substituted cyclodextrin. When required It is also possible to synthesize a cyclodextrin having a selective substituent only on the first hydroxyl group or a cyclodextrin that is selectively substituted only on one or two second hydroxyl groups. In addition, two or three different substitutions can be used Further synthetic derivative molecules. These substituents may be free It is placed or guided on a specific hydroxyl group regularly. For the purpose of the present invention, the cyclodextrin molecule needs to contain sufficient thermoplastic compatibility substituents M on the molecule to ensure that the cyclodextrin material can be uniformly dispersed in the thermoplastic And when it forms a transparent film, sheet or rigid structure, it will not damage the physical properties of the polymer. In addition to the substituents on the CD hydroxyl group, other paper standards can also be used. Chinese national standards ( CNS) A4 size (210 X 297 mm) (Please read the precautions on the back before filling this page)

-17-Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 490477 A7 B7 V. Description of the Invention (14) Molecular modification. Cyclodextrin molecules can be doped with other carbohydrate molecules. Its first hydroxyl group can be replaced by SN2, and it can form an oxalaldehyde or acid group for further reaction with a derivatizing group, etc. The second hydroxyl group can be reacted and removed to leave an unsaturated group, and a variety of known reagents can be added to it to add or cross double bonds to form derivative molecules. In addition, the oxygen in one or more rings of the glucose moiety can be opened to produce reactive sites. These techniques and others can be used to introduce compatible substituents on cyclodextrin molecules. A preferred preparation procedure for preparing a derivatized cyclodextrin material having a functional group compatible with a thermoplastic polymer includes reacting on the first or second hydroxyl group of a cyclodextrin molecule. We have roughly found that a wide range of side chain substituent moieties can be used on the molecule. These derivatized cyclodextrin molecules may include tritiated cyclodextrin, alkylated cyclodextrin, cyclodextrin esters such as tosylate, methanesulfonate and other related sulfonate derivatives, hydrocarbon amine cyclodextrin Essence, oxazolyl substituted cyclodextrin, pyridine substituted cyclodextrin, hydrocarbyl sulfur-containing cyclodextrin, silicon-containing cyclodextrin, carbonate and cyclodextrin with carbonate, carboxylic acid and related Replaces cyclodextrin and others. The substituent moiety must include regions that provide compatibility to the derivatized material. The fluorenyl groups usable as compatibilizing functional groups include ethyl fluorenyl, propyl fluorenyl, butyl fluorenyl, trifluoroethyl fluorenyl, benzyl fluorenyl, acryl fluorenyl and other well-known groups. The formation of these groups above the hydroxyl groups on the first or second ring of the cyclodextrin molecule includes well-known reactions. The tritiation reaction can be carried out using appropriate acid anhydrides, acid chlorides, and well-known synthetic procedures. Can be made into fully brewed cyclodextrin. In addition, cyclodextrin can be prepared by replacing less than all available hydroxyl groups with their groups and one or two remaining available hydroxyl groups with their functional groups. This paper size applies to Chinese National Standard (CNS) Α4 specification (210 × 297 mm) -18-(Please read the precautions on the back before filling this page)

490477 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Α7 Β7 i. Description of the Invention (15) The cyclodextrin substance can also be reacted with the melting base to make an alkylated cyclodextrin. Alkylated groups can be fully alkylated cyclodextrin by fully reacting available hydroxyl groups under sufficient reaction conditions. In addition, depending on the alkylating agent and the cyclodextrin molecule used in the reaction conditions, it can be made into a cyclodextrin substituted on less than all available hydroxyl groups. Typical examples of alkyl groups that can be used to form alkylated cyclodextrin include methyl, propyl, benzyl, isopropyl, third butyl, allyl, trityl, alkyl-benzyl and others Ordinary alkyl. Such alkyl groups can be prepared by conventional preparation methods, for example, by using alkyl halides under appropriate conditions, or by reacting alkyl sulfate alkyl reactants with hydroxyl groups. Tosylsulfonyl (4-methylbenzenesulfonyl), methanesulfonyl (methanesulfonyl) or other related alkyl or arylsulfonyl forming agents can be used to make phases used in thermoplastic resins. Capacitive cyclodextrin molecules. Cyclopyrene molecules are more reactive than the first hydroxyl group on the second hydroxyl group. However, the molecule can be substituted at almost any position to form a useful composition. These sulfofluorenyl-containing functional groups can be used to derive the second or first hydroxyl group of any glucose moiety contained in the cyclodextrin molecule. These reactions can be performed with a sulfonium chloride reactant that is capable of reacting effectively with the first or second hydroxyl group. The sulfonium chloride M is used in an appropriate molar ratio depending on the number of hydroxyl groups of the fluorene to be substituted in the molecule. It can be prepared using known reaction conditions either symmetrically (for compounds substituted with a single sulfofluorenyl moiety) or asymmetrically (substituting the first and second hydroxy groups with a base mixture including a sulfofluorenyl derivative). The sulfofluorenyl group can be combined with a fluorenyl or alkyl group generally chosen by the experimenter. Finally, M can be made into a monosubstituted cyclodextrin in which a single glucose moiety within the ring contains one to three sulfonyl substituents. The rest of the cyclodextrin molecules are in accordance with the Chinese national standard (CNS) Α4 size (210X297 mm). -19-(Please read the precautions on the back before filling this page) Order the staff of the Central Standards Bureau of the Ministry of Economy Printed by the cooperative 490477 A7 B7 _ 5. Description of the invention (16) Keep unreacted. Cyclodextrin amine groups and other ft nitrogen-based derivatives having a thermoplastic polymer moiety on the side of the chain can be used in the tablets, films or containers of the present invention. Cyclodextrin molecules derivatized with sulfonyl groups can be used to generate amine derivatives from sulfonyl groups by replacing the cyclodextrin molecules with sulfonyl groups through the nucleophilic substitution of azide 1) ions. The hydrazine derivative is then converted into a substituted amine compound via a reduction reaction. Most of these diurnal nitrogen or amine cyclodextrin derivatives have been produced. These derivatives can be made into symmetrically substituted amine derivatives (derivatives with two or more amine or azido groups symmetrically arranged on the cyclodextrin backbone) or asymmetrically substituted amines or fluorenes Nitrogen-derived cyclodextrin molecules. Due to the nucleophilic substitution reaction that produces a nitrogen-containing group, the first hydroxyl group on the 6-carbon atom is the most likely site for introducing a nitrogen-containing group. Examples of nitrogen-containing groups that can be used in the present invention include acetamido (-NHAC), alkylamines include methylamine, ethylamine, butylamine, isobutylamine, isopropylamine, hexylamine, and Other alkylamino substituents. The amino or alkylamino substituent may be reacted with other compounds capable of reacting with a nitrogen atom to further derivatize the amino group. Other possible nitrogen-containing substituents include dialkylamino groups such as dimethylamino, diethylamino, hexahydropyridyl, hexahydropyridyl, quaternary substituted alkyl or aryl ammonium chloride substituents. In addition, a halogen derivative of cyclodextrin can be used as the feedstock to manufacture a cyclodextrin molecule substituted with a compatible derivative. In their compounds, the first or second hydroxyl group may be substituted with M by a halogen group such as fluorine, chlorine, bromine, iodine or other substituents. The most likely position for the halogen substituent is the first hydroxyl group at the 6-position. Alkyl-substituted phosphonic acid groups or hydrocarbyl-substituted phosphate groups can be used to introduce compatible derivatives to cyclodextrin. Alkyl phosphate group and aryl phosphate group are available. This paper size applies to Chinese National Standard (CNS) A4 specification (210 x 297 mm) -20-(Please read the precautions on the back before filling this page)

Printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 490477 A7 B7 V. Description of the invention (17) Substitution on the first hydroxyl group of the cyclodextrin molecule. The second, second and third hydroxyl groups may be branched with an alkyl phosphate group. The cyclodextrin molecule may be substituted with a heterocyclic core, which includes a chain pendant oxazolyl group, a histidine, an oxazolyl group, a Btt steep group, and a substituted pyridyl group. Cyclodextrin derivatives can be modified with sulfur-containing functional groups to introduce compatible substitution groups on cyclodextrin. In addition to the above-mentioned sulfofluorenyl groups, cyclodextrin can be derivatized with a sulfur-containing group prepared based on M sulfhydryl chemistry. Their sulfur-containing groups include methylthio (™ SMe), propylthio (-SPr), third butylthio (-SC (CH3) 3), hydroxyethylthio (-S-CH2CH20H), imidazolyl Thio, phenylthio, substituted phenylthio, amine alkylthio, and other groups. Based on the above-mentioned ether or thioether chemistry, K can be prepared as a cyclodextrin having K-hydroxy, aldehyde, copper or carboxylic acid-functionalized substituents. These groups include hydroxyethyl, 3-hydroxypropyl, methoxyethyl and the corresponding 8-isomers, methylmethyl and its 1} -isomer, and carboxymethoxy (-〇-CH2 -C02H), carboxymethyl methoxy (-0-CH2-C02-CH3). Cyclodextrin derivatives formed using silicone chemistry may contain compatible functional groups. It can be prepared into cyclodextrin derivatives containing silicone functional groups. A silicone group generally refers to a group having a single substituted silicon atom or a repeating substituted silicon-oxygen backbone. Typically, a significant proportion of the silicon atoms in a silicone substituent carry a hydrocarbyl (alkyl or aryl) substituent. Silicone-substituted substances usually have increased thermal and oxidative stability and chemical inertness. In addition, silicone groups increase resistance to weather, add dielectric strength and improve surface tension. The molecular structure of the silicone group may vary, because the silicon group may have a single silicon atom or 2 to 20 値 silicon atoms in the silicone part, which may be linear or branched. It has a large paper size and is suitable for China. Standard (CNS) Α4 specification (210X297 mm) -21-(Please read the precautions on the back before filling this page) Order 5_I_____ Economy, then printed by the Central Standards Bureau Consumer Cooperatives Α7 Β7 Description of invention (18) Number It is a repeating silicon-oxy group and can be substituted with various functional groups. For the purposes of the present invention, simple silicon-containing substituent moieties are preferred, including trimethylsilyl, mixed methyl-phenylsilyl, and the like. We know that some of the / 5 CD and ethylated and hydroxyalkyl derivatives are available from American Maize-Products Co., Corn Processing Division, Hammond, IN. The preferred cyclodextrin derivative polyesters of the present invention Beverage containers are generally formulated by incorporating modified cyclodextrin into a polyolefin or polyester resin, and then forming useful nine capsules. Nine pellets were then formed into a prepreg shape and then transformed into a biaxially oriented stretched beverage container. Two techniques are generally used to make bottles. The first is a machine that converts nine pellets of resin into preform pellets on a heating rod. After conditioning, the preform is blown into bottles using a stick and the rest of the manufacturing equipment. The second technique involves forming a prepreg from a thermoplastic resin. The resin was removed from the prepreg manufacturing section and the preform was transferred to a blow molding apparatus. Thereafter, the prepreg is biaxially oriented into a useful container shape. The container may be self-supporting with a flap bottom or may be adhered to a polyethylene or polypropylene bottom cup support with an adhesive. In another embodiment, the finished beverage container may be at least two layers of laminate. The laminate may contain a layer of polyester material and a barrier polymer in a second layer. Derivatized cyclodextrins can be in either layer or in two layers. In a third embodiment, the beverage container may include a biaxially oriented stretched beverage container having a coating on the inside of the bottle. This coating can be placed in a prepreg with a sufficient thickness M to sufficiently cover the interior of the beverage container after blow molding. Alternatively, the coating may be formed on the inside of the container after blow molding. The raw materials used in any thermoforming process are pelletized thermoplastic polyester or the paper size is subject to Chinese National Standard (CNS) A4 (210X 297 mm) (Please read the precautions on the back before filling this page) -22- 490477 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of Invention (19) Polyolefins. The product obtained by the transesterification reaction to produce a thermoplastic polyester is in the form of a melt. The melt can be easily reduced to useful nine pellets or other small diameter flakes or granules. The flakes or granular polyesters can be dried and blended with the derivatized cyclodextrin material until uniform, and then melt-extruded under conditions that can obtain a uniform dispersion or solution of modified or derivatized cyclodextrin and polyester materials. Ml Poly JI granules are typically substantially transparent, uniform and of average size. The nine capsules preferably contain about 0.01 to about 10% by weight of modified cyclodextrin, more preferably about 0.1 to about 5% by weight of modified cyclodextrin and in some cases, the polymer The ester may contain 0.5 to 2% by weight of cyclodextrin material. Polyester pellets containing modified cyclodextrin material can be incorporated into traditional cyclodextrin or parison blow molding techniques. The products of these technologies contain similar proportions of materials. Molecular orientation can substantially improve the durability, ultimate tensile strength, yield strength, impact resistance, clarity, and permeability of many thermoplastic materials. Biaxially oriented PET plastic carbonated non-alcoholic beverage bottles can be polyethylene terephthalate MWyeth et al., US Patent No. 3,733,309 issued on May 15, 1973, and the invention name is "Biaxially Oriented Poly (Ethylene Terephthalate)" Bottle ". At present, most of the biaxially oriented PET beverage bottles are made by the so-called "reheat blow" method, each stage using a separate machine. In the first injection molding machine, the At a temperature of about 540 ° F (282.221) above the melting point of the polymer, the PET parison or prepreg is injection molded in a cooled mold at a melting temperature, and then cooled and removed from the injection molding machine as a feed for the individual later The second reheat blow molding machine is used to make a biaxial oriented bottle there. When entering the reheat blow molding machine, the shape is similar to a test tube, and the Chinese paper standard (CNS) Α4 specification (210 × 297) Mm) (Please read the notes on the back before filling this page), 1Τ

Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 490477 A7 B7_______ V. Description of the Invention (2Q) The cold parison with a threaded bottleneck at the open end is heated uniformly to its orientation temperature in the oven, which is about 190 for PET ° F (87.78 ° C) to 200 ° F (93.331C) (this is below the melting point of PET>). The temperature-conditioned parison is then placed in a cooled bottle blow mold and closed blow molded The neck of the parison is clamped during the mold. Then it is pushed into the metal and pushed into the parison through the open neck, and the parison, which has an initial length shorter than the finished bottle, is axially stretched to the bottom of the blow mold. Up to its final length, the axial or long axis orientation is completed. Secondly, compressed air is introduced inside the axially stretched parison to expand outward and contact the cooling surface of the bottle blow mold to reach radial or so-called "Circumferential" orientation. After cooling sufficiently for subsequent loading and unloading, the blow mold is opened and the biaxially oriented bottle is ejected from the machine. Although this method is suitable for orientable thermoplastics, it is used in injection molding machines and Heating blow molding machine and its related Substantial investment is required on the parison transfer equipment and heating oven. Furthermore, significant energy is consumed when cold parisons are placed in the oven and reheated, which also increases the cost of the finished orientation bottle. The "parison" injection stretch-blow molding machine called the in-line single-stage injection blow molding method to manufacture a biaxially oriented hollow object can avoid the reheating step. In the "hot parison" in-line method, The parison is formed by injection molding, cooled to an orientation temperature, and then axially stretched and blown radially to its final product shape without having to cool to room temperature. Many types of "hot" The "parison" injection stretch blow molding method and apparatus constitute the prior art. As announced in Yasu. ≪ 1.3〇81〇1 ^, U.S. Patent No. 3,470,282, a thermoplastic material is first used at a temperature above its melting point. The size of the paper used for injection is applicable to China National Standard (CNS) Α4 specification (210X297 mm) -24-(Please read the precautions on the back before filling this page)

Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 490477 A7 B7 V. Description of the Invention (21) The cylindrical core inside the cavity of the mold is called a hot plastic parison caused by the injection mold above the inner sleeve. . Then, while the parison is still on the core and in the injection mold, it is cooled to a narrow temperature range by suitable cooling tools installed therein, which includes the preferred orientation temperature of the processing material, which is fairly uniform and covers All points across the thickness and surface of the parison, and this temperature range is below the uniform melting temperature of the thermoplastic material. The narrow temperature range of the PET parison is approximately 190T (87.781> to 200 T (93.33¾). After reaching its narrow orientation temperature range, the uniformly cooled parison is removed from the injection mold and is still in its core. Above and below, transfer to a blow mold with a cooling tool in it. During transfer, or after being located in a closed blow mold, use the valve installed in the core of the parison forming the upper mold to extend outward and axially The parison is stretched. Secondly, while still inside the blow mold, the parison is inflated, so that the parison is stretched in the second axial or axial stretching direction. At the orientation temperature of the thermoplastic parison, Through the longitudinal or axial stretching of the valve installed in the core rod, and radial inflation, sometimes called "circumferential stretching", pre-stretching to obtain a biaxially oriented hollow object. The upper configuration has the aforementioned simplicity and The advantage of energy saving, but it can not operate at the high production rate required for economic production. For example, the parison must first reach the orientation temperature throughout its thickness. If the metal surfaces of the core and cavity of the injection mold are kept to be processed Thermoplastic The orientation temperature range or lower, for PET is 190T (87.78C) to 200 ° F (93.33 ° C), while the parison is still in the injection mold, it will finally be cooled to make it correspond to the entire thickness. The equilibrium temperature of the desired orientation temperature range. However, because of the small temperature difference between the parison, the core, and the surface of the mold, the $ paper size applies the Chinese National Standard (CNS) A4 specification (210X297 public attack) -25-( (Please read the notes on the back before filling out this page)

, 1T 490477 A7 B7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (22) The cooling rate of the obtained parison in the injection mold is extremely low. As such, the operating speed of the device is limited by the required long injection molding cycle. Conversely, if the core and cavity cavity system of the injection mold are kept at a very low temperature, the conventional cooling rate for PET is about 35 ° F (1.667 °) to 40T (4.44 ° C), and the cooling rate 卽 can be substantially increased. , But it will cause uneven temperature distribution across the thickness of the parison. If the rapid cooling of their parisons is completed within economically and commercially feasible cycle times, the surface temperature of the parisons will be substantially lower than the directional temperature range of the processed thermoplastic and will actually approach the core and injection molds. Temperature, and the center or center point of the parison wall is substantially higher than the desired orientation temperature range. Therefore, when the parison has its substantially poor temperature distribution across its thickness, and most of it is outside the directional temperature range of the thermoplastic being processed, it is not in the stretching and blow molding of the parison. A satisfactory orientation will be achieved. The cycle time limitation caused by the slow cooling of the parison or preform implicit in the Seal ora disclosure can be overcome to some extent in other techniques disclosed later, for example, in Valyi, U.S. Patent Nos. 3,966,378 and 4,151, No. 248. In U.S. Patent No. 3,966,378, a parison is first formed on a first core in an injection mold, cooled in the injection mold, transferred to the pre-blow mold on the core, and pierced the inner surface portion of the pre-blow mold. It swells to a shape between the parison and the finished article. Next, cooling is performed on the first core in the pre-blow mold to a uniform temperature within the desired orientation temperature range of the molded thermoplastic. The temperature-conditioned parison is then transferred to a second blow core and then to a third mold, where (please read the notes on the back before filling this page)

, 11

This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X297 mm) -26-Mouth / 7 Printed by A7 B7 1Λ Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (23) Extend it axially and The third mold of the last blow mold is expanded to form a hollow biaxially oriented article. If multiple sets of cores and molds are used, the individual parisons can be injection molded, pre-blown, and cooled to the orientation temperature, and finally stretch-blow molded. Because the parison is not conditioned in the injection mold to a uniform orientation temperature throughout its thickness, the injection mold can be operated at a reasonable and economical production rate. However, the need for additional pre-blow molds and additional cores and transfer tools greatly complicated the device and required greater investment. In addition, the pre-blow molding to the middle shape is actually a little self-deceiving, because it sacrifices the fixed vector that may be subsequently assigned to the parison. This is because the degree of orientation that can be applied is proportional to the position at which the parison reaches The amount of stretching that takes place after the orientation temperature is desired, and in this case it is performed in a pre-blow mold. Obviously, the amount of orientation-stretching that can be completed from stretching the intermediate shape of the parison to its final shape is lower than the amount obtained by stretching the parison from its original shape to its final shape at the orientation temperature. In Valyi, U.S. Patent No. 4,151,248, the need for participation in a pre-blow mold that would sacrifice the level of orientation that could be achieved can be avoided by a method of making a hollow oriented plastic object in which an injection mold is used A parison is formed inside the first core and quickly cooled to an average temperature suitable for orientation, but there is an unequal temperature distribution across the parison wall. Its outer surface is cold and its center is hot. Second, the cooled parison on the first core is transferred into a tempering mold, where it is peeled from the first core and deposited in the tempering mold. The cooled parison is then conditioned or tempered in the temperature-controlled tempering mold to equalize the temperature distribution across the parison wall to achieve a uniform temperature distribution corresponding to the desired orientation temperature of the molded thermoplastic material. The size of this paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -27-(Please read the precautions on the back before filling this page) Order printed by the Central Consumers Bureau of the Ministry of Economic Affairs, Consumer Cooperative 490477 A7 B7 5 2. Description of the invention (24) The fire system uses the yoke inside the parison and stretches against the parison to blow a core M to provide a compact contact between the parison and the tempering mold, thereby accelerating the two. Heat transfer is completed. The temperature-conditioned parison is then transferred to a third mold on a stretch-blow mold core, which is a stretch-blow mold, and the stretch-blow core is extended and stretched for final axial stretching through telescoping. Radial expansion and cooling are applied to the stretch-blow mold to form a biaxially oriented hollow object. Because the parison does not need to be conditioned in the injection mold to the extent that it has a uniform orientation temperature across its wall thickness, the parison can be removed from the injection mold as soon as possible, and the injection molding step can be operated at a reasonable rate, which may be less than Other methods are far faster. However, the need for additional cores, molds, and transfer tools greatly complicates the device and adds substantial cost. In Marcs, U.S. Patent No. 3,776,991, a method for manufacturing a biaxially oriented hollow plastic object in a rotary injection molding machine is disclosed, which has at least four stations, of which in the injection station, the first core is in the injection mold. A parison is formed thereon, cooled in the injection mold to a temperature higher than the orientation temperature, and pulled to an intermediate station on the first core, where the parison is pre-blown against the cold surface of the intermediate mold. It becomes larger than the shape of the prototype blank but smaller than the shape of the final desired object, cooled to the optimal orientation temperature in the intermediate mold, guided to the blow station on the first core and placed in the final blow mold, which The cavity has the shape of the final desired object. The pre-blown parison is then axially stretched in the closed last blow mold through the extension of the poppet valve stem installed in the first core rod, and finally expanded radially outward to Its final shape is pressed against the cavity wall of the blow mold and cooled to the proper injection temperature. After opening the blow mold, the core rod and the biaxial orientation are applied. The paper size applies to the Chinese National Standard (CNS) A4 (210X297 mm) -28-(Please read the precautions on the back before filling this page) Order

490477 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Α7 Β7 V. Description of the invention (25) The item is guided to the discharge station, where the biaxially oriented object is taken out. This method eliminates the need for additional cores as described in the Valyi patent, but still requires the use of pre-blow molding or intermediate molds and intermediate mold stations, along with the complexity and cost associated with them. In this method, some ability to impart a high level of orientation is still sacrificed because the object stretches from the intermediate shape to the final shape lower than the parison stretches from the prototype shape to the final object shape at the orientation temperature in other technologies The degree of income.

Marcus, U.S. Patent No. 4,065,246 mentions another injection blow molding method using at least three stations, in which a parison is formed on the core in the injection mold, cooled in the injection mold to the desired orientation temperature range, and on the same core Transfer to the last blow mold and stay in it to reach a uniform orientation temperature while the outer tip of the parison contacts a temperature control pin, and the rest of the parison except for the inner surface of its tip, slightly The withdrawal from the core M disengages the first core rod from the parison by briefly introducing low-pressure air into the interior of the parison. In addition, Marcus also mentioned that lubricants can be used to help the rib's first core detach from the parison. Next, the first core is taken out from the partially expanded parison, inserted into the second core and stretched out therein to stretch the parison longitudinally, thereby orienting the parison axially. Thereafter, high-pressure air M is introduced into the axially stretched parison to expand it radially outward until it contacts the floating surface of the blow mold cavity having the final shape and is cooled to an appropriate discharge temperature. The biaxially oriented object is then transferred to the discharge station on the second core, where it is discharged from the device. This method avoids duplication of molds but requires two sets of core and transfer tools, and additional stations, adding complexity and additional cost. This paper size applies to China National Standard (CNS) A4 specification (210X297mm) -29-(Please read the precautions on the back before filling this page), 1T 5 printed by the Central Consumers Bureau of the Ministry of Economic Affairs Consumer Cooperatives Α7 Β7 Invention Description (26) The methods disclosed in these patents are all typical beverage container manufacturing methods. However, the nine capsules of the present invention can be used in any method which can conveniently manufacture PET beverage containers. Similar to the methods described above, laminated bottles with an outer layer can be made typically comprising a thermoplastic having an inner layer containing a barrier polymer. Either or both of the barrier polymers or polyester materials may include modified or derivatized cyclodextrin materials as permeate capture molecules or as impurity capture molecules. The barrier polymer material may be any conventional thermoplastic that is capable of forming a laminate beverage container with polyethylene terephthalate. Thermoplastic materials can be used to form barrier film layers in bottles in a variety of ways. These methods are well-known manufacturing procedures. The properties of polymer thermoplastics that can lead to successful barrier film formation are described below. Skilled thermoplastic polymer technicians know that polymer materials are tailored for thermoplastic processing and special end-use applications by controlling molecular weight. (The melt index is selected by the thermoplastic industry as a measure of molecular weight-melt index and molecular weight. , Density and crystallinity are inversely proportional). For blown thermoplastic extrusion, polyolefins (LDPE, LLDPE, HDPE) are the most commonly used thermoplastic polymers, but polypropylene, nylon, nylon, and polycarbonate are sometimes used to make blown films. Polyolefins typically have a melt index of 0.2 to 3 grams / 10 minutes, a density of about 0.910 to about 0.940 grams per cubic centimeter, and a molecular weight of about 200,000 to 500,000. For biaxially oriented film extrusion, the most commonly used polymers are those with olefins as the matrix-mainly polyethylene and polypropylene (melting index is about 0.1 to 4, preferably 0.4 to 4 grams / 10 points, and molecular weight is about 200,000 to 600,000 >. Polyester and nylon can also be used. For casting, typically this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -30-(Please read the notes on the back before filling this page)

Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 490477 A7 B7 V. Description of the invention (27) It is a molten thermoplastic resin or monomer dispersion made of polyethylene or polypropylene. Sometimes it is padded with nylon, polyester and PVC. For roll coating of water strip acrylic urethane and PVDC, the dispersion is polymerized to the most appropriate crystallinity and molecular weight before coating. Various thermoplastic resins are also used. These materials include polyacrylonitrile, poly (acrylonitrile-co-butadiene-co-styrene) polymers, acrylic polymers such as polymethyl methacrylate, poly-n-butyl acrylate, poly (ethylene- Co-acrylic acid>, poly (ethylene-co-methacrylate), etc .; Saifan, celluloses include cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate Esters and cellulose triacetates, etc .; fluoropolymers include polytetrafluoroethylene (Teflon), poly (ethylene-co-tetrafluoroethylene) copolymers, (tetrafluoroethylene-co-propylene) copolymers, Polyfluoroethylene polymers, etc. Polyamines such as nylon 6, nylon 6,6, etc .; polycarbonates, polyesters such as poly (ethylene-co-terephthalate), poly (ethylene-co- 1,4-dicarboxylic acid esters), poly (butene-co-terephthalate); polyimide materials; polyethylene materials including low density polyethylene; linear low density polyethylene, high density polyethylene, High molecular weight, high density polyethylene, etc .; polypropylene, biaxially oriented polypropylene; polystyrene, biaxially oriented polystyrene; ethylene resin film including poly Ethylene, (vinyl chloride-co-vinyl acetate) copolymers, polyvinylidene chloride, polyvinyl alcohol, (vinyl chloride-co-vinylidene chloride) copolymers, special product films include polymaple, polyphenylene sulfide , Polyphenylene ether, liquid crystal polyester, polyetherketone, polyvinyl butyraldehyde, etc. When manufacturing laminated preform materials with a poly (ethylene terephthalate) outer layer and a barrier polymer inner layer, The preform is made by sequential injection molding technology. The first step is to create the injection mold for the first preform section. This paper size is applicable to the Chinese National Standard (CNS) A4 specification (21〇χ 297 mm) -31-( (Please read the notes on the back before filling out this page)

Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 Five Λ Description of Invention (28) The preform section may include barrier polymers or polyethylene terephthalate container materials. The preform can then be transferred to a second station where the auxiliary polymer is injection molded into the interior of the preform (the barrier polymer inside the PET) or formed outside the preform (the PET covers the barrier polymer). This multi-step formation can also be done on a single machine with appropriate internal operating components that can perform their injection molding operations. Between stages in operation, the preform must be cooled to a temperature sufficient to facilitate successful manufacturing. Additional layers can be used when needed, however, the preferred container is a two-layer construction. Two or more layers of the prepreg are then subjected to a reheat blow molding operation. The preform is reheated to a suitable temperature sufficient to facilitate blow molding into the desired shape. Not only does this blow molding operation achieve biaxial orientation of the layers, thereby improving strength, but it also produces the desired end product and, if necessary, the molded bottom. In the blow molding operation, the heat source is used to reach the proper blow molding temperature around the inside or outside of the bottle preform. In a preferred embodiment, the component-molded prepreg is subjected to a final molding operation, including biaxial orientation via stretch blow molding at a high blow molding temperature, typically 95-1501C. It is desirable to have an isothermal temperature distribution across the thermal plastic layers. The blow molding temperature must be sufficient to achieve satisfactory blow molding for both thermoplastic resins. The cyclodextrin material can be incorporated into the barrier cellulose sheet, which can be coated with the cellulose sheet or a similar structure containing a cellulose layer by applying a liquid coating composition containing an effective amount of cyclodextrin or substituted cyclodextrin Thing. These coating compositions are typically formed from a liquid medium. The liquid medium may include an aqueous medium or an organic solvent medium. Aqueous media are typically formed by combining water with additives and ingredients capable of forming a useful coatable aqueous dispersion. Μ This paper size is applicable to Chinese National Standard (CNS) Α4 specification (210 X 297 mm) -32-(Please read the precautions on the back before filling this page) Order

Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 490477 A7 B7 V. Description of the Invention (29) Organic solvent-based solvent strip dispersions can be made by using known solvent-based coating technology. In forming the barrier layer of the present invention, a coating may be formed on a film, which is then laminated on a film, which is then laminated on a fibrous sheet or may be coated on a cellulose sheet to form a film. Their coating methods include applying liquid to the cellulosic sheet being transferred. Their coating methods generally use machines having a coating section and a metering section. Careful control of the coating amount and coating thickness results in an optimized barrier layer without wasting material. There are many coating machines known such as tension-sensitive applicators, such as applicators using metering rods. The tension-insensitive coating station can maintain the coating weight even when the tension of the sheet varies. Application method, air knife applicator, etc. These coaters can be used to coat one or both sides of a flexible film or one or both sides of a cellulose pad. The liquid composition often applied by the above coater contains a film-forming substance, an additive that can help the ribs form and maintain the coating composition, and an effective amount of cyclodextrin or substituted cyclodextrin. Membrane-forming substances are often called adhesives. These adhesives are present in the form of high molecular weight polymers in the final coating. Thermoplastic polymers or cross-linkable polymers can be used. These adhesives are grouped into groups that include heavy-duty categories including acrylic, vinyl, alkyl resin, polyester, etc. In addition, the upper surface composition is a substance that can form a polymer film, and it also has a corresponding substance that can be used to form an aqueous and solvent coating composition. Their coating compositions can be made by combining a liquid medium with a solid substance containing a polymer, cyclodextrin and various useful additives. Generally, the cyclodextrin substance is a part of the solid component of M added to the coating composition. The solids contained in the coating composition may contain the total solids in the dispersing composition of the solvent strip. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -33-(Please read the precautions on the back before filling This page) Order 490477 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (30) Calculated as about 0.01 to about 10% by weight of the cyclodextrin compound, preferably about 0.1% to 5% by weight The most preferred is from about 0.1% to about 2% by weight of a cyclodextrin substance. A useful barrier layer can also be made by applying a coating on the inside of a prepreg or a shaped container, the coating typically being an aqueous dispersion of a useful polymeric substance containing a modified cyclodextrin substance or Suspension maker. In a preferred method, the preform or container is heated to 40 ° to 80 ° C, coated with an aqueous polymer dispersion, and then dried. The coating is applied at a temperature of 40 ° to 100 °, preferably 50 to 90 ° C. If the temperature is lower than 40 ° C, it is more unfavorable than coating the preform at room temperature. Only a very thin, about 3 micron thick, coating with insufficient adhesion can be obtained. If the preform is heated to 90 ° C, crystals may be induced and the proper transformation of the preform into a biaxially oriented container may be impaired during the blow molding operation, and the container may be caused by uneven relaxation of the molding strain. song. Although there is a need to prevent improper crystallinity of the body due to heating in the preform, it may be advantageous to promote surface crystallization by pretreating the preform with a suitable solvent, such as butyl (methyl ethyl ester). These treatments result in surface roughness, which is ribbed upon subsequent application to the coating to secure it to the prepreg. Its effect is proportional to the time and temperature of the treatment, and when using, for example, methyl ethyl ketone, the coarseness of fine scales (about 1 micron) can be obtained by treating at 40 ° to 901C for 1 to 2 minutes. The surface extends inwardly from 30 to 50 microns. Other solvents that can be used include acetone, chloroform, ethyl acetate, m-cresol and trichloroethylene. This paper size applies to China National Standard (CNS) Α4 specification (210X297 mm) -34-(Please read the precautions on the back before filling this page) Order

490477 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 i. Description of the invention (31) By coating at a temperature in the range of 40 to 90 ° C, it can be produced in a single coating step with a large thickness, such as 20 Adhesive and uniform coatings up to 30 meters. If the thickness of the coating is insufficient, the coated preform can be dried and then coated to obtain the required thickness. Preferably, the coated objects are heated to 40 to 80 ° C before applying their subsequent coatings. In order to prevent the amorphous PET from being improperly heated in the drying of the aqueous dispersion and developing crystallization in the PET preform, the heating is preferably performed using an infrared heater at a temperature of 10001 CM. At an operating temperature of 100 ° C, the radiation can be absorbed by the water in the aqueous dispersion without improperly heating the PET preform itself: water therefore acts as a filter against infrared radiation. During the drying step, the preform or bottle can be rotated to provide uniform heating and also provide a uniform thickness coating. For example, a PET prepreg in the form of a tube having a closed end may be arranged so that its longitudinal axis is horizontal and rotates about this longitudinal axis. If necessary, multiple coatings can be applied on PET. For example, the preform or bottle can be mounted so that its longitudinal axis is horizontal and rotated about this longitudinal axis. When it is rotating, it is first heated to 40 ° to 901C with an infrared heater, and then the water dispersion coating is picked up from the coating point, such as a soft doctor blade, and then the water is distilled off. Multiple infrared heaters heat the coated preform to 40 ° to 90 ° C to make the coating dry and reheat the preform before the preform rotates one turn: so that just after one turn The coating point is reached and another coating of the aqueous dispersion is applied on the dried coating. In this way, a multilayer coating in the form of a spiral can be formed on the prepreg. This paper size applies to Chinese National Standard (CNS) Α4 specification (210 × 297 mm) (Please read the precautions on the back before filling this page), ιτ

Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 490477 A7 _ B7___ V. Description of the invention (32) The coating can be applied on the inner or outer surface and can be applied by coating or dip coating. We have found that the coating inside is particularly advantageous where the resulting bottle is intended to be used for a sulfonic acid beverage. It can present a barrier layer between the beverage and the bottle wall and thus reduce the amount of carbon dioxide absorbed by the polyethylene terephthalate itself. This can lead to the use of a thinner coating M to achieve the specified sulphur dioxide loss. In this way, in some cases, a coating can be used inside the preform, the thickness of which is only half of the required thickness applied to the outside of the preform to achieve a similar amount of carbon dioxide escape. Furthermore, in the manufacture of carbonated beverage containers, carbon dioxide tends to diffuse through the bottle wall, and after a certain period of time, the outer coating layer is caused to lose adhesion and foaming occurs. In contrast, the coating on the inner surface will be firmly held in place by the pressure of the carbonic acid liquid even if its adhesion is lost for some reason. The polymer dispersion may be any one conventionally used to apply a barrier coating to a plastic material. Preferably it is an aqueous dispersion of a copolymer of vinylidene chloride and acryl and / or methyl acrylate optionally containing units derived from other monomers such as methyl methacrylate, vinyl chloride, acrylic acid or itaconic acid . Particularly useful vinylidene chloride copolymers are those containing 5 to 10% by weight of units derived from acrylic and / or methyl acrylate, and optionally up to 10% by weight of units derived from unsaturated carboxylic acids such as acrylic acid. The dispersion may preferably contain a surfactant such as sodium alkylsulfonate. The container of the present invention can be used to dispense a variety of beverages including milk (skimming, 1%, 2%, chocolate >, orange juice, carbonated beverage, water, flavored water, carbonated water, beer, mixed alcoholic beverage, distilled alcohol, alcohol, 200 Standard Alcohol This paper size applies Chinese National Standard (CNS) Α4 specification (210X 297 mm) -36-(Please read the precautions on the back before filling this page)

490477 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of Invention (33) or absolute alcohol; fruit juices such as apples, tomatoes, pears, etc .; distilled water, etc. Amaranth > Explanation of details Figure 1 is a general isometric diagram of the conceptual expression of various cyclodextrin molecular sizes. Figure 1 shows C (, / 3, and 7 cyclodextrin, which includes the external dimensions of the cyclodextrin ring and the internal pore volume size that can be used as a capture site for permeate or polymer impurities. As can be seen from Figure 1 The first and second hydroxyl groups are present at the rounded edges. It can be inferred that the cyclodextrin is relatively hydrophobic inside and is suitable for complexing and loading hydrophobic molecules. Figure 2 shows a substantially transparent two-liter sulfonic acid. Side view of a beverage container. The container 20 generally includes a one-piece portion 22, a bottom portion 24, and a lid portion 26. The shape of the container is formed during a thermoplastic blow molding operation. The bottom portion 24 is self-supporting during bottle manufacturing Bottom. Their bottles may include a second layer, which may be prepared from a parison having a second thermoplastic material formed in the formation of the parison, or derived from a liquid coating. The liquid coating It can be a parison coating or a bottle coating. The foregoing discussion outlines various application examples under the barrier and capture properties of the substances of the present invention. The following examples and data illustrate the invention in a row and include the best mode As a beverage container Model, we made the membrane and inspected the barrier properties of the membrane. We found that the cyclodextrin substance can be smoothly melted and incorporated into the thermoplastic material, causing the cyclodextrin substance to be uniformly dispersed throughout the transparent plastic. Extruding thermoplastic materials. In addition, we have found that cyclodextrin derivatives can be combined with a wide variety of thermoplastic films. Cyclodextrin substances can be used with a wide range of cyclodextrin. The paper size is applicable to China National Standard (CNS) A4 specifications (210X297) %) -37-(Please read the notes on the back before filling in this page)

, 1T

Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 490477 A7 B7 V. Description of the invention (34) The concentration is added to the membrane. Cyclodextrin-containing thermoplastic materials can be blown into films of different thicknesses and can be blown without melt cracking or other film or sheet variations. We found in experiments that the cyclodextrin derivative technology can achieve the barrier properties of para-aromatic hydrocarbons, aliphatic hydrocarbons, ethanol, and water vapor, that is, reduced transmittance. We have also found that the use of cyclodextrin materials can improve the surface properties of membranes. The surface tension and surface electrical properties of the film can also be improved. These properties increase the usability of the film of the present invention in coating, printing, lamination, handling, and the like. In the initial research, we also found that there are several modified cyclopaste selection materials that are compatible with LLDPE and have good compounding effects of residual LLDPE volatile impurities and reduce the diffusion of organic permeates through the membrane. (Unmodified) 3 CD adversely affects film transparency, thermal stability, machinability, and barrier properties. In contrast, the selected modified / SCD (acetylated and trimethylsilyl ether derivatives) have no effect on transparency and thermal stability. The machinability of the extruded plastic material is quite affected, resulting in a certain These surface defects are due to the reduced barrier properties of the membrane. (3) The membrane containing the modified / 3 CD composition (1% by weight >) can reduce permeate by 35% at 72T (22.22 ° C) and at 105 ° F (40.56O) was reduced by 38%; aliphatic permeates were reduced by only 9% at 72 ° F (22.221C). These results would be significantly improved if the membranes were not inspected using the worst-case shelf life inspection conditions. ⑷The recombination rate is different for aromatic and aliphatic permeate. The recombination rate of modified / 3CD film is higher for aromatic permeate (gasoline compound) than for aliphatic (printing ink compound). It is better. Conversely, the film coating is obviously better at the aliphatic compound than the aromatic compound. / 3 Acrylic coating with / 3 CD is an excellent performer, which can penetrate aliphatic Material is reduced from 46% to 88%, and aromatic permeate is reduced by 29%. This paper size applies Chinese National Standard (CNS) A4 Specifications (210X297mm)-38-(Please read the notes on the back before filling out this page) Customs · Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 490477 A7 B7 V. Preparation of the invention (35) temporary h Initially, we made four experimental membrane models. Three of these membranes contained 1%, 3%, and 5% (w / w) / 3-cyclodextrin CDs and the fourth was a control membrane. It is made by using the same batch of resin and additives but without ling CD. The compound effect of residual organic compounds in the test film was checked with a 5% CD film of / 3 CD. Although / 3 CD was found to be effective Residual organics in ground composite linear low density polyethylene (LLDPE) resins, but they are incompatible with the resin and form 々CI) particle adhesives. We have evaluated 9 modified cyclodextrins and one warp Grinding cyclodextrin (particle size 5 to 20 microns). These different cyclodextrins are modified to ethylated, octyl succinate, ethoxyhexyl-epoxypropyl ether, fourth amine, Tertiary amine, carboxymethyl, succinate, amphoteric and trimethylsilyl ether. Cyclodextrin (1% Amount, weight / weight) and low-density polyethylene (LLDPE) are mixed with a Littleford mixer and extruded with a twin-screw Brabender extruder. Nine modified cyclodextrin and honing cyclodextrin LLDPE The samples were placed under M 50 × and 200 × magnification inspection under a light microscope. The microscope inspection is used to visually check the compatibility between LLDPE resin and cyclodextrin. In the ten kinds of cyclodextrin selected products, visual inspection Three types (ethylated, octyl succinate and trimethylsilyl ether) were found to be compatible with LLDPE resins. Use low temperature capture procedures to test 5% / 3/3 CD film samples and those containing 1% (wt / wU acetylated / 3 CI), octyl succinate / 3 CD and trimethylsilyl ether / 3 CD, respectively. Three extruded patterns M measured composite residual film volatiles. This method includes three separate steps; the first two steps are performed simultaneously and the paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -39-(Please read the precautions on the back before filling this page)衣. -Order_ 490477 A7 B7 V. Description of the Invention (36) The third step is an instrument technology for separating and detecting volatile organic compounds, which is carried out subsequently. In the first step, volatiles are purged from the sample using inert pure, anhydrous gas. During the stripping step, the sample is heated at 120 υ. Immediately before analysis, surrogate (benzene-ds) was added to the sample. Benzene-de was used to correct the recovery of each set of test data for internal QC analysis. The second step is to concentrate the volatiles from the sample by freezing the compounds in the scrubber in a headspace vial immersed in a liquid nitrogen trap. At the end of the stripping step, the internal standard (toluene-de) was injected directly into the headspace vial and the vial was immediately capped. A method and a strip control were placed in the middle of the sample and the same way as the sample was Monitor impurities. The concentrated organic component M is then heated in the headspace high-resolution gas chromatography / mass spectrometry (HRGC / MS). The results of the residual volatiles are listed in the following table: Table 1 [品 I Relative to the control sample, the broadcast rate will be restored.% 5% / 3 CD blown film 80 1% Ethyl chloride CD type 47 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling in this Page) 1% octyl succinate / 3 CD type 0 1% trimethylsilyl ether type 48 1% honing / 3 CD type 29 In these preliminary screening tests, the / 3 CD derivative was It is proved that it can effectively compound the amount of volatile organic compounds contained in the low-density polyethylene resin used in the experimental film. About 80% of the organic paper in the CD-loaded LLDPE film is compatible with Chinese National Standard (CNS) A4 (210X297) Mm) 490477 Employees of Central Bureau of Standards, Ministry of Economic Affairs Printed by Fei Cooperatives Α? B7 5. Invention Description (37) The hair distribution is compounded. However, all of the / 9 CD films (1% and 5%) have discoloration (light brown) and off-flavors. Color and odor problems are reported according to It is believed to be the result of the direct decomposition of the impurities in CD or CD. Two odor-active compounds (2-H-furanal and 2-furanmethanol) were identified in the brown film samples. Among the three modified CD-compatible compounds (Acetylated, octyl succinate, and trimethylsilyl ether), both acetylated and trimethylsilyl ether CD have proven to be effective in compounding the amount of volatile organic compounds contained in LLDPE resins. .1% loading of acetylation and trimethylsilyl ether (TMSE) / 3 CD shows that it can compound about 50% residual LDPE organic volatiles, while octyl succinate CD does not compound residual LLDPE resin volatilization. Servings. Honed / 3 CD was found to be less effective (28%) than Acetylation and TMSE Modified / 9 CD. All plastic packaging materials have some degree of interaction with the food they protect. Plastic The main interaction between packaging and food is through the penetration of organic molecules from the environment through polymer membranes. The headspace of the package is absorbed by the food. During storage, the migration or transfer of organic molecules in the food package is affected by environmental conditions such as temperature, storage time, and other environmental factors (eg, temperature, organic molecule type and concentration). Impact. Bleeding may have both quality (consumer resistance) and toxicity effects. The purpose of the packaging film inspection is to measure how special barriers affect the quality of individual foods packaged. In order to simulate accelerated shelf life testing of low water active foods, Inspection is performed at 72 ° F (22.22 ° C) and 105T (40.56 ° C) and 60% relative humidity. These temperature and humidity conditions are probably similar to those in uncontrolled warehouses, during lotus delivery, and during storage. If the polymer is moisture sensitive, the relative humidity may affect the paper size of the film. Chinese National Standard (CNS) A4 (210X297 mm)-M (Please read the precautions on the back before filling this page). τ Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 490477 A 7 B7 ______ V. Description of the invention (38) Performance, especially in low water active foods. Because the packaging membrane is extremely separated at two humidity levels in actual end-use conditions, the relative humidity in the osmosis device must be controlled on both sides of the membrane. The environmental side represents the outside of the package and is maintained at 60% relative humidity, while the sample side represents the inside of the package containing the low water active product at 0.25. Permeate combinations were used to measure the function and utility of CD. It is practical to use a combination system, because gasoline (mainly aromatic hydrocarbon mixture) and printing ink solvent (mainly aliphatic hydrocarbon mixture) are not formed by using a single compound but a mixture of compounds. Aromatic permeate contains ethanol (20 PP), toluene (3 ppm), p-xylene (2 ppm), o-xylene (1 ppm), trimethylbenzene (0.5 ppm), and ban (0.5 ppm ). Aliphatic penetrant is a commercially available lacquer solvent blend containing about 20 perineum compounds in an amount of 20 ppm. The penetrant inspection device includes two glass permeation tubes or flasks with an internal cavity of 1200 Milliliter (environment tank tube or feed side) and 300 milliliter (sample tank tube or permeate side). Experimental membrane effectiveness was measured in a closed volume permeation device. High resolution operation using Μ Flame Free Detector (FID) operation Gas chromatograph (HRGC) to measure the cumulative permeate concentration over time. Calculate the compound concentration on the sample side (food side) from the response factor of each compound. The concentration is based on the volume / volume of the basic table components per million parts. (Ppm). Plot the cumulative permeate concentration on the sample side of the membrane versus time. We make four experimental inspection membranes. Three of these membranes contain 1%, 3%, and 5% (wt / wt) loadings. ) Of the / 9 CD and the fourth is a photo paper scale suitable for China Home Standard (CNS) A4 Specification (210X297mm) -42-(Please read the notes on the back before filling this page) Order 477 Five printed by the Central Standards Bureau Staff Consumer Cooperative of the Ministry of Economic Affairs A7 B7 Invention Description (39) Same Control film made of batch resin and additives but without / 3 CD. In addition, a second experimental technique was also used to determine whether / 3 CD sandwiched between two control sides would be compounded with organic vapors that penetrated the film. The experiment was performed by slightly spreading the / 9 CD between the two control membranes. The test showed that the control membrane performed better than the membrane loaded with / 3 CD. The results of the penetration test also showed that The higher the performance of the membrane as a barrier, the worse the performance of the 9 CD sandwiched between two control membranes. The cold CD has twice the effectiveness of reducing permeation vapor than the control without / 3 CD. This experiment confirms that if the barrier quality of the membrane does not change during the manufacturing process to make the membrane a more ineffective barrier, CD can indeed penetrate the organic vapor in the composite membrane. On 721 ^ (22.22¾) removal of aromatic permeate, 1% TMSE / 3 CD film is slightly better than U acetylated / 3 CD film (24% -to -26%), and more CD is added Does not seem to improve. For aromatic permeate at 105T (40.56 ° C), 1% TMSE / 3 CD and 1% acetidized / 3 CD are more effective at removing aromatic permeate than at 72 ° F (22.22 ° C) About 13%. The 1% TMSE membrane is again slightly better at removing aromatic permeate than the 1% membrane (36¾-to 31¾). At 72 ° F (22.221C) in the initial removal of aliphatic permeate, a 1% TMSE membrane is more effective than a 1% acetidized / 3 CD membrane. However, 1 ¾ TMSE / 3 CD was inferior to the control group in the examination, while 1% acetic acid CD only removed 6% of the aliphatic permeate. We prepared two experimental aqueous coating solutions. One solution contains hydroxyethyl θ CD (35 weight) and the other solution contains hydroxypropyl cold CD (35 weight%). This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) -43-(please first (Read the notes on the back and fill out this page)

11.11 490477 A7 B7 printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (40) Both solutions contain 10% acrylic emulsion, which includes polyacrylic acid (Poly sciences, Inc. .) The dispersion (15% by weight solids) was used as a film-forming adhesive. These solutions were used to pick up film samples by laminating two LLDPE films together. Two different coating techniques were used. The first technique is to stretch the two films very slightly to a flat surface. After applying the paint with a water roller, the films are flattened and laminated together. Rev. 1 samples are not stretched during the lamination procedure. All coated samples were finally placed in a vacuum laminator to remove air bubbles between the two membranes. The film coating thickness is approximately 0.0005 inches (.000127 mm). These CD-coated and hydroxymethylcellulose-coated control films were subsequently tested. In the first few hours of exposure to steam, the reduction in aromatic and aliphatic vapors of the hydroxyethyl Θ CD coating was greater but decreased gradually during the next 20 hours of inspection. The removal of aliphatic vapors by hydroxyethyl / 3 CD coatings is higher than the removal of aromatic vapors; this is believed to be due to differences in their molecular sizes (i.e., aliphatic compounds are smaller than aromatic compounds). During the 20-hour test period, the aliphatic permeate control was reduced by 46%. During the 17-hour test period, aromatic vapors were reduced by 29% compared to the control.

Rev. 1 coated hydroxyethyl PCD reduced aliphatic permeate by 87% relative to control during a 20-hour test. It is not known whether the coating method resulted in a 41% reduction rate over another hydroxyethyl BCD coating. The removal rate of hydroxyethyl BCD coating for aromatic penetration is slightly better than that of hydroxypropyl BCD coating at 72T (22.22¾ >) (29%--20%). Large-scale membrane inspection Cattle: > The size of this paper is prepared in accordance with Chinese National Standard (CNS) A4 (210X297 mm) -44-(Please read the precautions on the back before filling this page), 11 k · qing 477 Α7 Β7 Central Ministry of Economic Affairs Printed by the Consumer Bureau of the Standards Bureau. 5. Description of Invention (u) Examination of Example I obtained that each cyclodextrin contained 3,4 ethylamidine / 3-cyclodextrin on the first -0H base. Example I / 3 / 3-cyclodextrin trimethylsilyl ether was placed in a rotary evaporator equipped with a 4000-ml round-bottomed flask and a nitrogen atmosphere, and M was introduced into N2 at a rate of N2 / min at 100 ml and three liters Dimethylformamide. Add 750 grams of / 3-cyclodextrin to dimethylformamide. Spin the 3- / 3-cyclodextrin into dimethylformamide at 60 ° C. After dissolution Remove the flask from the rotary evaporator and cool the contents to about 18 ° C. Place the flask on a magnetic stirrer and place in a stir bar, then add 295 ml of hexamethyldisilazane (HMDS-Pierce Chemical No_84769), then carefully add 97 ml of trimethyl monochlorosilane (TMCS-Pierce Chemcial No. 88531). This careful addition is done by carefully adding the initial 20 ml of the feed dropwise and After the reaction has subsided, the subsequent 20 ml portion is carefully added until it is completely added. After the addition of TMCS is complete, and after the reaction has subsided, place the flask and its contents on a rotary evaporator and heat to At the same time, 601C kept 100 ml of N2 / split inert radon flowing through the rotary evaporator. After 4 hours of reaction, the solvent was removed, leaving 308 g of dry matter. The material was removed from the flask by filtration and washed with deionized water. The filtrate M was removed from the silylated product, dried in a vacuum oven (751C, 0.3 Hg) and stored in the form of a powdery substance for subsequent blending with thermoplastic materials. The subsequent spectroscopic examination showed that the cyclodextrin contained about 1, 7 Trimethylsilyl ether substituent / / 3 -cyclodextrin molecule. This substitution seems to occur in the first 6- (Please read the precautions on the back before filling this page) Φ, 1Τ

This paper size applies to Chinese National Standard (CNS) A4 specifications (210X 297 mm) 490477 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Α7 Β7 5. Description of the invention (42) carbon atom.

Examination of Example B showed that each molecule had a hydroxypropyl-cyclodextrin of 1.5 hydroxypropyl group on the first 6-0H group of BCD.

In Example IV, each molecule has hydroxyethyl / 3-cyclodextrin having 1.5 hydroxyethyl groups on the first 6-0H group of BCD. Preparation We use linear low-density polyethylene resin to prepare a row of film pieces as a model of a beverage container. BCD and acetylated or trimethylsilyl derivatives of BCD such as / S-cyclodextrin are used. Polymer particles were dry blended with powdered / 3-cyclodextrin and / 3-cyclodextrin derivative materials, a fluoropolymer lubricant (3M), and an antioxidant until the dry blend was uniform. The dry blend was mixed and extruded into nine pellets in a Haake System 90, 3/4 "conical extruder. The nine pellets were collected for film preparation. Table 1A shows typical pelletizing extruder conditions. Films It is blow-molded as follows. A hot plastic tube is extruded from the first die. The tube is then collapsed with a second die and laminated into a film with a roller. The extruded tube is then air-pressed under pressure Blow in from the air inlet tube. Melt the hot plastic in the extruder. The extruder temperature is the temperature in the mixing zone. The melting temperature is the melting zone and the die humidity is within the die. The air blowing flow of the cooling ring cools the extruded material. The general description of the former is a Kief el blown film extruder with a die diameter of 40 mm, which is used for the representative description of the actual production of the blown film. The film is manufactured according to the above procedure And the table is shown in Table IB. Use the film to test the transmittance under various environmental conditions. The environmental test conditions are listed in Table Π below. This paper size is applicable to China National Standard (CNS) Α4 specification (210X 297 mm) (Please read the notes on the back before filling this page)

-46 490477 A7 B7 V. Description of the Invention (43)

§ 1 Liig gradually mixed with Xue 00 S 0 min lu) wa) c 37 150 0 埘 0

Is 0 Λ 0 · 2 ·

Office 1 160 0 Λ 273VO • 3 Wen Λ® 镟 ®ΛίΠΓι (Please read the precautions on the back before filling in this page) Office 1 170 0 Μ 0 4866 涞 丨 Hang 0 · 0 mkiQimin 114 I _ 11 5_ shan ΙΑ0 · 5 % TMSE 磙 郄 1-19—94 0 0-· SSJ S4 > 1 Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs, oc oo on psi 1VD8 rpm 0% This paper size applies to China National Standard (CNS) A4 (210X 297) Mm) -47-490477 Α7Β7 V. Description of the invention (44)

An hour 500 pp said Irganox 1010 ^ «i ^ sifnl000ppm ^ gaFosl68o 1ΟΛ 17

2% Ex · II 2 t MX. II 500 Ρ3 500 ppm 422 {216boc} 422 {21σ \ · 6703 416 (213.330C) 415 {212 70002 K) Ο Ο 〇 ΜΗΗίΟΟΗΗΗΜΗ Male tn in in ycfj 肄 # ρ_ »pppp ? Μ Μ Μ ΜΜΜΜΜΜΜΜΜΜΜΜ Μ Μ Μ Μ Μ Μ Μ Μ Η Η ιη αι υ «υι υιυΐϋΐιπιηιηιηαιοοιη Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο gt Ο彐 彐 彐 彐 彐 3 彐 彐 彐 彐 η to uj oj uitorotototOHt ^ i ^ i ^ ro O m Μ Μ (ΟσνΗΜΜΜΟΟΗΜΜΟΟ ιο ro κ) κ > Μ Η ίο ίο Ο 00 Μ Η ο > · · Ο w σ » < η one wq ο ο ο ο ο ο • t ^ | t ^ Η »-* Η Η Ο U1 ιο ro ro W Η Μ Η ro ο ιο ιο {227 {227 H4 {21Throw (21crk {21 < rk {21cn (218 U22 22. 2 2203 440C} HHOnw 1102 lloc) 11. 3 S®G 220c) {220. 2 (227.220c) Offices Offices U) Offices | U Offices Office hhooov〇oh »h * mo Lnooki ^ bJ ^ jinuiirkV / io%

HHOOOOOfJMMO 7®ec) 70002 330c) 78.22 22.2 78.2 11.3 2.2 700OC) C) 78.2 22.2 780C) C} 2202 β ^ $ 0ί ii ^ 11551 涊 LLFr. Xue 555 β… i ii =--1 IJ --- φ (Please read the precautions on the back before filling out this page) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5 (212.780C) 20 · 5 30035 4μ5 {212 · 780220 · 5 w®tJLn Η Η Η Η ΗΗΗΗΗΗΜίΟΙΟΙΟΟ Ln ui in υr rfkcnuiLnLn * u * t ».〇〇〇cn ^ rotororo tororotototororoioiototo Η Η Η ΗΗΗΗΗΗΜΗΙ-»-0 to totototototototototototototototototototototototototototoio 22.2 220C) 78.2 700OC} 780C) 7803 22.3 7802 780C) 70002 7802 N) to ro to uroiototororo KJiorotJ O GO «J Η νΟίΓνΟΟΌνονονονοοονοο (OVO ^ Ji / 1 O ^ UJxJOOVOVOt inl ^ u > invncnuiininuiintninin 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇

m I Tsukuba U) U > U > liJ U > U) U) U > U > tJUitJU > U > K} I ^ q. oi in oi in ιηιηιηι / ΐΐηιηιηιηιηιηη ^^ i 蒎 -B · 埘 is 屮 ss ^ sisss 鲥 {ΓΓ Tibetan Φ 埘 趦 4 > 1 minus berry 诹 诹 The size of this paper is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) ΪΒ complies with Chen Tibet (Exxon LL3201) --- 1- 48 490477 A7 B7 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of Inventions (45)

ssss 58¾¾¾ s 翥 MMMMMM S15H 3S18H151518 MMM MMM MM MMMM M ^ S5SSS5 ss " ------s- E port

7 ppm ^ i salary 20 ppm ETOH 72 105 22.22 10S office 0 · ν1σ > 72 22.22

Rm% RH 0 · 25 Aw

Rm% RH • eo Aw 72 22 · 22 0.2s 72 22.22

Hm V HH m 72 Π) 22 · 22 rH »(Please read the precautions on the back before filling this page) Φ

Rm 蠏 RH 谢 I—i

1T 00 ^ Km% RH ice salary / ¾ Rm% RH ice salary \ step S-S ice salary \ 硪 30 t RHύίί ^ / Β Rm% RH ice salary \ s? 'IS% RH ice salary \ 骝 Rm% RH ^ t0 \ 0 This paper size applies to China National Standard (CNS) A4 (21 OX 297 mm) -49 490477

A

7 B Explanatory Note 5 5 4

7 ppm ^ i ^^ 20ppm EToH 40 ppmm & ii 10% MX. Ill in PVdC 72 20% MX. Ill in pvao 5% MX · III / 72 Is Ex · III / 铕 菰 # 7 72 iridium neck # 5 琎 ls # oo BS12 72 琎 菰 # 15 IDIS 蔼 薙 菰 # 15 铕 18 # 16 琎 菰 # 17 铕 eck # 15 105 φ (Please read the notes on the back before filling this page) 22.22 22.22 22.22 22b ^ α · ωω Π}

Rm% RH Rm% RH

Rrn% RH Urn% RH

Hm% UK R3% RH

0 · 25 Aw 60% RH 匁 3% RH is m% 50Λ #sn 壅 §0 Thank Π (fiber) ^ — 1 Order the printed ice salary \ job ice cream \ job ice cream \ Job m & lw This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -50-490477! A7 j B7 V. Description of the invention (47) The inspection results show that the present invention contains compatibility in the thermoplastic film Cyclodextrin materials can substantially improve barrier properties by reducing the permeability of various permeates. The data showing the transmittance improvement are listed in the data table below. This paper size applies Chinese National Standard (CNS) Λ4 specification (210X 297 mm) (Read the precautions on the back before filling this page)

-51-490477 A7 B7 V. Description of the Invention (48) ^ 00l.ocvcs-ool (铕 菰 # 2) 1.0 «\ ecs 丨 001 (Iridium 菰 # 3) 1.0 ^ CS 丨 001 (铕 菰 # 5) 1.0c \ ®cs_001 (Iridium M # 6) 3.35W 丨 0 Office 3.18WI0 Office 2.01M—0 Office 2 · (η7Ε 丨 0 Office 3.51W 丨 0 Office #! 0 .: 4 / Weng) 0 «\ ° 5 Foreign Office 0 Light 2S 丨 5 Envy 3.79E 丨 S 3.61E 丨 0 Office 2.55E 丨 2 3.31W 丨 0 Office 3.82W 丨 0 Office (Please read the precautions on the back before filling this page) Central Standard of the Ministry of Economic Affairs Printed by Bureau Consumers Cooperative

»» / 31 Saiyao Xiong—LDPE Collection Book Tree 3tb iga72! F (2: K > .22rf) Game Room “： 敝 3% R = Burma 葙 窻 ： _a ·% RH Order

0 «\ ° 5% 33 introduction 13 jealous — 3Λ i— This paper size applies to Chinese National Standard (CNS) Α4 specification (210'〆297 mm) -52-490477 A7 B7 V. Description of the invention (49)

crB 100 inM · To do 0 · 001 in · ¾¾¾ (Iridium # 1) 0.5% cs—001 (0M5 1% CS-001 (chain neck # 5) 2% CS-001 i2e 7.81Ε-2 7.67Ε 丨03 7 · 37Εέ < Λ · 53Μ 丨 03 »» / 8-Anchor kite ILDPE Mi- * 鍈 龅 «srr-b» Xue »72 ^ (22.22 ^) Miscellaneous room: 鲥 2 ·% KH« Reduction room : 敝 3% 50h (Please read the notes on the back before filling this page)

, 1T

Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs < τν σν to ο 01¾¾¾ 龅 ¼¾¾¾ This paper size applies to China National Standard (CNS) A4 (210X 297mm) -53-490477 A7 B7 V. Description of the invention (50 )

Ji Collection (Iridium s # l) 1.0 «\ ecs-001 (铕 菰 # 5) 2 · 0βνcs—001 ^ ss 5 · lmE 丨 o Office. 01Ε 丨 s 2.91E 丨 0 Office Ice Salary Tree · (Please read the notes on the back before filling this page)

ρ —τι ϋϋ Β1 series · I— ϋ—L οβ \ β 22 outside

5.63W 丨 0 Office 5.17M 丨 0 Office 3.08ES 00S00M, as far as έρΕϋφ 鍈 藤 树 31: 5. Xue Jian 72 ^ (22.22¾) ιίϊΗΠ Room: Post a-% RH. Myanmar World: 敝 a ·% g Order

Printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 0% 8% Office 5β \ · | _ This paper size applies to China National Standards (CNS) Α4 specifications (210X 297 mm)-54-490477 Α7 Β7 V. Description of the invention (S1 )

雔 涵 蒎 (铕 neck # 1) 0.5% CS-001 (铕 翦 # 7) 1% CS-001 (铕 翦 # 5) 2% cs-σοι iss * § Q.QQ1 in. 100 ϋ 24, -l · ® 7 · 81E-03 7.67W 丨 03 7 · 37Μ 丨 03 σι · 53Μ 丨 03 σ \ σ \ to 〇 «\ °« ν »· ν» «\ ® (Please read the precautions on the back before (Fill in this page)

Xue Zhe 72 ^ (22.22¾) Miscellaneous immersion: Post 2-¾ UH 瘌 菰 World: Post 2. x RH sigtb—Zan Zhan SMDPE Tibetan · * Sparse Tree stb 订 Order

Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. The paper size applies to the Chinese National Standard (CNS) A4 (210X 297 mm) -55-490477 A7 B7 V. Description of the invention (52 ¾¾¾ < mml) P5 «v» cs- 001 (Grandfather # 7) 0Λ CS-001 (Iridium 55) 2ev »cs — 001 (Iridium Neck # 8)

3.76E—S 2. »U2W 丨 0 Office 3.39E-0 Office 2.SE-CM% V, / 0 Envy 3m 铮 10 Envy 3 Office Envy Xue Jian 72 ^ (22.2210) * sn channeling: 0.25 Aw anchor channeling : 60% RH Ice Salary Tengzhayi ¾¾ «Hardness ^» still tree% (Please read the notes on the back before filling out this page) Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ||| $; 1菡 菡 tree * 3.75M 丨 CM 2.41M · ίΜ 3.38E-04 04 2 · 47E 丨 2 0 outside 3 &r; rkir 10β \ ° 3 jealousy ss ^ s_ This paper size applies to China National Standard (CNS) Α4 specifications ( 210X 297 mm) aistb-if Rong 3l: -LDPE§l-fr! JsH 龅 «srT-b 鵁

, 1T

-56-490477 A7 B7 V. Description of the invention (53 so inw · 24 / 』 Chain a # 3) 1 < A ° CS 丨 001 (iridium 菰 # 4) le \ ° cs — ool (铕 neck # 5) lo \ ° cs-001 (iridium 菰 # 6) 2 «v» cs-001 ( Iridium s # s) lo \ ° TMcow (Iridium 菰 # 12) Miscellaneous §0 1.03W—03 5.49E 丨 0 Office. 7 Office W 丨 0 Office σ1 · 41Ε 丨 0 Office 5.22W-0 Office · 13E_0 Office 5.95ES 8.32W 丨 0 Office 0 · 001 in ·

0〇 \ ° Office 7 «\ ° 5 Office β \ ° 38OV» Office Vo% 60〇 \ ° Office 20 \ ° lvoc \ ° (Please read the notes on the back before filling out this page) Staff Consumption of the Central Standards Bureau of the Ministry of Economic Affairs Printed by a cooperative

^ 11. 1.13ES 5.79ES 5.00E-04 < rv.SE-CM 5.54E-0 Office 39E-S 6.1S-04 8.SE_S s Office νοβ \ ° 5 jealous office 0 «¥» 51CV » 61 jealousy 5 `` \ ° 21% 000

Xue Jian S5 0F (40.56OC) Miscellaneous in room: 呦 2-x RH 鲡 »壅: 敝 a ·% RH

, 1T

This paper size applies Chinese National Standard (CNS) A4 specification (210 × 297 mm) -57-490477 A7 B7 V. Description of invention (54)

铕 2Iridium S 铕 S chain 雔 SD

Bingsu obstructs vines * Office. 34E 丨 CM Office · 03Ε 丨 0 Office 5 · §Ε-04 3.96E—CM

VDC ¥ »—Is printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs · 67E 丨 CM Office • Office 1W 丨 0 Office 5.33WI0 Office 3.VDI ^ W 丨 0 Office · 14ίτ m 00S00 ^

Xue Jian 105OF {40 · 56ο3 Miscellaneous BD cellar: _a-H UH Anchor cellar: N RH This paper size applies to China National Standard (CNS) A4 (210X 297 mm) -58-490477 A7 B7 V. Description of the invention ( 55) ¾¾¾ 0,5o \ ° TMcnw (iridium 琏 # 13) o, son ° tmcow (iridium 菰 # 14) lo \ ° TMcow (铕 翦 # 9) le \ eTMcnM le ¥ »TMSW (铕 翦 # 11) 10 \ ° TMSW (Iridium # 12) 20 \ eTMSW (Iridium # 15) 20 \ ° TMSW (Iridium # 16) 2 «\ eTMSra (Iridium # 17) 2.37E-2 2 · 67E-0» ^ Office .85E 丨 04L 2.58Ei4 2.15E 丨 S 2.5 ^ Μ · 2 2 · 73Ε · 04 2.81Ε 丨 04 crm · 0.001 in. 100 in- · 24 / hs. 3.09ES 2 · 50Ε 丨 0 to do the sound鍈 龅 树 益 Ιί $ ^ 00 ^, 000 ^ 0β \ ° 1VD jealous 23 «\ ° 1 office 0 \ ° • 57 ^ 3 31% 18% 10β \ ° νοβν» Office 5W 丨 0 Office 9 < nw 丨 0 Office {Λ7ΕΙ0 Office 05W—0 Office 27W 丨 0 Office VD2M 丨 0 Office 55W 丨 0 Office 0 Office w_04t 21 «_0 Office 2l ^ w—0 Office Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy iil #.

»» 73—Anchor Certificate®—LPDE 蒎 蒎 鍈 龅 3tt 戣 薛 52T (22.22 (rf) Miscellaneous §π 窻: 跗 2 * 7. RH 鲡 潞 窻: ^ 3% SOH ------ Order- ----- R-- .. (Please read the notes on the back before filling out this page) Λ------—fr I-....... _ οβν »一 办 介 33 ^ 12 «\ Β -53ίτ 155τ 2σν < Λβ 12β \ β 70V» This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) -59-490477 A7 B7 V. Description of Invention (56) Employees of the Central Standards Bureau of the Ministry of Economic Affairs Printed by Consumer Cooperatives

Jin Mi (Miscellaneous # 1) 1% TMSE at® # 12) 2% TMSE (铕 菰 # 15) VD. Office 3W 丨 0OJ 1.16E 丨 02 1.5mw — 02 σι to υι υ ο «Λβ« Λβ € \ 〇 杂 an ϋι «.

Xue Jian 72 ^ (22.22 (10) # 卽 食 ： 跗 a ·% g 缄 面 室 ： 敝 a-%? OH 迓 ® b I Myanmar-al-LPDESi- * 鯓 饭 树 stb® (Please read the (Please fill in this page again)

This paper size applies Chinese National Standard (CNS) A4 specification (21 OX297 mm) 60 — 490477 A7 B7 V. Description of the invention (57) S.0 (铕 a # l) 0 · 5 «λβΤΜ5Μ (铕 翦 # 14 ) 2% TMSEl

Printed by the Employees' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs »» / 9-Burma Zongxiong ILDPE Mi- & 鍈 龅 树 stt 戣 薛 渐 7rF (22.22ci) Miscellaneous ΒΠ 窻: Post 3X RH Anchor Reduction Ⅰ Post S% RH Miscellaneous Ian ^ is, lil «0e \ ° νο · 05Ε—0 Office 0 Envy 19β \ ° 7 · 25E—0 Office 2 Office Envy ίη · 81Μ—0 Office 25 Office 8.36E-CH < ri.77E_CH ch.36E -CM § · 001 in. 100 iH, · 24, > 0SS0000Mα (Please read the precautions on the back before filling in this page)

This paper size applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) -61 ~ 490477 A7 B7 V. Description of invention (58)

w 丨 CyD PVdCfi 涠 米 PVdC w / loCAPHP ω—cyD PVdC w / 2 0e \ ° ffip < r ».81w 丨 05 1 · Office 5W 丨 05 VD.71W 丨 05 i, §lj price miscellaneous 0 079 ! f 丨 Office 2 Jealousy (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs—11 «, 1.05E-CM 2.39E-05 1.12E 丨 Office 0

Xue Jian 72 ^ (22.22 (3) Miscellaneous: P25 Aw Anchor Chamber: 60% KH

, 1T

000 ocv 77 ^ 丨 7 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) ~ 62 ~ 490477 A7 B7 V. Description of the invention (59 PQ 彐 ^ 00§0 5e \ ®ffipmlcyD / 0§ 10e \ eKPW-cyD / 0§ Wei §π 100 inw · 24 ΦΦ 2.07W 丨 06 l.lnow 丨 0 Still to do · 13Μ 丨 0 Still 0.001 in. (Please read the precautions on the back before filling this page)

— I 27Sr Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 2.10E-05 2.0732-05 Office · 30Ε 丨 05 0β \ · ΟΛ 丨 105ο \ β This paper standard applies to China National Standard (CNS) Α4 specification (210 × 297 mm) ii «.

Xue Jian 72 ^ (22.22 (c?) ¾ ¾: 敝 3% RH »葙 room: 敝 3% RH Order -63-

i 'Inventive note (60) We prepared a series of water-based coatings containing hydroxypropyl BCD. These coatings can be used to coat the inside or outside of the bottle. One of these coatings is a 10% acrylic emulsion maker (a polyacrylic acid polymer available from Polysciences, Inc. with a molecular weight of about 150,000). The 10% acrylic emulsion contains 5% and 10% by weight of hydroxypropyl BCD. These solutions were used to verify the film samples by hand-laminating two films. The coating was applied to a linear low-density polyethylene film (Rol 1 No. 7 > and 2% acetic acid BCD) containing a second film using 0.5% ethyl acetate BCD using a hand roller, and then the films were laminated. These films are not stretched during lamination. All coated samples are placed in a vacuum laminator to remove air bubbles between the films. The thickness of the acrylic coating is about 0.0002 (.000051 mm) ). Acrylic coating was prepared in the same way as the control sample M but without hydroxypropyl BCD. The multilayer structure was tested with 0.5% acetylated BCD film facing the environmental flask side of the test tube slot. The second coating printed by the Employees' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs was prepared from vinylidene chloride latex (PVDC, 60% by weight solids) purchased from Dagax Laboratories, Inc. It was prepared using two levels of hydroxypropyl BCD PVDC Latex Coatings-10 and 20% by weight of derivatized cyclodextrin. Use these solutions to hand-coat a linear low-density polyethylene test film and laminate the two films together. Apply to the two control membranes with a coating roller (Rolled into one piece) and laminated together. The film is not stretched during the lamination. All coated The products were placed in a vacuum laminator to remove air bubbles between the membranes. The thickness of the PVDC coating was approximately 0.0004 (.0001 mm). The same way but without hydroxypropyl BCD was prepared as a PVDC coating. The same. The data showing the transmittance improvement after the preparation example is obtained by the following general inspection method. This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -64-A7 B7 V. Description of the invention ( 61) Method: This method includes an experimental technique designed to measure the permeability of selected organic molecules through food packaging films using a static concentration gradient. The inspection method is simulated by accelerating the shelf by providing various storage humidity, product water activity and temperature conditions Life test conditions and the concentration of organic molecules contained in the foods previously checked to select organic vapors outside the package in the test tube slot. This procedure can be used to determine the following compounds: ethanol, toluene, p-xylene, o- Xylene, 1,2,4-trimethylbenzene, naphthalene, petroleum spirit solvent blends, etc. Environmental check compounds Low limit odor concentration microliters / liter ppffl Tube tank concentration Liters / liter PPm ethanol 5-5000 20 toluene 0.10-20 3 p-xylene 0.5 2 o-xylene 0.03-12 1 1,2,3-trimethylbenzene NA 0.5 ban 0.001-0.03 0.5 petroleum solvent blending Compound ΝΑ 40 Table 1. Margin attractant test compounds (please read the precautions on the back before filling this page)

Printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economics In a typical penetration experiment, it consists of three steps. It is (a> instrument sensitivity calibration, (b) membrane inspection, M, measurement of transmittance and diffusivity, and (c) quality control of permeation experiments. Membrane samples are inspected in a sealed integrated permeation device. M flame free detection The high-resolution gas chromatograph (HRGC) operated by the filter (FID) measures the change of cumulative permeate concentration with respect to time. The test compound concentration on the sample side and the environmental side is based on the paper standard of each compound, which is applicable to Chinese national standards. (CNS) A4 specification (210X297 mm) -65-490477 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (62) Calculated by the response factor or calibration curve. Later, if the quality of the permeate is required For each specific group of permeation tube tanks, volume correction is performed for each concentration. The upstream side (environment side) and downstream side (sample side) of the membrane are plotted against the cumulative permeate concentration versus time. Data from the permeation curve Calculate the diffusion rate and transmittance. 1.0 Shibei and Reagent 1.1 Equipment equipped with a flame gas detector (HP 5880), six holes with a 1 ml sampling circle Thermal sampling valve and data integrator. J & W capillary column. DB-5, 30MX 0.250 mm ID, 1.0 umdf 〇 Glass penetration test tube or flask. Two glass flasks with about 1200 ml (environmental tube tank or feed side) ) And 300 ml (sample flask or permeate side) cavity. Permeate tube groove clamp (2). Permeate tube groove aluminum sealing ring (2). Natural rubber separator. 8 ml outer diameter standard wall or 9 mm 0D ( Aldrich Chemical Company, Milwaukee, WI) 〇 Various laboratory glassware and syringes. Various laboratory supplies. Ϊ́. 2 Reagents Reagent water. No interference water was observed in the target chemical analysis MDL. Use a water purification system to Produce reagent water, which is boiled to 80% by volume. The paper size applies the Chinese National Standard (CNS) Α4 specification (210X 297 mm) " -DO ~ (Please read the precautions on the back before filling this page). Order 490477 Α7 Β7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of Invention (63), cover it, and allow it to cool to room temperature before use. Ethanol / Aromatic Standard Stock Solution. Ethanol (〇 · 6030 g >, Benzene (0.172 g), p-xylene (〇1327 g), o-xylene (0.0666 g), trimethylbenzene (0.0375 g) and ban (0.0400 g) packed in a 1 ml sealed needle catheter The crude gasoline blend is a commercially available paint solvent blend containing about 20 individual group hydrocarbon compounds, which is available from Sunny Side Corporation, Consumer Porducts Division, Wheeling, IL Triton X-100. Nonanol Nonionic Surfactants (Rohm and Haas) ° 2.0 檩 Preparation for injection 2.1 Preparing for injection 檩 Injection Use osmotic test quasi stock solution. These quasi-preparatives were prepared by using pure certified reference compounds as shown in actual weight and weight percent. An ethanol / aromatic standard was prepared by injecting 250 liters of a standard stock solution into 100 ml of a reagent water containing 0.1 g of a surfactant (Triton X-100). It is important that the Triton X-100 is completely dissolved in reagent water before adding the permeate standard stock solution. This ensures that the test compound is dispersed in water. In addition, each time the sample is dispensed, the master sample must be thoroughly mixed. It is best to transfer the operating standard to a press-fit top vial M without headspace to reduce the loss due to the large headspace in the volumetric bottle used to prepare the standard. The quasi-samples of petroleum refined blends are processed by 800 microliters of "pure" (please read the precautions on the back before filling this page) __Γ Text · The size of the paper is applicable to China National Standard (CNS) Α4 size (210X 297 mm) -67-// Α7 Β7 V. Description of the invention (64) Injection of petroleum refining solvent blend printed into 100 ml 'containing 0.2 g of surfactant (Triton X-100) ) Reagent water. The opened stock solution must be transferred from the glass capped vial to the top-loaded vial for short-term storage. The vial must be stored in an explosion-proof refrigerator or freezer. 2.2 Injecting birch into the calibrator The calibration standard is a minimum of three concentration levels prepared by adding different volumes of operating standards to a measuring flask and diluting to volume with reagent water. One of the standard samples was prepared to a concentration close to, but above the detection limit of the method. Other concentrations correspond to those in the expected range of concentrations measured in the environment and the sample side tank. 3.0 Sample Preparation 3.1 Sample Preparation Before use, wash the environmental flask and sample flask in soapy water, rinse thoroughly with deionized water, and then dry. After cleaning, each flask is fitted with a rubber septum. The film test specimen was cut to the inside diameter of the aluminum seal ring using a template. The diameter of the membrane test sample is important in preventing diffusion loss along the circumference of the cut edge. Assemble the film sample, aluminum seal ring, and inspection flask. To prepare the test tube, first rinse the sample flask and the environmental flask M with anhydrous compressed air to remove the moisture from the sample and the two flasks. This can be accomplished by piercing the sample strip and the environmental barrier with a needle to intubate the assembly to allow a controlled flow of anhydrous air to flow through both flasks simultaneously. The clamp ring was loosely placed in the flask to eliminate the pressure accumulated on both sides of the membrane. Approx. 10 minutes in a two-wash flask. This paper is sized to the Chinese National Standard (CNS) A4 (210X 297 mm). (Please read the precautions on the back before filling this page.) Yiyi · 68 -C 0 _ 490477 A7 B7 V. Description of Invention (65) After printing by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, remove the needle and tighten the clamp ring to seal the membrane between the two flasks. The use of rubber M facing the lead spacers did ensure a gas-tight fit. Inject 2 μl water / 300 ml flask volume on the sample side. Due to the volume variation of the sample flask, the corresponding volume variation of water M should be supplemented. A volume of 2 microliters of water per 300 ml flask is equivalent to 0.25 water-active products at 72 ° F (22.22 ° C). Next, 40 microliters of a permeate ethanol / aromatic operating standard prepared according to paragraph 2.2 or 40 microliters of a petroleum spirit blend operating standard were injected into an environmental flask. Any of these procedures can produce 60% relative humidity at 72 ° F (22.221C) and the permeate concentration (parts per million parts) shown in Table I in a 1200 ml volumetric flask -Volume / volume). By using a wet and dry bulb hygrometer to determine the humidity and using gas escape to calculate the concentration of permeation, other humidity or permeate concentrations can be used in the test method. Record the time and place the infiltration tank tube in a constant temperature controlled oven. The samples can be staggered to fit the GC lotus time. Three identical osmotic units were prepared. Use triplicate prayers for QC purposes. At the end of each time period, a sample of the combination is removed from the oven. First analyze the side of the environmental flask and use a heated six-hole sampling valve with a 1 ml loop. Purge the circuit with one milliliter of ambient or sample side air. This circuit is then injected into the main capillary column. The GC / FII) protocol was initiated manually after injection. Up to 8 値 1ml of sample can be injected from the sample side and the environmental side of a single permeation experiment. Calculate the concentration of the test compound on the sample and environmental sides from the calibration curve or response factor (Equation 1 or 3) for each compound. Then, if the mass of the permeate is needed, the concentration volume calibration of the permeation flasks of each specific group (please read the precautions on the back before filling this page) The paper size of the book applies to the Chinese National Standard (CNS) Α4 specification (210X 297) 69) 490477 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Invention Description (66) Positive. L0 Sample analysis. Analysis 4 1 Instrument parameters Standard samples and samples are columns for gas chromatography analysis using the following methods: J & W column, DB-5, 30M, 0.25 mm ID, 1 umdf Carrier: Hydrogen analysis Gas flow rate: 9.4 ml / min. Injection port temperature: 105¾ Flame detector temperature: 2001C Oven temperature 1: 751C Program rate 1: 15 ° C Oven temperature 2 ·· 125 ° C Rate 2: 20Ό Last oven temperature: 2001C Last hold Time: The temperature of the 2 minute 6-hole sampling valve is set at 105C. 4-2 Proofreading Three-point calibration using the pseudo standard samples within the scope of the following test compounds: This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) (Please read the precautions on the back before filling this page)

70-V. Description of the invention (67) Test compound ethanol toluene A7 B7 Calibration curve range ρρπι (microliter) 2-20 0.3-3 Employee consumption cooperation of China Standards Bureau of the Ministry of Economic Affairs Du printed xylene 0.2-2 o- Xylene 0.1-1 1,2,4-trimethylbenzene 0.05-0 · 5 Naphthalene 0.05-0.5 Petrol solvent blend 4.0-40 To prepare the calibration standard, it should be placed in a volume of reagent water in a bottle tube Add an appropriate volume of working standard solution. 4,2,1. The secondary release of the re-injection is performed. The calibration curve is diluted 5 to 1: 5 ml of the working standard is placed in a 25-ml volumetric flask. After plugging, the volumetric flask is inverted. I M mixed. 2.5 to 1 dilution: Set a 10 ml working sample in a 25-mL volumetric flask. After plugging, invert the volumetric flask and mix with M. Analyze each calibration standard and list the compound spike area response values relative to the test compound concentration table in the ambient side tank. The results are used to prepare a calibration curve for each compound. A petroleum solvent blend is a commercially available paint solvent containing about 20 individual aliphatic compounds. Its response to concentration is measured by summing each area under 20 individual spikes. Use the least square method to match all the way to the calibration curve. Then calculate the slope M of the calibration curve for each test compound to determine the unknown concentration. Instead of the calibration curve, the average response factor can be used. The calibration curve or response factor can be checked every working day by measuring one or more calibration standards. If the variation of the response value of any compound exceeds the standard of this paper, the Chinese National Standard (CNS) A4 specification (210 × 297 mm) is applied (please read the precautions on the back before filling this page). · 11-71-490477 Central Standard of the Ministry of Economic Affairs Printed by the Consumer Cooperative of the Bureau A7 B7 V. Description of Invention (68) When the percentage exceeds 20%, the test can be repeated using the newly prepared calibration standard. If the results still do not agree, a new calibration curve must be made. 4.3 Analysis of Calibration Curves and Methods Samples at the Proficiency Level The recommended tomography files are those outlined above. Calibrate the system daily as described above. Check and adjust the divided gas flow rate and check rate with a soap film flow meter. In order to produce accurate data, samples must be analyzed under the same conditions, calibration standards and method detection level samples. Both calibration standards and method detection samples were prepared only in environmental flasks. It was completed by placing a 1 / 2-hour (.127 mm) plastic plate and aluminum plate plate (diameter with environmental flange) in a sample flask. Place a single ring on the flange of the environmental glass to place the aluminum sheet and then the plastic disc. Purify the environment flask with anhydrous compressed air to remove moisture from the sample and the environment flask. This is accomplished by piercing the environmental barrier with a needle and passing the assembly through a controlled dry air flow through the flask. Fit the clamp ring loosely to the flask M to eliminate pressure buildup. After washing the two flasks for about 10 minutes, remove the needle and tighten the clamp ring to seal the aluminum sheet to the sealing ring. Then, inject 40 microliters of osmotic ethanol / aromatic operating standard or a second dilution of the operating standard into an environmental flask. Alternatively, 40 liters of a petroleum spirit solvent blend or a second dilution of a processing standard was injected into an environmental flask. Record the time and place the flask in a thermostatically controlled oven. At the end of 30 minutes, the environmental flask was removed from the oven. An environmental flask was analyzed using a heated six-well sampling valve equipped with a 1 ml loop. Flush the circuit with 1 ml of ambient or sample side air. Inject the circuit into the capillary This paper size applies the Chinese National Standard (CNS) Α4 specification (210 × 297 mm) (Please read the precautions on the back before filling this page) Clothing · Order ^ uh / 7

5. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (69) Inside the pipe. The GC / FID system was started manually after injection. 4 1 4 Calibration of the results 4.4.1. The experimental compound shall be invited to calculate the concentration of the test compound on the sample side and the environmental side from the slope of the calibration curve or response factor (RF) of each compound. Then, if the mass of the permeate is required The concentration is adjusted to the volume for each time of the permeation tank tube of the composition. Compound concentration (ppm) Spike area ~ Calibration curve slope (1) Compound specificity RF = Compound concentration ppm " Spike area (2) Compound Concentration (PPIB) = peak area X RF (3) Plot the cumulative permeate mass on the upstream (environmental) side and downstream (sample side) of the membrane versus time. Calculate the diffusion rate of the permeate from the transmission curve data And permeation rate 4.4.2. When the permeate does not interact with the polymer, the permeability coefficient, R, is usually the characteristic value of the permeate-polymer system. This is a number of gases, such as hydrogen , Nitrogen, oxygen, and carbon dioxide, permeate through many types of polymers. If there is an interaction between the permeate and the polymer molecule, as in the case of permeate test compounds used in this method. Is a fixed value and may be related to pressure, film thickness, and other conditions. In those cases, a single P value cannot represent the characteristic permeability of the polymer film and it is necessary to know the correlation of P to all possible variables to obtain the polymer. Complete profile of permeability. For this paper size, China National Standard (CNS) A4 specification (210X 297 mm) is applied (please read the precautions on the back before filling this page). Clothes, 1T 73-Central Bureau of Standards, Ministry of Economic Affairs Printed by the employee consumer cooperative 490477 A7 _ B7 V. Description of the invention (70) In some cases, based on practical purposes, when the saturated vapor pressure of the permeate is applied at the specified temperature, the transmission rate, Q. membrane pair is often used. The permeability of water and organic compounds is often expressed in this way. (Amount of permeate) (film thickness) P =-(4) (area) (time) (transmembrane pressure drop) (amount of permeate) ( Membrane thickness) Q =-(5) (area) (time) In this application, Q is expressed in the following units: qffl-0.001 inch-〇100 inch 2-one of the main variables in determining the permeability coefficient is the span Membrane pressure drop due to The transmission rate Q does not include pressure or permeate concentration in its factors, so M needs to know the permeate vapor pressure or concentration M under the measurement conditions to correlate Q to P. Transmembrane pressure from the environmental side to the sample side The drop mainly comes from the water vapor pressure. The water concentration or humidity will not remain fixed and will not be measured during the time period of analysis of organic compounds, so the transmembrane pressure cannot be measured. The above heat containing various compatible cyclodextrin derivatives Examples of plastic films demonstrate that the present invention can be implemented in a variety of different thermoplastic films. In addition, there are a variety of compatible derivatized cyclodextrin materials that can be used in the present invention. Finally, a variety of film manufacturing techniques including extrusion and water dispersion coating can be used to make the film M to create a useful barrier. Penetration from counterfeit and beverage packaging materials This paper is sized to the Chinese National Standard (CNS) Α4 (210 × 297 mm) (Please read the precautions on the back before filling this page)

~ 74-Bamboo U477 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 1. Description of the invention (71) Sprinkling reaction and degradation products, additives, oligomers and monomers from food and beverage packaging may affect consumption Approval of regulations, product acceptability, product quality and packaging materials. The method obtained from The Center for Food Safety and Applied Nutrition of the US Food and Drug Administration (FDA) was used to measure the transport of these substances from the packaging film with or without acetylated cyclodextrin. This method simulates the Expected migration in packaging films for special food categories, but packaging inspection materials are subject to accelerated inspection, which simulates the migration of real food under normal packaging and storage conditions. We make six experimental high-density polyethylenes (HDPE & gt Test film. One of the films contains 0.5% (wt / wt) acetylated alpha-cyclodextrin, both of which contain 0.5% and 1.0% loading levels of ethyl alcohol / 3 cyclodextrin, and two It is a mixture of acetylated alpha and / 3 cyclodextrin with 0.5% and 1.0% loading levels. The sixth membrane is HOPE (Dow 640) and additives (Dynamar FX-9613 processing additive from the same batch; Irgafos 168 And Irganox 1076 antioxidant) but without cyclodextrin. They are made of blown film extrusion and have a normal thickness of 2 mils. According to the FDA's instructions for food simulated liquids Guidelines for osmotic inspection. The transfer tube system is used for unilateral flexible membrane and complies with ASTM F34-92. The food simulation liquid is 8% ethanol / deionized water and the test temperature is 401C. After seven days, the food simulation liquid (FSL) was aspirated from the extraction tube. The volume of the FSL was reduced, and it was exchanged with dichloromethane, and then analyzed by flame free detection M gas chromatography. The gas chromatograms of the FSL extracts of the six inspection membranes are attached in the following drawings. The chromatograms The spike shown is the diffusion from HDPE film to FSL. The paper size is applicable to China National Standard (CNS) A4 specification (210 × 297 mm) (Please read the precautions on the back before filling this page), 1T _ ~ h / 7 A7 B7 V. Reduction of extractables% Permeate of invention description (72). Quantitatively determine the reduction of permeate by comparing the peak area of the gas chromatographic peaks from 4 to 30 minutes. The refined film sample is compared with a control film made with the same HDPE resin and additives but without cyclodextrin. The following equation is used to determine the% reduction of extractable inclusions in 8% ethanol FSL: (total peak area of the control film- The total spike area of the sample film) The degree of permeation of reaction and degradation by-products, additives and oligomers contained in the ethyl acetate-containing cyclodextrin film is compared with the gas chromatography results of the resin containing ethyl acetate-cyclodextrin-free membrane. The results are listed in Table 1. (Please read the notes on the back before filling out this page)

Printed by the Central Consumers Cooperative Bureau of the Ministry of Economic Affairs. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) -76 ~ 490477 A7 B7 V. Description of the invention (73) Employee Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Print

ASTMsffitl: F34-92 銶 B Mushroom 蒗 叇 遒 蒗 叇 遒 3 3 Country 3 Lotus KS8S3S3 葙 # »Observation: & ¾ Acetylated c (and Acetylated / 3 Cyclodextrin Acetylated α and Acetylated / Cyclodextrin 1 Ethylated Θ Cyclodextrin II Ethyl Bacterium is Cyclodextrin || Ethylated α-Cyclodextrin || Control HDPE Film 0.5% ea. 1 0.25% ea. Η 〇〇〇〇 αι «\ β > The level of cortex filling in HDPE film 16,125 3,473 1,651 869 9,592 20,720 m msms Tibetan state 3 3 trees «cellar HDPE 蒎 strontium ^ GC / FID ^ slis» 8% INi§ \ 7km40r! Taaa? hh > H (Please read the notes on the back before filling this page)

This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -77 — / 7/7 Printed by the Consumers ’Cooperative of the Central Government Bureau of the Ministry of Economic Affairs Α7 Β7 i, invention description (74) The encapsulation of nine capsules of perineum permeates foods that are in direct contact with the polymer packaging material, which may cause volatiles to migrate or permeate into stored food. Even if packaging materials are approved as being in direct contact with food, they may still impart odor to food. Volatiles may be incorporated into the pellets during the manufacturing process. When these nine particles are turned into a film, the smell of the film may be affected by the residual volatiles. We have prepared four experimental polypropylene (Montel 8623) nine capsules. Three formulated nine capsules each contain ethylated α-cyclodextrin, ethylated Θ-cyclodextrin, and 50% / 50% ethylated ex / cold Cyclodextrins, each with a charge level of 0.75% (wt / wt>. The fourth is a polypropylene resin and additives (Dynamar FX-9613 processing additives; Irgafos 168 and Irganox 1076 antioxidants) from the same batch) but no ring Nine capsules made of dextrin. This method includes three separate steps; the first two steps are performed simultaneously, and the third step is the instrumentation technology for separating and detecting volatile organic compounds, which is performed in the first two steps. It is performed after the step. In the first step, the volatiles are purged from the sample using pure inert anhydrous gas. In the gas stripping step, the sample is heated at 120 ° F. Before the analysis, a subeduct (benzene-d6) is added to the sample. ) Benzene is used to correct the recovery of each set of test data for the internal ZC eluate M. The second step is to condense the volatiles from the sample through the head space immersed in the liquid nitrogen trap by condensing the compounds in the scrubber Concentrated in the vial. At the end of the stripping step Directly inject the internal standard (toluene-dB) into the vial in the headspace and immediately cap the vial. Disperse the method and the control sample in the sample and treat the M in the same way as the sample to monitor for contamination. Then, The concentrated organic components were separated, identified, and quantified by high-resolution gas chromatography-mass spectrometry (HRGC / MS) in a heated headspace. The analysis results of residual volatiles are listed in Table 1. GC / MS total ion layer The spectrum is shown in the diagram. The paper size is in accordance with the Chinese National Standard (CNS) Α4 specification (210X297 mm) ^ -78-(Please read the precautions on the back before filling this page)

490477 A7 B7 V. Description of the invention (75)

I Printed Acetylated α and Acetylated / 3 Cyclodextrin Nine Capsules (Repeated Sample)-£ 2 ^-Acetylated and Ethylated / 3 Cyclodextrin Nine Nine tablets of acetic acid / 3 cyclodextrin Nine tablets of acetic acid α-cyclodextrin & Nine tablets (Repeated sample) Nine tablets of Acetylated α-cyclodextrin control Nine tablets 1 1 Nine tablets of sample 0.375% ea. 0.375% ea. 0.75% 0.75% 0.75% > Μ 关 OFF® Card 1 * 0, 3 μm _ 荽 3T 3,896,854 2,938,261 8,977,360 4,109,950 2,365,120 16,294,162 Xie Jie a "S3 standard" 0 (array a $ 76% 82% 45% 75% 85%% Shanhan S + a distillate in 雔 Array 蹂. ^ IDCrf · cr '^ ^ p Dai 3: 恭 恭, leaven mixed als ^ ssslgB ^ SGC / MS ^ sss ^ Lai Bingfu & Shang_120r! (Please read the precautions on the back before filling out this page) Clothing and paper size are applicable to China National Standard (CNS) A4 (210X 297 mm) 79

'Invention Note (76) The above explanation of the nature of cyclodextrin derivatives, thermoplastic materials, coatings, and container and container manufacturing details provides an understanding of the techniques used to incorporate cyclodextrin substances into PET containers for barrier and capture Foundation. However, since many embodiments of the present invention can be completed without departing from the spirit and scope of the present invention, the present invention is covered by the scope of the patents attached below. (Please read the notes on the back before filling this page)

Component number comparison table 20 Container 22 Body 24 Bottom 26 Cover. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs

Claims (1)

490477, patent application scope JMJ No. 86103525 patent re-examination ~-is the amendment to the patent protection of Jia Ming This amendment date: November 1st 1990 _ A kind of use for improved resistance The thermoplastic pellets of the hard polymer beverage bottle produced, including: a large proportion of the thermoplastic polymer, which is uniformly cut in the polymer, acts as an effective barrier, and improves the absorption of extractable compounds in the beverage A cyclodextrin substance, which substantially does not contain a complex compound, has a bond side portion or a substituent group that can make the cyclodextrin substance compatible with the thermoplastic polymer, wherein the modification Cyclodextrin substances include fluorenyl cyclodextrin and polyester condensation and polymerization products of diols and aromatic diacid compounds, wherein the aromatic diacid compounds include terephthalic acid, dimethyl terephthalate, 2 , 6-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid dimethyl vinegar. -2. The pellet according to item 1 of the scope of the patent application, wherein the glycol alcohol or 1,4-butanediol. 3. The pellet according to item 1 of the scope of patent application, wherein the content of the cyclodextrin substance is from 0.1 to 10% by weight based on the host material. 4. The pellets according to item 2 of the scope of the patent application, wherein the polyester includes poly (ene-co-terephthalate) or poly (diene_co_2,6_naphthalene diacetate) 5. The pellet according to item (2) of the scope of the patent application, wherein the polymer is 9 polyene or polyacrylonitrile. 6. The pellet according to item (2) of the scope of the patent application, wherein the modified cyclodextrin includes silicone modification. Cyclodextrin. The standard of this paper is applicable to the national standard (⑽) A4 specification (21〇297297). Xu 丨 (Please read the notes on the back before filling in this page) 幷 VU4 / 7 A8 B8 C8 D8, Patent Application Fanyuan 7 · —A beverage container with improved barrier properties and resistance to soluble substances extracted from the container material. The container is the first item in the scope of patent application The container is made of thermoplastic pellets, and the container comprises a biaxially-oriented thermoplastic polymer and homocyclic dispersed in the polymer, an effective barrier and a modified cyclodextrin substance that is an absorbable amount of extractable compounds. The% dextrin substance is substantially free of an inclusion complex compound, which has a chain side portion or a substituent that makes the cyclodextrin substance compatible with the thermoplastic polymer. 8. Container according to item 7 of the scope of patent application (Ethylene-co-terephthalate). 9_ The container according to item 7 of the scope of patent application includes modified / 3 cyclodextrin. 10. The container according to item 7 of the scope of patent application. Ethylene or polyacrylonitrile. 11. The container according to item 7 of the scope of patent application contains 0.1-5% by weight of modified cyclodextrin. 12. The container according to item 7 of the scope of the patent application is enclosed in a cyclodextrin having one or more substituents on the base or second warp base. The container according to item 7 of the scope of the patent application, the modified cyclodextrin A cyclodextrin having a silicone substituent on the first or second hydroxyl group is included according to the stated patent | A container of item 7 wherein the modified cyclodextrin is included on the first or second hydroxyl group having an alkyl group Esters of cyclodextrin. 15. The container according to item 7 of the scope of patent application, wherein the modified cyclodextrin includes a cyclodextrin having a succinic acid substituent on the first or second base. Wherein the polymer includes polymer, where the modified cyclodextrin bag is included, where the polymer includes polymer, where the thermoplastic polymer is, which contains the modified cyclodextrin bag, bag (please read the precautions on the back before filling in this page) • Order 丨 I Paper ruler Qicaiguan family standard C8 '~ --- D8 6. Scope of patent application * I The container according to item 7 of the scope of patent application, wherein the succinic acid substituent includes an alkyl succinic acid substituent. The container according to item 1 of the Shen Yan patent scope, wherein the succinic acid substituent includes a half-ester succinic acid substituent. 18 > A beverage cereal, which is prepared by using thermoplastic pellets in the first patent application scope. The beverage container includes two layers, where the first layer includes a hot 塱 1 ± I & and the second layer Includes a thermoplastic polymeric poplar and an effective barrier that is owed in one layer by the sentence and is a modified cyclodextrin substance that is absorbed by beverage extractable compounds. The modified cyclodextrin substance is substantially free of inclusion complexation Compound, the cyclodextrin has a chain side portion or a substituent that makes the cyclodextrin substance compatible with thermoplastics. 19. A beverage container according to item 18 of the scope of patent application, wherein the first layer includes polyethylene-co-p-benzene, dicarboxylic acid. 20_ The beverage container according to item 18 of the scope of patent application, wherein the first layer comprises polyacrylonitrile. 21. The beverage container according to item 18 of the application, wherein the second layer comprises poly-α-olefin, polyethylene, polyvinyl alcohol or polyacrylonitrile. 22. The beverage container according to claim 18, wherein the cyclodextrin is dispersed in the second layer. 23. The beverage container according to item 18 of the application, wherein the liquid coating is a water-based coating. 24 _ —A method for manufacturing a beverage container, which uses the thermoplastic pellets of the first patent application scope. The beverage container includes two layers, the first layer includes a thermoplastic polymer and the first layer includes a thermoplastic polymer. For the paper size, the Chinese National Standard (CNS) A4 specification (210X297 mm) applies (Please read the precautions on the back before filling in this page) •, tr— 490477 A8 B8 C8 D8 The scope of patent application and-modified cyclodextrin f, which is evenly dispersed in the-layer and effectively barriers and absorbs the amount of beverage extractable compounds, the texture of the modified ring does not contain loss of complex Compound, the ring having a chain side portion or a substituent that makes the cyclodextrin compatible with the thermoplastic, the method includes blow molding-having a first layer containing a thermoplastic polymer and a first layer containing a thermoplastic polymer Two-layer parison. 25. The method according to claim 24, wherein the first layer comprises ethylene-co-terephthalate. " 26. According to item 24 of the scope of patent application (1), the first layer of side A includes polyethylene. 27. The method according to item 24 of the application, wherein the second layer comprises a-olefin, polyethylene, polyacrylic acid or polypropylene. Λ 28. The method according to item 24 of the application, wherein the cyclodextrin is in the second layer. Shell 1. 29. The container according to item 21 of the application, wherein the polymer is ethyl-co-terephthalate. Λ 30. The container according to item 21 of the scope of the patent application, wherein the modified cyclopeptone contains a mixture of modified α-cyclodextrin, modified cyclic cyclodextrin, modified 裒 dextrin, and the like. A Break 31. The container according to item 21 of the scope of patent application, wherein the container contains up to 10% by weight of modified cyclodextrin. 3 to 0.01 32. The container according to item 22 of the scope of patent application, wherein the modified organism is included in There is one m dextrin on the first carbon atom of the cyclodextrin. N The ring paper size Gu Zhong _ Xu Zhun (⑽) A4 size ⑽ X297 ^ D (Please read the precautions on the back before filling this page) 2. Patent application Fanyuan :: The container of the 22nd item of the scope of the patent application, where the second thermoplastic layer is a dilute hydrocarbon, "the ethylene, a polyvinyl polymer of acrylic. 4. The 22nd item of the scope of the patent application A container in which the modified ring is dispersed in the second layer. 35. The container according to item 22 of the scope of the application for a patent, in which the modified cyclodextrin is dispersed in the first layer 36.-A liquid food-like container made of thermoplastic pellets according to item 1 of the patent scope, the container comprising a liquid food which is contained substantially inside the packaging of the food, the packaging It includes a substantial thermoplastic shaft product with improved material properties. The thermoplastic composition includes: (a) a thermoplastic polymer sheet and (b) a modified cyclopaste that is uniformly dispersed in the sheet and effectively penetrates and absorbs. Essence having a chain side moiety or a substituent that makes the cyclodextrin compatible with the thermoplastic polymer. 37. A container for liquid food according to item 36 of the scope of the Shen patent, wherein the permeate includes the permeate removed from the thermoplastic. 38. A container for liquid food according to item 36 of the application, wherein the liquid food comprises milk. 39. A container for liquid food according to item 36 of the application, wherein the liquid food comprises a carbonated beverage. 40. A container for liquid food according to item 36 of the application, wherein the thermoplastic comprises polyester. 41 _Containers for liquid food according to item 36 of the scope of patent application, in which the paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 490477 A8 B8 C8 D8 Includes poly (ethylene-co-polyterephthalate). 42. The container for liquid food according to item 36 of the application, wherein the thermoplastic comprises a vinyl polymer. 43. The container for liquid food according to claim 36, wherein the vinyl polymer includes polyethylene. 44. The container for liquid food according to item 43 of the scope of patent application, wherein the polyethylene includes high density polyethylene. 45. The container for liquid food according to item 39 of the scope of patent application, wherein the container has a volume of 1.5 to 2.5 liters. 46. The container for liquid food according to item 38 of the scope of the patent application, wherein the volume of the container is selected from one pint, one quart, or one gallon. This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)