Polymeric compositions for medical packaging and devices.

Polymerizable composition for medical packaging and equipment

The present invention generally relates to thermoplastic polymer blends (thermoplastic polymer alloys) used to manufacture films, containers, pipe fittings and other equipment.

In the medical field, effective medicines are collected, processed, stored, and transported in containers, and finally delivered to patients through pipes to achieve therapeutic effects. The materials used to make containers and pipes must have unique properties. combination. For example, in order to visually check whether there are particulate impurities in the solution, the container or tube must be optically transparent. To inject the solution from the container by collapsing the container wall without introducing air into the container, the material forming the wall must be sufficiently flexible. The material must be effective in a wide temperature range. The material must function at low temperatures by maintaining its flexibility and toughness, because some solutions, for example, some pre-mixed drug solutions, are stored and transported in a container at a temperature of -25 to -30°C to reduce drug degradation . The material must also have its function at high temperatures to withstand the heat of sterilization; a degree to which most medical packaging and nutritional products must be processed before shipment. The sterilization procedure usually involves exposing the container to steam at a typical temperature of 121°C and high pressure. Therefore, the material needs to withstand the temperature and pressure without significant deformation ("heat distortion resistance").

In order to be easily manufactured into objects, the material needs to be sealed with a radio frequency ("RF"), usually about 27.12MHz. Therefore, the material must have sufficient dielectric loss properties to convert RF frequencies into thermal energy.

Another requirement is to reduce the impact on the environment when objects made of this material are disposed of after their intended use. For objects that are disposed of in a landfill, it is necessary to use as little material as possible and avoid mixing low-molecular-weight leaching ingredients to form the object. Therefore, the material must be lightweight and have good mechanical strength. In addition, other benefits can be achieved by using materials that can be reprocessed through thermoplastics, and the post-consumer items can be recycled into another useful item.

For containers discarded by incineration, it is necessary to use materials that help eliminate the risk of biological toxicity, and to reduce or completely eliminate inorganic acids that are harmful to the environment, irritating and corrosive, or harmful during incineration. The formation of products that are irritating or otherwise unacceptable.

In addition, the material also needs to contain no or only a low amount of low molecular weight additives, such as plasticizers, stabilizers, etc., which may be released into medicine or biological fluids or tissues, thus causing harm to patients when using this equipment. , Or contaminate the materials stored or processed in such equipment. For the container containing the infusion solution, this contamination may enter the infusion route and enter the patient's body and cause the patient to be injured or even die.

Traditional flexible polyvinyl chloride materials meet many, and in some cases, most of the above requirements. Polyvinyl chloride ("PVC") also offers its unique advantages as one of the most cost-effective materials for constructing equipment that meets the above requirements. However, when PVC is incinerated, it may produce an objectionable amount of hydrogen chloride (or hydrochloric acid when in contact with water), causing corrosion of the incinerator. PVC sometimes contains plasticizers, which may leach into drugs, or biological fluids or tissues in contact with PVC objects. Therefore, many kinds of materials have been designed to replace PVC. However, most of the replacement materials are too expensive to use and still have not met all the above requirements.

There have been many attempts to develop a film material to replace PVC, but most of the attempts have been unsuccessful for one reason or another. For example, US Patent No. 4,966,795 discloses a multilayer film composition that can withstand steam sterilization, but it cannot be welded by radio frequency dielectric heating, so this fast, low-cost, reliable and practical method cannot be used. To assemble. European Patent Application No. EP 0 310 14 A1 discloses a multilayer film that meets most of the requirements and can be RF welded. However, the components of the disclosed film are cross-linked by radiation, so they cannot be recycled using standard thermoplastic processing methods. In addition, because a significant amount of acetic acid is released during the irradiation step, it is embedded in the material. During steam sterilization, acetic acid will migrate into the package contents and become an impurity and change the pH value of the contents. At the same time, it may become a potential chemical reactant for the contents or act as a catalyst for the deterioration of the contents.

The main purpose of the present invention is to create a thermoplastic material, which, as a whole, is superior to the materials that we know so far in the art or have been used or sold commercially. The material must have sufficient optical transparency for visual inspection and can be steam sterilized at temperatures up to 121°C. The material must be able to accept considerable strain without showing strain whitening, which may show physical and aesthetic defects. Another purpose is that the material can be assembled using the RF method. Another purpose is that the material does not contain low molecular weight leachable additives, and can be safely processed by incineration without producing a significant amount of corrosive inorganic acid. Another purpose is that the material can be recycled using standard thermoplastic processing methods after use. In addition, the material can preferably also be mixed with reground material slag recovered in the manufacturing process to save material costs. Finally, the material must be used as a cost-effective substitute for various PVC parts currently used in medical equipment.

When more than one polymer is blended to form a blended composition, it is quite difficult to achieve all of the above objectives at the same time. For example, in most cases, the blended composition scatters light; therefore, it cannot meet the objective of optical transparency. The light scattering intensity (measured by turbidity) is determined by the domain size of the components in the micrometer (mμ) range and the similarity between the refractive indices of the components. Generally speaking, satisfactory It is a difficult task for the ground addition to work with a very small domain size, and at the same time, the selection of various components such as the smallest refractive index mismatch.

The present invention is proposed to solve these and other problems.

According to the present invention, certain thermoplastic polymer compositions have been developed that have substantial improvements over the compositions and objects we know. These compositions may be manufactured into pharmaceutical grade articles such as bags for storing medical solutions for the medical fluid delivery tube member, or be made to yield other components of the final product or products, e.g., a connector, should be connected Device, manifold, valve, catheter, cannula, etc.

An object of the present invention is to prepare a composition with the following physical properties: (1) The mechanical number measured according to ASTM D-882psi is less than 40,000 psi and more preferably less than 25,000 psi; (2) At initial deformation After 20%, the length recovery rate is greater than or equal to 70%, and more preferably greater than or equal to 75%; (3) The optical haze measured according to ASTM D-1003 with a 9 mil thick composition is less than 30 %, and preferably less than 15%; (4) The loss tangent measured at 1 Hz at the processing temperature is greater than 1.0, and more preferably greater than 2.0; (5) Elemental halogen The content is less than 0.1%, and more preferably less than 0.01%; (6) The content of low molecular weight water-soluble matter is less than 0.1%, and more preferably less than 0.005%; (7) The maximum dielectric loss is greater than or equal to 0.05 and more preferably greater than or equal to 0.1 between 1 to 60MHz and 25-250°C transition range; (8) through the sample creep at 121°C , The autoclave resistance measured under a load of 27 psi is less than or equal to 40% and more preferably less than or equal to 20%; and (9) strain to about 100% at a moderate rate of about 20 inches (50 cm) per minute After elongation, there is no strain whitening phenomenon, and record with or without strain whitening phenomenon.

The polymer matrix composition of the present invention that satisfies these physical properties includes a multi-component composition. The three-component composition contains flexible polyene as the first component, which can provide heat resistance and flexibility, and an RF-sensitive polymer as the second component, which enables the film to be RF sealed, and provides the first and second components. The third component of compatibility between the two components. The RF susceptible polymer of the present invention, which will be described in detail below, must have a dielectric loss of about 0.05 at a frequency in the range of 1-60 MHz and a temperature in the range of a peripheral temperature to 250°C. The first component must constitute 40-90% by weight of the composition, the second component must constitute 5-50% by weight of the composition, and the third component must constitute 5-30% by weight of the composition.

In another embodiment of the third component composition, the first component provides high temperature resistance, the second component is an RF sensitive polymer, so that the composition can be RF sealed and impart flexibility to the film, and the third component serves as The compatibilizer (compatabilizer) between the first two parts. The first component must constitute 30-60% by weight of the composition, the second component must constitute 30-60% by weight, and the third component must constitute 5-30% by weight.

The four-component composition contains propylene-based polyene as the first component, which may include isotactic and syndiotactic stereoisomers, and non-propylene-based polyene as the second component; the third component It is an RF sensitive polymer, making the composition RF sealable; and a compatibilizing polymer. Preferably, the first polyene is polypropylene, which occupies about 30-60% by weight of the composition, and most preferably 45%. The second polyene is preferably ultra-low density polyethylene or polybutene-1, which occupies about 25-50% by weight of the composition, and the most preferred is 45%. Preferably, the RF component is a dimeric fatty acid polyamide (which must be described as containing its halogenated derivative), which occupies about 5-40% by weight of the composition, and the best is 10%. The fourth component is a compatibilizing polymer, which can be selected from various block copolymers of styrene and diene or alpha ene; the compatibilizing polymer can be modified with a small amount of active functional substances. For example, the compatibilizing polymer may be a styrene ethylene-butylene styrene ("SEBS") block copolymer. The fourth component must account for 5-40% of the weight of the composition, and best 10%.

These three-component and four-component compositions can be respectively kneaded and extruded to form an RF active film that can be RF sealed to itself. For example, films and tubing can be used to make sterile fluid packaging, containers for blood and blood components, intravenous and medical solutions, nutritional and respiratory treatment products, and dialysis solutions. The composition can also be used to construct open tubes and access devices for containers. The composition can also be used to form other products through injection molding, blow molding, thermoforming, or other known thermoplastic processing methods.

These compositions are compatible with medical applications because the ingredients that make up the film have the lowest extractability to the fluids and contents that the composition comes into contact with. In addition, the film has environmental protection perfection, because it will not produce harmful degradation products during incineration. Finally, the film provides a cost-effective alternative to PVC.

Other features and advantages of the present invention will be explained in the detailed description of the preferred embodiments of the present invention.

<u style="single">Detailed description</u>

Although the present invention is susceptible to many different forms of embodiments, and will be described in detail herein, the preferred embodiments of the present invention are disclosed under the following understanding, that is, the disclosure of the present invention must be regarded as the present invention The principle is exemplified and is not intended to limit the broad part of the present invention to the illustrated embodiment.

More specifically, according to the present invention, it is appropriate to propose a composition that can be manufactured by a thermoplastic method into objects, equipment, products, etc. that meet the requirements listed above.

To achieve this goal, as mentioned above, it has been found that a composition with three components, four components or more can be used to prepare materials with these characteristics. The three-component composition and the four-component composition are discussed separately below.

<u style="single">Three-component composition</u>

In the first embodiment of the three-component system, the first component is the one that imparts heat resistance and flexibility to the composition. The component can be selected from a combination of amorphous poly-α-ene, and preferably a flexible poly-ene. Such polyolefins must resist high temperature deformation up to 121°C, have a peak melting point higher than 130°C, be highly flexible, and have a modulus not higher than 20,000 psi. This flexible polyene is sold under the product name Rexene FP0 90007 and has a peak melting point of 145°C and a modulus of 11,000 psi. In addition, certain highly syndiotactic polypropylene also has properties such as high melting point and low modulus. The first ingredient must constitute 40-90% by weight of the composition.

The second component of the three-component composition is an RF-sensitive polymer, which can impart RF sealing properties to the composition, and can be selected from any of the two groups of polar polymers. The first group includes ethylene copolymers, which have an ethylene content of 50-85%, and their co-monomer system is selected from the following combinations: acrylic acid, methacrylic acid, acrylic acid and alcohols with 1-10 carbons Ester derivatives, ester derivatives of methacrylic acid and alcohols with 1-10 carbons, vinyl acetate, and vinyl alcohol, etc. The RF-sensitive polymer can also be selected from the second group, which includes copolymers containing segments such as polyurethane, polyester, polyurea, polyimide, polyimide, and polyamide. These functions can constitute 5-100% of the RF-sensitive polymer. The RF susceptible polymer must constitute 5-50% by weight of the composition. Preferably, the RF component is a copolymer of ethylene and methyl acrylate, which accounts for 15-25% of the weight of the polymer.

The last component of the three-component composition is the one that ensures compatibility between the first two components and is selected from styrenic block copolymers, preferably functionalized with maleic anhydride Pass. The third component must account for 5-30% of the weight of the composition.

In the second embodiment of the three-component film, the first component imparts RF sealing and flexibility within the desired temperature range. Its first component imparts high temperature resistance ("temperature resistant polymer") and is selected from a combination of polyamide, polyimide, polyurethane, polypropylene and polymethylpentene, etc. By. Preferably, the first component occupies 30-60% of the weight of the composition, and more preferably polypropylene. Its second component imparts RF sealing and flexibility within the desired temperature range. The RF polymer is selected from the above-mentioned first group and second group except ethylene/vinyl alcohol copolymer. The second component must account for 30-60% of the weight of the composition. The third component ensures compatibility between the first two components. It is selected from SEBS block copolymers and the better one is functionalized with maleic anhydride. The third component must be composed 5-30% by weight of the composition.

<u style="single">Four-component composition</u>

The first component of the four-component film is to impart heat resistance. The component can be selected from polyolefins, preferably polypropylene, and more specifically, propylene/α-ene random copolymer (PPE). Preferably, the PPE has a narrow molecular weight range. The PPE has the required rigidity and yield resistance at an autoclave temperature of about 121°C. However, by itself, PPE's are too rigid to meet the flexibility requirements. After blending with certain low modulus polymers, good flexibility can be achieved. Examples of suitable PPE's include those sold under the product names Soltex 4208, and Exxon Escorene PD 9272.

Such low modulus copolymers may include ethylene copolymers, for example, ethylene-co-vinyl acetate ("EVA"), ethylene-co-α-ene, or so-called ultra-low density (typically less than 0. 90 kg/liter) polyethylene ("ULDPE"), etc. These ULDPEs include markets under the brand name TAFMER® (Mitsui Petrochemical Co.), brand name A485, Exact® (Exxon Chemical Company), brand name 4023-4024, and Insite® technical polymer (Dow Chemical Co.), etc. Sell goods. In addition, polybutene-1, such as PB-8010 and PB-8310 sold by Shell Chemical Company; thermoplastic elastomer based on SEBS block copolymer (Shell Chemical Company); polyisobutylene ("PIB"), such as Trade names Vistanex L-80, L-100, L-120, L-140 (Exxon Chemical Company); ethylene/alkyl acrylate, methyl acrylate copolymer ("EMA"), for example, the product name is EMAC 2707, and DS-1130 (Chevron), and n-butyl acrylate ("ENBA") (Quantum Chemical), etc. are all suitable copolymers. In addition, ethylene copolymers, such as acrylic acid and methacrylic acid copolymers and partially neutralized salts and ionic substances, such as PRIMACOR® (Dow Chemical Company) and SURYLI N® (EIDuPont de Nemours &amp; Company), etc. are also suitable for use. Typically, ethylene-based copolymers with melting points below about 110°C are not suitable for autoclave applications. In addition, as shown in some of the following opposed embodiments (eg, Example 8G), not all blending pairs have optical transparency that meets the quality required by visual inspection. Furthermore, only a limited range of component ratios can meet the requirements of flexibility and autoclave at the same time.

Preferably, the first component is selected from polypropylene homopolymers and random copolymers with α-olefins, which occupies about 30-60% by weight of the composition, more preferably 35-45%, and The best is 45%. For example, the ethylene content is 0-6% by weight of the polymer, and more preferably 2-4% propylene/ethylene random copolymer is more suitable as the first component.

The second component of the four-component composition provides flexibility and low-temperature ductility and is a second polyene ("non-propylene-based polyene") that does not contain propylene repeating units that is different from the first component. Preferably, it is an ethylene copolymer, including ULDPE, polybutene, butene/ethylene copolymer, ethylene/vinyl acetate copolymer with a vinyl acetate content of about 18-50%, and a methyl acrylate content of about 20-40 % Ethylene/methyl acrylate copolymer, ethylene/n-butyl acrylate copolymer with 20-40% n-butyl acrylate content, and ethylene/acrylic acid copolymer with acrylic acid content greater than about 15%, etc. Examples of these products include sellers under the product names Tafmer A-4085 (Mitsui), EMAC DS-1130 (Chevron), Exact 4023, 4024 and 4028 (Exxon). More preferably, the second component is ULDPE sold under the product name TAFMERA-4085 by Mitsui Petrochemical Company, or polybutene-1, PB8010 and PB8310 (Shell Chemical Co.), and it must occupy about 25% of the weight of the composition. -50%, better 35-45%, and best 45%.

In order to make the four-component composition have RF dielectric loss, some known high dielectric loss components ("RF-sensitive polymers") should be added to the composition. Such polymers can be selected from the RF polymer combinations in the first and second groups described above.

Other RF active materials include PVC, vinylidene chloride, and fluoride, and a bisphenol-A/epichlorohydrin copolymer called PHENOXYS® (Union carbide). However, significant levels of these chlorine-containing and fluoropolymers can make the composition environmentally imperfect due to the generation of inorganic acids when such materials are incinerated.

The polyamide in the RF-sensitive polymer is preferably selected from aliphatic polyamides obtained by condensation reaction of diamines having 2-13 carbons, and aliphatic polyamides obtained by condensation reaction of diamines having 2-13 carbons. Amide, polyamide obtained by condensation reaction of di-fatty acid, and copolymer containing amide (random, block, graft, etc.), etc. Polyamides, such as nylon, are widely used in film materials for their ability to provide film abrasion resistance. However, since nylon can contaminate the solution by leaching into the solution, it is rarely used in the layer contacting the medical solution. Nevertheless, the applicant of the present invention found that the most suitable RF-sensitive polymer is various dimer fatty acid polyamides sold by Henkel Corporation under the names MACROMELT and VERSAMID, which will not cause such pollution. Preferably, the RF-sensitive polymer must occupy about 5-30% by weight of the composition, more preferably 7-13%, and most preferably 10%.

The fourth component of the composition imparts compatibility between the polar and non-polar components contained in the composition (sometimes referred to as "compatibilizing polymer" (Compatibilizing polymer)) and preferably has a hydrocarbon soft Segmented SEBS block copolymer. More preferably, the fourth component is selected from SEBS block copolymers modified with functional substances such as maleic anhydride, epoxy, or carboxylate, and preferably contains maleic acid SEBS block copolymer with anhydride functionality ("functionalized"). This product is sold by Shell Chemical Company under the name KRATON RP-6509. The compatibilizing polymer must occupy 5-40% of the weight of the composition, preferably 7-13%, and most preferably 10%.

In addition, it is also necessary to add unfunctionalized SEBS block copolymers, such as those sold by Shell Chemical Company under the product names KRATON G-1652 and G-1657, as the fifth component. The fifth component must account for about 5-40% by weight of the composition, more preferably 7-13%, and make up the majority of the composition.

For each of the above-mentioned compositions, it may be necessary to add a small amount of other additives, such as lubricants, lubricants, waxes, and anti-blocking agents as required and well known in the art, as long as the final composition satisfies The above physical property requirements are sufficient.

The above-mentioned multi-component composition can be processed into various products, such as films. This film can be made by several techniques well known in the industry. For example, the above-mentioned ingredients can be placed in a high-intensity blender, such as a Welex blender, in a dry form, and then fed into an extruder. The ingredients can also be gravity fed into a high-strength mixing extruder with a twin-screw design, such as Werner Pfleiderer. The output can be quenched into multiple strands in a water bath, granulated and dried before being used. In the third method, the output of the mixing extruder can be directly fed into the film-making extruder to avoid the granulation step. In addition, a high-strength mixing section can also be incorporated in the film-making extruder and a single extruder can be used to form a blended film. The blend can be converted into other objects and shapes by other thermal plastic conversion machines, such as injection molding machines or injection blow molding machines. Of course, there are still many other known methods for processing blends into thin films, and therefore, the present invention is not limited to the use of these exemplary methods to make thin films.

After the composition having the various ingredients and weight percentages listed in the following examples is formed into a film, the following methods are used to test it.

(1)<u style="single">Autoclave</u>

The autoclave resistance is determined by measuring the creep of the sample under a load of 27 psi at 121°C for one hour, or the increase in length of the sample. The autoclave resistance must be lower than or equal to 40%.

(2)<u style="single">Low temperature and peripheral temperature ductility</u>

(A) Low temperature ductility

In an instrumented impact tester in a cryogenic environmental chamber cooled by concentrated liquid nitrogen, a film sample of about 7×7 inches (18 cm×18 cm) is mounted on a circular sample holder with a diameter of about 6 inches (15 cm).On the device. On the device. The hemispherical impact head equipped with a stress sensor is driven into the center of the pre-conditioned film at a high speed (typically about 3 m/s). Plot the stress-displacement curve, and integrate to calculate the impact energy. The impact energy rises sharply and the crushed sample changes from a brittle state to a ductile state. The temperature at the high strain state is used as a measure of the low temperature performance of the film ("L. Temp.").

(B) Mechanical modulus and recovery rate

A sample of the autoclaved film with a known geometry will be stretched on a servo-hydraulic driven mechanical testing machine with a crosshead. At a crosshead speed of 10 inches (25 cm)/min, stretch the sample to about 20% elongation. At this point, move the crosshead, and then move it in the opposite direction to the original direction to stretch the sample. Record the stress-strain behavior on the digital recorder. The elastic modulus ("E(Kpsi)) is measured from the initial slope of the stress-strain curve, and the recovery rate is measured from the excess sample size as a percentage of sample elongation.

(3)<u style="single">RF processability</u>

A rectangular brass die of approximately 0.25 (6.3 mm) × 4 inches (10 cm) is connected to the Callahan 27.12 MHz, 2KW radio frequency generator, and a flat flavone electrode is also connected to the opposite side. After sandwiching two pieces of material to be used between the die heads to seal them, RF powers of different sizes and durations are applied. When the RF cycle is over, the die is opened and the two pieces are manually pulled apart to inspect the resulting seal. The strength of the seal (relative to the strength of the film) and the method of fragmentation (peeling, tearing, or cohesive fragmentation, etc.) are used to evaluate the RF responsiveness of the material.

In addition, the film to be tested is first sputtered with gold or palladium to a thickness of 100 angstroms to make the surface conductive, then cut into a circular geometry and sandwiched between parallel electrodes of a dielectric capacitance measuring cell. Using Hewlett Packard 4092 automatic RF bridge, the dielectric constant and dielectric loss can be measured at different frequencies up to 10MHz and temperatures up to 150°C. This dielectric loss can be used to calculate the heat generation under the RF field. From the calculation results or the results associated with the RF sealing experiment, the lowest dielectric loss of performance can be obtained.

When each RF sealing performance is obtained from a Callahan sealing machine, the following grading scale is used:<tables><img file="TW264498B_D0001.tif" /></tables><tables><img file="TW264498B_D0002.tif" /></tables>

(4)<u style="single">Optical clarity</u>

The autoclaved film sample was first cut into a square of about 2×2 inches (5×5 cm), placed on a Hunter Colorimeter, and measured for its internal turbidity according to ASTM D-1003. Typically, an internal haze level of less than 30% is required, and preferably, less than 20% for this thickness ["Haze%" (Haze%)].

(5)<u style="single">Strain whitening</u>

Strain the autoclaved film at a moderate rate of about 20 inches (50 cm) per minute to about 100% elongation (twice the thickness of the length), and record the phenomenon of strain whitening (shown in 1) or no such phenomenon (Indicated by 0) ["S.Whitening"].

(6)<u style="single">Environmental compatibility</u>

Environmental compatibility includes three important properties: (a) the material does not contain low molecular weight plasticizers that will leach into the landfill during disposal, (b) the material can be thermoplastic after completing the main purpose of medical delivery Recycled into useful items and (c) When incinerating and undergoing energy regeneration treatment, it will not release significant amounts of inorganic acids that can harm the environment ["Environment" (Envir)]. The composition should also contain less than 0.1% by weight of halogen. In order to promote recovery through melt processing, the resulting composition must have a loss tangent value greater than 1.0 when the processing temperature is measured at 1 Hz.

(7)<u style="single">Solution compatibility</u>

Solution compatibility means that the solution contained in the film will not be contaminated by the ingredients constituting the composition ["solution compatibility" (S.Comp.)]. The low-molecular-weight water-soluble content of the composition should be less than 0.1%.

Use the above test to test the combinations listed below for three-component and four-component compositions. Each example shows some unexpected advantages obtained with these compositions

<u style="single">Example 1</u>

(1) Four-component and five-component composition, PPE, PE copolymer, modified SEBS, and RF active polymer.

<tables><img file="TW264498B_D0003.tif" /></tables>A. 60% Soltex 4208, 20% Mitsui Tafmer A-4085, 15% Kraton RP6509, 5% PA-12. B. 50% Soltex 4208, 30% Tafmer A-4085, 15% Kraton G1657, 5% PA-12 C. 50% Soltex 4208, 30% Chevron EMAC DS1130, 10% Kraton RP6509, 10% Henkel MM-6301. D. 50% Soltex 4208, 30% EMAC-DS1130, 10% Kraton RP6509, 5% PEU-103- 200,5% MM-6301. E. 45% Soltex 4208, 35% Tafmer A-4085, 10% Kraton RP6509, 10% Henkel MM-6239. F. 45% Soltex 4208, 35% Exxon EXACT4028, 10% Kraton RP6509 ,10% MM-6301. G. 45% Soltex 4208, 35% Exact-4024, 10% Kraton RP6509, 10% MM-6301. H. 45% Soltex 4208, 35% Exact-4023, 10% Kraton RP6509, 10% MM-6301. I. 40% Soltex 4208, 40% Tafmer A-4085, 10% Kraton RP6509, 10% Poly Vinyl Acetate(40% Hydrolyzed MW=72,000)

<u style="single">Example 2</u>

(2) Four-component composition: PPE, polybutene-1 (copolymer), modified SEBS, and polyamide blend.

<tables><img file="TW264498B_D0004.tif" /></tables>A. 55% Soltex 4208, 35% Shell PB8010, 10% 5% Kraton RP6509, 5% L-20. B. 55% Soltex 4208, 25% PB-8310, 10% Kraton RP6509, 10% Henkel MM-6301. C. 45% Soltex 4208, 35% PB-8310, 10% Kraton RP6509, 10% MM-6239. D. 45% Exxon Escorene PD9272, 35% PB-8010, 10% Kraton RP6509, 10% MM-6301. E . 45% Soltex 4208, 35% PB-8010, 10% Kraton RP6509, 10% MM-6301. F. 45% Soltex 4208, 35% PB-8010, 10% Kraton RP6509, 10% Uni-Rez2633. G. 45 % Soltex 4208, 35% PB-8310, 10% Kraton RP6509, 10% MM-6301.

<u style="single">Example 3</u>

(3) Four-component composition: PPE, polyisobutylene, modified SEBS, and polyamide blend.

<tables><img file="TW264498B_D0005.tif" /></tables>A. 50% Soltex 4208, 30% Exxon Vistanex L120, 5% Kraton RP6509, 10% Kraton G-1657, 5% PA-12. B. 35% Soltex 4208, 45% Vistanex L120, 15% Kraton RP6509, 5% PA-12. C. 45% Soltex 4208, 35% Vistanex L-80, 10% Kraton RP6509, 10% Henkel MM-6301. D. 45% Soltex 4208, 35% Vistanex L-100, 10% Kraton RP6509,10 % Hendel MM-6301. E. 45% Soltex 4208, 35% Vistanex L120, 10% Kraton RP6509, 10% Henkel MM-6301. F. 45% Soltex 4208, 35% Vistanex L-140, 10% Kraton RP6509,10 % Henkel MM-6301.

<u style="single">Example 4</u>

(4) Four-component and five-component composition: PPE, EMA, modified SEBS, a blend of the fourth and fifth components.

<tables><img file="TW264498B_D0006.tif" /></tables>A. 35% Soltex 4208, 45% EMAC2207, 10% Kraton RP6509, 10% Eastman PCCE9966. B. 30% Soltex 4208, 40% EMAC DS-1130, 10% Kraton RP6509, 15% PEU103-200, 5% Eastman Ecdel 9966 C. 35% Soltex 4208, 40% EMAC DS1130, 5% Kraton RP6509, 10% PEU103-200, 10% Kraton G1652. D. 35% Soltex 4208, 40% DS1130, 10% Kraton RP6509, 5% PEU103-200 ,10% Kraton G1652.

<u style="single">Example 5</u>

(5) Four-component composition: PPE, EMA, modified SEBS, RF activity enhancer blend (more than 150 formulas).

<tables><img file="TW264498B_D0007.tif" /></tables>A. 45% Fina 7825, 45% Chevron EMA (42%MA), 10% Morton PEU 192-100. B. 40% Soltex 4208, 40% Chevron EMAC2260, 10% Shell Kraton RP6509, 10% PEU192-100. C . 35% Soltex 4208, 45% EMAC2260, 10% Shell Kraton RP6509, 10% PEU192-100 D. 35% Soltex 4208, 45% EMAC2260, 10% Kraton G-1657, 10% PEU103-200. E. 40% Soltex 4208,40% EMAC2220T,10% Kraton RP6509,10% PEU103-200. F. 35% Soltex 4208,40% EMAC DS1130,10% Kraton RP6509,15% PEU103-200. G. 35% Mitsuit MA modified PP AdmerSF700, 40% EMAC DS1130, 10% Kraton RP6509, 15%. PEU103-200.

<u style="single">Example 6</u>

(6) Four-component composition: PPE, ENBA, modified SEBS blend.

<tables><img file="TW264498B_D0008.tif" /></tables>A. 40% Soltex 4208, 40% Quantum ENBA80807 (35% BA), 10% Kraton RP6509, 10% PEU103-200. B. 40% Soltex 4208, 40% ENBA80808 (35% BA), 10% Kraton RP6509, 10 % PEU103-200.

<u style="single">Example 7</u>

(7) Three-component and four-component composition: PPE, ethylene/vinyl acetate, polyamide, and modified SEBS blends.

<tables><img file="TW264498B_D0009.tif" /></tables>A. 55% Soltex 4208, 5% EVALCA LCE151A, 40% Shell Kraton RP6509. B. 55% Soltex 4208, 5% EVALCA ES-G110A, 5% Shell Kraton RP6509, 35% Shell Kraton 1652. C. 50% Soltex 4208 ,5% EVALCA LCE105A,42% Shell Kraton RP6509,3% PA-12.D.72% Soltex 4208,18% Kraton RP6509,10% EVALCA G-115A.E.55% Soltex 4208,10% PA-12, 35% Kraton G1901X. F. 60% Soltex 4208, 5% PA-12, 35% Kraton RP6509. G. 60% Soltex 4208, 5% Versalon 1164, 35% Kraton RP6509.

<u style="single">Example 8</u>

(8) Three-component and four-component composition: PPE, EVA, amide-based TPE, EMAA composition (flexible component and RF component are the same).

<tables><img file="TW264498B_D0010.tif" /></tables>A. 35% Fina 7825, 55% Dupont Elvax 170 (36% VA), 10% Shell Kraton RP6509. B. 35% Soltex 4208, 55% Elvax 170, 10% Kraton RP6509. C. 40% Soltex 4208, 50% Quantum UE659, 10% Kraton RP6509. D. 40% Soltex 4208, 50% UE634, 10% Kraton RP6509. E. 35% Soltex 4208, 40% UE659, 10% Kraton RP6509, 10% Morton PEU 192-100. F. (more than 100 formulations), Fina, Soltex, BASF, REXENE PP's (45%), 45% Quantum UE644-04, 10% Kraton RP6509. G. 50% PEBAX 4033, 35% Fina Z-7650, 15% Shell Kraton G1901X. H. 50% PEBAX 4033, 20% Fina 8473, 20% K-1901X, 10% EVA (28% VA). I. 50% PEBAX 2533, 25% Fina 8473, 15% K-1901X, 10% EVA (28% VA) ). J. 60% PEBAX 4033, 20% EVA (28% VA), 20% Shell Kraton G-1652. K. 60% PEBAX 4033, 20% PEBAX 2533, 20% EVA (28% VA). L. 30 % Fina 7825, 60% Morton PEU 103-200, 10% Shell Kraton RP6509. M. 35% Soltex 4208, 55 Chevron DS1009, 10% Shell Kraton RP6509. O. 45% Soltex 4208, 45% Dupont Nucrel(EMAA)925 , 10% Shell Kraton RP6509. P. 45% Soltex 4208, 45% Dupont Nucrel-035. 10% Kraton RP-6509. Q. 45% Soltex 4208, 45% Dupont Evaloy EP4051 (ENBACO), 10% Kraton RP-6509. R. 45% Soltex 4208, 45% Quantum UE648 (18% VA), 10% Kraton RP-6509.

<u style="single">Example 9</u>

(9) Three-component composition: PPE, EVA, and amide-based TPE blends (flexible components and high temperature resistant components are the same).

<tables><img file="TW264498B_D0011.tif" /></tables>C. 45% REXENE FPO 90007, 45% Elvax170, 10% Kraton RP6509. D. 60% FPO 90007, 30% EMAC (42%MA), 10% Shell Kraton RP6509.

<u style="single">Example 10</u>

(10) Tafmer, homopolymer high amorphous content PP, and PP random copolymer composition.

<tables><img file="TW264498B_D0012.tif" /></tables>A. 60% Tafmer A-4085, 40% Novolene 1300L. B. 50% Tafmer A-4085, 10% Dypro8473, 40% Novolene 1300L. C. 50% Tafmer A-4085, 20% Dypro8473, 30% Novolene 1300L.

Novolene is a homopolypropylene with high amorphous content produced by BASF; Dypro 8473 is a propylene/ethylene random copolymer with an ethylene content of approximately 3.5% produced by Cosden (Fina).

<u style="single">Example 11</u>

(11) Tafmer, PP and polybutene-1 blend.

<tables><img file="TW264498B_D0013.tif" /></tables>A. 30% Tafmer A-4085, 30% PB-8010, 40% Novolene 1300L. B. 50% Rexene 23M2, 25% PB-8010, 25% Tafmer A-4085. C. 40% Rexene 23M2, 30% PB -8010,30% Tafmer A-4085.

Rexene 23m2 is a random polypropylene/ethylene copolymer with an ethylene content of about 2%. PB-8010 is a poly-butene/ethylene copolymer produced by Shell Chemical.