WO1999062985A2 - A polymer composition comprising natural stabilizers - Google Patents

A polymer composition comprising natural stabilizers Download PDF

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Publication number
WO1999062985A2
WO1999062985A2 PCT/KR1999/000107 KR9900107W WO9962985A2 WO 1999062985 A2 WO1999062985 A2 WO 1999062985A2 KR 9900107 W KR9900107 W KR 9900107W WO 9962985 A2 WO9962985 A2 WO 9962985A2
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WO
WIPO (PCT)
Prior art keywords
natural
stabilizers
polymer
extract
resin
Prior art date
Application number
PCT/KR1999/000107
Other languages
French (fr)
Other versions
WO1999062985A3 (en
Inventor
Kweon Kim
Hak Soo Lee
Joon Seob Hwang
Won Seop Park
Original Assignee
Urichem Tech Ind., Inc.
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Publication date
Application filed by Urichem Tech Ind., Inc. filed Critical Urichem Tech Ind., Inc.
Priority to JP2000552191A priority Critical patent/JP2002528560A/en
Priority to AU28570/99A priority patent/AU2857099A/en
Publication of WO1999062985A2 publication Critical patent/WO1999062985A2/en
Publication of WO1999062985A3 publication Critical patent/WO1999062985A3/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0058—Biocides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1545—Six-membered rings

Definitions

  • the present invention is related to a polymer compositon comprising natural compounds as stabilizers, and more particularly to a polymer composition produced with the use of stabilizers including natural flavonoid and/or natural phenol and/or the natural polyphenols, etc.
  • these synthetic chemical compounds unlike those other inorganic substances, are apt to form a dispersion phase when they are mixed with or kneaded into polymer substances.
  • these synthetic chemical compounds being far more fluid-like than polymer substances due to their lower molecular weight comparing with polymer substances, are apt to elute while processed together with polymer substances or when used in their applied products. This often leads to many undesirable problems on account of their orally toxic effects on humans. Such problems are even more serious when polymer products are used for containers for packing foods and cosmetics, or for children's toys and household goods.
  • Endocrine disruptors are understood as substances disturbing human internal secretion by external causes. Chemical substances with a structure similar to that of female hormones like estrogen are called by this term currently.
  • endocrine disruptors There are some 70-odd known kinds of endocrine disruptors, the best known being dioxin, polyvinyl chloride, croldene, DDT, alkylphenol, bisphenol, phthalic acid ester, styrene dimer-trimer, etc.
  • alkylphenol, bisphenol, and styrene dimer- trimer are known to be related to such polymer substances as plastics, among others.
  • Styrene dimer-trimer comes into being during the process for producing styrene foam, while alkylphenol and bisphenol are used as additives for the production or processing of polymer materials when plastic and other similar products are manufactured.
  • Most additives, like antioxidants, used in the production or processing of polymeric substances, primarily has the chemical structures of alkylphenol and secondarily that of bisphenol. The negative synergistic effects of these substances are literally horrendous.
  • polystyrene being used variously for food-packing materials contains styrene dimer-trimer like endocrine disruptors as well as added stabilizers such as alkylphenol and bisphenol, therefore, considering styrene dimer-trimer as well, the negative synergistic effects can be quite grave and serious.
  • Stabilizers used as additive to polymer substances like plastics are required to withstand the high heat and other rigorous conditions during the processing of these polymer substances. Furthermore, they must perform their activity as antioxidants, and should naturally do not exert any negative influence on the melting and other physical properties of such polymer substances including their color and other outward appearances. There have been limits in the techniques to develop synthetic materials which meet all such requirements and are still not toxic to human.
  • the inventors of the present invention have continued search and study to develop some naturally-occurring substances, which can act as excellent stabilizers in production and processing of polymers like plastic and yet cause no problems at all like disturbance of internal secretion, etc..
  • the natural flavonoids, natural phenols, and natural polyphenols obtainable from apple, persimmon, persimmon tree leaves, green tea leaves, coffee bean, grape, sesame, cacao, jack fruit, rosemary, etc., have excellent properties as stabilizers, e.g. heat-resistance in addition to their superior antioxidation effects, enough to successfully replace the conventional synthetic alkyl and bisphenol stabilizers.
  • the objective of the present invention is to provide a polymer composition including natural compounds as stabilizers which are entirely harmless to human if they are in contact with, or taken in, by humans, and yet are excellent as the intended stabilizers.
  • the polymer composition of the present invention is characterized in that it does not use any of the existing synthetic stabilizers but contains a stabilizer in which the natural flavonoid or natural phenol and natural polyphenol are used.
  • the stabilizers originated from natural materials to be used in the present invention can be the natural flavonoids, natural phenols and natural polyphenols.
  • the natural flavonoids include those extracts of peanuts and cotton seeds, rice hulls, chia seeds, etc.
  • the natural phenols and polyphenols include the extracts of apple, green tea, coffee bean, rosemary, cacao, jack fruit, persimmon and persimmon tree leaf, licorice, sun flower seed, mustard and rape seed, sesame, grape, and other natural tannin extracts.
  • a stabilizer depends on the kinds of the polymer material in use, processing method and conditions. For instance, in case the melting temperature of the polymer material is low, its melting viscosity is low, and the processing time is relatively short, and therefore a short-time stabilization is required, a quantity around 0.01wt% may be sufficient. While, in case its melting temperature is high, the viscosity is high, and the processing time is very long, a considerable amount of the stabilizer may necessarily be prescribed to ensure a smooth processing of the polymer material and a long-time stabilization.
  • the quantity of the natural stabilizer of the present invention is preferably to remain within the range from 0.01wt% to 10wt% to the total amount of the polymer composition.
  • Such natural stabilizers can be used at any stage of the production of a polymer material, but, preferably, it is used in the stage of formation of the material. Also, during the formation process of polymer material, the natural stabilizers may be used variously at the stages, e.g. of injection, pressing out or extrusion for molding. But one of the preferable ways is to use, in cases, in the form of pretreatment master batch prepared in advance, at the time of the processing for molding.
  • these stabilizers also have, besides being safe to human, merits of greatly improving the quality of the end products, especially for package food, through enhancement of its deodorization and antibacterial characteristics.
  • the conventional stabilizers do only the stabilizing functions, but those derived from the natural compounds in the present invention are quite superior to the conventional ones for their added merits of reinforced deodorization and anti-bacterial features, in addition to the unique harmlessness to human.
  • the existing stabilizers it is always necessary to add other further additives in order to endow the polymer material with the desired deodorization and anti-bacterial features.
  • substances as silver and iodine compounds are used, and their toxicity has posed serious problems.
  • the stabilizers of the present invention unlike those of prior art, are characteristic in that they are not merely harmless to human but are excellent in stabilization itself and, in addition to the endowment of deodorization and anti-bacterial capacities.
  • the one of features of the present invention is to provide a method to lift the basic limits of the existing stabilizers in solving the toxicity problem to human, and also in maximizing the functions of polymer materials for food package containers by means of endowing such new capacities as anti-bacterial power and deodorization upon the materials.
  • thermosetting polymer materials include phenol resin, urea resin, melamine resin, furan resin, alkyd resin, unsaturated polyester, diarylphthalate, epoxy resin, silicon resin, polyurethane resin, etc.
  • the thermoplastic polymer materials include vinyl chloride resin, vinylidene chloride resin, nitric vinyl resin, polyvinyl alcohol resin, polyvinylacetal resin, polystyrene resin, ABS resin, methacryl resin, polyethylene resin, polypropylene resin, fluorine resin, polyamide resin, polyacetal resin, polycarbonate resin, polyphenylene oxide resin, polysulfon resin, celluloid, nitrocellulose acid resin, polyester resin, etc.
  • these various kinds of resin can be used either solely or in combination of two or more, and in either case the natural stabilizers of the present invention can be used.
  • Rubber can also be included in the group of polymer materials for the present invention, and it includes butadiene rubber, natural rubber, SBR rubber, NBR rubber, silicon rubber, etc.
  • additives as lubricant, pigmens, ultraviolet ray absorber, flame-retardant, filler, anti-static, can all be added in combination.
  • lubricants also the commonly used internal and external lubricants can both be used in the present invention.
  • metal salts of fatty acid can be used.
  • fatty acid stearic acid can be taken as an example, and of metals, calcium, magnesium, and zinc can be used.
  • EBS(ethylene bis stearamide) can also be used.
  • talc calcium carbonate (CaC0 3 ), and clay
  • coloring when adopted, too, these may be used.
  • coloring unlike other, a special care has to be taken of arrangement of coloring as the natural compounds have their particular colors, but this can not be a task technically difficult to handle.
  • hues too, all the existing ones can be embodied, and even in the case of applying them as master batch, all techniques in existence can be applied, choosing the matrix in consideration of the compatibility with the objected resin, and otherwise.
  • additives can fulfill their respective purposes if a small quantity is added mainly during the process of processing for molding, and it is also possible to use them in the form of a master batch prepared in advance. It is deemed economically more profitable to treat and process all the various additives at once in entirety if resin is to be processed for formation.
  • the polymer composition of the present invention is to be used for containers to pack foodstuffs it is as a matter of fact preferred to refrain as far as possible from using various other artificial synthetic additives than the aforesaid compounds. Save for some exceptional cases, all sorts of additives to the polymer composition for foodstuffs packing should be ones proven harmless to human. The most preferable composition to attain the objectives of the present invention should refrain as much as possible from using substances other than the stabilizers of the present invention, originated from natural sources.
  • the technique for extension at the time of processing for molding can be used with no particular discrimination from other, conventional techniques. Further, any particularly thorough mixing or kneading together is required, it can just be done by the use of an ordinary twin-screw extruder. Otherwise, a single-screw extruder will be enough to meet the purpose, and in the case of preparing a master batch an ordinary mixer or B anbury mixer, single-screw extruder, twin-screw extruder, etc. can be used, the choice only depending upon the particular degree of mixing required in a case.
  • Apple flesh is washed, well rinsed, crushed and compressed to obtain the juice.
  • the juice was then treated with pectinase, and afterwards it was passed to a filter, the filtered out juice was adsorbed by the use of a column, it was washed with hot water. After extracted with 65% ethanol, it was concentrated in vacuo and dried by means of spraying, thus the extract of apple in the form of powder was finally obtained.
  • this polyphenol being composed of tannin, caffeic acid, chlorogenic acid, paracumaric acid, phloretin, phloridzin, catechin, epicatechin, etc.
  • the aforesaid extract can be used in mixture with starch, lactose, dextrin, etc.
  • the green tea extract is used in mixture with starch, lactose, dextrin, etc.
  • the polyphenol content was 50% or more, this polyphenol being composed of chlorogenic acid, tannin, etc.
  • this extract was used with starch, lactose, dextrin, etc.
  • rosemary extract the polyphenol content was over 50%, this polyphenol being composed of chlorogenic acid, tannin, etc. As needed, it was used in mixture with starch, lactose, dextrin, etc.
  • cacao extract the content of polyphenol was over 50%, it being composed of chlorogenic acid, tannin, and other polymer polyphenol.
  • this extract is used in mixture with starch, lactose, dextrin, etc.
  • Jack fruit leaves l,000g was extracted with 60% acetone at a room temperature for
  • the obtained extract was then separated by centrifi ⁇ ge(3,000 rpm, for 30 minutes) into supernatant and precipitate.
  • the precipitate was extracted by means of method aforesaid four times. The supernatant each time was collected, concentrated, and filtered for removal of chlorophyll, and then concentrated to 2 litres. It was extracted with acetone to obtain the desired jack fruit extract.
  • the condensed tannin content was more than 50%, the polyphenol being composed of substances of the catechin group.
  • this extract was used in mixture with starch, lactose, dextrin, etc.
  • Dried persimmon leaves l,000g was extracted with 60% acetone at a room temperature for 24 hours. The obtained extract was then separated by a centrifuge (3,000 rpm, for 30 minutes) into the supernatant and precipitate. The precipitate was extracted by means of method aforesaid four times. The supernatant each time was collected, concentrated, filtered to remove chlorophyll, and then concentrated to 2 litres. It was extracted with acetone to obtain the desired persimmon tree leaf extract.
  • the content of condensed tannin was over 50%, and polyphenol is composed of catechins such as (+)gallocatechin and prodelpWnidine. When necessary, its was used in mixture with starch, lactose, dextrin, etc.
  • Extruder used 40 /, of Jinwoo Kiyon Ltd., Korea
  • Example 2 Exactly the same process was adopted as in Example 1 with the only exception that polyethylene was used instead of the polypropylene.
  • Example 4 Exactly the same process was adopted as in Example 1 with the only exception that high-impact polystyrene was used instead of the polypropylene.
  • Example 4 Exactly the same process was adopted as in Example 1 with the only exception that high-impact polystyrene was used instead of the polypropylene.
  • Example 2 Exactly the same process was adopted as in Example 1 with the only exception that ABS resin was used instead of the polypropylene.
  • Polypropylene by 5,000 parts by weight, calcium stearate as lubricant by 5 parts by weight, and the green tea extract, prepared in Preparation Example 2 as stabilizer, by 5 parts by weight were mixed well in a tumbler mixer, and then the mixture was extruded in a single-screw extruder. After extrusion process, the moisture was removed therefrom and thereafter the mixture was injected by the use of an injector.
  • the tensile strengths of the part that was injected without delay inside the injector (I) and the part injected after a delay inside the injector for five minutes ( ⁇ ) were respectively measured by the use of ASTM D638 for confirmation of their effectiveness as an agent in the manufacturing process.
  • Example 5 Exactly the same process was adopted as in Example 5 with the only exception that polyethylene was used instead of the polypropylene.
  • Example 8 Exactly the same process was adopted as in Example 5 with the only exception that high-impact polystyrene was used instead of the polypropylene.
  • Example 8 Exactly the same process was adopted as in Example 5 with the only exception that high-impact polystyrene was used instead of the polypropylene.
  • Example 5 Exactly the same process was adopted as in Example 5 with the only exception that ABS resin was used instead of the polypropylene.
  • Polypropylene by 5,000 parts by weight, calcium stearate as lubricant by 5 parts by weight, and the coffee extract, prepared in Preparation Example 3 as stabilizer, by 5 parts by weight were mixed well in a tumbler mixer, and then the mixture was extruded in a single-screw extruder. After the extrusion processes, moisture was removed therefrom and thereafter the mixture was injected by the use of an injector.
  • the tensile strength of the part that was injected without delay inside the injector (I) and the part injected after a delay inside the injector for five minutes (II) were respectively measured by the use of ASTM D638 for confirrnation of their effectiveness as an agent in the manufacturing process.
  • Example 9 Exactly the same process was adopted as in Example 9 with the only exception that polyethylene was used instead of the polypropylene.
  • Example 12 Exactly the same process was adopted as in Example 9 with the only exception that high-impact polystyrene was used instead of the polypropylene.
  • Example 12
  • Example 9 Exactly the same process was adopted as in Example 9 with the only exception that ABS resin was used instead of the polypropylene.
  • Polypropylene by 5,000 parts by weight, calcium stearate as lubricant by 5 parts by weight, and the rosemary extract, prepared in Preparation Example 4 as stabilizer, by 5 parts by weight were mked well in a tumbler mker, and then the mixture was extruded in a single-screw extruder. After the extrusion processes, the moisture was removed therefrom and thereafter the mixture was injected by the use of an injector.
  • the tensile strengths of the part that was injected without delay inside the injector (I) and the part injected after a delay inside the injector for five minutes (13) were respectively measured by the use of ASTM D638 for confirmation of their effectiveness as an agent in the manufacturing process.
  • Example 13 Exactly the same process was adopted as in Example 13 with the only exception that polyethylene was used instead of the polypropylene.
  • Example 16 Exactly the same process was adopted as in Example 13 with the only exception that high-impact polystyrene was used instead of the polypropylene.
  • Example 16
  • Example 13 Exactly the same process was adopted as in Example 13 with the only exception that ABS resin was used instead of the polypropylene.
  • Polypropylene by 5000 parts by weight, calcium stearate as lubricant by 5 parts by weight, and the cacao extract, prepared in Preparation Example 5 as stabilizer, by 5 parts by weight were mked well in a tumbler mker, and then the mixture was extruded in a single- screw extruder. After the extrusion processes, the mixture was rid of moisture and thereafter injected by the use of an injector.
  • the tensile strengths of the part that was injected without delay inside the injector (I) and the part injected after a delay inside the injector for five minutes (II) were respectively measured by the use of ASTM D638 for confirmation of their effectiveness as an agent in the manufacturing process.
  • Example 17 Exactly the same process was adopted as in Example 17 with the only exception that polyethylene was used instead of the polypropylene.
  • Example 20 Exactly the same process was adopted as in Example 17 with the only exception that high-impact polystyrene was used instead of the polypropylene.
  • Example 20
  • Example 17 Exactly the same process was adopted as in Example 17 with the only exception that ABS resin was used instead of the polypropylene.
  • Polypropylene by 5,000 parts by weight, calcium stearate as lubricant by 5 parts by weight, and the jack fruit leaf extract, prepared in Preparation Example 6 as stabilizer, by 5 parts by weight were mked well in a tumbler mker, and then the mixture was extruded in a single-screw extruder. After the extrusion processes, the moisture was removed therefrom and thereafter the mixture was injected by the use of an injector.
  • the tensile strengths of the part that was injected without delay inside the injector (J) and the part injected after a delay inside the injector for five minutes (H) were respectively measured by the use of ASTM D638 for confirmation of their effectiveness as an agent in the manufacturing process.
  • Example 21 Exactly the same process was adopted as in Example 21 with the only exception that polyethylene was used instead of the polypropylene.
  • Example 24 Exactly the same process was adopted as in Example 21 with the only exception that high-impact polystyrene was used instead of the polypropylene.
  • Example 24 Exactly the same process was adopted as in Example 21 with the only exception that high-impact polystyrene was used instead of the polypropylene.
  • Example 21 Exactly the same process was adopted as in Example 21 with the only exception that ABS resin was used instead of the polypropylene.
  • Polypropylene by 5,000 parts by weight, calcium stearate as lubricant by 5 parts by weight, and the persimmon leaf extract, prepared in Preparation Example 7 as stabilizer, by 5 parts by weight were mked well in a tumbler mker, and then the mixture was extruded in a single-screw extruder. After the extrusion processes, the moisture was removed therefrom and thereafter the mixture was injected by the use of an injector.
  • the tensile strengths of the part that was injected without delay inside the injector (I) and the part injected after a delay inside the injector for five minutes (II) were respectively measured by the use of ASTM D638 for confirmation of their effectiveness as an agent in the manufacturing process
  • Example 25 Exactly the same process was adopted as in Example 25 with the only exception that polyethylene was used instead of the polypropylene.
  • Example 28 Exactly the same process was adopted as in Example 25 with the only exception that high-impact polystyrene was used instead of the polypropylene.
  • Example 28
  • Example 25 Exactly the same process was adopted as in Example 25 with the only exception that ABS resin was used instead of the polypropylene.
  • Irganox® 1010 of Ciba-Geigy make was used as a conventional antioxidant instead of the natural stabilizer of the present invention.
  • Irganox® 1010 of Ciba-Geigy make was used as a conventional antioxidant instead of the natural stabilizer of the present invention.
  • Irganox® 1076 of Ciba-Geigy make was used as a conventional antioxidant instead of the natural stabilizer of the present invention.
  • the natural stabilizers of the present invention display identical or better effect as processing agent, compared with the conventional artificial synthetic stabilizers. Accordingly, they can replace the conventional synthetic stabilizers as processing agent, and thereby they can remove harmful elements from the polymer products.
  • test strain was put in the test solution, the solution was kept at 35 °C , and the number of living bacteria was calculated respectively after 6 hours and 24 hours.
  • MSRA staphylococcus
  • the natural stabilizers for the polymer compositions of the present invention display the effects as processing agents roughly identical to those of the conventional artificial stabilizers. Therefore, the present invention has opened a way to provide the ideal stabilizers which cannot merely replace the conventional synthetic stabilizers as processing agents but remove elements of various forms harmful to human from polymer products.
  • the polymer compositions to be produced with the use of the natural stabilizers of the present invention possess antibacterial capabilities, too, owing to the anti-bacterial effects of the natural stabilizers.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention is related to a polymer composition containing stabilizers including natural flavonoid and/or natural phenol and/or natural polyphenols. Because the polymer composition of the present invention does not contain any existing synthetic stabilizers which are toxic or may be toxic to human, it is harmless to human, and, moreover, because of the anti-bacterial effects of the natural stabilizers contained therein, it also brings about anti-bacterial effects.

Description

[SPECIFICATION]
[Title of Invention]
A Polymer Composition Comprising Natural Stabilizers
[Background of the Invention]
The present invention is related to a polymer compositon comprising natural compounds as stabilizers, and more particularly to a polymer composition produced with the use of stabilizers including natural flavonoid and/or natural phenol and/or the natural polyphenols, etc.
In the past, when producing polymer substances, especially at the time of producing plastic, rubber, fibre, etc, it has been mainly synthetic chemical substances of the alkylphenol and bisphenol group that have been used as stabilizers e.g., antioxidants. They included, for example, butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), propyl gallate (PG), dodecyl gallate (DG), tert-butyl, and such like compounds of the alkylphenol group and other bisphenol compounds of the Irganox series. These synthetic chemical substances, despite their superior chemical activity as stabilizers in the production and processing of polymer products, have never been free from the suspicion of being agents of harmful effects on human because of their own toxicity. Moreover, these synthetic chemical compounds, unlike those other inorganic substances, are apt to form a dispersion phase when they are mixed with or kneaded into polymer substances. And these synthetic chemical compounds, being far more fluid-like than polymer substances due to their lower molecular weight comparing with polymer substances, are apt to elute while processed together with polymer substances or when used in their applied products. This often leads to many undesirable problems on account of their orally toxic effects on humans. Such problems are even more serious when polymer products are used for containers for packing foods and cosmetics, or for children's toys and household goods.
According to available data and materials related to such existing synthetic stabilizers, there is theoretically no synthetic stabilizer at all that can do absolutely no harm to human. Hence it is necessary to strictly regulate the quantity of such stabilizers as additives. A great deal more care should be taken when these substances are to be used for containers of food or others supposedly in direct contact with human body especially when used for drinking containers and children's toys.
Additionally, concerns are being increasingly heard from many social institutions and environmental organizations all over the world about the influence of endocrine disruptors which are sometimes called as environmental hormones. Endocrine disruptors are understood as substances disturbing human internal secretion by external causes. Chemical substances with a structure similar to that of female hormones like estrogen are called by this term currently. There are some 70-odd known kinds of endocrine disruptors, the best known being dioxin, polyvinyl chloride, croldene, DDT, alkylphenol, bisphenol, phthalic acid ester, styrene dimer-trimer, etc.
Of these endocrine disruptors, alkylphenol, bisphenol, and styrene dimer- trimer are known to be related to such polymer substances as plastics, among others. Styrene dimer-trimer comes into being during the process for producing styrene foam, while alkylphenol and bisphenol are used as additives for the production or processing of polymer materials when plastic and other similar products are manufactured. Most additives, like antioxidants, used in the production or processing of polymeric substances, primarily has the chemical structures of alkylphenol and secondarily that of bisphenol. The negative synergistic effects of these substances are literally horrendous.
Particularly, polystyrene being used variously for food-packing materials contains styrene dimer-trimer like endocrine disruptors as well as added stabilizers such as alkylphenol and bisphenol, therefore, considering styrene dimer-trimer as well, the negative synergistic effects can be quite grave and serious.
In order to eliminate these elements harmful to human from such polymer products as plastic goods, efforts were made to minimize the use of polymerization catalysts and the unpolymerized remaining monomer during the process for polymerization. And other efforts were made to limit the coloring agents used in forming and processing such polymer products as toys for children, for instance, to only such pigments that are allowed as additives in the production of foods. However, in the formation and production of polymer substances, the kinds of additives used are not only pigments but also many other various kinds of additives which are used to develop another physical properties of polymer.
Of these, only the lubricants and fillers do not pose big physico-chemical characteristic problems, while the physico-chemical characteristics of the pigments or stabilizers require in depth consideration.
In the past, however, although using small amounts, the use of synthetic stabilizers and additives has not received serious consideration despite their harmfulness to human. Stabilizers used as additive to polymer substances like plastics are required to withstand the high heat and other rigorous conditions during the processing of these polymer substances. Furthermore, they must perform their activity as antioxidants, and should naturally do not exert any negative influence on the melting and other physical properties of such polymer substances including their color and other outward appearances. There have been limits in the techniques to develop synthetic materials which meet all such requirements and are still not toxic to human.
[Summary of the Invention]
In order to overcome such problems faced by use of artificial synthetic stabilizers, as stated above, the inventors of the present invention have continued search and study to develop some naturally-occurring substances, which can act as excellent stabilizers in production and processing of polymers like plastic and yet cause no problems at all like disturbance of internal secretion, etc.. Now it have been found that the natural flavonoids, natural phenols, and natural polyphenols obtainable from apple, persimmon, persimmon tree leaves, green tea leaves, coffee bean, grape, sesame, cacao, jack fruit, rosemary, etc., have excellent properties as stabilizers, e.g. heat-resistance in addition to their superior antioxidation effects, enough to successfully replace the conventional synthetic alkyl and bisphenol stabilizers. Besides the antioxidation effects, the natural phenol and polyphenol materials have been found to be excellent in anti-bacterial and bacteriostatic activities also, wherefore, the final products of such polymer substances wherein these natural compounds are used, it can be expected, will display good anti-bacterial and bacteriostatic effects, too. Instead of degrading the original properties of the resin, the addition of these natural compounds rather enhances the functions of the resin. In short, the objective of the present invention is to provide a polymer composition including natural compounds as stabilizers which are entirely harmless to human if they are in contact with, or taken in, by humans, and yet are excellent as the intended stabilizers.
[Detailed Description of the Invention]
The polymer composition of the present invention is characterized in that it does not use any of the existing synthetic stabilizers but contains a stabilizer in which the natural flavonoid or natural phenol and natural polyphenol are used.
The stabilizers originated from natural materials to be used in the present invention can be the natural flavonoids, natural phenols and natural polyphenols. The natural flavonoids include those extracts of peanuts and cotton seeds, rice hulls, chia seeds, etc. The natural phenols and polyphenols include the extracts of apple, green tea, coffee bean, rosemary, cacao, jack fruit, persimmon and persimmon tree leaf, licorice, sun flower seed, mustard and rape seed, sesame, grape, and other natural tannin extracts.
Generally, there are quite a few substances of natural raw materials which are used in prevention of deterioration or decomposition of food-stuffs, but a great majority of them are only for either frozen or refrigerated food, or more often than not for foods at relatively low temperatures, 100°C or lower. This is due to their rather poor anti-heat resistance. In the case of the aforesaid natural stabilizers of the present invention, however, they are especially excellent in anti- heat resistance, and are characterized in that they can serve as stabilizers at the relatively high temperature of around 200 °C, a condition for processing of polymer products.
In the present invention it is possible to use these natural stabilizers either solely or two or more in combination at a time. The amount of a stabilizer depends on the kinds of the polymer material in use, processing method and conditions. For instance, in case the melting temperature of the polymer material is low, its melting viscosity is low, and the processing time is relatively short, and therefore a short-time stabilization is required, a quantity around 0.01wt% may be sufficient. While, in case its melting temperature is high, the viscosity is high, and the processing time is very long, a considerable amount of the stabilizer may necessarily be prescribed to ensure a smooth processing of the polymer material and a long-time stabilization. But if the amount exceeds 10wt% or more, the ensuing degradation of the physico-chemical properties of the polymer material can hardly be avoided, although its effects as stabilizer may be obtained. Accordingly, in consideration of both the physico-chemical properties of the polymer material and the desired effects of the stabilizer the quantity of the natural stabilizer of the present invention is preferably to remain within the range from 0.01wt% to 10wt% to the total amount of the polymer composition.
Such natural stabilizers can be used at any stage of the production of a polymer material, but, preferably, it is used in the stage of formation of the material. Also, during the formation process of polymer material, the natural stabilizers may be used variously at the stages, e.g. of injection, pressing out or extrusion for molding. But one of the preferable ways is to use, in cases, in the form of pretreatment master batch prepared in advance, at the time of the processing for molding.
According to the present invention using the natural stabilizers entirely harmless to human, it is to be noted that these stabilizers also have, besides being safe to human, merits of greatly improving the quality of the end products, especially for package food, through enhancement of its deodorization and antibacterial characteristics.
In other words, it can be clearly seen that the conventional stabilizers do only the stabilizing functions, but those derived from the natural compounds in the present invention are quite superior to the conventional ones for their added merits of reinforced deodorization and anti-bacterial features, in addition to the unique harmlessness to human. In the cases of the existing stabilizers, it is always necessary to add other further additives in order to endow the polymer material with the desired deodorization and anti-bacterial features. For such purposes substances as silver and iodine compounds are used, and their toxicity has posed serious problems. The stabilizers of the present invention, unlike those of prior art, are characteristic in that they are not merely harmless to human but are excellent in stabilization itself and, in addition to the endowment of deodorization and anti-bacterial capacities. The one of features of the present invention is to provide a method to lift the basic limits of the existing stabilizers in solving the toxicity problem to human, and also in maximizing the functions of polymer materials for food package containers by means of endowing such new capacities as anti-bacterial power and deodorization upon the materials.
Thermoplastic and thermosetting materials can be used as polymer materials for the present invention. The thermosetting polymer materials include phenol resin, urea resin, melamine resin, furan resin, alkyd resin, unsaturated polyester, diarylphthalate, epoxy resin, silicon resin, polyurethane resin, etc. The thermoplastic polymer materials include vinyl chloride resin, vinylidene chloride resin, nitric vinyl resin, polyvinyl alcohol resin, polyvinylacetal resin, polystyrene resin, ABS resin, methacryl resin, polyethylene resin, polypropylene resin, fluorine resin, polyamide resin, polyacetal resin, polycarbonate resin, polyphenylene oxide resin, polysulfon resin, celluloid, nitrocellulose acid resin, polyester resin, etc. In the present invention these various kinds of resin can be used either solely or in combination of two or more, and in either case the natural stabilizers of the present invention can be used. Rubber can also be included in the group of polymer materials for the present invention, and it includes butadiene rubber, natural rubber, SBR rubber, NBR rubber, silicon rubber, etc.
To the polymer compositions in the present invention such ordinary additives as lubricant, pigmens, ultraviolet ray absorber, flame-retardant, filler, anti-static, can all be added in combination.
For lubricants also the commonly used internal and external lubricants can both be used in the present invention. As a representative, metal salts of fatty acid can be used. Of the fatty acid, stearic acid can be taken as an example, and of metals, calcium, magnesium, and zinc can be used. At times lubricants like
EBS(ethylene bis stearamide) can also be used.
As a filler for the present invention all at the embodiments of the prior art, for instance, talc, calcium carbonate (CaC03), and clay can be used. When coloring is adopted, too, these may be used. In the case of coloring, unlike other, a special care has to be taken of arrangement of coloring as the natural compounds have their particular colors, but this can not be a task technically difficult to handle. In the case of hues, too, all the existing ones can be embodied, and even in the case of applying them as master batch, all techniques in existence can be applied, choosing the matrix in consideration of the compatibility with the objected resin, and otherwise. These additives can fulfill their respective purposes if a small quantity is added mainly during the process of processing for molding, and it is also possible to use them in the form of a master batch prepared in advance. It is deemed economically more profitable to treat and process all the various additives at once in entirety if resin is to be processed for formation.
In case the polymer composition of the present invention is to be used for containers to pack foodstuffs it is as a matter of fact preferred to refrain as far as possible from using various other artificial synthetic additives than the aforesaid compounds. Save for some exceptional cases, all sorts of additives to the polymer composition for foodstuffs packing should be ones proven harmless to human. The most preferable composition to attain the objectives of the present invention should refrain as much as possible from using substances other than the stabilizers of the present invention, originated from natural sources.
In the present invention, the technique for extension at the time of processing for molding can be used with no particular discrimination from other, conventional techniques. Further, any particularly thorough mixing or kneading together is required, it can just be done by the use of an ordinary twin-screw extruder. Otherwise, a single-screw extruder will be enough to meet the purpose, and in the case of preparing a master batch an ordinary mixer or B anbury mixer, single-screw extruder, twin-screw extruder, etc. can be used, the choice only depending upon the particular degree of mixing required in a case.
Below, the present invention is described in further detail, making reference to examples of embodiment and comparative examples. The scope and range of the present invention will not be limited only to these examples. Preparation Example 1 : Production of apple extract
Apple flesh is washed, well rinsed, crushed and compressed to obtain the juice. The juice was then treated with pectinase, and afterwards it was passed to a filter, the filtered out juice was adsorbed by the use of a column, it was washed with hot water. After extracted with 65% ethanol, it was concentrated in vacuo and dried by means of spraying, thus the extract of apple in the form of powder was finally obtained.
In the finally obtained apple extract, the content of polyphenol was over
50%, this polyphenol being composed of tannin, caffeic acid, chlorogenic acid, paracumaric acid, phloretin, phloridzin, catechin, epicatechin, etc.
As needed, the aforesaid extract can be used in mixture with starch, lactose, dextrin, etc.
Preparation Example 2: Production of green tea extract
After tea leaves were placed in boiling hot water for 30 minutes for extraction, the extract was filtered with the use of activated charcoal. The filtered out extract liquid was concentrated in vacuo and dried by spraying. The extract became dried green tea extract in the powder form.
The green tea extract is used in mixture with starch, lactose, dextrin, etc.
Preparation Example 3 : Production of coffee extract
After crushing the raw coffee beans into a size of about 5 mm (in diameter) and after removing discolored beans and foreign substances, extraction was carried out with the use of de-ionized water. The extract was then dried by spraying to obtain coffee extract in the powder form.
In the coffee extract thus obtained, the polyphenol content was 50% or more, this polyphenol being composed of chlorogenic acid, tannin, etc.
When necessary, this extract was used with starch, lactose, dextrin, etc.
Preparation Example 4: Rosemary extract
After deodorizing dried rosemary by the way of steam distillation, and after drying that again, the extraction was carried out with viscous alcohol solution like ethanol of more than 60%. The extract was concentrated in vacuo. Further, extraction was carried out once again with diluted alcohol solution, and the extract was then filtered, washed in water, and dried, finally to obtain the desired rosemary extract.
In the thus obtained rosemary extract the polyphenol content was over 50%, this polyphenol being composed of chlorogenic acid, tannin, etc. As needed, it was used in mixture with starch, lactose, dextrin, etc.
Preparation Example 5: Cacao extract
Dried cacao beans and cacao hull were extracted with 60% acetone solution for 24 hours. The obtained extract was then separated by a centrifuge into supernatant and precipitate. The precipitate was extracted by means of method aforesaid four times. The supernatant obtained each time was then concentrated and filtered to remove chlorophyll and then concentrated to 2 litres. It was extracted with acetone to obtain the desired cacao extract.
In the thus obtained cacao extract, the content of polyphenol was over 50%, it being composed of chlorogenic acid, tannin, and other polymer polyphenol. When necessary, this extract is used in mixture with starch, lactose, dextrin, etc.
Preparation Example 6: Jack fruit leaf extract
Jack fruit leaves l,000g was extracted with 60% acetone at a room temperature for
24 hours. The obtained extract was then separated by centrifiιge(3,000 rpm, for 30 minutes) into supernatant and precipitate. The precipitate was extracted by means of method aforesaid four times. The supernatant each time was collected, concentrated, and filtered for removal of chlorophyll, and then concentrated to 2 litres. It was extracted with acetone to obtain the desired jack fruit extract.
In the thus obtained jack fruit extract, the condensed tannin content was more than 50%, the polyphenol being composed of substances of the catechin group. When necessary, this extract was used in mixture with starch, lactose, dextrin, etc.
Preparation Example 7: Persimmon leaf extract
Dried persimmon leaves l,000g was extracted with 60% acetone at a room temperature for 24 hours. The obtained extract was then separated by a centrifuge (3,000 rpm, for 30 minutes) into the supernatant and precipitate. The precipitate was extracted by means of method aforesaid four times. The supernatant each time was collected, concentrated, filtered to remove chlorophyll, and then concentrated to 2 litres. It was extracted with acetone to obtain the desired persimmon tree leaf extract. In the thus obtained persimmon tree leaf extract, the content of condensed tannin was over 50%, and polyphenol is composed of catechins such as (+)gallocatechin and prodelpWnidine. When necessary, its was used in mixture with starch, lactose, dextrin, etc.
Below are given the physical properties of the various resins used, the conditions of their extrusion, injection, and tensile strength tests.
<MI of used resins>
Figure imgf000015_0001
** PP: polypropylene PE: polyethylene HIPS: High-impact polystyrene ABS: ABS resin < Extrusion test>
1. Extruder used: 40 /, of Jinwoo Kiyon Ltd., Korea
2. Extrusion conditions (Unit : °C )
Figure imgf000016_0001
<Injection test>
1. Injector used: 140EN II (lOoz), of LG Machinery, Ltd.
2. Injection conditions (Unit: °C)
Figure imgf000016_0002
<Tensile Strength test>
1. Gauge used: J STRON4304
2. Measuring conditions: Cross head speed ( 15n__m/min)
Example 1
Polypropylene by 5,000 parts by weight, calcium stearate as lubricant by 5 parts by weight, and the apple extract, prepared in Preparation Example 1 as stabilizer, by 5 parts by weight, were correctly measured out, and they were mixed well in a tumbler mixer, and then the mixture was extruded in a single-screw extruder. After the extrusion processes, moisture was removed therefrom and thereafter the mixture was injected by the use of an injector. The tensile strengths of the part that was injected without delay inside the injector (I) and the part injected after a delay inside the injector for five minutes (H) were respectively measured by the use of ASTM D638 for confirmation of their effectiveness as agent in the manufacturing process.
Example 2
Exactly the same process was adopted as in Example 1 with the only exception that polyethylene was used instead of the polypropylene.
Example 3
Exactly the same process was adopted as in Example 1 with the only exception that high-impact polystyrene was used instead of the polypropylene. Example 4
Exactly the same process was adopted as in Example 1 with the only exception that ABS resin was used instead of the polypropylene.
Example 5
Polypropylene by 5,000 parts by weight, calcium stearate as lubricant by 5 parts by weight, and the green tea extract, prepared in Preparation Example 2 as stabilizer, by 5 parts by weight were mixed well in a tumbler mixer, and then the mixture was extruded in a single-screw extruder. After extrusion process, the moisture was removed therefrom and thereafter the mixture was injected by the use of an injector. The tensile strengths of the part that was injected without delay inside the injector (I) and the part injected after a delay inside the injector for five minutes (Η) were respectively measured by the use of ASTM D638 for confirmation of their effectiveness as an agent in the manufacturing process.
Example 6
Exactly the same process was adopted as in Example 5 with the only exception that polyethylene was used instead of the polypropylene.
Example 7
Exactly the same process was adopted as in Example 5 with the only exception that high-impact polystyrene was used instead of the polypropylene. Example 8
Exactly the same process was adopted as in Example 5 with the only exception that ABS resin was used instead of the polypropylene.
Example 9
Polypropylene by 5,000 parts by weight, calcium stearate as lubricant by 5 parts by weight, and the coffee extract, prepared in Preparation Example 3 as stabilizer, by 5 parts by weight were mixed well in a tumbler mixer, and then the mixture was extruded in a single-screw extruder. After the extrusion processes, moisture was removed therefrom and thereafter the mixture was injected by the use of an injector. The tensile strength of the part that was injected without delay inside the injector (I) and the part injected after a delay inside the injector for five minutes (II) were respectively measured by the use of ASTM D638 for confirrnation of their effectiveness as an agent in the manufacturing process.
Example 10
Exactly the same process was adopted as in Example 9 with the only exception that polyethylene was used instead of the polypropylene.
Example 11
Exactly the same process was adopted as in Example 9 with the only exception that high-impact polystyrene was used instead of the polypropylene. Example 12
Exactly the same process was adopted as in Example 9 with the only exception that ABS resin was used instead of the polypropylene.
Example 13
Polypropylene by 5,000 parts by weight, calcium stearate as lubricant by 5 parts by weight, and the rosemary extract, prepared in Preparation Example 4 as stabilizer, by 5 parts by weight were mked well in a tumbler mker, and then the mixture was extruded in a single-screw extruder. After the extrusion processes, the moisture was removed therefrom and thereafter the mixture was injected by the use of an injector. The tensile strengths of the part that was injected without delay inside the injector (I) and the part injected after a delay inside the injector for five minutes (13) were respectively measured by the use of ASTM D638 for confirmation of their effectiveness as an agent in the manufacturing process.
Example 14
Exactly the same process was adopted as in Example 13 with the only exception that polyethylene was used instead of the polypropylene.
Example 15
Exactly the same process was adopted as in Example 13 with the only exception that high-impact polystyrene was used instead of the polypropylene. Example 16
Exactly the same process was adopted as in Example 13 with the only exception that ABS resin was used instead of the polypropylene.
Example 17
Polypropylene by 5000 parts by weight, calcium stearate as lubricant by 5 parts by weight, and the cacao extract, prepared in Preparation Example 5 as stabilizer, by 5 parts by weight were mked well in a tumbler mker, and then the mixture was extruded in a single- screw extruder. After the extrusion processes, the mixture was rid of moisture and thereafter injected by the use of an injector. The tensile strengths of the part that was injected without delay inside the injector (I) and the part injected after a delay inside the injector for five minutes (II) were respectively measured by the use of ASTM D638 for confirmation of their effectiveness as an agent in the manufacturing process.
Example 18
Exactly the same process was adopted as in Example 17 with the only exception that polyethylene was used instead of the polypropylene.
Example 19
Exactly the same process was adopted as in Example 17 with the only exception that high-impact polystyrene was used instead of the polypropylene. Example 20
Exactly the same process was adopted as in Example 17 with the only exception that ABS resin was used instead of the polypropylene.
Example 21
Polypropylene by 5,000 parts by weight, calcium stearate as lubricant by 5 parts by weight, and the jack fruit leaf extract, prepared in Preparation Example 6 as stabilizer, by 5 parts by weight were mked well in a tumbler mker, and then the mixture was extruded in a single-screw extruder. After the extrusion processes, the moisture was removed therefrom and thereafter the mixture was injected by the use of an injector. The tensile strengths of the part that was injected without delay inside the injector (J) and the part injected after a delay inside the injector for five minutes (H) were respectively measured by the use of ASTM D638 for confirmation of their effectiveness as an agent in the manufacturing process.
Example 22
Exactly the same process was adopted as in Example 21 with the only exception that polyethylene was used instead of the polypropylene.
Example 23
Exactly the same process was adopted as in Example 21 with the only exception that high-impact polystyrene was used instead of the polypropylene. Example 24
Exactly the same process was adopted as in Example 21 with the only exception that ABS resin was used instead of the polypropylene.
Example 25
Polypropylene by 5,000 parts by weight, calcium stearate as lubricant by 5 parts by weight, and the persimmon leaf extract, prepared in Preparation Example 7 as stabilizer, by 5 parts by weight were mked well in a tumbler mker, and then the mixture was extruded in a single-screw extruder. After the extrusion processes, the moisture was removed therefrom and thereafter the mixture was injected by the use of an injector. The tensile strengths of the part that was injected without delay inside the injector (I) and the part injected after a delay inside the injector for five minutes (II) were respectively measured by the use of ASTM D638 for confirmation of their effectiveness as an agent in the manufacturing process
Example 26
Exactly the same process was adopted as in Example 25 with the only exception that polyethylene was used instead of the polypropylene.
Example 27
Exactly the same process was adopted as in Example 25 with the only exception that high-impact polystyrene was used instead of the polypropylene. Example 28
Exactly the same process was adopted as in Example 25 with the only exception that ABS resin was used instead of the polypropylene.
Comparative Example 1
In an experiment with Example 1, Irganox® 1010 of Ciba-Geigy make was used as a conventional antioxidant instead of the natural stabilizer of the present invention.
Comparative Example 2
In an experiment with Example 2, Irganox® 1010 of Ciba-Geigy make was used as a conventional antioxidant instead of the natural stabilizer of the present invention.
Comparative Example 3
In an experiment with Example 3, Irganox® 1076 of Ciba-Geigy make was used as a conventional antioxidant instead of the natural stabilizer of the present invention.
Comparative Example 4
In an experiment with Example 4, Irganox® 1076 of Ciba-Geigy make was used as a conventional antioxidant instead of the natural stabilizer of the present invention. < Measured results of tensile strength>
Figure imgf000025_0001
* I : injected without delay inside injector II : injected after a delay inside injector for five minutes
From the above results, it is seen that the natural stabilizers of the present invention display identical or better effect as processing agent, compared with the conventional artificial synthetic stabilizers. Accordingly, they can replace the conventional synthetic stabilizers as processing agent, and thereby they can remove harmful elements from the polymer products.
< Test on anti-bacterial property >
In order to check the anti-bacterial effects of the natural stabilizers of the present invention when used in polymer compositions, the following test was performed of the anti-bacterial property of the apple extract of Example 1 of the embodiment of the present invention, the results being given in Table 3.
Methods of test: (i) A physiological saline solution of the apple extract of Example 1 above (concentration: 2,000 ppm) was prepared and used as the test solution
(ii) The test strain was put in the test solution, the solution was kept at 35 °C , and the number of living bacteria was calculated respectively after 6 hours and 24 hours.
Test bacterial strain:
Methicillin, staphylococcus (MSRA)....pathogenic in hospitals;
Propionibacterium acnes...pathogenic for pimple;
Legionella pneumophila....parasitic in bath tubs for 24 hours;
E. coli (blood type 0-157: H7)....pathogenic Results of test:
Table 3 : Calculations of living bacteria from the test strain put in test solution
Figure imgf000027_0001
Here, the anti-bacterial effects of the apple extract in a 2,000 ppm solution against strain 4 are confirmed.
[Effects of the Invention]
From the above, it is noted that the natural stabilizers for the polymer compositions of the present invention display the effects as processing agents roughly identical to those of the conventional artificial stabilizers. Therefore, the present invention has opened a way to provide the ideal stabilizers which cannot merely replace the conventional synthetic stabilizers as processing agents but remove elements of various forms harmful to human from polymer products. The polymer compositions to be produced with the use of the natural stabilizers of the present invention possess antibacterial capabilities, too, owing to the anti-bacterial effects of the natural stabilizers.

Claims

[Claims]
What is claimed is:
L A composition for production of plastic materials, wherein said composition comprises polymer and natural stabilizer comprising natural flavonoid and/or natural phenol and/or natural polyphenol by 0.01% ~ 10% by weight.
2. The composition of Claim 1, wherein said natural stabilizer is one or more selected from the group consisting of the extracts of peanut, cotton seed, rice hull, chia seed, apple, green tea, coffee bean, rosemary, cacao, jack fruit leaf, persimmon or persimmon tree leaf, licorice, sun flower seed, mustard seed, rape seed, sesame and grape.
3. The composition of Claim 1, wherein said polymer is thermoplastic or thermosetting resin.
4. A composition of Claim 1, wherein said polymer is rubber.
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