五、發明說明（1 ) 本發明涉及一種可以用於光和生物降解塑膠製品的多 元組合物以及其在製造能夠障:解的各種一次性使用和包裝 領域的塑膠製品中的用途和所制得的能夠降解的各種一次 性使用和包裝領域的塑膠製品。 隨著塑膠工業岛迅速發展，當前世界塑膠產量已遠遠 超過億噸。據統計，1999年全世界合成樹脂的產量為1567 億嘲。其用途已滲透到國民經濟各部門以及人們生活的各 個領域。其中塑勝包裝材料和製品約占3〇0/〇，大致為46〇〇 萬噸。僅就中國而言，1999年的合成樹脂消費量為1866萬 噸，用於塑膠包裝業的製品就達5〇〇萬噸左右。就是說，用 於包裝領域的塑膠製品，用量是很大的。 塑膠消耗量的迅速增加和人們對環境意識的提高，使 得降解塑膠的研究日益為人們所關注。近年已有不少專利 (例如中國專利申請號·· 95191396)報導，採用合成的方法 製造容易被光和微生物直接作用的結構單元的新型高分子 聚合物（如微生物聚酯、脂肪族聚酯、聚乳酸等），當其在 使用後被廢棄時，利用光照或微生物直接作用而降解。用 這種方法制得的降解塑膠，降解性能是很好的，但由於其 合成難度大，成本高，很難在市場上大量應用。 另有專利（例如中國專利申請號·· 98106850.2申請號： 98101407.0)報導了‘‘光降解和光崩壞，，材料。他們採用在塑 膠原料中添加光敏劑，或光敏劑和碳酸鈣、滑石粉等礦物 粉的混合做法。由於這些材料只是進行光崩壞，其降解過 程是由大塊變小塊。很難得到滿意的效果β 1250184 A7V. INSTRUCTIONS (1) The present invention relates to a multi-component composition that can be used in light and biodegradable plastic articles and its use in the manufacture of plastic articles in various disposable and packaging fields capable of solving problems A variety of plastic products that can be degraded in a variety of single-use and packaging applications. With the rapid development of the plastic industrial island, the current world plastic production has far exceeded 100 million tons. According to statistics, the production of synthetic resin in the world in 1999 was 156.7 billion. Its use has penetrated into all sectors of the national economy and in all areas of people's lives. Among them, plastic packaging materials and products accounted for about 3〇0/〇, roughly 460,000 tons. As far as China is concerned, the consumption of synthetic resin in 1999 was 18.66 million tons, and the products used in the plastic packaging industry amounted to about 50,000 tons. That is to say, the amount of plastic products used in the packaging field is very large. The rapid increase in plastic consumption and the increase in people's awareness of the environment have led to the increasing interest in the study of degradable plastics. In recent years, many patents (for example, Chinese Patent Application No. 95191396) have reported that synthetic polymers are used to produce novel high molecular polymers (such as microbial polyesters, aliphatic polyesters, etc.) that are easily acted upon by light and microorganisms. Polylactic acid, etc., when it is discarded after use, is degraded by direct action by light or microorganisms. Degradable plastics obtained by this method have good degradation properties, but because of their difficulty in synthesis and high cost, it is difficult to be widely used in the market. Another patent (for example, Chinese Patent Application No. 98106850.2 Application No.: 98101407.0) reports ‘‘photodegradation and photo-disintegration, materials. They use a photosensitizer in the plastic raw material, or a mixture of photosensitizers and mineral powders such as calcium carbonate and talc. Since these materials only undergo photodisintegration, the degradation process is reduced from large to small. Difficult to get satisfactory results β 1250184 A7
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其他類型化合物’如月桂酸二τ基錫，二苯甲_及其衍生 物等。這些化合物中的一種或數種成分，其用量為 〇·1-8·0(重量百分數）。最佳用量為3,重量百分數卜 3·助生物降解成分：它是含有多羥基的羧酸酯 ，如硬 月曰&L水乙一醇g曰 '山梨糖醇棕櫚酸酯、山梨糖醇酐月桂酸 醋與環氧乙捷加合物、環氧大豆油、環氧乙醒菜麻油等。 其用量為0· 1-8.0(重量百分數）。 4.非金屬礦物質成分··它是含有滑石粉、碳酸鈣、高 嶺土、矽灰石等物質，其用量1〇到9〇(重量百分數）。 本發明所涉及的光和生物降解的多元組合物是由上述 1、2、3(或1、2)或者可以加入4中的一種或多種成分並按 各組份及其重量百分數含量，與聚合物樹脂原料等配伍， 經擠出造粒（或其化方式造粒）製成的降解複合體系。將其 按0.1-80(重量百分數）比例加入到通用型塑膠原料中，製成 的一次性使用或包裝領域的可降解塑膠製品，在自然界環 境下，可使聚合物的大分子逐漸變成分子量很低的小分子 含氧化合物。 實際的測試表明，這些分子量很低的含氧化合物，很 容易被微生物利用，放出二氧化碳和水，達到在自然界裏 完全被消納的效果。從而成為消除和減少‘‘白色污染，，，並 對環境友好化的新型材料。 實施例1光和生物降解多元組合物的組分及用量（重 量百分數） 低密度聚乙烯樹脂 85.8 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐〉 II— I I . I I (請先閱讀背面之注意事項再填寫本頁) 訂· -線- 7 1250184Other types of compounds such as di-t-t-butyl laurate, diphenyl- and its derivatives, and the like. One or more of these compounds is used in an amount of from -81 to 8·0 (% by weight). The optimum dosage is 3, the weight percentage is 3. Biodegradable component: it is a polyhydroxy-containing carboxylic acid ester, such as hard moon 曰 & L water ethoxylate g 曰 sorbitol palmitate, sorbitan Laurel vinegar and Epoxy Ethylene adduct, Epoxy soybean oil, Epoxy Ethylene sesame oil and so on. The amount thereof is from 0·1 to 8.0 (weight percent). 4. Non-metallic mineral component·· It contains talc, calcium carbonate, kaolin, ash, etc., and is used in an amount of 1 to 9 〇 (by weight). The light and biodegradable multicomponent composition of the present invention is one or more of the above 1, 2, 3 (or 1, 2) or may be added to 4 and in various components and their weight percentages, and polymerized. A degradable composite system prepared by extrusion granulation (or its granulation) by compatibility with raw materials such as resin. It is added to a general-purpose plastic raw material in a ratio of 0.1-80 (weight percent) to produce a degradable plastic product in a single-use or packaging field. In a natural environment, the macromolecule of the polymer gradually becomes a molecular weight. Low molecular oxygenates. Practical tests have shown that these low molecular weight oxygenates are easily used by microorganisms to release carbon dioxide and water to achieve full absorption in nature. This has become a new type of material that eliminates and reduces ‘white pollution, and is environmentally friendly. Example 1 Components and Amounts of Light and Biodegradable Multicomponent Composition (% by Weight) Low Density Polyethylene Resin 85.8 This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm > II - II . II ( Please read the notes on the back and fill out this page. Order · Line - 7 1250184
甲殼質 7.0 芥酸醯胺 L6 環氧大豆油 0.2 硬脂酸單甘油酯 0.8 環氧乙酿蓖麻油 0.4 7 -二茂鐵醯基丁酸 3.2 油酸鈷 0.8 月桂酸二丁基錫 0.2 按上述配方將低密度聚乙烯樹脂稱重，並置於別艺的 1請先閲讀背面之注意事頊再填寫本頁) 高速攪拌釜中，按配比量將環氧大豆油、環氧乙醯蓖麻油 稱重，並注入釜中，攪拌2-3分鐘。 然後將其他各種原料稱重，並置入蚤令，繼續搜拌3 分鐘。 將上述已攪拌好的混合料，用雙螺杆造粒機組（長徑比 36:1，各擠出區段溫度50-200°C，擠出機轉數25-450轉/分) 撥出造粒。 --------^-----Chitin 7.0 erucamide amide L6 Epoxidized soybean oil 0.2 Stearic acid monoglyceride 0.8 Epoxy E-castorous oil 0.4 7 - Ferrocene decyl butyric acid 3.2 Cobalt oleate 0.8 Dibutyltin laurate 0.2 According to the above formula Weigh the low-density polyethylene resin and place it on the other side of the art. Please read the back of the book first. Then fill in the page. In the high-speed stirring kettle, weigh the epoxy soybean oil and epoxy eucalyptus oil according to the ratio. It was poured into a kettle and stirred for 2-3 minutes. Then weighed the other ingredients and placed them in the order to continue mixing for 3 minutes. The above-mentioned stirred mixture is set up by a twin-screw granulating unit (length to diameter ratio of 36:1, temperature of each extrusion section: 50-200 ° C, extruder rotation number: 25-450 rpm) grain. --------^-----
ϋ n n I 經濟部智慧財產局員工消費合作社印製 實施例2可控光和生物降解地膜 將實施例1的多元組合物的粒子，按0·2-8(重量百分數） 加入到低密度聚乙烯（或線性低密度聚乙烯、高密度聚乙烯) 中，聚乙烯樹脂的用量為99.8-92(重量百分數）。 經均勻混合，將混合料置入擠出地膜機組的料斗中（機 組為PC-65型或其他類型），然後擠出吹塑成薄膜（薄膜厚度 為0.005-0.025mm)。此降解地膜的力學性能，基本與同厚 度的普通地膜相當，可以使用機械覆蓋地膜。該降解地膜 本紙張尺度適用t國國家標準（CNS)A4規格（210 X 297公釐） 1250184 A7 ___B7 五、發明說明（6 ) 對土壌和農作物無毒無害，同時具有丧好的光和生物降解 性能。該降解地膜的誘導期可以控制，通常有45土3天、60±5 天、90土7天、120土10天。該降解地膜覆蓋的當年，或第二 年，可完全降解，被微生物利用，放出二氧化碳和水，達 到完全被農田消納的效果。 使用上述多元組合物與線性低密度聚乙烯（或高密度 聚乙烯），按上述配比的混合料可以製成各種厚度的降解地 * 膜。特別是可製成厚度為〇.〇〇5mm的超薄降解地膜，其力 學性能及保溫、保墒性能完全符合農田覆蓋和作物的需 要，而每畝地膜用量可以大幅度降低。減少了農業投入。 . 裝--- (請先閱讀背面之注意事項再填寫本頁、) 力學性能測試結果 專案 標準值 測試結果 拉伸負荷N縱/橫 ^ 1.6 1.8/1.6 斷裂伸長率％縱/橫 ^ 160 300/380 直角撕裂負荷N縱/橫 ^0.6 0.7/0.9 -線- 經濟部智慧財產局員工消費^咋达沪挺 實施例3 —次性可降解塑膠購物袋 將含有實施例1的多元組合物的粒子，按0.2-8(重量百 分數）的比例加入到高密度聚乙烯（如曰本三井公司7000F) 中，後者的用量為99.8-92(重量百分數）。 經均勻混合，將其置入擠出吹膜機料斗中（擠出機螺杆 直徑45mm，長徑28:1)，並擠出吹塑成筒狀薄膜（薄膜厚度 為0.01-0.5mm均可）。然後通過印刷、沖裁、熱合等，製成 各種規格的可降解塑膠購物袋、食品袋等一次性包裝袋。 其力學性能與同厚度的普通購物袋相近。符合一次性塑膠 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 9 1250184 經濟部智慧財產局員工消費合作社印製 A7 --------— R7__ 五、發明說明（7 ) 購物袋的技術要求。其衛生性也符合國家標準g&9683-88 《食品包裝褒衛生標準》的要求^該降解袋使用後，如棄 之戶外，20-80天可降解成粉末狀，並進而完全降解被自然 環境消納，從感觀消失。 貫％例4光和生物降解多元組合物的組分及用量（重 量百分數） 聚乙烯樹脂 22.2 乾路素 8.0 芥酸醯胺 14 月桂酸始 5 4 二苯甲酮 〇·4 月桂酸二丁基錫 環氧大豆油 〇2 環氧乙醯藥麻油 0.4 硬脂酸聚乙二醇酯 〇.8 滑石粉 60 按上述配方，將聚乙烯樹脂、滑石粉稱重、並置於5〇 C的高速攪拌釜中，按配比量，將環氧大豆油、環氧乙醯 蓖麻油稱重，並注入蒼中，操作製備方法可參照實施例1 進行。制得多元組合物粒子。 實施例5 —次性可降解塑膠餐飲具 將實施例4的多元組合物的粒子按5-40(重量百分數） 加入到高密度聚乙烯（如大慶石化5121A)或聚丙烯（如燕山 石化1300)或聚苯乙婦（如燕山石化666D)等脂中，樹脂用量 本紙張尺度適用中関家標準（CNSM4規格（210 X 297公爱）ϋ nn I Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed Example 2 Controllable Light and Biodegradable Film The particles of the multicomponent composition of Example 1 were added to low density polyethylene at 0·2-8 (weight percent). (Or linear low density polyethylene, high density polyethylene), the amount of the polyethylene resin is 99.8-92 (weight percent). After homogeneous mixing, the mixture is placed in a hopper of an extrusion filming unit (machine type is PC-65 or other type) and then extruded into a film (film thickness 0.005-0.025 mm). The mechanical properties of this degraded film are basically equivalent to ordinary film of the same thickness, and a mechanical covering film can be used. The degradable film is applicable to the National Standard (CNS) A4 specification (210 X 297 mm). 1250184 A7 ___B7 V. Description of invention (6) Non-toxic and harmless to soil and crops, with good photo and biodegradability . The induction period of the degraded mulch film can be controlled, and generally has 45 soils, 3 days, 60±5 days, 90 soils, 7 days, and 120 soils and 10 days. The degraded film covers the same year, or the second year, it can be completely degraded, used by microorganisms, and emits carbon dioxide and water to achieve the effect of being completely absorbed by the farmland. Using the above multi-component composition and linear low-density polyethylene (or high-density polyethylene), the mixture of the above ratios can be used to form degraded films of various thicknesses. In particular, it can be made into an ultra-thin degradable mulch film with a thickness of 〇.〇〇5mm. Its mechanical properties, thermal insulation and moisture retention performance are in full compliance with the needs of farmland cover and crops, and the amount of mulch per acre can be greatly reduced. Reduced agricultural inputs. .--- (Please read the precautions on the back and fill out this page again) Mechanical properties test results Project standard value Test results Tensile load N longitudinal / horizontal ^ 1.6 1.8/1.6 Elongation at break % vertical / horizontal ^ 160 300 /380 Right angle tear load N vertical / horizontal ^ 0.6 0.7 / 0.9 - line - Ministry of Economic Affairs Intellectual Property Bureau staff consumption ^ 咋 沪 挺 实施 实施 Example 3 - The secondary degradable plastic shopping bag will contain the multi-component composition of Example 1. The particles are added to a high-density polyethylene (such as Sakamoto Mitsui Co., Ltd. 7000F) in a ratio of 0.2-8 (weight percent), and the latter is used in an amount of 99.8-92 (weight percent). After uniform mixing, it is placed in the hopper of the extrusion blown film machine (extruder screw diameter 45mm, long diameter 28:1), and extrusion blown into a cylindrical film (film thickness is 0.01-0.5mm) . Then, through printing, punching, heat sealing, etc., various kinds of disposable plastic bags such as degradable plastic shopping bags and food bags can be made. Its mechanical properties are similar to ordinary shopping bags of the same thickness. Compliant with disposable plastic paper size applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 9 1250184 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing A7 --------— R7__ V. Invention Description (7) Technical requirements for shopping bags. Its hygienicity also meets the requirements of the national standard g&9683-88 "Food packaging hygiene standards". After the degradable bag is used, if it is abandoned outdoors, it can be degraded into powder in 20-80 days, and then completely degraded by the natural environment. Dissipate, disappear from the senses. % Component 4 Light and biodegradable multi-component composition and amount (% by weight) Polyethylene resin 22.2 Dry 8.0 erucamide laurate 14 Lauric acid starting 5 4 Dibenzophenone oxime · 4 Dibutyl tin laurate Oxygen Soybean Oil 〇2 Ethylene epoxide sesame oil 0.4 Polyethylene glycol stearate 〇.8 Talc 60 According to the above formula, polyethylene resin and talc are weighed and placed in a high-speed stirred tank at 5 °C. According to the ratio, the epoxy soybean oil and the epoxy eucalyptus oil are weighed and injected into the sky. The preparation method can be carried out by referring to the first embodiment. Multicomponent particles were prepared. Example 5 - Sub-degradable plastic tableware The particles of the multi-component composition of Example 4 were added to high-density polyethylene (such as Daqing Petrochemical 5121A) or polypropylene (such as Yanshan Petrochemical 1300) at 5-40 (weight percent). Or polystyrene (such as Yanshan Petrochemical 666D) and other fats, the amount of resin used in this paper scale applies to the standard of the Guanzhong (CNSM4 specification (210 X 297 public)
----^---------rM 丨 (請先閱讀背面之注意事項再填寫本頁) 10 1250184 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（8 ) 為95-60(重量百分數）。經均勻混合並擠出成型月材，再經 熱成型，可製成一次性可降解塑膠餐盒、面碗、飲水杯、 託盤等。 製成的上述餐飲具符合GB9688-88國家《食品包裝用 聚丙烯成型品》衛生標準。如上述餐飲具使用後棄之戶外， 在前述自然界條件下，1-4個月可降解成粉末狀，並進一步 降解，被微生物利用，放出二氧化碳和水，達到完全被自 | 然環境消納，從感觀消失的效果。 實施例6 —次性可降解塑膠刀、叉、勺等速食用具 將實施例4的多元組合物的粒子按1 -1 〇(重量百分數） 加入到實施例5提到的聚乙烯（聚丙烯或聚苯乙烯）中，樹脂 用量為99-90(重量百分數）。經均勻混合，並置於注射成型 機中，可製成一次性可降解塑膠刀、叉、勺等速食用具。 其衛生性符合GB9688-88《食品包裝用聚丙烯成型品》的 國家衛生標準。降解性能在戶外自然界條件下1-2個月破 碎，4-6月可完全被自然環境消納，從感觀消失。 實施例7光和生物降解水土保持用塑膠護網 將實施例4的多元組合物的粒子按30-80(重量百分 數），加入到高密度聚乙烯（如齊魯石化DGDB2480)，或低 密度聚乙烯（如燕山石化2K1.5A)，或線性低密度聚乙烯（如 齊魯石化DFDA7059)，或乙烯-醋酸乙烯共聚物（如北京有 機化工廠EVA5/2)等樹脂中，樹脂用量為70-20(重量百分 數）。經均勻混合並送入擠出機料斗，通過擠出制網成型， * 可製成不同降解期的水土保持用塑膠護網。該護網應用前 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ^--------^---------線 (請先閱讀背面之注意事項再填寫本頁) 11 1250184 A7 B7 五、發明說明（9 後對土壌、植物無毒害，有良好的物理機械性能，可滿足 水土保持對護網使用的要求。最終也完全降解，被自然環 境消納。 實施例8 —次性可降解塑膠打火機外殼 將實施例1的多元組合物的粒子按丨„6(重量百分數）， 加入到聚笨乙烯或丙烯晴-苯乙烯共聚物樹脂中，樹脂用量 為99-94(重量百分數）。經均勻混合後，送入注射成型機， 可制得一次性可降解的塑膠打火機外殼。其物理機械性能 基本與普通塑膠打火機相當，然而它卻具有可在自然界中 良好降解的性能，成為對環境友好化的塑膠材料。 (請先閱讀背面之注意事項再填寫本頁} • n I n n 訂---------線4 本纸張尺度適用尹國國家標準（CNSM4規格（2J0 X 297公釐）----^---------rM 丨(Please read the notes on the back and fill out this page) 10 1250184 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 B7 V. Invention description (8) It is 95-60 (weight percent). After uniformly mixing and extruding the moon material, and then thermoforming, it can be made into a disposable degradable plastic lunch box, a noodle bowl, a drinking cup, a tray, and the like. The above-mentioned catering utensils are made to meet the sanitary standard of GB9688-88 national "polypropylene moldings for food packaging". If the above-mentioned tableware is abandoned after use, under the above-mentioned natural conditions, it can be degraded into powder in 1-4 months, and further degraded, used by microorganisms, releasing carbon dioxide and water, and completely absorbed by the environment. The effect of disappearing from the senses. Example 6 - Sub-degradable plastic knife, fork, spoon and the like. The particles of the multi-component composition of Example 4 were added to the polyethylene (polypropylene) mentioned in Example 5 in a weight ratio of 1:1 (weight percent). Or polystyrene), the amount of the resin is from 99 to 90 (weight percent). After being uniformly mixed and placed in an injection molding machine, it can be made into a disposable degradable plastic knife, fork, spoon and the like. Its hygienicity meets the national sanitary standard of GB9688-88 "Polypropylene molded products for food packaging". The degradation performance is broken in the outdoor natural conditions for 1-2 months, and it can be completely absorbed by the natural environment from April to June, and disappears from the sense. Example 7 Light and Biodegradable Soil and Water Conservation Plastic Grid The particles of the multicomponent composition of Example 4 were added to a high density polyethylene (e.g., Qilu Petrochemical DGDB 2480), or low density polyethylene, in an amount of 30-80 (weight percent). (such as Yanshan Petrochemical 2K1.5A), or linear low-density polyethylene (such as Qilu Petrochemical DFDA7059), or ethylene-vinyl acetate copolymer (such as Beijing Organic Chemical Plant EVA5/2) and other resins, the amount of resin is 70-20 ( Weight percentage). It is uniformly mixed and sent to the extruder hopper, and is formed by extrusion and meshing. * It can be used as a plastic net for soil and water conservation with different degradation periods. Before the application of the net, the paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ^--------^--------- line (please read the back first) Note: Please fill in this page again) 11 1250184 A7 B7 V. Invention description (9 After being harmless to soil and plants, it has good physical and mechanical properties, can meet the requirements of soil and water conservation for the use of nets. Finally, it is completely degraded and naturally Example 8 - Sub-degradable plastic lighter shell The particles of the multi-component composition of Example 1 were added to a polystyrene or acrylonitrile-styrene copolymer resin in an amount of 6% (by weight). The amount of resin is 99-94 (weight percent). After homogeneous mixing, it can be sent to the injection molding machine to produce a disposable degradable plastic lighter shell. Its physical and mechanical properties are basically the same as ordinary plastic lighters, but it has Good degradation properties in nature, becoming environmentally friendly plastic materials. (Please read the notes on the back and fill out this page again) • n I nn Book --------- Line 4 Paper Size Applicable to Yin Guo National Standard (CNSM4 Regulation) Grid (2J0 X 297 mm)