TWI733195B - 生物可分解材料 - Google Patents
生物可分解材料 Download PDFInfo
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- TWI733195B TWI733195B TW108133554A TW108133554A TWI733195B TW I733195 B TWI733195 B TW I733195B TW 108133554 A TW108133554 A TW 108133554A TW 108133554 A TW108133554 A TW 108133554A TW I733195 B TWI733195 B TW I733195B
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- 239000000463 material Substances 0.000 title claims abstract description 34
- 230000015556 catabolic process Effects 0.000 claims abstract description 21
- 238000006731 degradation reaction Methods 0.000 claims abstract description 21
- 239000004014 plasticizer Substances 0.000 claims abstract description 21
- 102000004190 Enzymes Human genes 0.000 claims abstract description 16
- 108090000790 Enzymes Proteins 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 5
- 150000002148 esters Chemical class 0.000 claims description 20
- 239000004800 polyvinyl chloride Substances 0.000 claims description 14
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 150000001298 alcohols Chemical class 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- 239000003549 soybean oil Substances 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 239000003925 fat Substances 0.000 claims description 3
- 239000000378 calcium silicate Substances 0.000 claims description 2
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 230000000704 physical effect Effects 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 239000012620 biological material Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 20
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 231100000770 Toxic Equivalency Factor Toxicity 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 231100000315 carcinogenic Toxicity 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 241001148471 unidentified anaerobic bacterium Species 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241001214714 Niea Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- YXVJNOXXPKIWIM-UHFFFAOYSA-N n-(2-hydroxyethyl)-n-(2-hydroxypropyl)nitrous amide Chemical compound CC(O)CN(N=O)CCO YXVJNOXXPKIWIM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
一種生物可分解材料，其包含：聚氯乙烯粉100 phr；可塑劑 40~160 phr；酶 0.5~4 phr；以及該生物可分解材料於無氧環境下之降解率為90%以上；本發明利用可塑劑與少量酶成分，達到高度可降解的特性，且因其中未添加任何天然生分解材料，例如澱粉或植物纖維粉體，因此不會導致產品的物性或機械性質下降，且本發明係於無氧環境中透過厭氧菌產生降解的效果，因此利用本發明所製得的產品在一般環境中/含氧環境中不產生降解，可維持良好的品質，係一新穎且創新之材料。
Description
一種生物可分解的材料，特別是一種生物可分解且燃燒也不產生戴奧辛的材料。
聚氯乙烯(Polyvinyl Chloride, PVC)目前的全球產能已接近6,000萬公噸，幾乎可算是全球產量最大的泛用塑膠之一，其耐酸鹼、阻燃以及加工性良好等特性，被廣泛應用於建築材料、工業製品以及民生用品等領域中。
然而，聚氯乙烯雖然應用性極佳，但隨著近年來環保意識的抬頭，此種材料無法被環境分解以及焚化時會產生致癌污染物戴奧辛等環境污染或人體傷害等問題，都使其應用受到限制。
為了改善聚氯乙烯無法被環境分解的問題，逐漸發展出透過添加一些天然全生分解材料，例如澱粉或植物纖維粉體，來達到減少聚氯乙烯使用量的目的，但是添加大量的天然生分解材料卻會導致聚氯乙烯原本的物性與機械性質下降。
因此，現階段有必要開發一種不僅具有生物可分解特性且燃燒時不產生戴奧辛或含量極低，並同時可以維持聚氯乙烯物性與機械性質的新興材料，順應市場需要並同時達到環境保護的訴求。
為了克服現有聚氯乙烯材料無法被環境分解與焚化時會產生致癌污染物戴奧辛的缺點，以及添加天然全生分解材料會導致物性與機械性質下降等種種問題，本發明提供一種生物可分解材料，其包含：聚氯乙烯粉 (Polyvinyl Chloride, PVC) 100 phr；可塑劑 40~160 phr；酶 0.5~4 phr；以及該生物可分解材料於無氧環境下之降解率為90%以上。
其中，該可塑劑為不含苯環的可塑劑。
較佳地，該可塑劑為不含苯環且化學結構為線性的可塑劑。
更佳地，該可塑劑包含大豆油。
其中，該酶包含酯類酶。
較佳地，該酯類包含無機酸與醇合成的酯類、油脂與醇合成的酯類、羧酸氯化衍生物的酯類或前述三種酯類的混合物。
更佳地，該無機酸包含磷酸或硫酸。
其中，該生物可分解材料中進一步包含一填充料 20 phr以下。
較佳地，該填充料包含碳酸鈣。
藉由上述說明可知，本發明具有以下優點：
1. 本發明係於無氧環境中透過厭氧菌食用塑膠材料達到降解的效果，因此利用本發明所製得的產品在一般環境中/含氧環境中不產生降解，可維持良好的品質，待廢棄品回收時再營造無氧環境使材料降解；經測試，本發明不僅具有高度降解能力，且焚化後戴奧辛含量僅國家標準含量之千分之一，遠低於國家規定的標準值。
2. 本發明利用可塑劑與少量酶成分，達到整體塑膠材料高度可降解的特性，且因其中未添加任何天然全生分解材料，例如澱粉或植物纖維粉體，因此不會導致產品的物性或機械性質下降，係一新穎且創新之材料。
一種生物可分解材料，其包含：
聚氯乙烯粉 (Polyvinyl Chloride, PVC) 100 phr；
可塑劑 40~160 phr；以及
酶 0.5~4 phr。
其中，上述該可塑劑較佳是化學結構中不含苯環的可塑劑，更佳的是不含苯環且化學結構為線性的可塑劑，例如大豆油。
該酶(或可稱為酵素)則主要為酯類材料。所謂的酯類包含無機酸(例如以磷酸或硫酸等)與醇合成的酯類、油脂(官能基:RCOOR”)與醇合成的酯類、羧酸氯化衍生物的酯類或前述三種酯類的混合物。該可塑劑與該酶的搭配提供本發明達到生物可分解的功效。本發明所謂之生物可分解指得是利用本發明材料所製得之產品，其整體(包含聚氯乙烯塑膠成分)在一段時間內可達到高度(至少90%)或甚至是完全降解。
本發明利用不含苯環且化學結構為線性的該可塑劑以及酯類酶所產生之降解機制，主要是兩者產生的添加，可使本發明進行酶分解進而誘使環境中大量厭氧菌食用塑膠成分材料，並逐步消化分解成數種氣體，達到降解之功效。
進一步地，本發明可添加填充料 20phr或以下，例如碳酸鈣、矽酸鈣、硫酸鈣、滑石粉或二氧化鈦等，達到降低成本之效果，且不影響本發明降解與不產生戴奧辛之效果。
請參考下表1，其為證實本發明確效性的相關測試樣品參數：
| 樣品代號 | PVC粉含量 | 可塑劑含量 | 酶含量 |
| POSITIVE | 0 (全生分解材料100phr) | 0 | 0 |
| NEGETIVE | 100phr | 0 | 0 |
| 1565 (本發明) | 100phr | 40 phr | 1.5 phr |
| 1566 (對照組) | 100phr | 40 hr | 0 |
表1中本發明代號1565之樣品中，可塑劑較佳為大豆油，酶則較佳為無機酸(例如以磷酸或硫酸等)與醇合成的酯類，更可進一步包含碳酸鈣20phr或1.5~5phr的安定劑，作為填充或加工添加助劑，但經本發明實驗確認，添加此些填充或加工添加助劑並不影響本發明之降解與不產生戴奧辛之效果。另外，上述表1中之實施範例僅為本發明最佳樣品效果呈現，並非用以限定本發明僅包含該實施例或僅該範圍能實施，上述本發明所指之各成分範圍或其他可選用成分皆已經實驗證明其確效性。
請參考下表2、圖1以及圖2，本發明利用上述樣品以片材(厚度1.15 mm，單位重量686 g/m
2)形式進行降解測試，採用無氧環境ASTM D5511-12之厭氧菌生物降解測試作為測試標準，進行為期一年之降解測試。自表2與圖1的氣體含量測試，本發明之樣品所累積產生之氣體相較於其他組別所累積產生之氣體最多，可證實本發明1565樣品具有降解之效果，且本發明相較於POSITIVE可全生分解之樣品於一定時間內所產生的氣體量更多，可證實本發明有加速塑膠降解之功能，而NEGETIVE與編號1566對照組兩個樣品則幾乎沒有氣體產生，無降解之跡象。表2與圖2可看出為期一年的降解試驗，本發明1565樣品具有降解之效果，且降解率可達近100%，甚至高於POSITIVE可全生分解之樣品的降解率，而NEGETIVE與編號1566對照組兩個樣品則無法降解或降解率極低。
表2。
| NEGETIVE | POSITIVE | 1565 (本發明) | 1566 (對照組) | |
| 累積氣體體積(mL) | 3175.9 | 11454.1 | 16650.6 | 3171.2 |
| 甲烷含量 (CH 4%) | 43.7 | 35.0 | 49.3 | 43.6 |
| 甲烷體積 (CH 4 mL) | 1387.2 | 4014.6 | 8205.7 | 1381.4 |
| 甲烷質量(CH 4g) | 0.99 | 2.87 | 5.86 | 0.99 |
| 二氧化碳含量 (CO 2%) | 36.5 | 42.8 | 42.8 | 42.5 |
| 二氧化碳體積 (CO 2mL) | 1159.8 | 4905.5 | 7120.8 | 1348.1 |
| 二氧化碳質量 (CO 2g) | 2.28 | 9.64 | 13.99 | 2.65 |
| 降解質量 (g) | 1.43 | 1.36 | 4.78 | 8.21 |
| 降解率 (%) | -0.8 | 79.3 | 91.3 | 0.4 |
進一步地，本發明將前述表1本發明所製得之樣品片材進行焚化，所得的灰渣利用NIEA M801.13B進行戴奧辛檢測測試，此測試標準戴奧辛含量大於1.0 ng I-TEQ/g為有檢出，但本發明之灰渣中戴奧辛及呋喃僅測得0.001ng I-TEQ/g，低於國家環保標準，係一環保又品質優異之產品。
請參考表3，其為本發明利用表1所述1565樣品片材所測試之物性與機械性質數。經測試，本發明在具有高度降解特性下，依然維持有良好的機械性質，更相較於一般無法分解之塑料差異不大。
表3。
| 測試性能 | 測試標準 | 數據 | |
| 拉力 (Tensile Strength) | JIS-K-6772 拉力速度: 200 mm/min | 經 (Warp) | 22.38 (kg/3cm) |
| 緯 (Woof) | 18.35 (kg/3cm) | ||
| 伸張率 (Elogation) | JIS-K-6772 同上，切斷時測試 | 經 (Warp) | 143 (%) |
| 緯 (Woof) | 169 (%) | ||
| 撕裂強度 (Tearing Strength) | JIS-K-6772 | 經 (Warp) | 2.53 (kg) |
| 緯 (Woof) | 2.36 (kg) | ||
| 剝離強度 (Strip Off Strength) | JIS-K-6772 | 經 (Warp) | 2.8 (kg/3cm) |
| 緯 (Woof) | 1.89 (kg/3cm) | ||
| 常溫屈曲性 (Flexulus Resistance) | JIS-K-6545 (25 oC) | 經 (Warp) | 10000次/5級 (Timew/Grade 次) |
| 緯 (Woof) | |||
| 破裂強度 (Bursting Strength) | Mullen Type MEULEN 型破裂測試 | 10.5 (kg/cm 2) | |
| 不黏著性 (70 oC) (Blocking Test) | JIS-K-6772 | 5 (級 Grade) | |
| 色落試驗 (Color Fastness Test / Rubbing Test) | JIS-K-6772 | 乾 (Dry) | 5 (級 Grade) |
| 濕 (Wet) | 5 (級 Grade) |
本發明所提供的材料配方可應用於製造建築材料、工業製品以及民生用品，特別是因材料具有彈性，特別適用於製造人造皮革之產品。
上述僅為本發明的較佳實施例而已，並非用以限定本發明主張的權利範圍，凡其它未脫離本發明所揭示的精神所完成的等效改變或修飾，均應包括在本發明的主張範圍內。
圖1為本發明各實施例之氣體累積含量測試。
圖2為本發明各實施例之降解測試。
Claims (6)
- 一種生物可分解材料，其包含：聚氯乙烯粉(Polyvinyl Chloride,PVC)100phr；可塑劑40~160phr，該可塑劑為不含苯環且化學結構為線性的可塑劑；酶0.5~4phr，該酶包含酯類酶；以及該生物可分解材料於無氧環境下之降解率為90%以上。
- 如申請專利範圍第1項之生物可分解材料，該可塑劑包含大豆油。
- 如申請專利範圍第1或2項之生物可分解材料，該酯類包含無機酸與醇合成的酯類、油脂與醇合成的酯類、羧酸氯化衍生物的酯類或前述三種酯類的混合物。
- 如申請專利範圍第3項之生物可分解材料，該無機酸包含磷酸或硫酸。
- 如申請專利範圍第1或2項之生物可分解材料，該生物可分解材料中進一步包含一填充料20phr或20phr以下。
- 如申請專利範圍第5項之生物可分解材料，該填充料包含碳酸鈣、矽酸鈣、硫酸鈣、滑石粉或二氧化鈦。
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| TW108133554A TWI733195B (zh) | 2019-09-18 | 2019-09-18 | 生物可分解材料 |
| US16/666,733 US20210079205A1 (en) | 2019-09-18 | 2019-10-29 | Bio-Degradable Composition |
| US17/731,404 US20220259407A1 (en) | 2019-09-18 | 2022-04-28 | Bio-Degradable Artificial Leather Composition |
| US19/303,504 US20250368813A1 (en) | 2019-09-18 | 2025-08-19 | Bio-degradable artificial leather composition |
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|---|---|---|---|---|
| TW201319149A (zh) * | 2011-10-11 | 2013-05-16 | Bilcare Ltd | 藥物包裝用可生物分解的聚氯乙烯薄膜及其製備的方法 |
| CN103842428A (zh) * | 2011-09-30 | 2014-06-04 | 陶氏环球技术有限责任公司 | 将聚氯乙烯与基于生物质的增塑剂混合的方法 |
| CN107337872A (zh) * | 2017-06-12 | 2017-11-10 | 上海延锋金桥汽车饰件系统有限公司 | 一种汽车内饰件用低气味pvc粉末及其制备方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103842428A (zh) * | 2011-09-30 | 2014-06-04 | 陶氏环球技术有限责任公司 | 将聚氯乙烯与基于生物质的增塑剂混合的方法 |
| TW201319149A (zh) * | 2011-10-11 | 2013-05-16 | Bilcare Ltd | 藥物包裝用可生物分解的聚氯乙烯薄膜及其製備的方法 |
| CN107337872A (zh) * | 2017-06-12 | 2017-11-10 | 上海延锋金桥汽车饰件系统有限公司 | 一种汽车内饰件用低气味pvc粉末及其制备方法 |
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