JP2006022307A - Master batch pellet for thermoplastic resin composition and thermoplastic resin composition - Google Patents
Master batch pellet for thermoplastic resin composition and thermoplastic resin composition Download PDFInfo
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- JP2006022307A JP2006022307A JP2005082050A JP2005082050A JP2006022307A JP 2006022307 A JP2006022307 A JP 2006022307A JP 2005082050 A JP2005082050 A JP 2005082050A JP 2005082050 A JP2005082050 A JP 2005082050A JP 2006022307 A JP2006022307 A JP 2006022307A
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- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 131
- 239000011342 resin composition Substances 0.000 title claims abstract description 103
- 239000008188 pellet Substances 0.000 title claims abstract description 60
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 47
- 239000002245 particle Substances 0.000 claims abstract description 138
- 238000002485 combustion reaction Methods 0.000 claims abstract description 104
- 239000003054 catalyst Substances 0.000 claims abstract description 69
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 11
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- 239000007900 aqueous suspension Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229920003169 water-soluble polymer Polymers 0.000 claims description 9
- 125000000129 anionic group Chemical group 0.000 claims description 7
- 239000003945 anionic surfactant Substances 0.000 claims description 7
- 239000003093 cationic surfactant Substances 0.000 claims description 7
- 239000002736 nonionic surfactant Substances 0.000 claims description 7
- 125000002091 cationic group Chemical group 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 abstract description 15
- 230000001737 promoting effect Effects 0.000 abstract description 14
- 239000000126 substance Substances 0.000 abstract description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 87
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 33
- 239000010408 film Substances 0.000 description 30
- 238000004519 manufacturing process Methods 0.000 description 30
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 23
- 238000000034 method Methods 0.000 description 23
- 229920005989 resin Polymers 0.000 description 22
- 239000011347 resin Substances 0.000 description 22
- 239000000843 powder Substances 0.000 description 21
- 238000011156 evaluation Methods 0.000 description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 16
- 229920001684 low density polyethylene Polymers 0.000 description 15
- 239000004702 low-density polyethylene Substances 0.000 description 15
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 13
- 238000002156 mixing Methods 0.000 description 13
- -1 platinum group metals Chemical class 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000567 combustion gas Substances 0.000 description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 description 11
- 239000001569 carbon dioxide Substances 0.000 description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000001125 extrusion Methods 0.000 description 11
- 229910052763 palladium Inorganic materials 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 150000002894 organic compounds Chemical class 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 229920013716 polyethylene resin Polymers 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 235000013372 meat Nutrition 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- 235000013311 vegetables Nutrition 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000010849 combustible waste Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 239000013502 plastic waste Substances 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- SNNYSJNYZJXIFE-UHFFFAOYSA-L 2-(benzenesulfinyl)ethylsulfinylbenzene;palladium(2+);diacetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O.C=1C=CC=CC=1S(=O)CCS(=O)C1=CC=CC=C1 SNNYSJNYZJXIFE-UHFFFAOYSA-L 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000012494 Quartz wool Substances 0.000 description 1
- 229910000629 Rh alloy Inorganic materials 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008131 herbal destillate Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011998 white catalyst Substances 0.000 description 1
Abstract
Description
本発明は、熱可塑性樹脂組成物の着色を抑制できるとともに、優れた燃焼促進効果が付与された熱可塑性樹脂組成物、詳述すれば、焼却時に完全燃焼を促進し、有害な有機化合物の発生を抑制できる熱可塑性樹脂組成物及び該熱可塑性樹脂組成物に用いるマスターバッチペレットに関するものである。 The present invention is a thermoplastic resin composition that can suppress coloring of the thermoplastic resin composition and has an excellent combustion promotion effect, and more specifically, promotes complete combustion during incineration and generates harmful organic compounds. It is related with the masterbatch pellet used for the thermoplastic resin composition which can suppress this, and this thermoplastic resin composition.
近年、生活様式の変化や生活水準、所得水準の向上等により、新しい商品があふれ、豊かな物質文化が形成されたが、それにともない工場や家庭から排出される一般廃棄物および産業廃棄物が多量に発生しており、これらの処理に関する問題は大きな社会問題ともなってきている。 In recent years, due to lifestyle changes, improvement of living standards and income levels, new products have overflowed and a rich material culture has been formed, but with this, a large amount of general and industrial waste discharged from factories and households. The problems related to these treatments have also become major social problems.
とりわけ、合成樹脂はその優れた機械的、物理的性質及び成形性から現代社会においては欠くことのできない材料としてあらゆる分野で膨大な量が使用されており、それに伴ってその廃棄物の総量も年間数百万トン以上にものぼっている。したがって、合成樹脂の廃棄物処理は一般廃棄物及び産業廃棄物に関する問題の中でも特に重要な課題となってきている。また、合成樹脂は人類に与えられた貴重な資源である石油を原材料としたものであることから、一旦使用した後でも再利用あるいはエネルギー源として活用する技術を確立することが強く求められている。 In particular, synthetic resins are used in large quantities in all fields as materials that are indispensable in modern society because of their excellent mechanical, physical properties and moldability. Over millions of tons. Therefore, waste treatment of synthetic resin has become a particularly important issue among the problems related to general waste and industrial waste. In addition, since synthetic resins are made from petroleum, which is a valuable resource given to humankind, there is a strong demand to establish technology that can be reused or used as an energy source even after being used once. .
これらの廃棄物処理のうち、一般廃棄物に関しては、一般にポリエチレン樹脂で代表される熱可塑性樹脂に各種顔料を添加した自治体指定のプラスチック製ごみ袋に詰められたごみを、自治体所有の焼却炉で焼却するという方法が多く採られている。 Of these waste treatments, for general waste, waste packed in plastic garbage bags designated by local governments, in which various pigments are added to thermoplastic resins typically represented by polyethylene resin, is stored in an incinerator owned by the local government. Many methods of incineration are used.
近年における商品の特性向上は、安全性や機能性等の本質的特性を有していることはもちろん、殊に視覚的、心理的な面からの改良と環境面からの改良が強く要求されており、上記買物袋やごみ袋等の品質特性の改良もその傾向が強く、使用に際して優れた透明性と低い彩度とを有していることが強く要求されている。 In recent years, the improvement of product characteristics has essential characteristics such as safety and functionality, as well as improvements in visual and psychological aspects and environmental aspects. In addition, improvement in quality characteristics of the shopping bags and garbage bags has a strong tendency, and it is strongly required to have excellent transparency and low saturation when used.
更に、環境面からプラスチック製の買物袋やごみ袋等は、使用済後に廃棄処分する必要があるが、可燃ごみの焼却処理には以下のような問題があった。即ち、燃焼中に発生するＮＯｘによる大気汚染、焼却後に多量に発生する残灰や燃え残りを処分する埋め立て地等の不足、残灰中の有害成分の埋め立て地での漏洩、あるいは有害なダイオキシンの生成等の問題に加えて、可燃ごみ中に燃焼カロリーの高いプラスチック廃棄物やプラスチック製ごみ袋が多量に含まれている場合には、焼却炉の炉内温度の上昇の原因となって焼却炉が破損する等の問題があった。 Furthermore, from the environmental viewpoint, plastic shopping bags, garbage bags, etc. need to be disposed of after being used, but there are the following problems in the incineration treatment of combustible waste. That is, air pollution due to NOx generated during combustion, shortage of residual ash generated after incineration and landfill to dispose of unburned residue, leakage of harmful components in residual ash in landfill, or harmful dioxin In addition to problems such as generation, if the combustible waste contains a large amount of high-calorie plastic waste or plastic waste bags, the incinerator will increase the temperature in the incinerator. There were problems such as damage.
従来、燃焼効率を付与したプラスチック製の買物袋やごみ袋として、熱可塑性樹脂中に長軸径が０．０２〜２．０μｍの含水酸化第二鉄粒子又は平均粒子径０．０３〜１．０μｍの酸化鉄粒子を０．１〜２０．０重量％含有させたプラスチック製の買物袋やごみ袋が既に実用化されている。（特許第２８２４２０３号、特許第２９０５６９３号） Conventionally, as a plastic shopping bag or garbage bag imparted with combustion efficiency, hydrous ferric oxide particles having a major axis diameter of 0.02 to 2.0 μm or an average particle diameter of 0.03 to 1. Plastic shopping bags and garbage bags containing 0.1 to 20.0% by weight of 0 μm iron oxide particles have already been put into practical use. (Patent No. 2,824,203, Patent No. 2,905,693)
また、無機質担体に白金族元素を０．００１〜０．２ｗｔ％担持させた微粒子の燃焼促進剤を、該白金族元素の濃度が０．５〜１００ｐｐｍになるように熱可塑性樹脂に配合した熱可塑性樹脂組成物が開示されている。（特開２００２−１６７５１６号公報） Further, a heat in which a particulate combustion accelerator in which 0.001 to 0.2 wt% of a platinum group element is supported on an inorganic carrier is blended with a thermoplastic resin so that the concentration of the platinum group element is 0.5 to 100 ppm. A plastic resin composition is disclosed. (JP 2002-167516 A)
一方、白金族金属は、非常に高価な金属であるが、触媒反応における歴史は非常に古く、とくに白金とパラジウムの触媒作用は種々の反応において広く研究されてきた。白金とパラジウムが炭化水素の水素添加、脱水素の好触媒であることはよく知れている。また、アンモニア酸化に白金や白金−ロジウム合金が使われ（Ｋｕｈｌｍａｎｎ法）、炭化水素の酸化や含酸素化合物の分解反応に白金やパラジウムが金属の形で使われており、各種燃焼触媒用途にも幅広く利用されている。 On the other hand, platinum group metals are very expensive metals, but the history of catalysis is very old. In particular, the catalytic action of platinum and palladium has been extensively studied in various reactions. It is well known that platinum and palladium are good catalysts for hydrocarbon hydrogenation and dehydrogenation. In addition, platinum and platinum-rhodium alloys are used for ammonia oxidation (Kuhlmann method), and platinum and palladium are used in the form of metals for oxidation of hydrocarbons and decomposition of oxygen-containing compounds. Widely used.
強度や安全性等の本質的特性を有していることはもちろん、使用後の焼却時に完全燃焼を促進して有害な有機化合物の発生を抑制でき、且つ、所望の色調に着色可能な優れた透明性を有する熱可塑性樹脂組成物は、現在最も要求されているところであるが、上記諸特性を十分満足する熱可塑性樹脂組成物は未だ得られていない。 In addition to having essential characteristics such as strength and safety, it is possible to suppress the generation of harmful organic compounds by promoting complete combustion at the time of incineration after use, and excellent coloration to a desired color tone A thermoplastic resin composition having transparency is currently most demanded, but a thermoplastic resin composition that sufficiently satisfies the above properties has not yet been obtained.
即ち、前出特許文献１及び２記載の技術は、特定の酸化鉄粒子の燃焼促進作用を利用したものであって、焼却処分時に低温、低酸素濃度下であっても熱可塑性樹脂を完全燃焼させることができるという効果を有しているが、酸化鉄特有の赤色，黄色等に着色することは避けられず、このため、酸化鉄の配合量を少なくしても、例えば、野菜や肉等の食料品、衣料品等の包装用途に好まれる無色透明性を得ることは不可能であった。 That is, the technologies described in the above-mentioned Patent Documents 1 and 2 utilize the combustion promoting action of specific iron oxide particles, and completely burn the thermoplastic resin even at low temperatures and low oxygen concentrations during incineration. Although it has the effect of being able to be made, it is inevitable that the iron oxide is colored in red, yellow, etc., so even if the amount of iron oxide is reduced, for example, vegetables and meat It was impossible to obtain the colorless transparency preferred for packaging applications such as foodstuffs and clothing.
また、前出特許文献３記載の熱可塑性樹脂組成物は、白金族元素を担持した白色無機質微粒子を配合しているため、無色透明な色調が得られ、且つその燃焼促進作用を利用して、焼却時の完全燃焼を促進させることができるが、十分な燃焼促進効果を得ることは困難であった。 Moreover, since the thermoplastic resin composition described in Patent Document 3 contains white inorganic fine particles supporting a platinum group element, a colorless and transparent color tone is obtained, and its combustion promoting action is used. Although complete combustion at the time of incineration can be promoted, it has been difficult to obtain a sufficient combustion promotion effect.
そこで、本発明は、安全性等の本質的特性を有していることはもちろん、焼却時に完全燃焼を促進することで有害な有機化合物の発生を抑制でき、且つ所望の色調に着色可能な優れた透明性を有する熱可塑性樹脂組成物及び該熱可塑性樹脂組成物を製造するためのマスターバッチペレットを提供することを目的とする。 Therefore, the present invention not only has essential characteristics such as safety, but also can suppress the generation of harmful organic compounds by promoting complete combustion during incineration, and can be colored to a desired color tone. Another object of the present invention is to provide a thermoplastic resin composition having high transparency and master batch pellets for producing the thermoplastic resin composition.
前記技術的課題は、次の通りの本発明によって達成できる。 The technical problem can be achieved by the present invention as follows.
即ち、本発明は、熱可塑性樹脂中に白色燃焼触媒を配合した熱可塑性樹脂組成物用マスターバッチペレットであって、前記白色燃焼触媒は平均粒子径が０．１〜１．０μｍの酸化アルミニウム、酸化ケイ素、炭酸カルシウム又は酸化チタンの中から選ばれる１種以上の無機担体粒子の表面に、平均粒子径１０ｎｍ以下の金属Ｐｄコロイド粒子を０．００１〜０．１０ｗｔ％担持させた白色燃焼触媒であり、該白色燃焼触媒を熱可塑性樹脂に２．０〜６０ｗｔ％配合したことを特徴とする熱可塑性樹脂組成物用マスターバッチペレットである（本発明１）。 That is, the present invention is a master batch pellet for a thermoplastic resin composition in which a white combustion catalyst is blended in a thermoplastic resin, wherein the white combustion catalyst has an average particle diameter of 0.1 to 1.0 μm of aluminum oxide, A white combustion catalyst in which 0.001 to 0.10 wt% of metal Pd colloidal particles having an average particle diameter of 10 nm or less are supported on the surface of one or more inorganic carrier particles selected from silicon oxide, calcium carbonate, or titanium oxide. A master batch pellet for a thermoplastic resin composition, wherein the white combustion catalyst is blended in a thermoplastic resin in an amount of 2.0 to 60 wt% (Invention 1).
また、本発明は、無機担体粒子が酸化アルミニウムである前記熱可塑性樹脂組成物用マスターバッチペレットである（本発明２）。 Moreover, this invention is the said masterbatch pellet for thermoplastic resin compositions whose inorganic support particle | grains are aluminum oxide (this invention 2).
また、本発明は、白色燃焼触媒が、陽イオン性、陰イオン性若しくは非イオン性の界面活性剤又は水溶性高分子から選ばれる１種以上を含む金属Ｐｄヒドロゾルと無機担体粒子粉末を含む水懸濁液とを接触混合させ、無機担体粒子表面に金属Ｐｄコロイド粒子を電気的に担持させた白色燃焼触媒であることを特徴とする本発明１又は２の熱可塑性樹脂組成物用マスターバッチペレットである（本発明３）。 The present invention also provides a water in which the white combustion catalyst contains a metal Pd hydrosol containing at least one selected from a cationic, anionic or nonionic surfactant or a water-soluble polymer, and an inorganic carrier particle powder. A masterbatch pellet for a thermoplastic resin composition of the present invention 1 or 2, characterized in that it is a white combustion catalyst obtained by contacting and mixing a suspension and electrically supporting metal Pd colloidal particles on the surface of inorganic carrier particles (Invention 3).
また、本発明は、熱可塑性樹脂中に白色燃焼触媒を配合した熱可塑性樹脂組成物であって、前記白色燃焼触媒は平均粒子径が０．１〜１．０μｍの酸化アルミニウム、酸化ケイ素、炭酸カルシウム又は酸化チタンの中から選ばれる１種以上の無機担体粒子の表面に、平均粒子径１０ｎｍ以下の金属Ｐｄコロイド粒子を０．００１〜０．１０ｗｔ％担持させた白色燃焼触媒であり、該白色燃焼触媒を熱可塑性樹脂に０．１〜２．０ｗｔ％配合したことを特徴とする熱可塑性樹脂組成物である（本発明４）。 The present invention also relates to a thermoplastic resin composition in which a white combustion catalyst is blended in a thermoplastic resin, wherein the white combustion catalyst has an average particle size of 0.1 to 1.0 μm of aluminum oxide, silicon oxide, carbonic acid. A white combustion catalyst in which 0.001 to 0.10 wt% of metal Pd colloidal particles having an average particle diameter of 10 nm or less is supported on the surface of one or more inorganic carrier particles selected from calcium or titanium oxide, A thermoplastic resin composition characterized by blending a combustion catalyst in a thermoplastic resin in an amount of 0.1 to 2.0 wt% (Invention 4).
また、本発明は、無機担体粒子が酸化アルミニウムである請求項４の熱可塑性樹脂組成物である（本発明５）。 Moreover, this invention is a thermoplastic resin composition of Claim 4 whose inorganic support particle | grains are aluminum oxide (this invention 5).
また、本発明は、白色燃焼触媒が、陽イオン性、陰イオン性若しくは非イオン性の界面活性剤又は水溶性高分子から選ばれる１種以上を含む金属Ｐｄヒドロゾルと無機担体粒子粉末を含む水懸濁液とを接触混合させ、無機担体粒子表面に金属Ｐｄコロイド粒子を電気的に担持させた白色燃焼触媒であることを特徴とする本発明４又は５の熱可塑性樹脂組成物である（本発明６）。 The present invention also provides a water in which the white combustion catalyst contains a metal Pd hydrosol containing at least one selected from a cationic, anionic or nonionic surfactant or a water-soluble polymer, and an inorganic carrier particle powder. The thermoplastic resin composition of the present invention 4 or 5, wherein the thermoplastic resin composition of the present invention is a white combustion catalyst in which a suspension is contact-mixed and the metal Pd colloidal particles are electrically supported on the surface of the inorganic carrier particles (this book) Invention 6).
本発明に係る熱可塑性樹脂組成物用マスターバッチペレットは、該マスターバッチペレットを用いて作製した熱可塑性樹脂組成物中に白色燃焼触媒を容易に均一に分散させることができるので、熱可塑性樹脂組成物用マスターバッチペレットとして好適である。 The master batch pellet for the thermoplastic resin composition according to the present invention can easily and uniformly disperse the white combustion catalyst in the thermoplastic resin composition produced using the master batch pellet. Suitable as a master batch pellet for goods.
本発明に係る熱可塑性樹脂組成物は、強度や安全性等の本質的特性を有していることはもちろん、使用後の焼却時に完全燃焼を促進して有害な有機化合物の発生を抑制でき、且つ、透明性が高く所望の色調に容易に着色することができるので、野菜や肉等の食料品、衣料品の包装用途等の幅広い用途に好適である。 The thermoplastic resin composition according to the present invention not only has essential properties such as strength and safety, but can promote the complete combustion during incineration after use and suppress the generation of harmful organic compounds, And since it is highly transparent and can be easily colored to a desired color tone, it is suitable for a wide range of uses such as foods such as vegetables and meat, and packaging for clothing.
次に、本発明実施にあたっての諸条件について述べる。 Next, various conditions for carrying out the present invention will be described.
まず、本発明における白色燃焼触媒について述べる。 First, the white combustion catalyst in the present invention will be described.
本発明における白色燃焼触媒は、平均粒子径０．１〜１．０μｍの酸化アルミニウム、酸化ケイ素、炭酸カルシウム又は酸化チタンの中から選ばれる１種以上の無機担体粒子の表面に、平均粒子径１０ｎｍ以下の金属Ｐｄコロイド粒子を０．００１〜０．１０ｗｔ％担持させたものである。 The white combustion catalyst in the present invention has an average particle diameter of 10 nm on the surface of one or more inorganic carrier particles selected from aluminum oxide, silicon oxide, calcium carbonate or titanium oxide having an average particle diameter of 0.1 to 1.0 μm. The following metal Pd colloidal particles are supported on 0.001 to 0.10 wt%.
本発明における無機担体粒子としては、通常に市販されているα型、γ型等の酸化アルミニウム、酸化ケイ素、炭酸カルシウム、またはルチル型、アナターゼ型の酸化チタンの中から選ばれる１種以上を使用することができる。好ましくは、熱可塑性樹脂と加熱混練時に、熱的に安定で樹脂を熱劣化させることのないα型の酸化アルミニウムである。 As the inorganic carrier particles in the present invention, one or more kinds selected from commercially available aluminum oxides such as α-type and γ-type, silicon oxide, calcium carbonate, or rutile-type and anatase-type titanium oxide are used. can do. Preferably, it is α-type aluminum oxide which is thermally stable and does not thermally deteriorate the resin during kneading with a thermoplastic resin.
本発明における無機担体粒子の平均粒子径は０．１〜１．０μｍである。平均粒子径が１．０μｍを超える場合には、熱可塑性樹脂組成物の透明性が低下するため、好ましくない。平均粒子径が０．１μｍ未満の場合は、熱可塑性樹脂中に均一分散し難くなるため、好ましくない。好ましくは０．１〜０．８μｍ、より好ましくは０．３〜０．８μｍである。 The average particle diameter of the inorganic carrier particles in the present invention is 0.1 to 1.0 μm. When the average particle diameter exceeds 1.0 μm, the transparency of the thermoplastic resin composition is lowered, which is not preferable. When the average particle diameter is less than 0.1 μm, it is difficult to uniformly disperse in the thermoplastic resin, which is not preferable. Preferably it is 0.1-0.8 micrometer, More preferably, it is 0.3-0.8 micrometer.
本発明における無機担体粒子の表面に担持する金属Ｐｄコロイド粒子の平均粒子径は１０ｎｍ以下である必要がある。平均粒子径が１０ｎｍを超える場合は、触媒成分である金属Ｐｄの比表面積が小さくなり、燃焼促進効果が低下する。好ましくは９ｎｍ以下である。平均粒子径の下限値は１ｎｍ程度である。 The average particle size of the metal Pd colloidal particles supported on the surface of the inorganic carrier particles in the present invention needs to be 10 nm or less. When the average particle diameter exceeds 10 nm, the specific surface area of the metal Pd, which is a catalyst component, becomes small, and the combustion promoting effect is reduced. Preferably it is 9 nm or less. The lower limit of the average particle diameter is about 1 nm.
金属Ｐｄコロイド粒子の無機担体粒子への担持量は０．００１〜０．１０ｗｔ％である。担持量が０．００１ｗｔ％未満の場合は、燃焼促進効果が低下するため好ましくない。担持量が０．１０ｗｔ％を超える場合は、コストが高くなるだけでなく、着色が目立つようになるため、好ましくない。好ましくは０．００５〜０．０８ｗｔ％、より好ましくは０．０１〜０．０８ｗｔ％である。 The amount of the metal Pd colloid particles supported on the inorganic carrier particles is 0.001 to 0.10 wt%. When the loading amount is less than 0.001 wt%, the combustion promoting effect is lowered, which is not preferable. When the loading amount exceeds 0.10 wt%, not only the cost increases, but also coloring becomes conspicuous, which is not preferable. Preferably it is 0.005-0.08 wt%, More preferably, it is 0.01-0.08 wt%.
次に、本発明における白色燃焼触媒の製造法について述べる。 Next, a method for producing a white combustion catalyst in the present invention will be described.
無機担体粒子に金属Ｐｄコロイド粒子を担持させる方法としては、無機担体粒子粉末の水懸濁液に、陽イオン性、陰イオン性若しくは非イオン性の界面活性剤又は水溶性高分子から選ばれる１種以上を含む金属Ｐｄヒドロゾルを混合して、電荷的に担持した後、濾過、水洗し、乾燥する方法が好ましい。上記方法を用いることによって、無機担体粒子の表面のみに効率的かつ強固に金属Ｐｄコロイド粒子を担持させることができる。 As a method for supporting the metal Pd colloidal particles on the inorganic carrier particles, the aqueous suspension of the inorganic carrier particle powder is selected from a cationic, anionic or nonionic surfactant or a water-soluble polymer 1 A method is preferred in which a metal Pd hydrosol containing more than seeds is mixed and charged and then filtered, washed with water, and dried. By using the above method, the metal Pd colloidal particles can be supported efficiently and firmly only on the surface of the inorganic carrier particles.
なお、無機担体粒子粉末として酸化アルミニウム担体粒子を用いる場合は、水懸濁液中では正電荷を有するので、陰イオン性若しくは非イオン性の界面活性剤又は水溶性高分子によって負電荷を有したＰｄコロイド粒子を含むＰｄヒドロゾルを用いることができる。
また、酸化ケイ素、炭酸カルシウム及び酸化チタン担体粒子の場合は、水懸濁液中では負電荷を有するので、陽イオン性界面活性剤によって正電荷を有したＰｄコロイド粒子を含むＰｄヒドロゾルを用いることができる。
When aluminum oxide carrier particles are used as the inorganic carrier particle powder, they have a positive charge in the aqueous suspension, and therefore have a negative charge due to an anionic or nonionic surfactant or a water-soluble polymer. Pd hydrosols containing Pd colloidal particles can be used.
Further, in the case of silicon oxide, calcium carbonate and titanium oxide carrier particles, since they have a negative charge in an aqueous suspension, use a Pd hydrosol containing Pd colloid particles having a positive charge by a cationic surfactant. Can do.
なお、Ｐｄヒドロゾルは、塩化パウジウム、硝酸パラジウム等のＰｄ化合物の水溶液に、界面活性剤または水溶性高分子の存在下にて、水素化ホウ素ナトリウム等の還元剤を添加することによって得ることができる。 The Pd hydrosol can be obtained by adding a reducing agent such as sodium borohydride to an aqueous solution of a Pd compound such as paudium chloride or palladium nitrate in the presence of a surfactant or a water-soluble polymer. .
本発明においては、Ｐｄの触媒作用を促進するために、他の各種触媒成分や助触媒成分を併用して無機担体粒子に担持させることも可能である。 In the present invention, in order to promote the catalytic action of Pd, other various catalyst components and promoter components can be used together and supported on the inorganic carrier particles.
通常、無機担体粒子にＰｄ粒子を担持させる方法としては、含浸法、イオン交換法等が用いられている。この方法では、Ｐｄ元素を含有する溶液で処理した後、乾燥および４００〜８００℃で焼成するため、Ｐｄ粒子の内部まで酸化した状態（ＰｄＯ）となっており、本発明の方法で得られる金属Ｐｄコロイド粒子に比べると燃焼促進効果が小さい。 Usually, an impregnation method, an ion exchange method, or the like is used as a method for supporting Pd particles on inorganic carrier particles. In this method, after treatment with a solution containing the Pd element, it is dried and fired at 400 to 800 ° C., so that the inside of the Pd particles is oxidized (PdO), and the metal obtained by the method of the present invention Compared to Pd colloidal particles, the combustion promoting effect is small.
次に、本発明に係る熱可塑性樹脂組成物用マスターバッチペレットについて述べる。 Next, the master batch pellet for the thermoplastic resin composition according to the present invention will be described.
本発明に係る熱可塑性樹脂組成物用マスターバッチペレットの熱可塑性樹脂としては、通常の押出成形に適するものであれば特に制限なく使用できる、例えば、ポリエチレン系樹脂、ポリプロピレン系樹脂等のオレフィン系樹脂、ナイロン６、ナイロン６６等のポリアミド樹脂又はポリ塩化ビニル樹脂等が好ましく、殊に、低密度ポリエチレン、高密度ポリエチレン、エチレンと（メタ）アクリル酸エステル、酢酸ビニル等の他の重合性単量体との共重合体等のポリエチレン系樹脂が大量に入手でき、安価であるので好適に使用できる。 The thermoplastic resin of the masterbatch pellet for the thermoplastic resin composition according to the present invention can be used without particular limitation as long as it is suitable for ordinary extrusion molding, for example, olefinic resins such as polyethylene resins and polypropylene resins. Polyamide resin such as nylon 6, nylon 66 or polyvinyl chloride resin is preferable, and other polymerizable monomers such as low density polyethylene, high density polyethylene, ethylene and (meth) acrylic acid ester, vinyl acetate, etc. A polyethylene resin such as a copolymer is available in a large amount and is inexpensive and can be suitably used.
本発明に係る熱可塑性樹脂組成物用マスターバッチペレットは、平均長径２〜６ｍｍが好ましく、より好ましくは２〜５ｍｍの範囲である。平均短径は１〜５ｍｍが好ましく、より好ましくは１〜４ｍｍである。平均長径が１ｍｍ未満の場合には、ペレット製造時の作業性が悪くなり好ましくない。６ｍｍを越える場合には、希釈用結合材樹脂ペレットなどとの大きさの違いが大きくなり、十分に分散させるのが困難となる。また、その形状は種々のものができ、不定形及び球形等の粒状、円柱形、フレーク状等にできる。
なお、マスターバッチペレット中の熱可塑性樹脂は、目的とする熱可塑性樹脂組成物用の樹脂と同一の樹脂を用いても、また、異なる樹脂を用いてもよいが異なる樹脂を使用する場合には、樹脂同士の相溶性により決まる諸特性を考慮して決めればよい。
The master batch pellet for the thermoplastic resin composition according to the present invention preferably has an average major axis of 2 to 6 mm, more preferably 2 to 5 mm. The average minor axis is preferably 1 to 5 mm, more preferably 1 to 4 mm. When the average major axis is less than 1 mm, the workability at the time of pellet production is deteriorated, which is not preferable. When it exceeds 6 mm, the difference in size from the binder resin pellet for dilution becomes large, and it becomes difficult to sufficiently disperse. Moreover, the shape can be various, and can be indefinite and spherical, cylindrical, flakes, and the like.
In addition, the thermoplastic resin in the master batch pellet may be the same resin as the resin for the desired thermoplastic resin composition, or a different resin may be used. It may be determined in consideration of various characteristics determined by the compatibility between the resins.
マスターバッチペレット中の白色燃焼触媒の含有量は、マスターバッチペレットに対して２．０〜６０ｗｔ％、好ましくは３．０〜５０ｗｔ％、より好ましくは４．０〜５０ｗｔ％である。２．０ｗｔ％未満の場合には、混練時の溶融粘度が不足し、白色燃焼触媒の良好な分散混合が困難である。６０ｗｔ％を越える場合には、熱可塑性樹脂が不足し微細な白色燃焼触媒の良好な分散混合が難しく、また、マスターバッチペレットの添加量のわずかな変化によってフィルム中に配合される微細な白色燃焼触媒粒子の含有量が大きく変化するため所望の含有量に調整するのが困難となり好ましくない。また、機械摩耗が激しく適当でない。 Content of the white combustion catalyst in a masterbatch pellet is 2.0-60 wt% with respect to a masterbatch pellet, Preferably it is 3.0-50 wt%, More preferably, it is 4.0-50 wt%. If it is less than 2.0 wt%, the melt viscosity at the time of kneading is insufficient, and it is difficult to achieve good dispersion mixing of the white combustion catalyst. If it exceeds 60 wt%, the thermoplastic resin is insufficient, making it difficult to disperse fine white combustion catalyst, and the fine white combustion blended into the film due to slight changes in the amount of master batch pellets added. Since the content of the catalyst particles greatly changes, it is difficult to adjust the content to a desired content, which is not preferable. Also, mechanical wear is severe and not suitable.
本発明に係るマスターバッチペレットは、着色剤、紫外線吸収剤、帯電防止剤、フィラー等の各種添加剤を配合することができる。 The master batch pellet according to the present invention may contain various additives such as a colorant, an ultraviolet absorber, an antistatic agent, and a filler.
本発明に係る熱可塑性樹脂組成物用マスターバッチペレットは、熱可塑性樹脂ペレットなどと白色燃焼触媒とを、必要により、リボンブレンダー、ナウターミキサー、ヘンシェルミキサー、スーパーミキサー等の混合機で混合した後、周知の単軸混練押出機や二軸混練押出機等で混練、成形した後切断するか、又は、上記混合物をバンバリーミキサー、加圧ニーダー等で混練して得られた混練物を粉砕又は成形、切断することにより製造される。 The master batch pellet for the thermoplastic resin composition according to the present invention is obtained by mixing the thermoplastic resin pellet and the white combustion catalyst with a mixer such as a ribbon blender, a Nauter mixer, a Henschel mixer, and a super mixer, if necessary. Kneaded with a well-known single-screw kneading extruder or twin-screw kneading extruder, molded and then cut, or kneaded or molded from the kneaded product obtained by kneading the above mixture with a Banbury mixer, pressure kneader, etc. It is manufactured by cutting.
次に、本発明に係る熱可塑性樹脂組成物について述べる。 Next, the thermoplastic resin composition according to the present invention will be described.
熱可塑性樹脂としては、前記熱可塑性樹脂組成物用マスターバッチペレットに用いる熱可塑性樹脂と同様のものを用いればよく、例えば、ポリエチレン系樹脂、ポリプロピレン系樹脂等のオレフィン系樹脂、ナイロン６、ナイロン６６等のポリアミド樹脂又はポリ塩化ビニル樹脂等が好ましく、殊に、低密度ポリエチレン、高密度ポリエチレン、エチレンと（メタ）アクリル酸エステル、酢酸ビニル等の他の重合性単量体との共重合体等のポリエチレン系樹脂が大量に入手でき、安価であるので好適に使用できる。 As the thermoplastic resin, the same thermoplastic resin as that used for the master batch pellet for the thermoplastic resin composition may be used. For example, olefinic resins such as polyethylene resins and polypropylene resins, nylon 6, nylon 66 Polyamide resin or polyvinyl chloride resin, etc. are preferred, especially low density polyethylene, high density polyethylene, copolymers of ethylene with other polymerizable monomers such as (meth) acrylic acid ester, vinyl acetate, etc. Can be suitably used because they are available in large quantities and are inexpensive.
熱可塑性樹脂組成物中の白色燃焼触媒の配合割合は、熱可塑性樹脂に対して０．１〜２．０ｗｔ％である。配合割合が０．１ｗｔ％未満の場合は燃焼促進効果が小さく、また、２．０ｗｔ％を越える場合は、濃度に見合った燃焼促進効果が期待できないので、必要以上に配合する意味がない。好ましくは０．１〜１．５ｗｔ％、より好ましくは０．３〜１．５ｗｔ％である。 The blending ratio of the white combustion catalyst in the thermoplastic resin composition is 0.1 to 2.0 wt% with respect to the thermoplastic resin. When the blending ratio is less than 0.1 wt%, the combustion promoting effect is small, and when it exceeds 2.0 wt%, the combustion promoting effect corresponding to the concentration cannot be expected, so it is meaningless to blend more than necessary. Preferably it is 0.1-1.5 wt%, More preferably, it is 0.3-1.5 wt%.
熱可塑性樹脂組成物中の無機担体粒子に担持された金属Ｐｄコロイド粒子の含有量は０．２〜２０ｐｐｍが好ましい。金属Ｐｄコロイド粒子の含有量が０．２ｐｐｍ未満の場合は、燃焼促進効果が顕著に低下するため好ましくない。２０ｐｐｍを超える場合は、コストが高くなるだけでなく、着色が目立つようになるため好ましくない。好ましくは０．３〜１５ｐｐｍ、より好ましくは０．４〜１０ｐｐｍである。 The content of the metal Pd colloidal particles supported on the inorganic carrier particles in the thermoplastic resin composition is preferably 0.2 to 20 ppm. When the content of the metal Pd colloidal particles is less than 0.2 ppm, the combustion promoting effect is remarkably lowered, which is not preferable. If it exceeds 20 ppm, not only is the cost high, but coloration becomes conspicuous, which is not preferable. Preferably it is 0.3-15 ppm, More preferably, it is 0.4-10 ppm.
熱可塑性樹脂組成物は、着色剤、紫外線吸収剤、帯電防止剤、フィラー等の各種添加剤を配合することができる。熱可塑性樹脂組成物は、押出成形法、射出成形法又は圧縮成形法等の通常の成形法を用いて、フィルム状、板状、棒状、ブロック状、中空状、球状等の任意の形状に成形することができる。また、紡糸することで繊維状の形状とすることも可能である。本発明に係る熱可塑性樹脂組成物の色調は、無色又は白色、乳白色であり、フィルム状などの薄膜とした場合には、優れた透明性が得られる。また、着色剤を配合することで、その所望の色調と透明性を得ることができる。 The thermoplastic resin composition can contain various additives such as a colorant, an ultraviolet absorber, an antistatic agent, and a filler. The thermoplastic resin composition is molded into an arbitrary shape such as a film shape, a plate shape, a rod shape, a block shape, a hollow shape, and a spherical shape by using a normal molding method such as an extrusion molding method, an injection molding method, or a compression molding method. can do. Moreover, it can also be made into a fibrous shape by spinning. The color tone of the thermoplastic resin composition according to the present invention is colorless, white, or milky white, and excellent transparency can be obtained when it is a thin film such as a film. Moreover, the desired color tone and transparency can be obtained by mix | blending a coloring agent.
本発明に係る熱可塑性樹脂組成物に白色燃焼触媒を配合する方法としては、前記熱可塑性樹脂組成物用マスターバッチペレットを希釈用の熱可塑性樹脂に配合する方法を用いることができ、熱可塑性樹脂組成物用マスターバッチペレットを経由して熱可塑性樹脂組成物を製造した場合には、白色燃焼触媒を容易に均一分散できるので好ましい。また、熱可塑性樹脂に無機粒子粉末を配合する通常の方法を用いることもできる。 As a method of blending the white combustion catalyst with the thermoplastic resin composition according to the present invention, a method of blending the masterbatch pellet for the thermoplastic resin composition into the thermoplastic resin for dilution can be used. When a thermoplastic resin composition is produced via the master batch pellet for the composition, the white combustion catalyst can be easily and uniformly dispersed, which is preferable. Moreover, the normal method of mix | blending inorganic particle powder with a thermoplastic resin can also be used.
＜作用＞
本発明に係る熱可塑性樹脂組成物に配合する白色燃焼触媒は、高温加熱することなく得られているので、Ｐｄコロイド粒子が酸化しにくく金属状態を維持している。
一方、通常の含浸法、イオン交換法等では、Ｐｄ元素を含有する溶液で処理した後、乾燥及び４００〜８００℃の温度範囲で焼成するため、Ｐｄ粒子の内部まで酸化した状態（ＰｄＯ）となっている。
一般的には、Ｐｄはいったん酸化されてＰｄＯとなり、その酸素で相手物質を酸化させると言われているが、Ｐｄ粒子がＰｄＯに酸化された状態よりも金属Ｐｄの状態の方が、金属Ｐｄ粒子の表層に吸着された酸素原子が容易に活性化されるものと本発明者は考えている。
<Action>
Since the white combustion catalyst blended in the thermoplastic resin composition according to the present invention is obtained without heating at a high temperature, the Pd colloidal particles are hardly oxidized and maintain a metallic state.
On the other hand, in a normal impregnation method, an ion exchange method, etc., after processing with a solution containing Pd element, it is dried and baked in a temperature range of 400 to 800 ° C., so that the inside of Pd particles is oxidized (PdO) It has become.
In general, it is said that Pd is once oxidized to PdO, and its partner substance is oxidized by the oxygen. However, the state of the metal Pd is higher than that of the Pd particles oxidized to PdO. The present inventor believes that oxygen atoms adsorbed on the surface layer of particles are easily activated.
また、通常の含浸法などによってＰｄ粒子を担持させる場合には、無機粒子担体の内部までＰｄが担持されている。
一方、本発明における白色燃焼触媒では、その製造法に起因してＰｄコロイド粒子が無機担体粒子の粒子表面に均一担持されるために、Ｐｄコロイドのほぼ全量が触媒作用に寄与し、前述したとおりの金属Ｐｄコロイドの有する高い触媒機能を十分に発揮することができるため、高い燃焼促進効果を有するものと本発明者は考えている。
Further, when Pd particles are supported by a normal impregnation method or the like, Pd is supported up to the inside of the inorganic particle carrier.
On the other hand, in the white combustion catalyst according to the present invention, Pd colloidal particles are uniformly supported on the particle surface of the inorganic carrier particles due to the production method thereof, so that almost the entire amount of Pd colloid contributes to the catalytic action. The present inventor believes that the high catalytic function of the metal Pd colloid can be sufficiently exerted, and therefore has a high combustion promoting effect.
陽イオン性、陰イオン性若しくは非イオン性の界面活性剤又は水溶性高分子から選ばれる１種以上を含むＰｄコロイド中の金属Ｐｄコロイド粒子は、凝集が抑制されて無機担体粒子に強固に担持されるので、Ｐｄが有する触媒活性を十分に発揮することができ、更に、前記金属Ｐｄコロイド粒子は、表面に界面活性剤又は水溶性高分子を吸着しているので、熱可塑性樹脂とのなじみがよく樹脂中での分散性に優れる。 Metal Pd colloidal particles in Pd colloids containing one or more selected from cationic, anionic or nonionic surfactants or water-soluble polymers are firmly supported on inorganic carrier particles with aggregation suppressed Therefore, the catalytic activity of Pd can be sufficiently exerted, and further, the metal Pd colloidal particles adsorb a surfactant or a water-soluble polymer on the surface, so that they are compatible with thermoplastic resins. Good dispersibility in resin.
また、本発明に係る熱可塑性樹脂組成物用マスターバッチペレットと希釈用熱可塑性樹脂とを混練した後、成形してなる熱可塑性樹脂組成物は、樹脂組成物中の白色燃焼触媒の均一度が高く、焼却時に完全燃焼を促進することで有害な有機化合物の発生を抑制でき、且つ所望の色調に着色可能な優れた透明性を有するものである。 In addition, the thermoplastic resin composition obtained by kneading the thermoplastic resin composition masterbatch pellets and the dilution thermoplastic resin according to the present invention and then forming the thermoplastic resin composition has a uniform degree of white combustion catalyst in the resin composition. It has high transparency that can suppress the generation of harmful organic compounds by promoting complete combustion during incineration and can be colored in a desired color tone.
本発明に係る熱可塑性樹脂組成物用マスターバッチペレットを用いて得られた熱可塑性樹脂組成物は、熱可塑性樹脂に直接、白色燃焼触媒を配合して得られた熱可塑性樹脂組成物に比べて、安定且つ優れた燃焼特性を有する。安定且つ優れた燃焼特性を有する理由について、白色燃焼触媒は微粒子で分散しにくいが、予めマスターバッチペレットを調製した後、希釈用熱可塑性樹脂と混練することで、熱可塑性樹脂組成物中における微細な白色燃焼触媒の分散性がより向上したことによって、本来の酸化活性がより充分発揮されたものと本発明者は考えている。 The thermoplastic resin composition obtained by using the master batch pellet for the thermoplastic resin composition according to the present invention is compared with the thermoplastic resin composition obtained by directly blending the thermoplastic resin with the white combustion catalyst. , Have stable and excellent combustion characteristics. The reason why it has stable and excellent combustion characteristics is that the white combustion catalyst is difficult to disperse with fine particles, but after preparing a master batch pellet in advance, it is kneaded with a dilution thermoplastic resin, so that the fineness in the thermoplastic resin composition can be reduced. The present inventor believes that the original oxidation activity is more sufficiently exhibited by further improving the dispersibility of the white combustion catalyst.
本発明の代表的な実施の形態は次の通りである。 A typical embodiment of the present invention is as follows.
白色燃焼触媒の無機担体粒子およびそれに担持されたＰｄコロイド粒子の平均粒子径は、透過型電子顕微鏡写真に示される粒子３５０個の粒子径を測定し、その平均値で示した。 The average particle size of the inorganic support particles of the white combustion catalyst and the Pd colloid particles supported thereon was measured by measuring the particle size of 350 particles shown in the transmission electron micrograph and showing the average value.
白色燃焼触媒中のＰｄ担持量は、白色燃焼触媒１．００ｇを濃硝酸／濃塩酸（１／３容積比）溶液をイオン交換水で２倍に希釈した溶液３０ｍｌに煮沸溶解した後、濾過し濾液にイオン交換水を加えて１００ｍｌに希釈して、高周波プラズマ発光分光分析装置（日本ジャーレル・アゥシュ（株）製ＩＣＡＰ−５７５）で測定した。 The amount of Pd supported in the white combustion catalyst was obtained by boiling and dissolving 1.00 g of the white combustion catalyst in 30 ml of a solution obtained by diluting a concentrated nitric acid / concentrated hydrochloric acid (1/3 volume ratio) solution with ion-exchanged water twice. Ion exchanged water was added to the filtrate to dilute to 100 ml, and measurement was performed with a high-frequency plasma emission spectroscopic analyzer (ICAP-575 manufactured by Nippon Jarrell-Aush Co., Ltd.).
熱可塑性樹脂組成物用マスターバッチペレットを経由して得られた熱可塑性樹脂組成物中の白色燃焼触媒含有量は、熱可塑性樹脂組成物１．０ｇを磁性ルツボに入れて、空気中８００℃にて１時間熱処理した際の重量差から計算した。尚、熱処理により白色触媒担体が変態するものについては，その変態による重量変化も加味して計算した。 The white combustion catalyst content in the thermoplastic resin composition obtained via the master batch pellet for the thermoplastic resin composition was as follows: 1.0 g of the thermoplastic resin composition was placed in a magnetic crucible and 800 ° C. in air. And calculated from the weight difference when heat-treated for 1 hour. For the case where the white catalyst support was transformed by heat treatment, the calculation was made taking into account the weight change due to the transformation.
＜熱可塑性樹脂組成物の燃焼特性評価＞
内径１４ｍｍφ×長さ６５ｍｍの石英試料管中に、熱可塑性樹脂組成物試料３５ｍｇを入れ、その試料を石英ウールで両端から挟んで固定した。酸素ガス２００ｍＬ／ｍｉｎで４分間流しながら、７００℃で燃焼させ、その間に生成した燃焼ガスの全量を１Ｌのテドラバック中に捕集して、そのガス組成と量の測定を行った。燃焼ガス組成は、ガスクロマトグラフによって、一酸化炭素、二酸化炭素及びベンゼンを測定することにより評価した。二酸化炭素の生成量が多く、一酸化炭素及びベンゼンが少ないほど、完全燃焼の度合いが高いことを示している。
<Combustion characteristic evaluation of thermoplastic resin composition>
35 mg of a thermoplastic resin composition sample was placed in a quartz sample tube having an inner diameter of 14 mmφ and a length of 65 mm, and the sample was fixed by being sandwiched from both ends by quartz wool. Burning at 700 ° C. while flowing oxygen gas at 200 mL / min for 4 minutes, the entire amount of combustion gas generated during that time was collected in 1 L of tedra bag, and the gas composition and amount were measured. The combustion gas composition was evaluated by measuring carbon monoxide, carbon dioxide and benzene by gas chromatography. It shows that the more carbon dioxide is produced and the less carbon monoxide and benzene, the higher the degree of complete combustion.
＜熱可塑性樹脂組成物によるダイオキシン低減試験評価＞
熱可塑性樹脂組成物９０ｗｔ％と塩化ビニル樹脂１０ｗｔ％を１７０℃にて３分間混練した後、厚さ１ｍｍシートに成形して試料とした。７００℃に加熱した内径１５ｍｍφ×長さ３００ｍｍの石英管中に、１回当たり上記試料２０ｍｇを乗せた石英ボート（幅１０ｍｍ×長さ５０ｍｍ×高さ１０ｍｍ）を入れ、空気１．８Ｌ／ｍｉｎを流しながら燃焼させた。
その間に生成した燃焼ガスを、氷浴中でガス上流側より、イオン交換水、ジエチレングリコール、アンバーライトＸＡＤ−２（オルガノ（株）製）にてトラップした。この操作を７０回繰り返した。実験終了後、石英管出口部分から吸収ユニットまでをイオン交換水、アセトンおよびジクロロメタンにより洗浄し、分析試料として回収した。さらに、上記洗液、イオン交換水及びジエチレングリコール溶液は濾過した後、残渣はＸＡＤ−２樹脂とともにトルエンにてソックスレー抽出し、濾液はトルエンを加えて振とう抽出した。
このトルエン吸収液中のダイオキシン類をガスクロマトグラフィー質量分析計（ＭＩＣＲＯＭＡＳＳ社製ＡＵＴＯＳＰＥＣ ＵＬＴＩＭＡ）で定量した。
<Evaluation of dioxin reduction test by thermoplastic resin composition>
A thermoplastic resin composition 90 wt% and a vinyl chloride resin 10 wt% were kneaded at 170 ° C. for 3 minutes, and then molded into a 1 mm thick sheet to prepare a sample. A quartz boat (width 10 mm × length 50 mm × height 10 mm) loaded with 20 mg of the above sample is placed in a quartz tube having an inner diameter of 15 mmφ × length of 300 mm heated to 700 ° C., and air of 1.8 L / min. Burned while flowing.
The combustion gas generated during that time was trapped with ion-exchanged water, diethylene glycol, and Amberlite XAD-2 (manufactured by Organo Corporation) from the gas upstream side in an ice bath. This operation was repeated 70 times. After the experiment was completed, the part from the quartz tube outlet to the absorption unit was washed with ion-exchanged water, acetone and dichloromethane and collected as an analysis sample. Furthermore, after the said washing | cleaning liquid, ion-exchange water, and the diethylene glycol solution were filtered, the residue was Soxhlet-extracted with toluene with XAD-2 resin, and the filtrate was shake-extracted by adding toluene.
Dioxins in the toluene absorption liquid were quantified with a gas chromatography mass spectrometer (AUTOSPEC ULTIMA manufactured by MICROMASS).
＜Ｐｄコロイド液１の調製＞
１８．５Ｌのイオン交換水に０．１ｍｏｌ／Ｌの塩化パラジウム水溶液５００ｍＬと１ｗｔ％ポリビニルアルコール水溶液５００ｍＬを攪拌下にて混合した。さらに、上記混合溶液に０．４ｍｏｌ／Ｌの水素化ホウ素ナトリウム水溶液５００ｍｌを攪拌下にて添加混合することによって、負電荷を有する黒色の２．５ｍｍｏｌ／ＬのＰｄコロイド液１を得た。
<Preparation of Pd colloid solution 1>
To 18.5 L of ion exchange water, 500 mL of a 0.1 mol / L palladium chloride aqueous solution and 500 mL of a 1 wt% polyvinyl alcohol aqueous solution were mixed with stirring. Furthermore, a black 2.5 mmol / L Pd colloidal solution 1 having a negative charge was obtained by adding and mixing 500 ml of a 0.4 mol / L sodium borohydride aqueous solution with stirring to the above mixed solution.
＜Ｐｄコロイド液２の調製＞
１８．５Ｌのイオン交換水に０．１ｍｏｌ／Ｌの塩化パラジウム水溶液５００ｍＬを混合した後、さらに０．８ｗｔ％塩化ステアリルトリメチルアンモニウム水溶液５００ｍＬと０．４ｍｏｌ／Ｌの水素化ホウ素ナトリウム水溶液５００ｍｌを攪拌下にて同時に添加混合することによって、正電荷を有する黒色の２．５ｍｍｏｌ／ＬのＰｄコロイド液２を得た。
<Preparation of Pd colloid solution 2>
After mixing 500 mL of 0.1 mol / L palladium chloride aqueous solution with 18.5 L of ion exchange water, 500 mL of 0.8 wt% stearyltrimethylammonium chloride aqueous solution and 500 mL of 0.4 mol / L sodium borohydride aqueous solution were further stirred. At the same time, a black 2.5 mmol / L Pd colloidal solution 2 having a positive charge was obtained.
製造例１＜白色燃焼触媒１＞
平均粒子径０．６μｍのα−アルミナ担体粒子の５０ｗｔ％水懸濁液２０ｋｇに、攪拌下にて前記Ｐｄコロイド液１を１５Ｌ滴下混合して、α−アルミナ担体粒子表面にＰｄコロイド粒子を担持した。その後、上記懸濁液を濾過、水洗した後、１２０℃にて８時間乾燥し、得られた乾燥物を粉砕して、Ｐｄコロイド粒子が０．０４ｗｔ％担持された乳白色のα−アルミナ粒子粉末１０ｋｇを得た。α−アルミナ粒子粉末に担持されたＰｄコロイド粒子の平均粒子径は３ｎｍであった。
Production Example 1 <White Combustion Catalyst 1>
15 L of the Pd colloid liquid 1 is dropped and mixed with 20 kg of a 50 wt% aqueous suspension of α-alumina carrier particles having an average particle diameter of 0.6 μm with stirring to support the Pd colloid particles on the surface of the α-alumina carrier particles. did. Thereafter, the suspension was filtered, washed with water, dried at 120 ° C. for 8 hours, and the resulting dried product was pulverized to give milky white α-alumina particle powder carrying 0.04 wt% of Pd colloidal particles. 10 kg was obtained. The average particle diameter of the Pd colloidal particles supported on the α-alumina particle powder was 3 nm.
製造例２＜白色燃焼触媒２＞
平均粒子径０．５μｍのアナターゼ型酸化チタン担体粒子の５０ｗｔ％水懸濁液１０ｋｇに、攪拌下にて前記Ｐｄコロイド液２を１５Ｌ混合して、酸化チタン担体粒子表面にＰｄコロイド粒子を担持した。その後、上記懸濁液を濾過、水洗した後、１２０℃にて８時間乾燥し、得られた乾燥物を粉砕して、Ｐｄコロイド粒子が０．０８ｗｔ％担持された灰色の酸化チタン粒子粉末５．０ｋｇを得た。酸化チタン粒子粉末に担持されたＰｄコロイド粒子の平均粒子径は６ｎｍであった。
Production Example 2 <White Combustion Catalyst 2>
15 kg of the Pd colloid liquid 2 was mixed with 10 kg of a 50 wt% aqueous suspension of anatase-type titanium oxide carrier particles having an average particle diameter of 0.5 μm with stirring, and Pd colloid particles were supported on the surface of the titanium oxide carrier particles. . Thereafter, the suspension was filtered, washed with water, dried at 120 ° C. for 8 hours, and the resulting dried product was pulverized to obtain gray titanium oxide particle powder 5 carrying 0.08 wt% Pd colloidal particles. 0.0 kg was obtained. The average particle size of the Pd colloidal particles supported on the titanium oxide particle powder was 6 nm.
製造例３＜白色燃焼触媒３＞
平均粒子径０．６μｍの炭酸カルシウム担体粒子の５０ｗｔ％水懸濁液２０ｋｇに、攪拌下にて前記Ｐｄコロイド液２を１．９Ｌ滴下混合して、炭酸カルシウム担体粒子表面にＰｄコロイド粒子を担持した。その後、上記懸濁液を濾過、水洗した後、１２０℃にて８時間乾燥し、得られた乾燥物を粉砕して、Ｐｄコロイド粒子が０．００５ｗｔ％担持された乳白色の炭酸カルシウム粒子粉末１０ｋｇを得た。炭酸カルシウム粒子粉末に担持されたＰｄコロイド粒子の平均粒子径は３ｎｍであった。
Production Example 3 <White Combustion Catalyst 3>
1.9 L of the Pd colloid liquid 2 is dropped and mixed with 20 kg of a 50 wt% aqueous suspension of calcium carbonate carrier particles having an average particle diameter of 0.6 μm with stirring to support the Pd colloid particles on the surface of the calcium carbonate carrier particles. did. Thereafter, the suspension was filtered, washed with water, dried at 120 ° C. for 8 hours, and the resulting dried product was pulverized to give 10 kg of milky white calcium carbonate particle powder carrying 0.005 wt% of Pd colloidal particles. Got. The average particle size of the Pd colloidal particles supported on the calcium carbonate particle powder was 3 nm.
製造例４＜白色燃焼触媒４＞
平均粒子径０．６μｍのα−アルミナ担体粒子粉末１０ｋｇに、７．５ｍｍｏｌ／Ｌのジニトロジアンミンパラジウム水溶液５．０Ｌを含浸させ、１２０℃にて８時間乾燥後、５００℃にて２時間焼成した。焼成物を粉砕して、０．０４ｗｔ％Ｐｄが担持された乳白色のα−アルミナ粒子粉末１０ｋｇを得た。α−アルミナ粒子粉末に担持されたＰｄ粒子の平均粒子径は１０ｎｍであった。
Production Example 4 <White Combustion Catalyst 4>
10 kg of α-alumina carrier particle powder having an average particle size of 0.6 μm was impregnated with 5.0 L of 7.5 mmol / L dinitrodiammine palladium aqueous solution, dried at 120 ° C. for 8 hours, and then calcined at 500 ° C. for 2 hours. . The fired product was pulverized to obtain 10 kg of milky white α-alumina particle powder carrying 0.04 wt% Pd. The average particle size of the Pd particles supported on the α-alumina particle powder was 10 nm.
製造例５＜白色燃焼触媒５＞
α−アルミナ粒子粉末に担持されたＰｄコロイド粒子を、Ｘ線回折装置で同定するために、製造例１のα−アルミナ担体粒子水懸濁液を、１ｗｔ％水懸濁液８ｋｇに変えた以外は、製造例１と同様な方法で調製し、Ｐｄコロイド粒子が５．０ｗｔ％担持された灰色のα−アルミナ粒子粉末８０ｇを得た。α−アルミナ粒子粉末に担持されたＰｄコロイド粒子は、Ｘ線回折装置で解析した結果、金属Ｐｄの結晶面（１１１）のピークが確認された。また、ＰｄＯの結晶面のピークは確認されなかった。
Production Example 5 <White Combustion Catalyst 5>
In order to identify the Pd colloidal particles supported on the α-alumina particle powder with an X-ray diffractometer, the α-alumina carrier particle aqueous suspension of Production Example 1 was changed to 8 kg of 1 wt% aqueous suspension. Was prepared in the same manner as in Production Example 1 to obtain 80 g of gray α-alumina particle powder carrying 5.0 wt% of Pd colloidal particles. As a result of analyzing the Pd colloidal particles supported on the α-alumina particle powder with an X-ray diffractometer, the peak of the crystal plane (111) of the metal Pd was confirmed. Moreover, the peak of the crystal plane of PdO was not confirmed.
製造例６＜白色燃焼触媒６＞
α−アルミナ粒子粉末に担持されたＰｄ粒子を、Ｘ線回折装置で同定するために、製造例４のα−アルミナ粒子粉末を１ｋｇに、ジニトロジアンミンパラジウム水溶液を０．１９ｍｏｌ／Ｌ、５００ｍＬに変えた以外は、製造例４と同様な方法で調製し、Ｐｄ粒子が１．０ｗｔ％担持された灰色のα−アルミナ粒子粉末１．０ｋｇを得た。α−アルミナ粒子粉末に担持されたＰｄコロイド粒子は、Ｘ線回折装置で解析した結果、ＰｄＯの結晶面（１０１）のピークが確認された。また、金属Ｐｄの結晶面のピークは確認されなかった。
Production Example 6 <White Combustion Catalyst 6>
In order to identify the Pd particles supported on the α-alumina particle powder with an X-ray diffractometer, the α-alumina particle powder of Production Example 4 was changed to 1 kg, and the dinitrodiammine palladium aqueous solution was changed to 0.19 mol / L, 500 mL. Except for the above, it was prepared in the same manner as in Production Example 4 to obtain 1.0 kg of gray α-alumina particle powder carrying 1.0 wt% of Pd particles. As a result of analyzing the Pd colloidal particles supported on the α-alumina particle powder with an X-ray diffractometer, the peak of the crystal plane (101) of PdO was confirmed. Moreover, the peak of the crystal plane of the metal Pd was not confirmed.
実施例１＜熱可塑性樹脂組成物用マスターバッチペレットＡ＞
８５ｗｔ％の低密度ポリエチレン樹脂ペレットと１５ｗｔ％の製造例１の白色燃焼触媒とを二軸混練機により１６０℃で混練、押出後、切断をして円柱状（３ｍｍφ×３ｍｍ）のマスターバッチペレットＡを得た。
Example 1 <Masterbatch Pellets A for Thermoplastic Resin Composition>
85 wt% low density polyethylene resin pellets and 15 wt% of the white combustion catalyst of Production Example 1 were kneaded at 160 ° C. with a twin-screw kneader, extruded, cut, and cylindrical (3 mmφ × 3 mm) master batch pellet A Got.
実施例２＜熱可塑性樹脂組成物用マスターバッチペレットＢ＞
９５ｗｔ％の低密度ポリエチレン樹脂ペレットと５ｗｔ％の製造例２の白色燃焼触媒とを二軸混練機により１６０℃で混練、押出後、切断をして円柱状（３ｍｍφ×３ｍｍ）のマスターバッチペレットＢを得た。
Example 2 <Masterbatch Pellet B for Thermoplastic Resin Composition>
95 wt% low-density polyethylene resin pellets and 5 wt% of the white combustion catalyst of Production Example 2 are kneaded at 160 ° C. with a twin-screw kneader, extruded, cut, and cylindrical (3 mmφ × 3 mm) master batch pellet B Got.
実施例３＜熱可塑性樹脂組成物用マスターバッチペレットＣ＞
５０ｗｔ％の低密度ポリエチレン樹脂ペレットと５０ｗｔ％の製造例３の白色燃焼触媒とを二軸混練機により１６０℃で混練、押出後、切断をして円柱状（３ｍｍφ×３ｍｍ）のマスターバッチペレットＣを得た。
Example 3 <Masterbatch Pellet C for Thermoplastic Resin Composition>
A 50 wt% low density polyethylene resin pellet and 50 wt% of the white combustion catalyst of Production Example 3 were kneaded at 160 ° C. with a twin-screw kneader, extruded, cut, and cylindrical (3 mmφ × 3 mm) master batch pellet C Got.
比較例１＜熱可塑性樹脂組成物用マスターバッチペレットＤ＞
８５ｗｔ％の低密度ポリエチレン樹脂ペレットと１５ｗｔ％の製造例４の白色燃焼触媒とを二軸混練機により１６０℃で混練、押出後、切断をして円柱状（３ｍｍφ×３ｍｍ）のマスターバッチペレットＤを得た。
Comparative Example 1 <Master Batch Pellet D for Thermoplastic Resin Composition>
85 wt% low-density polyethylene resin pellets and 15 wt% of the white combustion catalyst of Production Example 4 are kneaded at 160 ° C. with a twin-screw kneader, extruded, cut, and cylindrical (3 mmφ × 3 mm) master batch pellet D Got.
＜熱可塑性樹脂組成物の燃焼特性評価＞
実施例４
９９．５ｗｔ％の低密度ポリエチレンペレットと０．５ｗｔ％の製造例１の白色燃焼触媒とを１８０℃にて加熱混練し、インフレーション押出成形法で厚み５０μｍのフィルム（熱可塑性樹脂組成物１）を調製した。上記フィルムの色調は無色透明であった（Ｐｄ含有量：２ｐｐｍ）。
<Combustion characteristics evaluation of thermoplastic resin composition>
Example 4
99.5 wt% of low density polyethylene pellets and 0.5 wt% of the white combustion catalyst of Production Example 1 were heat-kneaded at 180 ° C., and a film (thermoplastic resin composition 1) having a thickness of 50 μm was formed by inflation extrusion molding. Prepared. The color tone of the film was colorless and transparent (Pd content: 2 ppm).
本フィルムを用いて、前記＜熱可塑性樹脂組成物の燃焼特性評価＞にて燃焼ガス測定を行ったところ、二酸化炭素、一酸化炭素およびベンゼンの生成量は、それぞれ８６．２％、４．５％および０．７％（ポリエチレン炭素換算比率）であった。 Using this film, the combustion gas was measured in the above <Evaluation of combustion characteristics of thermoplastic resin composition>. As a result, the production amounts of carbon dioxide, carbon monoxide and benzene were 86.2% and 4.5 respectively. % And 0.7% (polyethylene carbon conversion ratio).
実施例５
９９．０ｗｔ％の低密度ポリエチレンペレットと１．０ｗｔ％の製造例２の白色燃焼触媒とを１８０℃にて加熱混練し、インフレーション押出成形法で厚み５０μｍのフィルム（熱可塑性樹脂組成物２）を調製した。上記フィルムの色調は無色透明であった（Ｐｄ含有量：８ｐｐｍ）。
Example 5
99.0 wt% of low density polyethylene pellets and 1.0 wt% of the white combustion catalyst of Production Example 2 were heat-kneaded at 180 ° C., and a film (thermoplastic resin composition 2) having a thickness of 50 μm was formed by inflation extrusion molding. Prepared. The color tone of the film was colorless and transparent (Pd content: 8 ppm).
本フィルムを用いて、前記＜熱可塑性樹脂組成物の燃焼特性評価＞にて燃焼ガス測定を行ったところ、二酸化炭素、一酸化炭素およびベンゼンの生成量は、それぞれ９３．４％、１．５％および０．０５％（ポリエチレン炭素換算比率）であった。 Using this film, the combustion gas was measured in <Evaluation of combustion characteristics of thermoplastic resin composition>. As a result, the production amounts of carbon dioxide, carbon monoxide and benzene were 93.4% and 1.5%, respectively. % And 0.05% (polyethylene carbon conversion ratio).
実施例６
９９．０ｗｔ％の低密度ポリエチレンペレットと１．０ｗｔ％の製造例３の白色燃焼触媒とを１８０℃にて加熱混練し、インフレーション押出成形法で厚み５０μｍのフィルム（熱可塑性樹脂組成物３）を調製した。上記フィルムの色調は無色透明であった（Ｐｄ含有量：０．５ｐｐｍ）。
Example 6
99.0 wt% of low density polyethylene pellets and 1.0 wt% of the white combustion catalyst of Production Example 3 were kneaded at 180 ° C., and a film (thermoplastic resin composition 3) having a thickness of 50 μm was formed by an inflation extrusion molding method. Prepared. The color tone of the film was colorless and transparent (Pd content: 0.5 ppm).
本フィルムを用いて、前記＜熱可塑性樹脂組成物の燃焼特性評価＞にて燃焼ガス測定を行ったところ、二酸化炭素、一酸化炭素およびベンゼンの生成量は、それぞれ８０．２％、５．１％および０．９％（ポリエチレン炭素換算比率）であり、少量のＰｄ担持量でも完全燃焼を促進する効果が確認された。 Using this film, the combustion gas was measured in the above <Evaluation of Combustion Characteristics of Thermoplastic Resin Composition>. The production amounts of carbon dioxide, carbon monoxide and benzene were 80.2% and 5.1, respectively. % And 0.9% (polyethylene carbon conversion ratio), and the effect of promoting complete combustion was confirmed even with a small amount of Pd supported.
実施例７
９６．７ｗｔ％の低密度ポリエチレン樹脂ペレットと３．３ｗｔ％の実施例１のマスターバッチペレットＡを、リボンブレンダーにて１８０℃で加熱混練し、インフレーション押出成形法で厚み５０μｍのフィルム（熱可塑性樹脂組成物４）を調製した。上記フィルムの色調は無色透明であった（白色燃焼触媒含有量０．５０ｗｔ％、Ｐｄ含有量：２ｐｐｍ）。
Example 7
96.7 wt% of low density polyethylene resin pellets and 3.3 wt% of master batch pellet A of Example 1 were heat-kneaded at 180 ° C. in a ribbon blender, and a film (thermoplastic resin having a thickness of 50 μm was obtained by an inflation extrusion molding method. Composition 4) was prepared. The color tone of the film was colorless and transparent (white combustion catalyst content: 0.50 wt%, Pd content: 2 ppm).
本フィルムを用いて、前記＜熱可塑性樹脂組成物の燃焼特性評価＞にて燃焼ガス測定を行ったところ、二酸化炭素、一酸化炭素およびベンゼンの平均生成量は、それぞれ８９．２％、４．３％および０．６％（ポリエチレン炭素換算比率）であった。 Using this film, the combustion gas was measured in the above <Evaluation of Combustion Characteristics of Thermoplastic Resin Composition>. The average production amounts of carbon dioxide, carbon monoxide and benzene were 89.2% and 4. They were 3% and 0.6% (polyethylene carbon conversion ratio).
実施例８
８０．０ｗｔ％の低密度ポリエチレン樹脂ペレットと２０ｗｔ％の実施例２のマスターバッチペレットＢとを、リボンブレンダーにて１８０℃で加熱混練し、インフレーション押出成形法で厚み５０μｍのフィルム（熱可塑性樹脂組成物５）を調製した。上記フィルムの色調は無色透明であった（白色燃焼触媒含有量１．０ｗｔ％、Ｐｄ含有量：８ｐｐｍ）。
Example 8
80.0 wt% of low density polyethylene resin pellets and 20 wt% of master batch pellets B of Example 2 were heat-kneaded at 180 ° C. in a ribbon blender, and a film (thermoplastic resin composition) having a thickness of 50 μm was obtained by inflation extrusion molding. Article 5) was prepared. The color tone of the film was colorless and transparent (white combustion catalyst content: 1.0 wt%, Pd content: 8 ppm).
本フィルムを用いて、前記＜熱可塑性樹脂組成物の燃焼特性評価＞にて燃焼ガス測定を行ったところ、二酸化炭素、一酸化炭素およびベンゼンの平均生成量は、それぞれ９６．０％、１．４％および０．０５％（ポリエチレン炭素換算比率）であった。 Using this film, the combustion gas was measured in the above <Evaluation of Combustion Characteristics of Thermoplastic Resin Composition>. The average production amounts of carbon dioxide, carbon monoxide and benzene were 96.0% and 1. They were 4% and 0.05% (polyethylene carbon conversion ratio).
実施例９
９８．０ｗｔ％の低密度ポリエチレンペレットと２．０ｗｔ％の実施例３のマスターバッチペレットＣとを１８０℃にて加熱混練し、インフレーション押出成形法で厚み５０μｍのフィルム（熱可塑性樹脂組成物６）を調製した。上記フィルムの色調は無色透明であった（白色燃焼触媒含有量１．０ｗｔ％、Ｐｄ含有量：０．５ｐｐｍ）。
Example 9
98.0 wt% of low density polyethylene pellets and 2.0 wt% of master batch pellet C of Example 3 were heated and kneaded at 180 ° C., and a film having a thickness of 50 μm (thermoplastic resin composition 6) by an inflation extrusion molding method. Was prepared. The color tone of the film was colorless and transparent (white combustion catalyst content: 1.0 wt%, Pd content: 0.5 ppm).
本フィルムを用いて、前記＜熱可塑性樹脂組成物の燃焼特性評価＞にて燃焼ガス測定を行ったところ、二酸化炭素、一酸化炭素およびベンゼンの平均生成量は、それぞれ７９．０％、４．９％および０．８％（ポリエチレン炭素換算比率）であった。 Using this film, the combustion gas was measured in the above <Evaluation of Combustion Characteristics of Thermoplastic Resin Composition>. The average production amounts of carbon dioxide, carbon monoxide and benzene were 79.0% and 4. They were 9% and 0.8% (polyethylene carbon conversion ratio).
比較例２
９９．５ｗｔ％の低密度ポリエチレンペレットと製造例４の０．５ｗｔ％の白色燃焼触媒を１８０℃にて加熱混練し、インフレーション押出成形法で厚み５０μｍのフィルム（熱可塑性樹脂組成物７）を調製した。上記フィルムの色調は無色透明であった（Ｐｄ含有量：２ｐｐｍ）。
Comparative Example 2
99.5 wt% of low density polyethylene pellets and 0.5 wt% of the white combustion catalyst of Production Example 4 were kneaded at 180 ° C., and a 50 μm thick film (thermoplastic resin composition 7) was prepared by inflation extrusion molding. did. The color tone of the film was colorless and transparent (Pd content: 2 ppm).
本フィルムを用いて、前記＜熱可塑性樹脂組成物の燃焼特性評価＞にて燃焼ガス測定を行ったところ、二酸化炭素、一酸化炭素およびベンゼンの生成量は、それぞれ７８．４％、５．２％および１．０％（ポリエチレン炭素換算比率）であった。 Using this film, the combustion gas was measured in the above <Evaluation of Combustion Characteristics of Thermoplastic Resin Composition>. The production amounts of carbon dioxide, carbon monoxide and benzene were 78.4% and 5.2, respectively. % And 1.0% (polyethylene carbon conversion ratio).
比較例３
低密度ポリエチレンペレット単体を１８０℃にて加熱混練し、インフレーション押出成形法で厚み５０μｍのフィルム（熱可塑性樹脂組成物８）を調製した。上記フィルムの色調は無色透明であった。
Comparative Example 3
A single low-density polyethylene pellet was heat-kneaded at 180 ° C., and a film (thermoplastic resin composition 8) having a thickness of 50 μm was prepared by an inflation extrusion molding method. The color tone of the film was colorless and transparent.
本フィルムを用いて、前記＜熱可塑性樹脂組成物の燃焼特性評価＞にて燃焼ガス測定を行ったところ、二酸化炭素、一酸化炭素およびベンゼンの生成量は、それぞれ７２．９％、７．８％および１．７％（ポリエチレン炭素換算比率）であった。 Using this film, combustion gas measurement was performed in the above <Evaluation of combustion characteristics of thermoplastic resin composition>. As a result, the production amounts of carbon dioxide, carbon monoxide and benzene were 72.9% and 7.8, respectively. % And 1.7% (polyethylene carbon conversion ratio).
比較例４
９６．７ｗｔ％の低密度ポリエチレン樹脂ペレットと比較例１の３．３ｗｔ％のマスターバッチペレットＤを、リボンブレンダーにて１８０℃で加熱混練し、インフレーション押出成形法で厚み５０μｍのフィルム（熱可塑性樹脂組成物９）を調製した。上記フィルムの色調は無色透明であった（白色燃焼触媒含有量０．５０ｗｔ％、Ｐｄ含有量：２ｐｐｍ）。
Comparative Example 4
96.7 wt% low density polyethylene resin pellets and 3.3 wt% masterbatch pellet D of Comparative Example 1 were heat-kneaded at 180 ° C in a ribbon blender, and a film (thermoplastic resin having a thickness of 50 µm was obtained by inflation extrusion molding. Composition 9) was prepared. The color tone of the film was colorless and transparent (white combustion catalyst content: 0.50 wt%, Pd content: 2 ppm).
本フィルムを用いて、前記＜熱可塑性樹脂組成物の燃焼特性評価＞にて燃焼ガス測定を行ったところ、二酸化炭素、一酸化炭素およびベンゼンの平均生成量は、それぞれ８０．６％、５．１％および０．９％（ポリエチレン炭素換算比率）であった。 Using this film, the combustion gas was measured in the above <Evaluation of combustion characteristics of thermoplastic resin composition>. The average production amounts of carbon dioxide, carbon monoxide and benzene were 80.6% and 5. 1% and 0.9% (polyethylene carbon conversion ratio).
＜熱可塑性樹脂組成物によるダイオキシン低減試験評価＞
実施例１０
実施例４の熱可塑性樹脂組成物１を用いて、前記＜熱可塑性樹脂組成物によるダイオキシン低減試験評価＞にてダイオキシン測定を行った結果、ダイオシキシン生成量は７０ｐｇ−ＴＥＱ／ｇ試料であった。
<Evaluation of dioxin reduction test by thermoplastic resin composition>
Example 10
Using the thermoplastic resin composition 1 of Example 4, the dioxin measurement was carried out in the above <Dioxin reduction test evaluation with thermoplastic resin composition>, and as a result, the amount of diosixin produced was 70 pg-TEQ / g sample.
実施例１１
実施例７の熱可塑性樹脂組成物４を用いて、前記＜熱可塑性樹脂組成物によるダイオキシン低減試験評価＞にてダイオキシン測定を行った結果、ダイオシキシン生成量は６０ｐｇ−ＴＥＱ／ｇ試料であった。
Example 11
Using the thermoplastic resin composition 4 of Example 7, dioxin measurement was performed in the above <Dioxin reduction test evaluation using thermoplastic resin composition>. As a result, the amount of diosixin produced was 60 pg-TEQ / g sample.
比較例５
比較例２の熱可塑性樹脂組成物７を用いて、前記＜熱可塑性樹脂組成物によるダイオキシン低減試験評価＞にてダイオキシン測定を行った結果、ダイオシキシン生成量は２５０ｐｇ−ＴＥＱ／ｇ試料であった。
Comparative Example 5
Using the thermoplastic resin composition 7 of Comparative Example 2, dioxin measurement was performed in the above <Dioxin reduction test evaluation using thermoplastic resin composition>. As a result, the amount of diosixin produced was 250 pg-TEQ / g sample.
比較例６
比較例３の熱可塑性樹脂組成物８を用いて、前記＜熱可塑性樹脂組成物によるダイオキシン低減試験評価＞にてダイオキシン測定を行った結果、ダイオシキシン生成量は７００ｐｇ−ＴＥＱ／ｇ試料であった。
Comparative Example 6
Using the thermoplastic resin composition 8 of Comparative Example 3, dioxin measurement was performed in the above <Dioxin reduction test evaluation using thermoplastic resin composition>. As a result, the amount of diosixin produced was 700 pg-TEQ / g sample.
比較例７
比較例４の熱可塑性樹脂組成物９を用いて、前記＜熱可塑性樹脂組成物によるダイオキシン低減試験評価＞にてダイオキシン測定を行った結果、ダイオシキシン生成量は２３０ｐｇ−ＴＥＱ／ｇ試料であった。
Comparative Example 7
Using the thermoplastic resin composition 9 of Comparative Example 4, dioxin measurement was performed in the above <Dioxin reduction test evaluation using thermoplastic resin composition>. As a result, the amount of diosixin produced was 230 pg-TEQ / g sample.
本発明に係る熱可塑性樹脂組成物用マスターバッチペレットは、該マスターバッチペレットを用いて作製した熱可塑性樹脂組成物中に白色燃焼触媒を容易に均一に分散させることができるので、熱可塑性樹脂組成物用マスターバッチペレットとして好適である。 The master batch pellet for the thermoplastic resin composition according to the present invention can easily and uniformly disperse the white combustion catalyst in the thermoplastic resin composition produced using the master batch pellet. Suitable as a master batch pellet for goods.
本発明に係る熱可塑性樹脂組成物は、強度や安全性等の本質的特性を有していることはもちろん、使用後の焼却時に完全燃焼を促進して有害な有機化合物の発生を抑制でき、且つ、透明性が高く所望の色調に容易に着色することができるので、野菜や肉等の食料品、衣料品の包装用途等の幅広い用途に好適である。
The thermoplastic resin composition according to the present invention not only has essential properties such as strength and safety, but can promote the complete combustion during incineration after use and suppress the generation of harmful organic compounds, And since it is highly transparent and can be easily colored to a desired color tone, it is suitable for a wide range of uses such as foods such as vegetables and meat, and packaging for clothing.
Claims (6)
A white combustion catalyst contacts a metal Pd hydrosol containing at least one selected from a cationic, anionic or nonionic surfactant or a water-soluble polymer and an aqueous suspension containing inorganic carrier particles. 6. The thermoplastic resin composition according to claim 4, wherein the thermoplastic resin composition is a white combustion catalyst which is mixed and electrically supported with metal Pd colloidal particles on the surface of the inorganic carrier particles.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59160536A (en) * | 1983-03-04 | 1984-09-11 | Hitachi Ltd | Combustion-catalyst and its manufacture |
| JPH03202153A (en) * | 1989-12-28 | 1991-09-03 | Mitsubishi Heavy Ind Ltd | Preparation of catalyst |
| JPH04313340A (en) * | 1991-04-12 | 1992-11-05 | Toda Kogyo Corp | Noble metal hydrosol and its production |
| JPH05293383A (en) * | 1990-09-11 | 1993-11-09 | Daiso Co Ltd | Composite material with deposition of metal particle and/ or metal compound particle, and its production |
| US6197720B1 (en) * | 1997-12-02 | 2001-03-06 | Basf Aktiengesellschaft | Palladium clusters and their use as catalysts |
| JP2002167516A (en) * | 2000-09-20 | 2002-06-11 | Okura Ind Co Ltd | Thermoplastic resin composition and molding thereof |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59160536A (en) * | 1983-03-04 | 1984-09-11 | Hitachi Ltd | Combustion-catalyst and its manufacture |
| JPH03202153A (en) * | 1989-12-28 | 1991-09-03 | Mitsubishi Heavy Ind Ltd | Preparation of catalyst |
| JPH05293383A (en) * | 1990-09-11 | 1993-11-09 | Daiso Co Ltd | Composite material with deposition of metal particle and/ or metal compound particle, and its production |
| JPH04313340A (en) * | 1991-04-12 | 1992-11-05 | Toda Kogyo Corp | Noble metal hydrosol and its production |
| US6197720B1 (en) * | 1997-12-02 | 2001-03-06 | Basf Aktiengesellschaft | Palladium clusters and their use as catalysts |
| JP2002167516A (en) * | 2000-09-20 | 2002-06-11 | Okura Ind Co Ltd | Thermoplastic resin composition and molding thereof |
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