JPH0352961A - Molded article for colored food - Google Patents
Molded article for colored foodInfo
- Publication number
- JPH0352961A JPH0352961A JP18741689A JP18741689A JPH0352961A JP H0352961 A JPH0352961 A JP H0352961A JP 18741689 A JP18741689 A JP 18741689A JP 18741689 A JP18741689 A JP 18741689A JP H0352961 A JPH0352961 A JP H0352961A
- Authority
- JP
- Japan
- Prior art keywords
- molded article
- pts
- thermoplastic resin
- hindered amine
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 235000013305 food Nutrition 0.000 title claims abstract description 19
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 13
- 150000001412 amines Chemical class 0.000 claims abstract description 8
- 239000004611 light stabiliser Substances 0.000 claims abstract description 6
- 239000002530 phenolic antioxidant Substances 0.000 claims abstract description 5
- 238000002845 discoloration Methods 0.000 abstract description 11
- -1 dimethyl cinnamate Chemical compound 0.000 abstract description 9
- 230000032683 aging Effects 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000006068 polycondensation reaction Methods 0.000 abstract description 2
- STEYNUVPFMIUOY-UHFFFAOYSA-N 4-Hydroxy-1-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CC(O)CC(C)(C)N1CCO STEYNUVPFMIUOY-UHFFFAOYSA-N 0.000 abstract 1
- 229940114081 cinnamate Drugs 0.000 abstract 1
- 229920002857 polybutadiene Polymers 0.000 abstract 1
- 229920005672 polyolefin resin Polymers 0.000 abstract 1
- 239000003381 stabilizer Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229920005604 random copolymer Polymers 0.000 description 4
- 235000013311 vegetables Nutrition 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- 244000300264 Spinacia oleracea Species 0.000 description 3
- 235000009337 Spinacia oleracea Nutrition 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 238000010411 cooking Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 3
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- 235000010149 Brassica rapa subsp chinensis Nutrition 0.000 description 2
- 235000000536 Brassica rapa subsp pekinensis Nutrition 0.000 description 2
- 241000499436 Brassica rapa subsp. pekinensis Species 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 244000131522 Citrus pyriformis Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WXCZUWHSJWOTRV-UHFFFAOYSA-N but-1-ene;ethene Chemical compound C=C.CCC=C WXCZUWHSJWOTRV-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000000576 food coloring agent Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 229920001179 medium density polyethylene Polymers 0.000 description 2
- 239000004701 medium-density polyethylene Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229940116351 sebacate Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- DOTYDHBOKPPXRB-UHFFFAOYSA-N 2-butyl-2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]propanedioic acid Chemical compound CCCCC(C(O)=O)(C(O)=O)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 DOTYDHBOKPPXRB-UHFFFAOYSA-N 0.000 description 1
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 241000473391 Archosargus rhomboidalis Species 0.000 description 1
- 241000512259 Ascophyllum nodosum Species 0.000 description 1
- 240000007124 Brassica oleracea Species 0.000 description 1
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 1
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 1
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 1
- 235000007516 Chrysanthemum Nutrition 0.000 description 1
- 240000005250 Chrysanthemum indicum Species 0.000 description 1
- 244000000626 Daucus carota Species 0.000 description 1
- 235000002767 Daucus carota Nutrition 0.000 description 1
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 240000009088 Fragaria x ananassa Species 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 244000155437 Raphanus sativus var. niger Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004708 Very-low-density polyethylene Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229940069428 antacid Drugs 0.000 description 1
- 239000003159 antacid agent Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 235000021438 curry Nutrition 0.000 description 1
- 229940087101 dibenzylidene sorbitol Drugs 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 235000002864 food coloring agent Nutrition 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 235000008960 ketchup Nutrition 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 235000021018 plums Nutrition 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 235000021067 refined food Nutrition 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000020384 spinach juice Nutrition 0.000 description 1
- 235000021012 strawberries Nutrition 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 229920001866 very low density polyethylene Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は、野菜、果物などの有色食品に接触してち変色
の起りにくい有色食品用成形品に関する.
(従来の技術)
熱可塑性樹脂は、廉価であり、かつ優れた成形加工特性
等を有するため食品容器や同器具としても広く使用され
ている.
しかしながら、熱可塑性樹脂製の成形品は、ホウレン草
、白菜等の野菜類や果物等の有色食品との接触により、
変色が起こる.これを解決するため、例えば特開昭59
−36 1 50や特開昭61−113632ではパラ
オキシ安息香酸や高級脂肪酸アルコールのような添加剤
を配合したボリプロビレンが知られているが、効果は十
分でなく、さらに改良が望まれている.
一般に野菜・果物の青果およびその加工品の有色食品に
よる成形品の変色については、その原因として,それら
に含まれている色素による着色、野菜類の腐敗による着
色、食品用着色剤による変色,さらに種々の添加剤と色
素の相互作用による着色などがあげられるが,明らかと
はなっていない.
また、一般に熱可塑性樹脂は、その化学構造上、加工時
および使用時の熱酸化、さらには耐光劣化を起しやすい
.熱可塑性樹脂にて成形された食品用成形品は、窓際に
置くことがあったり、また水銀灯等の殺菌灯にさらされ
ることもあり、耐光性も重要な要求品質である.また電
子レンジ容器などで使用する場合の耐熱老化性も重要な
品質である.そのため通常、酸化防止剤、光安定剤を配
合して劣化を抑え、初めて実用に耐える製品を得ること
ができるが、この酸化防止剤により有色食品からの着色
がより著しくなることが問題となっている.
(発明が解決しようとする課題)
本発明は、このような有色食品と接触したことに起因す
る変色が起りにくく、かつ耐熱老化性及び耐候性が優れ
た有色食品用成形品を提供することを目的とする.
(課題を解決するための手段)
本発明は、熱可塑性樹脂100重量部に、ヒンダードア
ミン系光安定剤0.01〜l重量部を配合したことを特
徴とする有色食品用成形品である.
本発明で用いる熱可塑性樹脂としては、プタジエン樹脂
、ボリスチレン、AS樹脂、ABS樹脂、ボリフェニレ
ンエーテル、ポリアクリロニトリル、ふっ素樹脂、ポリ
メタクリルスチレン、メタクリル樹脂、ナイロン、ポリ
エチレンテレフタレート、ポリブチレンテレフタレート
、ポリカーボネート、ポリビニルアルコール、ボリアセ
ターノレ、ポリアリノレサノレフ才ン、ポリアリレート
、ヒドロキシ安息香酸ポリエステル、ポリ塩化ビニル、
ポリ塩化ビニリデン及びポリオレフィンなどがあげられ
る.
上記ボリ才レフィンは、エチレン、ブロビレン、1−ブ
テン、1−ペンテン、1−ヘキセン、4−メチルベンテ
ン−1等のα一才レフィン単独重合体,α−オレフィン
同志またはこれらα−オレフィンと他の共重合性単量体
(酢酸ビニル等のビニルエステル、アクリル酸、無水マ
レイン酸、アクリル酸エチル等の不飽和有機酸またはそ
のエステル等)とのランダム共重合体、ブロック重合体
、交互重合体、グラフト重合体などを含むものである.
具体的には、低密度ポリエチレン、中密度ポリエチレン
、高密度ポリエチレン、線状低密度ポリエチレン、超低
密度ポリエチレン、ブロビレン単独重合体、ブロビレン
ーエチレンランダムおよびブロック共重合体,プロピレ
ン−1−ブテン共重合体、ブロビレンーエチレン−1−
ブテン共重合体、ボリ4−メチルベンテン−1等が含ま
れる。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to molded articles for colored foods that are less likely to discolor when they come into contact with colored foods such as vegetables and fruits. (Prior Art) Thermoplastic resins are widely used in food containers and utensils because they are inexpensive and have excellent molding properties. However, molded products made of thermoplastic resin may deteriorate due to contact with colored foods such as vegetables and fruits such as spinach and Chinese cabbage.
Discoloration occurs. In order to solve this problem, for example,
-36 1 50 and JP-A-61-113632 disclose polypropylene containing additives such as paraoxybenzoic acid and higher fatty acid alcohol, but the effects are not sufficient and further improvements are desired. In general, the causes of discoloration of molded products due to colored foods such as fruits and vegetables and their processed products include discoloration due to the pigments contained in them, discoloration due to rotting vegetables, discoloration due to food coloring agents, and Coloring may be due to interactions between various additives and pigments, but this is not clear. Additionally, thermoplastic resins are generally susceptible to thermal oxidation during processing and use, as well as light resistance deterioration due to their chemical structure. Food products made of thermoplastic resin are sometimes placed near windows or exposed to germicidal lamps such as mercury lamps, so light resistance is also an important quality requirement. Heat aging resistance is also an important quality when used in microwave containers, etc. Therefore, it is usually possible to obtain a product that can be put to practical use by suppressing deterioration by adding antioxidants and light stabilizers, but the problem is that these antioxidants make the coloring from colored foods more pronounced. There is. (Problems to be Solved by the Invention) The present invention aims to provide a molded article for colored foods that is unlikely to discolor due to contact with such colored foods and has excellent heat aging resistance and weather resistance. Purpose. (Means for Solving the Problems) The present invention is a colored food molded article characterized in that 0.01 to 1 part by weight of a hindered amine light stabilizer is blended with 100 parts by weight of a thermoplastic resin. Thermoplastic resins used in the present invention include putadiene resin, polystyrene, AS resin, ABS resin, polyphenylene ether, polyacrylonitrile, fluororesin, polymethacrylstyrene, methacrylic resin, nylon, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, and polyvinyl. Alcohol, boriacetanol, polyalinoresanolefin, polyarylate, hydroxybenzoic acid polyester, polyvinyl chloride,
Examples include polyvinylidene chloride and polyolefin. The polyolefins mentioned above are α-olefin homopolymers such as ethylene, brobylene, 1-butene, 1-pentene, 1-hexene, 4-methylbentene-1, α-olefins, or these α-olefins and other α-olefins. Random copolymers, block polymers, alternating polymers with copolymerizable monomers (vinyl esters such as vinyl acetate, unsaturated organic acids such as acrylic acid, maleic anhydride, ethyl acrylate, or their esters), This includes graft polymers, etc.
Specifically, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, very low-density polyethylene, brobylene homopolymer, brobylene-ethylene random and block copolymer, propylene-1-butene copolymer, Polymer, brobylene-ethylene-1-
These include butene copolymers, poly-4-methylbentene-1, and the like.
食品容器として好ましいのは、ポリオレフィンであり、
特に好ましくは、低密度ポリエチレン、中密度ポリエチ
レン、高密度ポリエチレン、線状低密度ポリエチレン、
ブロビレン単独重合体、ブロビレンーエチレンランダム
およびブロック共重合体、ブロビレンー1−ブテン共重
合体、ブロビレンーエチレン−1−プテン共重合体など
があげられるが、中でも最も好ましいものは、ブロビレ
ン単独重合体とブロビレンーエチレンランダムおよび同
ブロック共重合体である.
これらの熱可塑性樹脂はフェノール系酸化防止剤を実質
的に含有していないことが必要である.フェノール系酸
化防止剤が実質的に存在すると、本発明の効果の発現を
阻害するので好ましくない。Preferred as food containers are polyolefins,
Particularly preferably, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene,
Examples include brobylene homopolymer, brobylene-ethylene random and block copolymer, brobylene-1-butene copolymer, and brobylene-ethylene-1-butene copolymer, among which the most preferred one is brobylene homopolymer. These are brobylene-ethylene random and block copolymers. These thermoplastic resins must be substantially free of phenolic antioxidants. Substantial presence of phenolic antioxidants is undesirable because it inhibits the effects of the present invention.
本発明で用いるヒンダードアミン系光安定剤の具体的な
例としては、
(1)コハク酸ジメチルと1−(2−ヒドロキシエチル
)−4−ヒドロキシ−2.2、6.6一テトラメチルビ
ベリジンとの重縮合物(2)ポリ[[6− (1.1.
3.3−テトラメチルブチル)イミノー1,3.5−1
−リアジン−2.4−ジイル] [(2.2,6.6
−テトラメチル−4−ビベリジル)イミノ]へキサメチ
レン[(2.2.6.6−テトラメチル−4−ビペリジ
ル)イミノ]]
(3)2− (3.5−ジーt−プチルー4−ヒドロキ
シベンジル)−2−n−プチルマロン酸のビス(1.2
.2,6.6−ペンタメチル−4−ビペリジル)エステ
ル
(4)テトラキス(2,2,6.6−テトラメチル−4
−ビベリジル)1.2.3.4−ブタンテトラカルポキ
シレート
(5)ビス(2,2,6.6−テトラメチルー4−ビベ
リジル)セバケート
(6)N,N’−ビス(2.2,6.6−テトラメチル
−4−ビペリジル)へキサメチレンジアミンと1.2−
ジブロモエタンとの重縮合(7)ボリ[2−N,N′−
ビス(2.2,6.6−テトラメチル−4−ビベリジル
)へキサメチレンジアミン−4−(N−モルホリノ)シ
ムトリアジン]
(8)1.1′ − (1.2−エタンジイル)一ビス
(3.3,5.5−テトラメチルビペラジノン)
(9)トリス(2.2.6.6−テトラメチル−4−ベ
ビリジル)一ドデシル−1.2,3.4−ブタンテトラ
カルポキシレート
(10) トリス(1.2,2,6.6−ペンタメチル
−4−ビベリジル)一ドデシル−1.2.3.4−ブタ
ンテトラカルボキシレート(11)ビス(1,2,2.
6.6−ペンタメチル−4−ビベリジル)セバケート
などがあげられる.特に分子量500以上のものが相溶
性および効果の優秀性の点で好ましい.中でも最も適し
た化合物は、上記(1).(2).(4)および(7)
の化合物である.このヒンダードアミン成分の配合量は
、熱可塑性樹脂100重量部あたり0.01〜1重量部
、好ましくは0.02〜0.5重量部である.この量未
満では製品の耐熱性、耐候性が十分ではなく、方、過剰
では、不経済であるばかりか変色の問題、ブリードの問
題が発生し好ましくない.本発明ではこれら成分のほか
に、発明の効果を著しく損なわない範囲で他の付加的成
分を配合することができる.具体的には、フォスファイ
ト及びフ才スフォナイト系酸化防止剤、イオウ系酸化防
止剤、フィラー不活性化剤、脂肪酸アミドやシリコンオ
イル等の滑剤、脂肪酸のグリセリンエステルやアミン系
またはアミド系等の帯電防止剤、タルクや硫酸バリウム
等の無機充填材、過酸化物等の分子量調整剤、発泡剤、
有機系あるいは無機系の顔料、蛍光増白剤、紫外線吸収
剤、有機系及び銀イオンや、鯛イ才ン等無機系の抗菌剤
、中和剤、制酸剤、有機系、無機系の増核剤等が挙げら
れる.
さらには、エチレンーブテン系ゴム、エチレンーブロビ
レン系ゴムを添加する系でもよく、これらの合成ゴムの
添加は、衝撃強度向上の点で有効である.
本発明で用いるこれらの成分からなる組成物は、通常の
方法にて製造することができる。例えば、熱可塑性樹脂
のパウダーに上記の成分および必要に応じて他の成分を
添加し、ヘンシエルミキサーにて撹拌混合した後、押出
機にて溶融混練して押出し、ベレットとする.その後、
このベレットを射出成形、圧縮成形、シート成形、ブロ
ー成形、真空成形等の成形機にて目的とする成形品に加
工するのが一般的であるが、添加成分を高濃度に濃縮し
たマスターバッチを作り、これを成形加工時に添加する
方法でもよい.好ましくは、射出成形による容器が外観
や厚さの均一性の点で好ましい.
本発明でいう有色食品とは、ホウレン草、白菜、キャベ
ツ、ニンジン、梅干、大根、春菊,苺、レモン、コンブ
等の野菜、果物、海草類およびカレー、ケチャップ等の
色素を有する食品及びこれらの加工食品をいう.成形品
とは、これらを移送、保存、調理および漬け物用等のた
めに使用するシール容器,漬け物樽、食器、弁当箱,カ
ップ、ボール、水切りかご、食品輸送用コンテナー、電
子レンジ等加熱調理用容器、袋、オーバーラップフィル
ム、冷蔵庫内装等の容器、並びにまな板、はし、スプー
ン、へら、フォーク、し+Lじ、流しの水切用コーナー
、流し用すのこ、ジューサ一部品、ミキサ一部品、食器
洗い機部品等の器具として用いることができるものであ
る.特に好ましくは、シール容器、電子レンジ等加熱調
理用容器において本発明の効果が大きく奏される.
(実施例)
実施例1〜8、比較例1〜3
プロピレンーエチレンブロックコボリマー(MFR=1
0g/10分、エチレン含量=5重量%)100重量部
に対し、下記成分を表1の記載量(重量%)配合し、ヘ
ンシェルミキサーにてブレンド後、30mmφ押出機(
240℃)にて混練した。得られたペレットを射出成形
機(260”C)にかけ、2mm厚x7cm(タテ)x
llcm(ヨコ)x4.5cm(高さ)の射出容器を成
形した。Specific examples of hindered amine light stabilizers used in the present invention include (1) dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2.2,6.6-tetramethylbiveridine; Polycondensate (2) with poly[[6- (1.1.
3.3-tetramethylbutyl)imino 1,3.5-1
-Ryazine-2,4-diyl] [(2.2,6.6
-tetramethyl-4-biveridyl)imino]hexamethylene[(2.2.6.6-tetramethyl-4-biperidyl)imino]] (3) 2-(3.5-di-t-butyl-4-hydroxybenzyl )-2-n-butylmalonic acid bis(1.2
.. 2,6.6-pentamethyl-4-biperidyl) ester (4) tetrakis(2,2,6.6-tetramethyl-4
-biveridyl) 1.2.3.4-butanetetracarpoxylate (5) bis(2,2,6.6-tetramethyl-4-biveridyl) sebacate (6) N,N'-bis(2.2,6 .6-tetramethyl-4-biperidyl)hexamethylenediamine and 1,2-
Polycondensation with dibromoethane (7) Poly[2-N,N'-
bis(2.2,6.6-tetramethyl-4-biveridyl)hexamethylenediamine-4-(N-morpholino)simtriazine] (8) 1.1′-(1.2-ethanediyl)monobis( 3.3,5.5-tetramethylbiperazinone) (9) Tris(2.2.6.6-tetramethyl-4-beviridyl)monododecyl-1.2,3.4-butanetetracarpoxylate (10) Tris(1.2,2,6.6-pentamethyl-4-biveridyl)-dodecyl-1.2.3.4-butanetetracarboxylate (11) bis(1,2,2.
Examples include 6.6-pentamethyl-4-biveridyl) sebacate. In particular, those having a molecular weight of 500 or more are preferred in terms of compatibility and excellent effects. Among them, the most suitable compounds are those listed in (1) above. (2). (4) and (7)
It is a compound of The blending amount of the hindered amine component is 0.01 to 1 part by weight, preferably 0.02 to 0.5 part by weight, per 100 parts by weight of the thermoplastic resin. If the amount is less than this, the heat resistance and weather resistance of the product will not be sufficient, while if it is in excess, it is not only uneconomical but also causes discoloration and bleeding problems, which is not desirable. In the present invention, in addition to these components, other additional components may be blended within a range that does not significantly impair the effects of the invention. Specifically, phosphite and sulfonite-based antioxidants, sulfur-based antioxidants, filler deactivators, lubricants such as fatty acid amides and silicone oils, and charged substances such as fatty acid glycerin esters, amine-based or amide-based antioxidants, etc. inhibitors, inorganic fillers such as talc and barium sulfate, molecular weight regulators such as peroxides, foaming agents,
Organic or inorganic pigments, optical brighteners, ultraviolet absorbers, organic and silver ions, inorganic antibacterial agents such as sea bream, neutralizers, antacids, organic and inorganic additives. Examples include nucleating agents. Furthermore, a system in which ethylene-butene rubber or ethylene-brobylene rubber is added may be used, and the addition of these synthetic rubbers is effective in improving impact strength. A composition comprising these components used in the present invention can be produced by a conventional method. For example, the above components and other components as necessary are added to a thermoplastic resin powder, stirred and mixed in a Henschel mixer, and then melt-kneaded and extruded in an extruder to form a pellet. after that,
This pellet is generally processed into the desired molded product using a molding machine such as injection molding, compression molding, sheet molding, blow molding, or vacuum forming. Alternatively, it may be added to the molding process. Preferably, containers made by injection molding are preferred in terms of appearance and uniformity of thickness. Colored foods in the present invention include vegetables such as spinach, Chinese cabbage, cabbage, carrots, pickled plums, daikon radish, chrysanthemums, strawberries, lemons, and kelp, as well as foods with pigments such as curry and ketchup, and processed foods thereof. It means. Molded products include sealed containers, pickling barrels, tableware, lunch boxes, cups, bowls, colanders, containers for food transportation, microwave ovens, etc. used for heating and cooking, such as sealed containers used for transporting, storing, cooking, and pickling. Containers, bags, overwrap films, refrigerator interior containers, cutting boards, chopsticks, spoons, spatulas, forks, chopsticks, sink draining corners, drainboards, juicer parts, mixer parts, dishwashers It can be used as a device such as parts. Particularly preferably, the effects of the present invention are greatly exhibited in sealed containers and cooking containers such as microwave ovens. (Example) Examples 1 to 8, Comparative Examples 1 to 3 Propylene-ethylene block copolymer (MFR=1
0g/10 minutes, ethylene content = 5% by weight), the following components were blended in the amounts listed in Table 1 (% by weight), blended in a Henschel mixer, and then mixed in a 30mmφ extruder (
The mixture was kneaded at 240°C. The obtained pellets were put into an injection molding machine (260"C) and molded into 2mm thick x 7cm (vertical) x
An injection container measuring 11 cm (width) x 4.5 cm (height) was molded.
この容器の中へ、ミキサーにかけたホウレン草汁を入れ
、30’C/5日間保存した。その後、内容物を取り出
し、水洗後、容器の変色度合いを目視判定した。結果は
表1に示す.
判定基準は、以下のような基準である
0 :ほとんど変化が認められない
○“:わずかな変化のみ認められる
○ :少し変色する程度
△ :変色明確にあり
× :かなり強く変色する
また、このホウレン草汁に浸した成形品を水洗後キセノ
ンランプ型耐候試験機にかけ、表面クラックの発生時間
を計った(ブラックパネル温度=63℃、降雨無し)。Spinach juice mixed with a mixer was put into this container and stored at 30'C for 5 days. Thereafter, the contents were taken out, washed with water, and the degree of discoloration of the container was visually determined. The results are shown in Table 1. The judgment criteria are as follows: 0: Almost no change observed ○": Only a slight change observed ○: Slight discoloration △: Discoloration clearly present ×: Quite strongly discolored In addition, this spinach After washing the molded product soaked in water, it was subjected to a xenon lamp weather tester and the time required for surface cracks to occur was measured (black panel temperature = 63°C, no rain).
さらにまた、この試料を120℃設定のギャーオーブン
に入れ、脆化時間を計った.結果を表1に示す。Furthermore, this sample was placed in a gear oven set at 120°C, and the embrittlement time was measured. The results are shown in Table 1.
実施例9,10、比較例4
レモン汁を用いた以外は、実施例lと同様な方法でテス
トした.結果を表lに示す.
ヒンダードアミン系光安定剤
前記(1)の化合物
〃 (2)の化合物
〃 (4)の化合物
〃 (5)の化合物
〃 (7)の化合物
その他の添加物
CAST :ステアリン酸カルシウム
DSTP :ジステアリルチ才ジブロビ才ネート
IRIOIO:テトラキス[メチレンビス−3一(3′
.5′−ジーt−ブチルー
4′−ヒドロキシフエニル)プロ
ビオネート]メタン
TPNC: 1.1.3−トリス(2−メチル−4−ヒ
ドロキシ−5−t−プチ
ルフエニル)ブタン
B H T:2.6−ジーt−プチルフェノール
E C I:l.3.2.4−ジーベンジリデンソル
ビトール
タフマーA20090 :メルトフローレイト(AST
M D1238、190
’C)=1 8g/10分のエチレン
ーブテン系ゴム
(発明の効果)
上記試験結果から明らかなように、本発明の組成の熱可
塑性樹脂成形品は、有色食品と長く接触させても変色が
おこらず、有色食品用成形品,とりわけシール容器、電
子レンジ加熱用容器としての問題を解決するものである
.Examples 9 and 10, Comparative Example 4 Tests were conducted in the same manner as in Example 1, except that lemon juice was used. The results are shown in Table 1. Hindered amine light stabilizer Compound of (1) Compound of (2) Compound of (4) Compound of (5) Compound of (7) Other additives CAST: Calcium stearate DSTP: Distearyl dibrobinate IRIOIO: Tetrakis[methylenebis-3-(3'
.. 5'-di-t-butyl-4'-hydroxyphenyl)probionate]methane TPNC: 1.1.3-Tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane B H T: 2.6 -di-t-butylphenol E C I: l. 3.2.4-Dibenzylidene Sorbitol Tafmer A20090: Melt Flow Rate (AST
M D1238, 190'C) = 1 8g/10min Ethylene-butene rubber (Effect of the invention) As is clear from the above test results, the thermoplastic resin molded article having the composition of the present invention can be kept in contact with colored foods for a long time. It does not cause discoloration and solves the problem of colored food molded products, especially sealed containers and containers for heating in microwave ovens.
Claims (1)
樹脂100重量部に、ヒンダードアミン系光安定剤0.
01〜1重量部を配合したことを特徴とする有色食品用
成形品。0.0 parts by weight of a hindered amine light stabilizer is added to 100 parts by weight of a thermoplastic resin substantially free of phenolic antioxidants.
1. A colored food molded article, characterized in that it contains 1 to 1 part by weight of 0.01 to 1 part by weight.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP18741689A JPH0352961A (en) | 1989-07-21 | 1989-07-21 | Molded article for colored food |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP18741689A JPH0352961A (en) | 1989-07-21 | 1989-07-21 | Molded article for colored food |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0352961A true JPH0352961A (en) | 1991-03-07 |
Family
ID=16205662
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP18741689A Pending JPH0352961A (en) | 1989-07-21 | 1989-07-21 | Molded article for colored food |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0352961A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0578532A (en) * | 1991-09-13 | 1993-03-30 | Mitsubishi Petrochem Co Ltd | Molded article for colored food |
JPH05239352A (en) * | 1992-03-02 | 1993-09-17 | Polyplastics Co | Polyarylene sulfide resin composition resistant to photodiscoloration |
JP2001527109A (en) * | 1997-12-18 | 2001-12-25 | ビーエーエスエフ アクチェンゲゼルシャフト | Use of ethylene homopolymers and copolymers stabilized by sterically hindered amines or their N-hydroxy or N-oxyl derivatives for the production of plastic products and moldings for storage and transport of vegetable oil esters |
-
1989
- 1989-07-21 JP JP18741689A patent/JPH0352961A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0578532A (en) * | 1991-09-13 | 1993-03-30 | Mitsubishi Petrochem Co Ltd | Molded article for colored food |
JPH05239352A (en) * | 1992-03-02 | 1993-09-17 | Polyplastics Co | Polyarylene sulfide resin composition resistant to photodiscoloration |
JP2001527109A (en) * | 1997-12-18 | 2001-12-25 | ビーエーエスエフ アクチェンゲゼルシャフト | Use of ethylene homopolymers and copolymers stabilized by sterically hindered amines or their N-hydroxy or N-oxyl derivatives for the production of plastic products and moldings for storage and transport of vegetable oil esters |
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