JP4490058B2 - Deodorant and thermoplastic resin composition containing the same - Google Patents
Deodorant and thermoplastic resin composition containing the same Download PDFInfo
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- JP4490058B2 JP4490058B2 JP2003184497A JP2003184497A JP4490058B2 JP 4490058 B2 JP4490058 B2 JP 4490058B2 JP 2003184497 A JP2003184497 A JP 2003184497A JP 2003184497 A JP2003184497 A JP 2003184497A JP 4490058 B2 JP4490058 B2 JP 4490058B2
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- Prior art keywords
- acid
- amino
- thermoplastic resin
- clay mineral
- resin composition
- Prior art date
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Description
【0001】
【発明の属する技術分野】
本発明は、脱臭剤及びそれを含有する熱可塑性樹脂組成物に関する。詳しくは、イオン交換性層状粘土鉱物の層間に、アミノ基含有有機化合物がインターカレートしている複合無機層状粘土鉱物を有効成分とする脱臭剤に関し、更に詳しくは、アルデヒド系の物質を主とする悪臭、悪味の除去性能に優れた基材に適した複合無機層状粘土鉱物を有効成分とする脱臭剤又は防悪味剤、及びそれを含有する熱可塑性樹脂組成物に関する。
【0002】
【従来の技術】
近年、脱臭剤においては、基材として使用されている物質のうち、活性炭等は有力な基材となりうるが、炭素からなるために黒色を呈しており、他の基材と混合して使用すると着色が出来ない等の不便がある。さらに、活性炭の場合、脱臭機構は物理吸着であるため、吸着した物質が脱離しやすいという欠点も持っている。また、その他の脱臭基材としてポリアミン系の吸着剤(例えば、特許文献1参照)も提案されているが、特に生活環境で使う際において、ポリアミン等の物質は生理活性を持っており、遺伝子阻害物質となる可能性もあり、危険性が高く、特に経口で使用する付近の基材としては適さないと考えられる(例えば、非特許文献1〜3参照)。
特に熱可塑性樹脂は食品用の包装材料に多用されており、長期保存、消費者ニーズの適応に貢献しているが、添加剤の分解物、重合時の残留モノマーの酸化物等が内容物に付着、移行し、熱可塑性樹脂特有の異臭、味として内容物に悪影響を与えやすい。
こういった現状に鑑みて、例えば熱可塑性樹脂の製造段階においてサイロに熱風を還流させて乾燥と共に脱臭処理を施す等の対応が行われているが、完全に異臭、雑味成分の除去ができないこと、その後の酸化劣化、熱劣化、分解などにより発生する異臭、雑味に関しては効果が無いなどの問題があった。
【特許文献1】
特開平9−276380号公報
【非特許文献1】
Stenesh編、「生理・生化学用語辞典」、化学同人、1985年、266頁
【非特許文献2】
山田常雄他編、「生物学辞典第3版」、岩波書店、1983年3月、1228頁
【非特許文献3】
化学工業日報社編、「14102の化学商品」、化学工業日報社、2002年、388頁
【0003】
【課題を解決するための手段】
本発明者らは、上記事情に鑑み、イオン交換性無機層状物質(粘土鉱物)にアミノ酸等を層間挿入して複合化させることにより、アルデヒド系の分子を反応吸着し固定化でき、これを熱可塑性樹脂に複合することにより、特にアルデヒド系の異臭、雑味成分に対して効果的な除去ができることを発見し、本発明を完成するに至った。
【0004】
即ち本発明の要旨は、ハイドロタルサイト類化合物の層間に、アミノ基を有するカルボン酸又はその塩から選ばれるアミノ基含有有機化合物がインターカレートしている脱臭剤に存する。
また、本発明の他の要旨は、熱可塑性樹脂100重量部に対して、ハイドロタルサイト類化合物の層間に、アミノ基を有するカルボン酸又はその塩から選ばれるアミノ基含有有機化合物がインターカレートしている脱臭剤0.01〜100重量部を含有することを特徴とする熱可塑性樹脂組成物に存する。
また、本発明の他の要旨は、上記熱可塑性樹脂組成物を成形してなる脱臭性成形品又はアルデヒド吸着性成形品にあり、更に他の要旨は、上記熱可塑性樹脂組成物を成形することを特徴とする成形品の脱臭方法にある。
【0005】
以下、本発明について詳細に説明する。
本発明で原料として用いられるイオン交換性層状粘土鉱物は、カチオン交換性層状粘土鉱物又はアニオン交換性層状粘土鉱物である。両者は通常、どちらか単独で使用されるが混合して使用することもできる。インターカレーションのしやすさから,インターカレーションの前、即ち原料段階では単独で用いる方が好ましい。インターカレーションの後であれば、特に制限なく適宜混合して使用することができる。
【0006】
(1)カチオン交換性層状粘土鉱物
カチオン交換性層状粘土鉱物としては、ケイ酸塩類、金属リン酸塩、金属酸化物等が挙げられる。ケイ酸塩類は、化学組成・結晶構造など変化に富んでおり、多種類の物質が知られているが、一般的には層状結晶であって鉱物学上はフィロシリケートに属する。特に二枚の四面体層と一枚の八面体層からなる2:1型フィロシリケートと一枚の四面体層と一枚の八面体層からなる1:1型フィロシリケートがある。
2:1型フィロシリケートX2〜3(Si,Al)4O10(OH)2(式中、XはAl3+、Mg2+,Fe3+、Fe2+などを表す)の代表的な鉱物としては、スメクタイト、バーミキュライト、マイカ、パイロフィライト、雲母、脆雲母、緑泥石族等があり、1:1型フィロシリケートAl2Si2O5(OH)4としては、カオリナイト族、蛇紋石族等がある。
スメクタイト群には、サポナイト、ヘクトライト、ソーコナイト、モンモリロナイト、バイデライト、ノントロナイト、ステブンサイト等があり、バーミキュライト群には、トリオクタヘドラルバーミキュライト、ジオクタヘドラルバーミキュライト等があり、マイカ群には、フロゴパイト、バイオタイト、レピドライト、マスコバイト、パラゴナイト、クロライト、マーガライト、テニオライト、テトラシリシックマイカ等があり、緑泥石族にはクッケアイト、スドーアイト、クリノクロア、シャモサイト、ニマイト等の組成物が挙げられる。
カオリナイト族にはカオリナイト,ディッカサイト、ハロイサイト等が、蛇紋石族にはクリソタイル、リザーダイト、アメサイトなどがある。
また、これらに分類できないフィロシリケートとしては、イライト(ハイドロマイカ)、セリサイトなどがある。これらのフィロシリケートは天然から産出されるもの、或いは、水熱法、溶融法、固相法等による合成品であってもよい。
【0007】
金属リン酸塩としては、リン酸ジルコニウムやリン酸チタン等の4価金属の酸性リン酸塩、三リン酸二水素アルミニウム二水和物を、単独もしくは2種以上を混合して使用できる。4価金属の酸性リン酸塩は、A.Clearfield編,“Inorganic Ion Exchange Materials”、第3章(1982年)CRC Press社に大要が述べられているが、一般式MIV(HPO4)2・nH2O(式中のMIVは4価金属を示す。n=0〜2)のように表わされ、一水和物(n=1)のα型、二水和物(n=2)のγ型などが一般的によく知られている。また、三リン酸二水素アルミニウム二水和物は化学式AlH2P3O10・2H2Oで表される。
【0008】
金属酸化物としては、バナジウム、ニオブ、タンタル、チタン、鉄等の酸化物、酸塩等が挙げられ、具体的には、5酸化バナジウム、4酸化バナジウム、3酸化バナジウム、2酸化バナジウム、バナジル、バナジン酸、5酸化ニオブ、4酸化ニオブ、3酸化ニオブ、2酸化ニオブ、ニオブ酸、5酸化タンタル、4酸化タンタル、3酸化タンタル、2酸化タンタル、6タンタル酸、オルトタンタル酸、2酸化チタン、3酸化チタン、4酸化チタン、チタン酸、2酸化鉄、3酸化鉄、これらの塩類が挙げられる。塩類としては、ナトリウム、カリウム、リチウム、セシウム等のアルカリ金属塩、ベリリウム、マグネシウム、カルシウム、ストロンチウム、バリウム等のアルカリ土類金属塩などが挙げられる。
このうちで、後述するアミノ基を有するカルボン酸、スルホン酸若しくはフェノール又はそれらの塩から選ばれるアミノ基含有有機化合物(このアミノ基含有有機化合物を「ゲスト分子」ということがある。)を比較的容易に取り込むことから、ケイ酸塩類、金属リン酸塩類が望ましく、更に望ましくは、ケイ酸塩類である。
【0009】
ケイ酸塩類の層状粘土鉱物は、珪酸塩層と、アルカリ金属及び/又はアルカリ土類金属カチオンとそれに配位した水分子からなる層とが互層配列した層状珪酸塩鉱物の1種である。雲母も同じような構造を持つ層状珪酸塩鉱物であるが、カチオン交換性層状粘土鉱物では、雲母に比べて珪酸塩層のもつ負電荷が小さく、層間の結合が弱いため、層間カチオンが交換性であり、層間に水分子が容易に入り込み、カチオンと配位する。
【0010】
(2)アニオン交換性層状粘土鉱物
アニオン交換性粘土鉱物は、下記の一般式(i)または(ii)で示される層状複水酸化物である。
基本層:[M2+ 1-XM3+ X(OH)2]X+・・・・・・(i)
中間層:[An- X/n・yH2O]X-
(但し、式中、M2+は2価の金属イオンを表し、例えば、Mg2+、Mn2+、Fe2+、Co2+、Ni2+、Cu2+、Zn2+等が挙げられる。また、M3+は3価の金属イオンを表し、例えば、Al3+、Cr3+、Fe3+、Co3+、In3+等が挙げられる。An-はn価のアニオンであり、これらのアニオンとしてはOH- 、F- 、Cl- 、NO3 -、SO4 2-、CO3 2-、Fe(CN)6 4-、V10O28 6-、Br-、I-、ClO4 -、H2PO4 -、HBO3 2-、CO3 2-、SiO3 2-、HPO4 2-、PO4 3-、Fe(CN)4 4-等が挙げられる。xは0.2〜0.33の範囲であり、yは乾燥温度により異なるがその値は0<y<1であり、nは整数である。)上記化合物の例示としては、[Mg2+ 0.75Al3+ 0.25(OH)- 2]0.25+[(CO3)2- 1/8・0.5H2O]0.25-、[Mg2+ 0.75Al3+ 0.25(OH)2]0.25+[Cl- 1/8・0.5H2O]0.25-などが挙げられる。
また、
基本層:[M1+ 1-XM3+ X(OH)2](2x-1)+・・・・・(ii)
中間層:An- (2x-1)/n・yH2O
(M1+は1価の陽イオンを表し、Li+がある。また、M3+は3価の金属イオンを表し、例えば、Al3+、Cr3+、Fe3+、Co3+、In3+等が挙げられる。An-はn価のアニオンであり、これらのアニオンとしてはOH- 、F- 、Cl- 、NO3 -、SO4 2-、CO3 2-、Fe(CN)6 4-、V10O28 6-、Br-、I-、ClO4 -、H2PO4 -、HBO3 2-、CO3 2-、SiO3 2-、HPO4 2-、PO4 3-、Fe(CN)4 4-等が挙げられる。xは0.2〜0.33の範囲であり、yは乾燥温度により異なるがその値は0<y<1であり、nは整数である。)上記化合物の例示としては、[Li+ 0.33Al3+ 0.67(OH)- 2]0.34+[(CO3)2- 1/6・0.5H2O]0.34-などが挙げられる。
該アニオン交換性粘土鉱物は、ブルーサイト構造[Mg(OH)2 ]類似の正の電荷を持つ2次元基本層と、アニオンおよび層間水からなる負の電荷を持つ中間層とからなる積層構造化合物である。
【0011】
これらの層状複水酸化物は天然のものであっても合成品でもかまわないが、構造の安定性から合成品を用いることが好ましい。上記層状複水酸化物は通称ハイドロタルサイト類化合物とよばれるが、例えばマグネシウム−亜鉛ハイドロタルサイト類化合物が例示される。製造方法の一例としては、硝酸マグネシウム六水和物、硝酸亜鉛六水和物および硝酸アルミニウム九水和物を純水に溶解したもの(I液) と、水酸化ナトリウムおよび炭酸ナトリウムを純水に溶解したもの(II 液) とを攪拌しながら徐々に加える。その際、溶液のpHを約8〜12、好ましくは9〜11に保つのが好ましい。約20〜80℃で24時間〜7日間程度反応させることにより沈澱物を得、ついでこの沈澱物を熟成させた後、洗浄、脱水、乾燥することにより、製造することができる。
なお、上記の沈澱物を製造する際の反応温度、反応時間および反応系における攪拌速度を適宜調節することにより、使用目的や使用対象に応じた所望の結晶形や粒子径を有するハイドロタルサイト類化合物を容易に製造することができる。マグネシウム−亜鉛ハイドロタルサイト類化合物の市販品としては、協和化学社製DHT6A、水沢化学社製ミズカラック等が挙げられる。
【0012】
これらのイオン交換性層状粘土鉱物の粒径は、臭い、味の吸着面積が大きい方が好ましいという観点から、本発明では平均粒径は10μm以下が好ましく、特に1μm以下が好ましい。
層状構造とは、単位結晶層が互いに積み重なって構成されていることをいう。その結晶層同士の結合は比較的弱く、層状構造を破壊することなくこの層間に種々のイオンや分子または化合物、即ちゲスト分子をインターカレート(層間挿入)することができる
イオン交換性粘土鉱物は、層間距離が広いほどインターカレートしやすいという意味で有効であるが、本発明において層が負電荷をもつ層状構造を有する粘土鉱物であるなら特に制限されない。層間距離は一般的に30Å(300nm)以下の場合が好ましく、より好ましくは20Å(200nm)以下である。
【0013】
層状粘土鉱物の有するイオン交換容量は、0.1〜500meq/100gが好ましく、特に1〜300meq/100gが好ましい。なお、層状粘土鉱物の陽イオン交換容量(以下「CEC」)、及び陰イオン交換容量(以下「AEC」)は、層状粘土鉱物の種類、産地、組成によってそれぞれ異なるので予め測定しておくことが好ましい。CECの測定法としては、例えば、メチレンブルー吸着法、AECの測定法としては、例えば、硝安を用いる方法(日本粘土学会編「粘土ハンドブック第2版」、技報堂、1987年、114,588頁)等が挙げられる。
【0014】
ここでインターカレーションとは、層状粘土の層間に目的の化合物が挿入することである。一般的にインターカレーションに用いる層状粘土鉱物のことをホスト分子、挿入される化合物のことをゲスト分子と呼ぶ。
【0015】
(インターカレーション)
インターカレーションの方法としては、特に限定はされず、ゲスト分子の溶液と層状粘土鉱物を懸濁させる方法、層状粘土鉱物にゲスト分子の蒸気を接触させる方法、層状粘土鉱物の合成時の溶媒にゲスト分子を介在させる方法等がある。これらの中では、ゲスト分子の溶液と層状粘土鉱物を懸濁させる方法が簡易で好ましい。以下、これを詳細に説明する。
【0016】
層状粘土鉱物を水等の溶媒と混合、さらには、必要に応じて混練して、層間に溶媒を含ませ、膨潤させる。溶媒としては、一般に水が用いられるが、これ以外の極性溶媒、たとえば、メタノール、エタノール等のアルコール、ジメチルホルムアミド(DMF)、ジメチルスルホキシド(DMSO)、アセトン、メチルエチルケトン等のケトン、ジオキサン、テトラヒドロフラン等のエーテル等を用いてもよい。
【0017】
イオン交換性粘土鉱物がカチオン交換性粘土鉱物の場合には、溶媒は、酸性条件の方が好ましく、更に好ましくはpH3〜7である。それ以外では、インターカレーションがスムーズに行われない場合がある。
イオン交換性粘土鉱物がアニオン交換性粘土鉱物の場合には、溶媒は、アルカリ性条件の方が好ましく、更に好ましくはpH7〜9である。それ以外では、該アニオン交換性層状粘土鉱物が溶解するなど、インターカレーションがスムーズに行われない場合がある。
また、該アニオン交換性層状粘土化合物は、一度300〜500℃程度にて焼成した後、溶媒中でインターカレーションする方が、層に分子が取り込まれやすく好ましい。
溶媒は、1種のみを用いてもよいし、2種以上を併用してもよい。溶媒処理は20〜80℃、好ましくは40〜80℃、時間としては1〜72時間が適当であるが、5〜48時間が効率の面からも好ましい。
【0018】
また、インターカレーションの進行を速やかにするために、予め極性有機分子(以下、ピラーという)で粘土を有機化処理しておくことで層間距離を広げておき、更に本発明で使用するゲスト分子を取り込ませる手法も有効である。その際のピラーとしては、特に制限は無いが、アルキルアミン、アリルアミン、ピリジン系化合物などの有機アミン化合物が一般的である。ピラーでの処理も20〜80℃、好ましくは40〜80℃、時間としては1〜72時間が適当であるが、5〜48時間が効率の面からも好ましい。
【0019】
上記のようにして、層状粘土鉱物を膨潤させ、層間隔を膨潤前に比べて大きく拡大させたところへ、ゲスト分子の溶液を添加混合し、さらには、必要に応じて混練することにより、イオン交換もしくは酸塩基反応の作用でゲスト分子を層状粘土鉱物の層間へインターカレーション(挿入)する。その後、乾燥することにより、複合無機層状粘土鉱物が得られる。乾燥方法としては、たとえば、自然乾燥、熱風乾燥、凍結乾燥、超臨界乾燥等が挙げられ、特に限定はされないが、真空下ですることが好ましい。更に好ましくは、層間の溶媒分子を完全に除去するために、熱風乾燥が好ましく、また、出来上がりの粉体の粉砕のし易さから凍結乾燥により乾燥させたものがやりやすい。乾燥後もゲスト分子は層間にとどまり、結果的に初期に比べて層状粘土鉱物の層間隔は拡大されたまま保持される。
【0020】
インターカレート後のイオン交換性粘土鉱物の粒径は、使用用途に対し任意に選択できるが、脱臭剤として用いる場合、粒径が小さい方が好ましく、具体的には10μm以下、更には1μm以下がより好ましい。
インターカレート後のイオン交換性粘土鉱物は層間距離は、原料として使用した粘土鉱物の種類及びゲスト分子の大きさに依存し、吸収するアルデヒドの大きさが空隙よりも大きいと吸収できない。従って、層間距離は通常、0.1〜50nm、好ましくは0.5〜5nmの範囲から選択される。
インターカレート後のイオン交換性粘土鉱物のゲスト分子の量は、アルデヒド吸着の性能の面から多い方が好ましく、イオン交換容量の0.1%以上、好ましくは1%以上である。
【0021】
(インターカレーションの確認方法)
得られた処理粘土鉱物にゲスト分子がインターカレートしたか否かは、たとえば、粉末X線回折測定、炭素・水素・窒素元素分析、示差熱分析などによって判定することができる。たとえば、ゲスト分子がイオン交換性粘土鉱物にインターカレートすると、原体であるイオン交換性粘土鉱物の層間距離は、大きく広がる(X線回折ピークが低角度側へ大きくシフトする)ので、粉末X線回折測定でイオン交換性粘土鉱物の層間距離を測定することにより、ゲスト分子がイオン交換性粘土鉱物の層間にインターカレートしたか否かを判定することができる。また、炭素、水素、窒素の元素分析値から、インターカレートしたゲスト分子の量を測定することができる。
【0022】
次に本発明で用いられるアミノ基を有するカルボン酸、スルホン酸若しくはフェノール又はそれらの塩から選ばれるアミノ基含有有機化合物(ゲスト分子)について説明する。
ゲスト分子は1分子中の炭素数が1〜20であるものが好ましく、より好ましくは1〜10である。以下、更に具体的に例示する。
【0023】
(1)1分子中に、アミノ基1個を有するモノカルボン酸
例えば、グリシン、ロイシン、システイン、チロシン、フェニルアラニン、アラニン、セリン、イソロイシン、バリン、スレオニン、メチオニン、トリプトファン、ヒスチジン、
アミノ酢酸、アミノ酪酸、アミノ吉草酸、アミノペンタン酸、アミノヘキサン酸、アミノドデカン酸、アミノシクロプロパン-1-カルボン酸、アミノイソ酪酸、アミノクロトン酸、アミノシクロブタンカルボン酸、アミノ馬尿酸、アミノシクロプロパンカルボン酸、アミノカプロン酸、アミノカプリル酸、o,m,p-アミノ安息香酸、アミノフェニル酢酸、アミノサリチル酸、1-アミノ-1-シクロヘキサンカルボン酸、1-アミノ-1-シクロペンタンカルボン酸、1-アミノ-1-シクロプロパンカルボン酸、5-アミノイソフタル酸、3-アミノ-2-ナフチル酸、6-アミノニコチン酸、3-アミノ-1,2,4-トリアゾール-5-カルボン酸、アンピシリン、シクラシリン、シクロロイシン、5-アミノ-3-メチル-2,4-チオフェンジカルボン酸、5-アセチル-2-アミノ-4,5,6,7-テトラヒドロチエノ[3,2-c]ピリジン-3-カルボン酸、3-アリル-4-アミノ-2-チオキソ-2,3-ジヒドロ-1,3-チアゾール-5-カルボン酸、4-アミノ-3-(2-ブロモフェニル)-2-チオキソ-2,3-ジヒドロ-1,3-チアゾール-5-カルボン酸、5-アミノ-1-(4-クロロベンジル)-1H-4-ピラゾールカルボン酸、4-アミノ-3-(3-クロロ-4-フルオロフェニル)-2-チオキソ-2,3-ジヒドロ-1,3-チアゾール-5-カルボン酸、5-アミノ-1-(4-クロロフェニル)-1H-4-ピラゾールカルボン酸5-アミノ-1-(4-クロロフェニル)-1H-4-ピラゾールカルボン酸、4-アミノ-3-(4-クロロフェニル)-2-チオキソ-2,3-ジヒドロ-1,3-チアゾール-5-カルボン酸、2-アミノ-4,5-ジメチルチオフェン-3-カルボン酸、4-アミノ-3-(2-フルオロフェニル)-2-チオキソ-2,3-ジヒドロ-1,3-チアゾール-5-カルボン酸、2-アミノ-8-フルオロ-4H-チエノ[3,2-c]クロメン-3-カルボン酸、2-アミノ-4-(2-フリル)-3-チオフェンカルボン酸、5-アミノ-1-(2-ヒドロキシエチル)-1H-4-ピラゾールカルボン酸、2-アミノ-4-メチルチアゾール-5-カルボン酸、4-アミノ-5-メチルチエノ[2,3-d]ピリミジン-6-カルボン酸、2-アミノ-4-メチルチオフェン-3-カルボン酸、4-アミノ-3-(1-ナフチル)-2-チオキソ-2,3-ジヒドロ-1,3-チアゾール-5-カルボン酸、5-アミノ-1-フェニル-4-ピラゾールカルボン酸、4-アミノ-1-ピペリジンカルボン酸、3-アミノ-4-ピラゾールカルボン酸エチル、メフェナム酸、2-アミノ-4,5-ジメチル-3-チオフェンカルボン酸、3-アミノ-4-メチルチオフェン-2-カルボン酸、2-アミノ-4-フェニル-3-チオフェンカルボン酸、3-アミノ-2-チオフェンカルボン酸、ニコチンアミド、ニアラミド、フェネチシリン等が挙げられる。
【0024】
(2)1分子中に、アミノ基1個を有するジカルボン酸
例えば、グルタミン酸、アスパラギン酸、アミノシクロペンタンジカルボン酸、アミノシクロプロパンジカルボン酸、5-アミノ-1,3-ベンゼンジカルボン酸、アミノマレイン酸、アミノアジピン酸,アミノスベリン酸等が挙げられる。
【0025】
(3)1分子中に、アミノ基を2個以上有するカルボン酸
例えば、グルタミン、リジン、アスパラギン、アルギニン、ジアミノ安息香酸、ジアミノ酪酸、2,6−ジアミノピメリン酸等が挙げられる。
【0026】
(4)1分子中、アミノ基を1個以上有するスルホン酸
例えば、アミノメタンスルホン酸、2-アミノ-1,5-ナフタレンジスルホン酸、2-アミノ-1,4-ベンゼンジスルホン酸、o-アミノベンゼンスルホン酸、1-アミノ-4-ブロモアントラキノン-2-スルホン酸、4-アミノ-2-クロロトルエン-5-スルホン酸、S-(2-アミノエチル)チオスルホン酸、3-アミノ-4-ヒドロキシ-5-ニトロベンゼンスルホン酸、4-アミノ-5-メトキシ-2-メチルベンゼンスルホン酸、2-アミノ-5-メチルベンゼン-1-スルホン酸、4-アミノ-2-メチルベンゼン-1-スルホン酸、5-アミノ-2-メチルベンゼン-1-スルホン酸、1-アミノ-3,8-ナフタレンジスルホン酸、3-アミノ-1,5-ナフタレンジスルホン酸、4-アミノナフタレン-1-スルフォン酸、4-アミノ-1-ナフタレンスルホン酸、6-アミノ-1-ナフタレンスルホン酸、5-アミノ-1-ナフタレンスルホン酸、1-アミノ-8-ナフタレンスルホン酸、4-アミノナフタレン-1-スルホン酸、5-アミノナフタレン-1-スルホン酸、8-アミノナフタレン-1-スルホン酸、7-アミノ-1,3,6-ナフタレントリスルホン酸、8-アミノ-1-ナフトール-3,6-ジスルホン酸、4-アミノ-5-ナフトール-2,7-ジスルホン酸、1-アミノ-2-ナフトール-4-スルホン酸、1-アミノ-5-ナフトール-7-スルホン酸、4-アミノ-3-メチルベンゼン-1-スルホン酸、アニリン-2,5-ジスルホン酸、アゾフクシン、アゾリトミン、N,N-ビス(2-ヒドロキシエチル)-2-アミノエタンスルホン酸、4,4'-ビス(4-アミノ-1-ナフチルアゾ)-2,2'-スチルベンジスルホン酸、4,4'-ジアミノスチルベン-2,2'-ジスルホン酸、m-アミノ安息香酸エチルメタンスルホン酸、メタニル酸、1-ナフチルアミン-6-スルホン酸、4-ニトロアニリン-2-スルホン酸、スルファニルアミド、スルファニル酸、スラミンナトリウム、タウリン、トリパンブルー、ジアミノベンゼンスルホン酸、4,4'-ジアミノスチルベン-2,2'-ジスルホン酸などが挙げられる。
【0027】
(5)アミノ基を有するフェノール化合物
例えば、p-アセトアミノフェノール、o-アセトアミノフェノール、アセトアミノフェン、2-アミノ-4-クロロフェノール、5-アミノ-o-クレゾール、3-アミノ-4-ヒドロキシベンゼンスルホンアミド、4-アミノ-3-メチルフェノール、2-アミノ-4-ニトロフェノール、2-アミノ-5-ニトロフェノール、m-アミノフェノール、o-アミノフェノール、p-アミノフェノール、o-アニシジン、2,4-ジアミノフェノール、m-ジエチルアミノフェノール、4-ヒドロキシジフェニルアミン、ジアミノフェノール、チロシンなどが挙げられる。
【0028】
以上例示したように、本発明で用いられるアミノ基含有有機化合物(ゲスト分子)は、1分子中に、アミノ基を少なくとも1個有し、かつカルボン酸基、スルホン酸基若しくはフェノール性水酸基を少なくとも1個有する化合物、又はそれらの塩から選ばれるものである。上記(1)〜(5)はそれらの例示であってそれらに限定されるものではない。また、上記の分類は便宜的なものであって、複数の類に属する化合物も、これらのいずれにも分類されない化合物もある。
アミノ基含有有機化合物を塩として用いる場合には、ナトリウム塩、カリウム塩、リチウム塩、マグネシウム塩、カルシウム塩などアルカリ(土類)金属塩があげられる。1分子中に、カルボン酸基及び/又はスルホン酸基が2個以上存在する多塩基酸については、一塩、二塩(例えば、アミノナフタリンジカルボン酸一ナトリウム塩、アミノナフタリンジカルボン酸二ナトリウム塩)いずれも使用できる。遊離酸として用いる場合と比較して、塩の場合は水への溶解性がよいので取扱い易いメリットがある。しかし層間に金属イオンもまた取り込まれることがある。この場合、脱臭剤の使用態様として特に支障はないが、当該脱臭剤を熱可塑性樹脂に配合して使用するとき、着色の原因となることがあるので、用途に制限がでる。
【0029】
上記のアミノ基含有有機化合物がカチオン交換性層状粘土鉱物にインターカレートすることにより、粘土鉱物の層間にゲスト分子が固定される。ゲスト分子の固定をより完全にするためには、上記(1)、(2)、(3)で示したモノカルボン酸又はジカルボン酸が好ましい。
中でも、入手のし易さ、人体への影響の少なさからアミノ酸が好ましく、例としてグリシン、ロイシン、システイン、チロシン、フェニルアラニン、アスパラギン酸、リジン、アラニン、セリン、アスパラギン、イソロイシン、グルタミン酸、アルギニン、バリン、スレオニン、グルタミン、メチオニン、トリプトファン、ヒスチジンなどが挙げられる。
【0030】
また、本発明には脱臭の機能を損なわない範囲において、他の機能、例えば抗菌、芳香などの目的で、上記のアミノ基含有有機化合物又はその他の物質を同時にインターカレートすることが可能である。例えば抗菌機能を付与するためにベンザルコニウム、セチルピリジニウムクロライド等の物質を同時にインターカレートしても構わない。具体的にはゲスト分子のインターカレーションに際して、ゲスト分子と共にこれらの物質を所定量配合して使用すればよい。場合によっては、インターカレーションの後、これらの物質で再処理する方法、これらの物質で処理後、インターカレーションする方法でもよい。
【0031】
本発明の脱臭剤は、複合無機層状粘土鉱物を有効成分とするものであり、酸系の臭気、フェノール系の臭気、アルデヒド系の臭気に対しては、効果がある。
具体的には、酸系の臭気として、ギ酸、酢酸、プロピオン酸、酪酸、コハク酸、安息香酸、アミノ酸、アセチルサリチル酸などのカルボン酸、フェノール系の臭気としてフェノール、クレゾールなどのフェノール化合物、アルデヒド系の臭気として、ホルムアルデヒド、アセトアルデヒド、エチルアルデヒド、プロピルアルデヒド、t−ブチルアルデヒド、イソプロピルアルデヒド、ベンズアルデヒド、パラトルアルデヒド、ナフチルアルデヒドなどの除去に有効である。これらの中でも、特に、アルデヒド系の臭気に対しては、本発明の脱臭剤は効果が高大きい。
【0032】
脱臭剤としての使用方法としては、上記製造法により乾燥したものを、任意の方法、例えばミル、粉砕機、すり鉢等、粉砕が可能な方法により粉末状にしたもの、もしくはチップ状等にしたもの、若しくはプレス等により固体上に凝集加工した形状により、単体において使用、若しくは塗料、粉末コーティング、シリカゲルなどと混合、セラミックとの混合など、周知の粉体の使用方法により脱臭の効果が得られる。特に取り扱いのし易さ、応用の広さ、表面積の大きさなどの理由から、粉末状に加工して使用することが好ましい。
脱臭剤の粒径は、使用目的により選ばれるが、粒径が小さいほど表面積が大きくなり、脱臭機能が有効に発現され、好ましくは100μm以下、更に好ましくは20μ以下である。これらの粒子は粉末のまま使用することも可能であるが、圧縮凝集などの方法で加工して任意の形で利用することも可能である.
【0033】
本発明の脱臭剤は、上記のようにそれ自体単独で、又は他の物質と複合して用いることができるが、より好ましい複合化の方法として、熱可塑性樹脂との複合化が挙げられる。
熱可塑性樹脂は、熱によって可塑化可能であれば全て利用可能であり、例として、高密度ポリエチレン、高圧法低密度ポリエチレン、直鎖状低密度ポリエチレン、ポリプロピレン、プロピレン・エチレンブロック共重合体、プロピレン・エチレンランダム共重合体、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、ポリスチレン、ポリカーボネート、ポリブタジエン、ポリイソプレン、AS、ABS、EPR、EPDM、SEBS、NBRなどが挙げられる。
特に食品容器に利用できるという観点から、ポリプロピレン系熱可塑性樹脂、ポリエチレン系熱可塑性樹脂、ポリエチレンテレフタレート系樹脂、ポリスチレンが好ましい。
【0034】
複合化の方法は任意の公知の方法で可能であるが、例として押出機による複合化、ロール混練等が挙げられる。予めドライブレンド等により混ぜておき、単軸、ないしは2軸押出機などにより溶融混練することにより複合化させる方法が、分散が良いという点で好ましい。また、予め高濃度のマスターバッチを作成しておき、成形加工の段階で添加して使用するという方法も好ましい。
脱臭剤の配合量は、熱可塑性樹脂の種類及び複合体の用途などにも左右されるが、脱臭効果が発現する限度で、かつ熱可塑性樹脂の成形性を損なわない範囲で、熱可塑性樹脂100重量部当り、通常、0.01〜100重量部、好ましくは0.03〜1重量部使用される。
【0035】
上記の熱可塑性樹脂組成物は、ペレット、パウダーとして材料又は他の物質の配合剤とすることもできるが、通常、公知の成形方法により成形加工され、脱臭性成形品とされる。成形品としては、フィルム、シートなどのほか、容器、パック、トレー、中空ボトルなど任意の形状に加工できる。
その成形法としては、例えばTダイによる押出成形、インフレーションフィルム成形、ブロー成形、インジェクション成形、熱成形、圧空成形、プレス成形などが使用可能である。
また、本発明はポリオレフィン多層成形品に適用することが可能であり、例えば中間層に酸素バリアのための層を配置することができる。バリア層としては、アルミ箔、紙等をラミネーションすることが可能である。多層成形品を食品用容器として使用する場合は、脱臭、脱雑味効果を有効に保持するためには本発明に係る熱可塑性樹脂を内層に配することが好ましい。
【0036】
また、押出しブレンド等で熱可塑性樹脂に複合化させる方法のほかに、例えば表面にコーティングして熱可塑性樹脂と複合化させる方法、ロールによる塗布方法なども挙げられる。
本発明に係る脱臭成形品は各種の用途に応用可能であり、例えば輸液バック、バックインボックス、食品容器、食品容器用の蓋、容器をシールする際のフィルム、ブローボトル、カップ、インジェクショントレー、ポーションカップなどに適し、特に低臭低味の要請が大きい、水、米飯などの臭いや味の影響を受けやすい内容物、さらには異物の影響を人体に受けやすい幼児向け、病人向けの食品包材に適する。
【0037】
【実施例】
以下、本発明の実施例を記載して、より具体的に説明するが、本発明はこれらの実施例により何ら限定されるものではない。尚、以下の実施例及び比較例での共通事項は次の通りである。
(1)元素分析
ファイソンズ社製、EA1110型CHNS−O分析計。燃焼管1000℃、カラム70℃、錫製のサンプルパン、He流量130ml/分
(2)粉末X線回折
島津製作所社製、RAD−RD。測定角2θ=2〜30°、Cu−Kα線原、50kV、300mA
【0038】
(3)ガス吸着実験1
シャーレに(脱臭剤)サンプル0.5gをとり、対象となる臭気物質をサンプルビンに10ml入れた。密閉デシケーター中に両者を介在し、30℃にて吸着実験を行った。予めサンプル及びシャーレの重量を測定しておき、経時変化の重量増減により臭気物質の吸着量を測定した。
(4)ガス吸着実験2
4Lの密閉系容器を作成し、アセトアルデヒド(和光純薬社製)を約200ppmの濃度になるまで気化させ、サンプルパンを接続して室温にて容器中のガス濃度(単位ppm)の経時変化を追った。ガス濃度の測定は、アセトアルデヒド用ガス検知管(ガステック社製アセトアルデヒド用ガス検知管No92)を使用し、1回の測定で密閉容器中の気体200mlを採取して測定した。
(5)臭気の官能試験
パネラー5人によって以下の基準で点数化し、評価点の平均値をとった。
0級:無臭。全く臭気が感じられない。
1級:やっと臭気を感じる。何の臭気か判別できない。
2級:臭気が感じられる。何の臭気か判別できる。
3級:かなり臭う、楽に感じる。
4級:強く臭う。
5級:激しく臭う、耐えられないほど強烈な臭気。
【0039】
[実施例1]
(1)インターカレーションの方法
ゲスト分子としてグルタミン酸(和光純薬社製)0.03molを蒸留水300mlに溶解し、上記溶液にイオン交換性層状粘土鉱物としてモンモリロナイト(クニミネ工業社製、クニピアF、層間距離12.8Å、分子量594、カチオン交換容量=115meq/100g)5gを攪拌しながら投入し、室温(23℃)下、24時間反応させた。その後、メンブランフィルター(3μm)にて吸引ろ過した。ろ過残渣を、減圧下、−20℃で24時間凍結乾燥し、その後、70℃で24時間真空熱風乾燥を行った。得られた粉体を乳鉢で粉砕し(約1〜10μm)評価に用いた。インターカレーション後の層間距離は14.8Åに拡大していた。また、元素分析から求めたインターカレーション量はモンモリロナイトの1組成式(Al5/3Mg1/3Si4O10(OH)2W1/3・mH2O)に対して0.75分子であった。
その後、シリンダー温度230℃の15ミリ2軸押出機にて、ポリプロピレンパウダー(日本ポリケム社製、MA3Q、MFR=15g/10分)100重量部に対して、上記で得られた脱臭剤を、5重量部、酸化防止剤(チバスペシャリティーケミカル社製、イルガノックス1010)を0.1重量部、加工安定剤(チバスペシャリティーケミカル社製、イルガフォス168)を0.2重量部、ミキサーでブレンドし、造粒した。得られたペレットの色相は乳白色であった。
そのペレットについて、オクチルアルデヒド(和光純薬社製)を用いてガス吸着実験1を行ったところ、アルデヒドの吸着量はペレット重量に対して、5時間後で0.33重量%、24時間後で0.49重量%、72時間後に0.52重量%であることが確認された。
【0040】
[実施例2]
ゲスト分子としてグルタミン酸、無機層状粘土鉱物としてγ‐リン酸チタン(テイカ社製、層間距離11.6Å、分子量296、カチオン交換容量=100meq/100g)を用い、上記の方法にてインターカレーションを行った。インターカレーション後の層間距離は13.2Å、インターカレーション量はγ‐リン酸チタン1組成式(Ti(HPO4)2.2H2O)に対して0.3分子であった。
その後、実施例1と同様にしてポリプロピレンパウダーと造粒した。得られたペレットの色相は白色であった。そのペレットについて、オクチルアルデヒドを用いてガス吸着実験1を行ったところ、アルデヒドの吸着量はペレット重量に対して、5時間後で0.24重量%、24時間後で0.32重量%、72時間後に0.33重量%であることが確認された。
【0041】
[実施例3]
ゲスト分子としてフェニルアラニン(和光純薬社製)、無機層状粘土鉱物としてモンモリロナイトを用い、上記の方法にてインターカレーションを行った。インターカレーション後の層間距離は14.9Å、インターカレーション量はモンモリロナイト1組成式に対して0.91分子であった。
その後、実施例1と同様にしてポリプロピレンパウダーと造粒複合化した。得られたペレットの色相は乳白色であった。そのペレットについて、オクチルアルデヒドを用いてガス吸着実験1を行ったところ、アルデヒドの吸着量はペレット重量に対して、5時間後で0.19重量%、24時間後で0.22重量%、72時間後に0.25重量%であることが確認された。
【0042】
[比較例1]
シリンダー温度230℃の15ミリ2軸押出機にて、ポリプロピレンパウダー100重量部に対して、モンモリロナイト5重量部、酸化防止剤(チバスペシャリティーケミカル社製、イルガノックス1010)を0.1重量部、加工安定剤(チバスペシャリティーケミカル社製、イルガフォス168)を0.2重量部をミキサーでブレンドし、造粒複合化した。得られたペレットの色相は乳白色であった。そのペレットについて、オクチルアルデヒドを用いてガス吸着実験1を行ったところ、72時間後でもガス吸着は確認されなかった。結果を表2に示した。
【0043】
[比較例2]
シリンダー温度230℃の15ミリ2軸押出機にて、ポリプロピレンパウダー100重量部に対して、γ−リン酸チタン5重量部を用い、比較例1と同様にしてポリプロピレンパウダーと造粒した。得られたペレットの色相は白色であった。そのペレットについて、オクチルアルデヒドを用いてガス吸着実験1を行ったところ、72時間後でもガス吸着は確認されなかった。
【0044】
[比較例3]
シリンダー温度230℃の15ミリ2軸押出機にて、ポリプロピレンパウダーのみを用い造粒化した。得られたペレットの色相は無色(透明)であった。そのペレットについて、オクチルアルデヒドを用いてガス吸着実験1を行ったところ、72時間後でもガス吸着は確認されなかった。
【0045】
【表1】
【0046】
【表2】
【0047】
[実施例4]
ゲスト分子にグルタミン酸ナトリウム0.03molを蒸留水300mlに溶解し、無機層状粘土物質としてMgAl系ハイドロタルサイト(協和化学工業社製、DHT6、M=603.98、アニオン交換容量=220meq/100g)を事前に500℃で5時間焼結処理したもの(不定形のため層間距離は検出できない)を5gを攪拌しながら投入し、室温(23℃)下、24時間反応させた。その後、メンブランフィルター(3μm)にて吸引ろ過した。ろ過残渣を、真空中80℃にて24時間乾燥させ、乳鉢にて粒径約1μmに粉砕し、CHN元素分析、ガス吸着実験2を行った。結果を表3に示す。
【0048】
[実施例5]
ゲスト分子にグルタミン酸0.03molを蒸留水300mlに溶解し、無機層状粘土物質としてMgAl系ハイドロタルサイト5gを攪拌しながら投入し、さらに濃度0.1MのNH4OH水溶液を投入しpHを8に調整し、室温(23℃)下、24時間反応させた。実施例4と同様に乾燥し、評価を行った。結果を表3に示す。
【0049】
[実施例6]
無機層状粘土物質として事前に500℃で5時間焼結処理したMgAl系ハイドロタルサイトを用い、以下実施例5と同様の方法にて複合化、評価を行った。結果を表3に示す。
【0050】
[実施例7]
ゲスト分子にフェニルアラニンを用い、以下実施例4と同様の方法により複合化を行った。結果を表3に示す。
【0051】
[比較例4]
ゲスト分子を用いず、無機層状粘土物質としてMgAl系ハイドロタルサイトを用い、実施例4と同様の評価を行った。結果を表3に示す。
【0052】
[実施例8]
実施例4にて作成した粉体を、ポリプロピレンパウダー100重量部に対して5重量部、酸化防止剤(チバスペシャリティーケミカル社製、イルガノックス1010)を0.1重量部、加工安定剤(チバスペシャリティーケミカル社製、イルガフォス168)を0.2重量部をミキサーでドライブレンドし、15mmφ2軸押出機で230℃、窒素パージにて混練、5mm径のダイスから押し出し、ストランドを水冷した後、ペレタイザーにて約3mm角のペレットに造粒した。得られたペレットの色相は白色であった。そのペレットにてガス吸着実験2及び臭い官能試験を行った。結果を表4に示す。
【0053】
【実施例9】
実施例5にて作成した粉体を用い、実施例8と同様の方法にて混練、造粒、評価を行った。結果を表4に示す。
【0054】
[実施例10]
実施例6にて作成した粉体を用い、実施例8と同様の方法にて混練、造粒、評価を行った。結果を表4に示す。
【0055】
[実施例11]
実施例7にて作成した粉体を用い、実施例8と同様の方法により混練、造粒、評価を行った。結果を表4に示す。
【0056】
[比較例5]
比較例4にて用いた粉体を用い、実施例8と同様に混練、造粒、評価を行った。結果を表4に示す。
【0057】
[比較例6]
ポリプロピレンパウダー100重量部に対して、酸化防止剤(チバスペシャリティーケミカル社製、イルガノックス1010)を0.1重量部、加工安定剤(イルガフォス168)0.2重量部をミキサーでドライブレンドし、以下実施例8と同様に混練、造粒、評価を行った。結果を表4に示す。
【0058】
【表3】
【0059】
【表4】
【0060】
【発明の効果】
本発明によれば、アルデヒド系の物質、酸系物質等の悪臭、悪味の除去性能に優れた脱臭剤が得られる。この脱臭剤はポリオレフィン樹脂など熱可塑性樹脂基材に配合することができ、該脱臭剤を配合した熱可塑性樹脂組成物からは、脱臭性成形品、アルデヒド吸着性成形品が得られ、食品用容器、食品包装資材等に有用である。また、該脱臭剤を配合した熱可塑性樹脂組成物は成形時に微量発生することのある臭気を吸着する作用があるので、成形加工が行われる雰囲気の脱臭にも寄与する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a deodorizing agent and a thermoplastic resin composition containing the same. Specifically, it relates to a deodorizing agent comprising a composite inorganic layered clay mineral in which an amino group-containing organic compound is intercalated between the layers of the ion-exchangeable layered clay mineral, and more specifically, mainly an aldehyde-based substance. The present invention relates to a deodorant or an anti-taste agent comprising a composite inorganic layered clay mineral suitable for a substrate having an excellent odor and bad taste removal performance as an active ingredient, and a thermoplastic resin composition containing the same.
[0002]
[Prior art]
In recent years, in deodorizers, among substances used as a base material, activated carbon and the like can be a powerful base material, but since it is made of carbon, it exhibits a black color and when used in combination with other base materials There are inconveniences such as inability to color. Furthermore, in the case of activated carbon, since the deodorizing mechanism is physical adsorption, it has a drawback that the adsorbed substance is easily desorbed. In addition, polyamine-based adsorbents (for example, see Patent Document 1) have been proposed as other deodorizing base materials, but especially when used in living environments, substances such as polyamines have physiological activity, and gene inhibition There is also a possibility of becoming a substance, and there is a high risk, and it is considered that it is not particularly suitable as a base material in the vicinity for oral use (for example, see Non-Patent Documents 1 to 3).
In particular, thermoplastic resins are widely used in food packaging materials, contributing to long-term storage and adapting to consumer needs, but the contents of additives such as decomposition products of additives and residual monomer oxides during polymerization Adhering and migrating, it tends to adversely affect the contents as a strange odor and taste peculiar to thermoplastic resins.
In view of the current situation, for example, in the manufacturing stage of thermoplastic resins, countermeasures such as refluxing hot air in a silo and drying and deodorizing treatment are performed, but it is not possible to completely remove off-flavors and miscellaneous components In addition, there was a problem that there was no effect with respect to odor and miscellaneous taste generated by subsequent oxidation deterioration, heat deterioration, decomposition, etc.
[Patent Document 1]
JP-A-9-276380
[Non-Patent Document 1]
Edited by Stenesh, “Dictionary of Physiology and Biochemistry”, Chemistry Doujin, 1985, 266
[Non-Patent Document 2]
Yamada Tsuneo et al., Biology Dictionary 3rd Edition, Iwanami Shoten, March 1983, p. 1228
[Non-Patent Document 3]
Edited by Chemical Industry Daily, “14102 Chemical Products”, Chemical Industry Daily, 2002, p. 388
[0003]
[Means for Solving the Problems]
In view of the above circumstances, the present inventors can adsorb and immobilize aldehyde-based molecules by intercalating amino acid or the like with an ion-exchangeable inorganic layered material (clay mineral) to form a complex. It has been discovered that by compounding with a plastic resin, it is possible to effectively remove aldehyde-based odors and miscellaneous components, and the present invention has been completed.
[0004]
That is, the gist of the present invention is as follows.Carboxylic acid having an amino group or a salt thereof between layers of hydrotalcite compoundsIt exists in the deodorizing agent in which the amino group containing organic compound chosen from is intercalating.
Moreover, the other gist of the present invention is based on 100 parts by weight of the thermoplastic resin.Carboxylic acid having an amino group or a salt thereof between layers of hydrotalcite compoundsThe present invention resides in a thermoplastic resin composition characterized by containing 0.01 to 100 parts by weight of an intercalating deodorant selected from the group consisting of amino group-containing organic compounds.
Further, another gist of the present invention resides in a deodorizing molded product or an aldehyde adsorbing molded product formed by molding the thermoplastic resin composition, and another gist is molding the thermoplastic resin composition. In the deodorizing method of the molded product characterized by this.
[0005]
Hereinafter, the present invention will be described in detail.
The ion exchange layered clay mineral used as a raw material in the present invention is a cation exchange layered clay mineral or an anion exchange layered clay mineral. Both are usually used alone, but may be used in combination. From the viewpoint of ease of intercalation, it is preferable to use it alone before intercalation, that is, in the raw material stage. If it is after intercalation, it can mix and use suitably without a restriction | limiting especially.
[0006]
(1) Cation exchange layered clay mineral
Examples of the cation exchange layered clay mineral include silicates, metal phosphates, metal oxides and the like. Silicates are rich in changes in chemical composition and crystal structure, and many kinds of substances are known, but they are generally layered crystals and belong to phyllosilicates in terms of mineralogy. In particular, there are 2: 1 type phyllosilicate composed of two tetrahedral layers and one octahedral layer, and 1: 1 type phyllosilicate composed of one tetrahedral layer and one octahedral layer.
2: 1 type phyllosilicate X2~Three(Si, Al)FourOTen(OH)2(Where X is Al3+, Mg2+, Fe3+, Fe2+As representative minerals, there are smectite, vermiculite, mica, pyrophyllite, mica, brittle mica, chlorite group, etc., and 1: 1 type phyllosilicate Al.2Si2OFive(OH)FourThese include the kaolinite group and the serpentine group.
The smectite group includes saponite, hectorite, saconite, montmorillonite, beidellite, nontronite, and stevensite.The vermiculite group includes trioctahedral vermiculite and dioctahedral vermiculite. There are phlogopite, biotite, lepidrite, mascobite, paragonite, chlorite, margarite, teniolite, tetrasilicic mica, etc., and the chlorite group has compositions such as kukeite, sudoite, clinochlore, chamosite, nimite, etc. Can be mentioned.
The kaolinite group includes kaolinite, diccasite, halloysite, and the serpentine group includes chrysotile, lizardite, and amesite.
In addition, phyllosilicates that cannot be classified into these include illite (hydromica) and sericite. These phyllosilicates may be produced from nature, or may be synthesized by hydrothermal method, melting method, solid phase method or the like.
[0007]
As metal phosphates, acidic phosphates of tetravalent metals such as zirconium phosphate and titanium phosphate, and aluminum dihydrogen triphosphate dihydrate can be used alone or in admixture of two or more. Acidic phosphates of tetravalent metals are outlined in A. Clearfield, “Inorganic Ion Exchange Materials”, Chapter 3 (1982) CRC Press.IV(HPOFour)2・ NH2O (M in the formulaIVRepresents a tetravalent metal. n = 0 to 2), and the α form of monohydrate (n = 1) and the γ form of dihydrate (n = 2) are generally well known. In addition, aluminum dihydrogen triphosphate dihydrate has the chemical formula AlH.2PThreeOTen・ 2H2Represented by O.
[0008]
Examples of the metal oxide include oxides such as vanadium, niobium, tantalum, titanium, and iron, and acid salts. Specifically, vanadium pentoxide, vanadium tetroxide, vanadium trioxide, vanadium dioxide oxide, vanadyl, Vanadic acid, niobium pentoxide, niobium tetroxide, niobium trioxide, niobium dioxide, niobic acid, tantalum pentoxide, tantalum tetroxide, tantalum trioxide, tantalum tantalum oxide, tantalum tantalate, orthotantalic acid, titanium dioxide, Examples include titanium trioxide, titanium oxide, titanic acid, iron dioxide, iron oxide, and salts thereof. Examples of the salts include alkali metal salts such as sodium, potassium, lithium and cesium, and alkaline earth metal salts such as beryllium, magnesium, calcium, strontium and barium.
Among these, an amino group-containing organic compound selected from carboxylic acids having a amino group, sulfonic acid, phenol, or salts thereof described later (this amino group-containing organic compound is sometimes referred to as “guest molecule”) is relatively. Silicates and metal phosphates are desirable because they are easily incorporated, and silicates are more desirable.
[0009]
Silicate layered clay minerals are one type of layered silicate mineral in which a silicate layer and an alkali metal and / or alkaline earth metal cation and a layer composed of water molecules coordinated with each other are arranged alternately. Mica is also a layered silicate mineral with a similar structure, but in cation-exchanged layered clay minerals, the negative charge of the silicate layer is smaller than that of mica and the bonding between layers is weak, so interlayer cations are exchangeable. Water molecules easily enter between the layers and coordinate with cations.
[0010]
(2) Anion exchange layered clay mineral
The anion exchangeable clay mineral is a layered double hydroxide represented by the following general formula (i) or (ii).
Basic layer: [M2+ 1-XM3+ X(OH)2]X +(I)
Intermediate layer: [An- X / n・ YH2O]X-
(However, in the formula, M2+Represents a divalent metal ion, for example Mg2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+Etc. M3+Represents a trivalent metal ion, for example, Al3+, Cr3+, Fe3+, Co3+, In3+Etc. An-Is an n-valent anion, and these anions include OH-, F-, Cl-, NOThree -, SOFour 2-, COThree 2-, Fe (CN)6 Four-, VTenO28 6-, Br-, I-, ClOFour -, H2POFour -, HBOThree 2-, COThree 2-, SiOThree 2-, HPOFour 2-, POFour 3-, Fe (CN)Four Four-Etc. x is in the range of 0.2 to 0.33, and y varies depending on the drying temperature, but its value is 0 <y <1, and n is an integer. ) Examples of the above compounds include [Mg2+ 0.75Al3+ 0.25(OH)- 2]0.25+[(COThree)2- 1/8・ 0.5H2O]0.25-, [Mg2+ 0.75Al3+ 0.25(OH)2]0.25+[Cl- 1/8・ 0.5H2O]0.25-Etc.
Also,
Basic layer: [M1+ 1-XM3+ X(OH)2](2x-1) +(Ii)
Intermediate layer: An- (2x-1) / n・ YH2O
(M1+Represents a monovalent cation, Li+There is. M3+Represents a trivalent metal ion, for example, Al3+, Cr3+, Fe3+, Co3+, In3+Etc. An-Is an n-valent anion, and these anions include OH-, F-, Cl-, NOThree -, SOFour 2-, COThree 2-, Fe (CN)6 Four-, VTenO28 6-, Br-, I-, ClOFour -, H2POFour -, HBOThree 2-, COThree 2-, SiOThree 2-, HPOFour 2-, POFour 3-, Fe (CN)Four Four-Etc. x is in the range of 0.2 to 0.33, and y varies depending on the drying temperature, but its value is 0 <y <1, and n is an integer. ) Examples of the above compounds include [Li+ 0.33Al3+ 0.67(OH)- 2]0.34+[(COThree)2- 1/6・ 0.5H2O]0.34-Etc.
The anion exchange clay mineral has a brucite structure [Mg (OH)2] A layered structure compound composed of a two-dimensional basic layer having a similar positive charge and an intermediate layer having a negative charge composed of an anion and interlayer water.
[0011]
These layered double hydroxides may be natural or synthetic, but it is preferable to use synthetic products from the viewpoint of structural stability. The layered double hydroxide is commonly called a hydrotalcite compound, and examples thereof include a magnesium-zinc hydrotalcite compound. Examples of production methods include magnesium nitrate hexahydrate, zinc nitrate hexahydrate and aluminum nitrate nonahydrate dissolved in pure water (solution I), and sodium hydroxide and sodium carbonate in pure water. Slowly add the dissolved solution (solution II) with stirring. At that time, it is preferable to maintain the pH of the solution at about 8 to 12, preferably 9 to 11. The precipitate can be obtained by reacting at about 20 to 80 ° C. for about 24 hours to 7 days, and after aging the precipitate, it can be produced by washing, dehydrating and drying.
It should be noted that hydrotalcites having a desired crystal shape and particle size according to the purpose of use and the object of use by appropriately adjusting the reaction temperature, reaction time, and stirring speed in the reaction system in producing the above precipitate. The compound can be easily produced. As a commercial item of a magnesium- zinc hydrotalcite compound, Kyowa Chemical Co., Ltd. DHT6A, Mizusawa Chemical Co., Ltd. Mizukarak, etc. are mentioned.
[0012]
In the present invention, the average particle size is preferably 10 μm or less, and particularly preferably 1 μm or less, from the viewpoint that the ion exchange layered clay mineral preferably has a larger odor and taste adsorption area.
The layered structure means that unit crystal layers are stacked on each other. The bonds between the crystal layers are relatively weak, and various ions, molecules or compounds, that is, guest molecules, can be intercalated (intercalated) between layers without destroying the layered structure.
The ion-exchangeable clay mineral is effective in the sense that the intercalation is easier as the interlayer distance is wider. However, in the present invention, the layer is not particularly limited as long as the layer is a clay mineral having a layered structure having a negative charge. In general, the interlayer distance is preferably 30 mm (300 nm) or less, more preferably 20 mm (200 nm) or less.
[0013]
The ion exchange capacity of the layered clay mineral is preferably 0.1 to 500 meq / 100 g, particularly preferably 1 to 300 meq / 100 g. The cation exchange capacity (hereinafter “CEC”) and the anion exchange capacity (hereinafter “AEC”) of the layered clay mineral are different depending on the type, place of origin, and composition of the layered clay mineral and may be measured in advance. preferable. Examples of the CEC measurement method include a methylene blue adsorption method, and examples of the AEC measurement method include a method using ammonium nitrate (edited by the Japan Clay Society, “Clay Handbook 2nd Edition”, Gihodo, 1987, pages 114,588). It is done.
[0014]
Here, the intercalation means that a target compound is inserted between layers of layered clay. In general, layered clay minerals used for intercalation are called host molecules, and inserted compounds are called guest molecules.
[0015]
(Intercalation)
The intercalation method is not particularly limited, and includes a method of suspending a solution of a guest molecule and a layered clay mineral, a method of contacting the layered clay mineral with the vapor of the guest molecule, and a solvent for the synthesis of the layered clay mineral. There is a method of interposing a guest molecule. In these, the method of suspending the solution of a guest molecule and a layered clay mineral is simple and preferable. This will be described in detail below.
[0016]
The layered clay mineral is mixed with a solvent such as water, and further kneaded as necessary to contain the solvent between the layers and swell. As the solvent, water is generally used, but other polar solvents such as alcohols such as methanol and ethanol, ketones such as dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone and methyl ethyl ketone, dioxane, tetrahydrofuran and the like Ether or the like may be used.
[0017]
When the ion-exchangeable clay mineral is a cation-exchangeable clay mineral, the solvent is preferably under acidic conditions, more preferably pH 3-7. Otherwise, the intercalation may not be performed smoothly.
When the ion-exchangeable clay mineral is an anion-exchangeable clay mineral, the solvent is preferably under alkaline conditions, more preferably pH 7-9. Otherwise, the intercalation may not be performed smoothly, for example, the anion exchange layered clay mineral is dissolved.
The anion-exchange layered clay compound is preferably baked at about 300 to 500 ° C. and then intercalated in a solvent so that molecules can be easily taken into the layer.
Only 1 type may be used for a solvent and it may use 2 or more types together. The solvent treatment is 20 to 80 ° C., preferably 40 to 80 ° C., and the time is suitably 1 to 72 hours, but 5 to 48 hours is also preferable from the viewpoint of efficiency.
[0018]
In addition, in order to speed up the progress of intercalation, the interlaminar distance is increased by previously treating the clay with a polar organic molecule (hereinafter referred to as “pillar”), and the guest molecule used in the present invention. It is also effective to take in. The pillar at that time is not particularly limited, but organic amine compounds such as alkylamines, allylamines, and pyridine compounds are generally used. The treatment with the pillar is also 20 to 80 ° C., preferably 40 to 80 ° C., and the time is suitably 1 to 72 hours, but 5 to 48 hours is also preferred from the viewpoint of efficiency.
[0019]
As described above, the layered clay mineral is swollen and the layer spacing is greatly expanded as compared with that before the swelling, and then the guest molecule solution is added and mixed, and further kneaded as necessary, so that ions are added. Guest molecules are intercalated (inserted) between layers of layered clay minerals by the action of exchange or acid-base reaction. Thereafter, a composite inorganic layered clay mineral is obtained by drying. Examples of the drying method include natural drying, hot air drying, freeze drying, supercritical drying, and the like, and are not particularly limited, but are preferably performed under vacuum. More preferably, in order to completely remove solvent molecules between layers, hot air drying is preferable, and from the ease of pulverization of the finished powder, a product dried by freeze drying is easy to do. Even after drying, the guest molecules stay between the layers, and as a result, the layer spacing of the layered clay mineral is kept larger than in the initial stage.
[0020]
The particle size of the ion-exchangeable clay mineral after intercalation can be arbitrarily selected for the intended use, but when used as a deodorant, a smaller particle size is preferred, specifically 10 μm or less, and further 1 μm or less. Is more preferable.
The intercalated ion-exchangeable clay mineral cannot be absorbed when the interlayer distance depends on the type of the clay mineral used as a raw material and the size of the guest molecule, and the size of the aldehyde to be absorbed is larger than the void. Therefore, the interlayer distance is usually selected from the range of 0.1 to 50 nm, preferably 0.5 to 5 nm.
The amount of guest molecules in the ion-exchangeable clay mineral after intercalation is preferably larger from the viewpoint of aldehyde adsorption performance, and is 0.1% or more, preferably 1% or more of the ion-exchange capacity.
[0021]
(Intercalation check method)
Whether or not a guest molecule intercalates in the obtained treated clay mineral can be determined by, for example, powder X-ray diffraction measurement, carbon / hydrogen / nitrogen element analysis, differential thermal analysis, and the like. For example, when a guest molecule is intercalated into an ion-exchangeable clay mineral, the interlayer distance of the original ion-exchangeable clay mineral increases greatly (the X-ray diffraction peak is greatly shifted to the low angle side), so that the powder X By measuring the interlayer distance of the ion-exchangeable clay mineral by line diffraction measurement, it can be determined whether or not the guest molecule has intercalated between the layers of the ion-exchangeable clay mineral. In addition, the amount of intercalated guest molecules can be measured from the elemental analysis values of carbon, hydrogen, and nitrogen.
[0022]
Next, an amino group-containing organic compound (guest molecule) selected from carboxylic acid having an amino group, sulfonic acid, phenol, or a salt thereof used in the present invention will be described.
The guest molecule preferably has 1 to 20 carbon atoms in one molecule, more preferably 1 to 10. Hereinafter, more specific examples will be given.
[0023]
(1) Monocarboxylic acid having one amino group in one molecule
For example, glycine, leucine, cysteine, tyrosine, phenylalanine, alanine, serine, isoleucine, valine, threonine, methionine, tryptophan, histidine,
Aminoacetic acid, aminobutyric acid, aminovaleric acid, aminopentanoic acid, aminohexanoic acid, aminododecanoic acid, aminocyclopropane-1-carboxylic acid, aminoisobutyric acid, aminocrotonic acid, aminocyclobutanecarboxylic acid, aminohippuric acid, aminocyclopropane Carboxylic acid, aminocaproic acid, aminocaprylic acid, o, m, p-aminobenzoic acid, aminophenylacetic acid, aminosalicylic acid, 1-amino-1-cyclohexanecarboxylic acid, 1-amino-1-cyclopentanecarboxylic acid, 1- Amino-1-cyclopropanecarboxylic acid, 5-aminoisophthalic acid, 3-amino-2-naphthylic acid, 6-aminonicotinic acid, 3-amino-1,2,4-triazole-5-carboxylic acid, ampicillin, cyclacillin , Cycloleucine, 5-amino-3-methyl-2,4-thiophenedicarboxylic acid, 5-acetyl-2-amino-4,5,6,7-tetrahydrothieno [3,2 -c] pyridine-3-carboxylic acid, 3-allyl-4-amino-2-thioxo-2,3-dihydro-1,3-thiazole-5-carboxylic acid, 4-amino-3- (2-bromophenyl) ) -2-Thioxo-2,3-dihydro-1,3-thiazole-5-carboxylic acid, 5-amino-1- (4-chlorobenzyl) -1H-4-pyrazolecarboxylic acid, 4-amino-3- (3-Chloro-4-fluorophenyl) -2-thioxo-2,3-dihydro-1,3-thiazole-5-carboxylic acid, 5-amino-1- (4-chlorophenyl) -1H-4-pyrazolecarboxylic Acid 5-amino-1- (4-chlorophenyl) -1H-4-pyrazolecarboxylic acid, 4-amino-3- (4-chlorophenyl) -2-thioxo-2,3-dihydro-1,3-thiazole-5 -Carboxylic acid, 2-amino-4,5-dimethylthiophene-3-carboxylic acid, 4-amino-3- (2-fluorophenyl) -2-thioxo-2,3-dihydro-1,3-thiazole-5 -Carboxylic acid, 2-amino-8-fluoro-4H-thieno [3,2-c] chromene-3-carboxylic acid, 2-amino-4- (2-furyl)- 3-thiophenecarboxylic acid, 5-amino-1- (2-hydroxyethyl) -1H-4-pyrazolecarboxylic acid, 2-amino-4-methylthiazole-5-carboxylic acid, 4-amino-5-methylthieno [2 , 3-d] pyrimidine-6-carboxylic acid, 2-amino-4-methylthiophene-3-carboxylic acid, 4-amino-3- (1-naphthyl) -2-thioxo-2,3-dihydro-1, 3-thiazole-5-carboxylic acid, 5-amino-1-phenyl-4-pyrazolecarboxylic acid, 4-amino-1-piperidinecarboxylic acid, ethyl 3-amino-4-pyrazolecarboxylate, mefenamic acid, 2-amino -4,5-dimethyl-3-thiophenecarboxylic acid, 3-amino-4-methylthiophene-2-carboxylic acid, 2-amino-4-phenyl-3-thiophenecarboxylic acid, 3-amino-2-thiophenecarboxylic acid Nicotinamide, niaramide, pheneticillin and the like.
[0024]
(2) Dicarboxylic acid having one amino group in one molecule
For example, glutamic acid, aspartic acid, aminocyclopentanedicarboxylic acid, aminocyclopropanedicarboxylic acid, 5-amino-1,3-benzenedicarboxylic acid, aminomaleic acid, aminoadipic acid, aminosuberic acid and the like can be mentioned.
[0025]
(3) Carboxylic acid having two or more amino groups in one molecule
For example, glutamine, lysine, asparagine, arginine, diaminobenzoic acid, diaminobutyric acid, 2,6-diaminopimelic acid and the like can be mentioned.
[0026]
(4) Sulfonic acid having one or more amino groups in one molecule
For example, aminomethanesulfonic acid, 2-amino-1,5-naphthalenedisulfonic acid, 2-amino-1,4-benzenedisulfonic acid, o-aminobenzenesulfonic acid, 1-amino-4-bromoanthraquinone-2-sulfone Acid, 4-amino-2-chlorotoluene-5-sulfonic acid, S- (2-aminoethyl) thiosulfonic acid, 3-amino-4-hydroxy-5-nitrobenzenesulfonic acid, 4-amino-5-methoxy-2 -Methylbenzenesulfonic acid, 2-amino-5-methylbenzene-1-sulfonic acid, 4-amino-2-methylbenzene-1-sulfonic acid, 5-amino-2-methylbenzene-1-sulfonic acid, 1- Amino-3,8-naphthalenedisulfonic acid, 3-amino-1,5-naphthalenedisulfonic acid, 4-aminonaphthalene-1-sulfonic acid, 4-amino-1-naphthalenesulfonic acid, 6-amino-1-naphthalenesulfonic acid Acid, 5-amino-1-naphthalenesulfonic acid, 1-amino-8-naphthalenesulfo Acid, 4-aminonaphthalene-1-sulfonic acid, 5-aminonaphthalene-1-sulfonic acid, 8-aminonaphthalene-1-sulfonic acid, 7-amino-1,3,6-naphthalenetrisulfonic acid, 8-amino -1-naphthol-3,6-disulfonic acid, 4-amino-5-naphthol-2,7-disulfonic acid, 1-amino-2-naphthol-4-sulfonic acid, 1-amino-5-naphthol-7- Sulfonic acid, 4-amino-3-methylbenzene-1-sulfonic acid, aniline-2,5-disulfonic acid, azofuxin, azolithamine, N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid, 4 , 4′-bis (4-amino-1-naphthylazo) -2,2′-stilbene disulfonic acid, 4,4′-diaminostilbene-2,2′-disulfonic acid, m-aminobenzoic acid ethylmethanesulfonic acid, Methanylic acid, 1-naphthylamine-6-sulfonic acid, 4-nitroaniline-2-sulfonic acid, sulfanilamide, sulfanilic acid, slurry Min sodium, taurine, trypan blue, diaminobenzenesulfonic acid, 4,4′-diaminostilbene-2,2′-disulfonic acid and the like.
[0027]
(5) Phenolic compounds having amino groups
For example, p-acetaminophenol, o-acetaminophenol, acetaminophen, 2-amino-4-chlorophenol, 5-amino-o-cresol, 3-amino-4-hydroxybenzenesulfonamide, 4-amino- 3-methylphenol, 2-amino-4-nitrophenol, 2-amino-5-nitrophenol, m-aminophenol, o-aminophenol, p-aminophenol, o-anisidine, 2,4-diaminophenol, m -Diethylaminophenol, 4-hydroxydiphenylamine, diaminophenol, tyrosine and the like.
[0028]
As exemplified above, the amino group-containing organic compound (guest molecule) used in the present invention has at least one amino group in one molecule and has at least a carboxylic acid group, a sulfonic acid group, or a phenolic hydroxyl group. A compound having one or a salt thereof is selected. Said (1)-(5) is those illustrations, and is not limited to them. In addition, the above classification is for convenience, and there are compounds belonging to a plurality of classes and compounds not classified in any of these.
When the amino group-containing organic compound is used as a salt, alkali (earth) metal salts such as sodium salt, potassium salt, lithium salt, magnesium salt, calcium salt and the like can be mentioned. For polybasic acids having two or more carboxylic acid groups and / or sulfonic acid groups in one molecule, monosalts and disalts (for example, aminonaphthalene dicarboxylic acid monosodium salt, aminonaphthalene dicarboxylic acid disodium salt) Either can be used. Compared with the case where it is used as a free acid, a salt has a merit that it is easy to handle because of its good solubility in water. However, metal ions may also be incorporated between the layers. In this case, there is no particular problem as a usage mode of the deodorizing agent, but when the deodorizing agent is used in a thermoplastic resin, it may cause coloring, so that the use is limited.
[0029]
The above-mentioned amino group-containing organic compound intercalates with the cation exchange layered clay mineral, so that guest molecules are fixed between the layers of the clay mineral. In order to make the fixation of the guest molecule more complete, the monocarboxylic acid or dicarboxylic acid shown in the above (1), (2), (3) is preferable.
Among them, amino acids are preferable because they are easily available and have little influence on the human body. Examples include glycine, leucine, cysteine, tyrosine, phenylalanine, aspartic acid, lysine, alanine, serine, asparagine, isoleucine, glutamic acid, arginine, and valine. , Threonine, glutamine, methionine, tryptophan, histidine and the like.
[0030]
In the present invention, the amino group-containing organic compound or other substance can be simultaneously intercalated for the purpose of other functions such as antibacterial and fragrance as long as the deodorizing function is not impaired. . For example, in order to impart an antibacterial function, substances such as benzalkonium and cetylpyridinium chloride may be simultaneously intercalated. Specifically, when intercalating the guest molecules, a predetermined amount of these substances may be used together with the guest molecules. In some cases, a method of reprocessing with these substances after intercalation, or a method of intercalating after treatment with these substances may be used.
[0031]
The deodorizer of the present invention comprises a composite inorganic layered clay mineral as an active ingredient, and is effective against acid-based odors, phenol-based odors, and aldehyde-based odors.
Specifically, formic acid, acetic acid, propionic acid, butyric acid, succinic acid, benzoic acid, amino acids, acetylsalicylic acid and other carboxylic acids as phenolic odor, phenolic compounds such as phenol and cresol, aldehyde It is effective for removing formaldehyde, acetaldehyde, ethyl aldehyde, propyl aldehyde, t-butyraldehyde, isopropyl aldehyde, benzaldehyde, p-tolualdehyde, naphthyl aldehyde and the like. Among these, the deodorizer of the present invention is particularly effective for aldehyde-based odors.
[0032]
As a deodorizing agent, the product dried by the above production method is powdered by any method, for example, a mill, a pulverizer, a mortar, or the like that can be pulverized, or a chip or the like Alternatively, the effect of deodorization can be obtained by using a known powder using methods such as a single body, mixing with a paint, powder coating, silica gel or the like, mixing with a ceramic, etc., depending on the shape of agglomeration processing on a solid by pressing or the like. In particular, it is preferable to process and use it in powder form for reasons such as easy handling, wide application, and large surface area.
The particle size of the deodorizing agent is selected depending on the purpose of use, but the smaller the particle size, the larger the surface area and the more effective the deodorizing function is expressed, preferably 100 μm or less, more preferably 20 μm or less. These particles can be used as powders, but they can also be used in any form after being processed by methods such as compression agglomeration.
[0033]
The deodorizing agent of the present invention can be used alone or in combination with other substances as described above, and more preferable compounding method includes compounding with a thermoplastic resin.
Any thermoplastic resin can be used as long as it can be plasticized by heat. Examples include high-density polyethylene, high-pressure low-density polyethylene, linear low-density polyethylene, polypropylene, propylene / ethylene block copolymer, propylene. -Ethylene random copolymer, polyethylene terephthalate, polybutylene terephthalate, polystyrene, polycarbonate, polybutadiene, polyisoprene, AS, ABS, EPR, EPDM, SEBS, NBR and the like.
In particular, polypropylene-based thermoplastic resins, polyethylene-based thermoplastic resins, polyethylene terephthalate-based resins, and polystyrene are preferable from the viewpoint that they can be used for food containers.
[0034]
The compounding method can be any known method, and examples thereof include compounding by an extruder and roll kneading. A method of mixing in advance by dry blending and then compounding by melt kneading with a single screw or twin screw extruder is preferable in terms of good dispersion. Also preferred is a method in which a high-concentration master batch is prepared in advance and added and used at the stage of molding.
The blending amount of the deodorizer depends on the type of the thermoplastic resin and the use of the composite, but the thermoplastic resin 100 is within the range where the deodorizing effect is exhibited and the moldability of the thermoplastic resin is not impaired. Usually, 0.01 to 100 parts by weight, preferably 0.03 to 1 part by weight is used per part by weight.
[0035]
The thermoplastic resin composition can be used as a material or a compounding agent of other substances as pellets and powder, but is usually molded by a known molding method to obtain a deodorized molded product. The molded product can be processed into an arbitrary shape such as a container, a pack, a tray, or a hollow bottle in addition to a film and a sheet.
As the molding method, for example, extrusion molding with a T-die, inflation film molding, blow molding, injection molding, thermoforming, pressure forming, press molding and the like can be used.
In addition, the present invention can be applied to a polyolefin multilayer molded article. For example, a layer for an oxygen barrier can be disposed in the intermediate layer. As the barrier layer, aluminum foil, paper or the like can be laminated. When the multilayer molded article is used as a food container, it is preferable to dispose the thermoplastic resin according to the present invention in the inner layer in order to effectively retain the deodorizing and deodorizing taste effects.
[0036]
In addition to the method of compounding with a thermoplastic resin by extrusion blending or the like, for example, a method of coating on the surface and compounding with a thermoplastic resin, a coating method with a roll, and the like can also be mentioned.
The deodorized molded article according to the present invention can be applied to various uses, such as infusion bags, back-in boxes, food containers, food container lids, films for sealing containers, blow bottles, cups, injection trays, Suitable for potion cups, etc., especially for low odor and low taste, contents that are susceptible to odors and tastes such as water and cooked rice, and food packages for infants and sick people who are easily affected by foreign bodies Suitable for materials.
[0037]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition, the common matters in the following examples and comparative examples are as follows.
(1) Elemental analysis
EA1110 type CHNS-O analyzer manufactured by Phisons. Combustion tube 1000 ° C, column 70 ° C, tin sample pan, He flow 130 ml / min
(2) Powder X-ray diffraction
RAD-RD manufactured by Shimadzu Corporation. Measurement angle 2θ = 2 to 30 °, Cu-Kα radiation source, 50 kV, 300 mA
[0038]
(3) Gas adsorption experiment 1
A 0.5 g sample (deodorant) was taken in a petri dish, and 10 ml of the target odor substance was placed in a sample bottle. Adsorption experiments were conducted at 30 ° C. with both interposed in a sealed desiccator. The weight of the sample and petri dish was measured in advance, and the amount of odorous substances adsorbed was measured by increasing or decreasing the weight with time.
(4) Gas adsorption experiment 2
Create a 4L sealed container, vaporize acetaldehyde (made by Wako Pure Chemical Industries, Ltd.) to a concentration of about 200 ppm, connect a sample pan and change the gas concentration (unit ppm) in the container over time at room temperature. followed. The gas concentration was measured by using a gas detector tube for acetaldehyde (gas detector tube No. 92 for acetaldehyde manufactured by Gastec Co., Ltd.) and collecting 200 ml of gas in a sealed container in one measurement.
(5) Odor sensory test
Five panelists scored according to the following criteria and took the average evaluation score.
Grade 0: Odorless. There is no odor at all.
1st grade: I finally feel odor. I can't tell what odor is.
Second grade: Odor is felt. It is possible to determine what odor is.
3rd grade: It smells pretty much and feels easy.
Grade 4: Smells strongly.
5th grade: Smelling violently, unbearably intense odor.
[0039]
[Example 1]
(1) Intercalation method
As a guest molecule, 0.03 mol of glutamic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 300 ml of distilled water, and montmorillonite (manufactured by Kunimine Industry Co., Ltd., Kunipia F, interlayer distance 12.8Å, molecular weight 594) was dissolved in the above solution as an ion-exchangeable layered clay mineral. Cation exchange capacity = 115 meq / 100 g) was added while stirring and reacted at room temperature (23 ° C.) for 24 hours. Then, it suction-filtered with the membrane filter (3 micrometers). The filtration residue was freeze-dried under reduced pressure at −20 ° C. for 24 hours, and then vacuum hot-air drying was performed at 70 ° C. for 24 hours. The obtained powder was pulverized in a mortar (about 1 to 10 μm) and used for evaluation. The interlayer distance after the intercalation was increased to 14.8 mm. The amount of intercalation obtained from elemental analysis is one compositional formula of montmorillonite (Al5/3Mg1/3SiFourOTen(OH)2W1/3・ MH20.75 molecule for O).
Thereafter, the deodorizer obtained above was applied to 5 parts of polypropylene powder (manufactured by Nippon Polychem, MA3Q, MFR = 15 g / 10 min) with a 15 mm twin screw extruder having a cylinder temperature of 230 ° C. Part by weight, 0.1 parts by weight of antioxidant (Ciba Specialty Chemicals, Irganox 1010) and 0.2 parts by weight of processing stabilizer (Ciba Specialty Chemicals, Irgaphos 168) were blended in a mixer. , Granulated. The hue of the obtained pellet was milky white.
The pellet was subjected to gas adsorption experiment 1 using octyl aldehyde (manufactured by Wako Pure Chemical Industries, Ltd.). The amount of aldehyde adsorbed was 0.33% by weight after 5 hours and 24 hours after the pellet weight. It was confirmed to be 0.49% by weight and 0.52% by weight after 72 hours.
[0040]
[Example 2]
Intercalation is carried out by the above method using glutamic acid as a guest molecule, and γ-titanium phosphate (manufactured by Teika Co., Ltd., interlayer distance 11.6 Å, molecular weight 296, cation exchange capacity = 100 meq / 100 g) as an inorganic layered clay mineral. It was. The intercalation distance between layers was 13.2 mm, and the amount of intercalation was γ-titanium phosphate 1 composition formula (Ti (HPOFour)2. 2H20.3 molecule for O).
Thereafter, it was granulated with polypropylene powder in the same manner as in Example 1. The hue of the obtained pellet was white. When the gas adsorption experiment 1 was performed on the pellet using octyl aldehyde, the amount of aldehyde adsorbed was 0.24% by weight after 5 hours, 0.32% by weight after 24 hours, and 72%. After 3 hours, it was confirmed to be 0.33% by weight.
[0041]
[Example 3]
Intercalation was performed by the above method using phenylalanine (manufactured by Wako Pure Chemical Industries, Ltd.) as a guest molecule and montmorillonite as an inorganic layered clay mineral. The interlayer distance after intercalation was 14.9 mm, and the amount of intercalation was 0.91 molecule relative to the montmorillonite 1 composition formula.
Thereafter, it was granulated and composited with polypropylene powder in the same manner as in Example 1. The hue of the obtained pellet was milky white. When the gas adsorption experiment 1 was performed on the pellet using octylaldehyde, the adsorption amount of the aldehyde was 0.19% by weight after 5 hours, 0.22% by weight after 24 hours, and 72%. It was confirmed to be 0.25% by weight after time.
[0042]
[Comparative Example 1]
In a 15 mm twin screw extruder with a cylinder temperature of 230 ° C., 5 parts by weight of montmorillonite and 0.1 parts by weight of an antioxidant (manufactured by Ciba Specialty Chemicals, Irganox 1010) with respect to 100 parts by weight of polypropylene powder, 0.2 parts by weight of processing stabilizer (manufactured by Ciba Specialty Chemical Co., Ltd., Irgaphos 168) was blended with a mixer to form a granulated composite. The hue of the obtained pellet was milky white. When the pellet was subjected to gas adsorption experiment 1 using octyl aldehyde, gas adsorption was not confirmed even after 72 hours. The results are shown in Table 2.
[0043]
[Comparative Example 2]
In a 15 mm twin-screw extruder with a cylinder temperature of 230 ° C., 5 parts by weight of γ-titanium phosphate was used for 100 parts by weight of polypropylene powder, and granulated with polypropylene powder in the same manner as in Comparative Example 1. The hue of the obtained pellet was white. When the pellet was subjected to gas adsorption experiment 1 using octyl aldehyde, gas adsorption was not confirmed even after 72 hours.
[0044]
[Comparative Example 3]
Using a 15 mm twin screw extruder with a cylinder temperature of 230 ° C., granulation was performed using only polypropylene powder. The hue of the obtained pellet was colorless (transparent). When the pellet was subjected to gas adsorption experiment 1 using octyl aldehyde, gas adsorption was not confirmed even after 72 hours.
[0045]
[Table 1]
[0046]
[Table 2]
[0047]
[Example 4]
As a guest molecule, 0.03 mol of sodium glutamate is dissolved in 300 ml of distilled water, and MgAl-based hydrotalcite (manufactured by Kyowa Chemical Industry Co., Ltd., DHT6, M = 603.98, anion exchange capacity = 220 meq / 100 g) is used as an inorganic layered clay material. What was sintered at 500 ° C. for 5 hours (the interlaminar distance cannot be detected due to the irregular shape) was added while stirring, and allowed to react at room temperature (23 ° C.) for 24 hours. Then, it suction-filtered with the membrane filter (3 micrometers). The filtration residue was dried in vacuum at 80 ° C. for 24 hours, pulverized in a mortar to a particle size of about 1 μm, and CHN elemental analysis and gas adsorption experiment 2 were performed. The results are shown in Table 3.
[0048]
[Example 5]
In the guest molecule, 0.03 mol of glutamic acid is dissolved in 300 ml of distilled water, and 5 g of MgAl hydrotalcite is added as an inorganic layered clay material with stirring.FourAn aqueous OH solution was added to adjust the pH to 8, and the reaction was allowed to proceed at room temperature (23 ° C.) for 24 hours. It dried and evaluated similarly to Example 4. The results are shown in Table 3.
[0049]
[Example 6]
Using an MgAl-based hydrotalcite that was previously sintered at 500 ° C. for 5 hours as an inorganic layered clay material, composite and evaluation were performed in the same manner as in Example 5. The results are shown in Table 3.
[0050]
[Example 7]
Phenylalanine was used as a guest molecule, and complexed by the same method as in Example 4 below. The results are shown in Table 3.
[0051]
[Comparative Example 4]
Evaluation similar to Example 4 was performed using MgAl-based hydrotalcite as the inorganic layered clay material without using guest molecules. The results are shown in Table 3.
[0052]
[Example 8]
5 parts by weight of the powder prepared in Example 4 with respect to 100 parts by weight of polypropylene powder, 0.1 part by weight of an antioxidant (manufactured by Ciba Specialty Chemicals, Irganox 1010), and a processing stabilizer (Ciba 0.2 parts by weight of Special Chemical Co., Ltd. Irgafos 168) were dry blended with a mixer, kneaded with a 15 mmφ twin screw extruder at 230 ° C. and nitrogen purge, extruded from a 5 mm diameter die, the strand was water cooled, and the pelletizer Was granulated into approximately 3 mm square pellets. The hue of the obtained pellet was white. The pellet was subjected to a gas adsorption experiment 2 and an odor sensory test. The results are shown in Table 4.
[0053]
[Example 9]
Using the powder prepared in Example 5, kneading, granulation and evaluation were performed in the same manner as in Example 8. The results are shown in Table 4.
[0054]
[Example 10]
Using the powder prepared in Example 6, kneading, granulation and evaluation were performed in the same manner as in Example 8. The results are shown in Table 4.
[0055]
[Example 11]
Using the powder prepared in Example 7, kneading, granulation and evaluation were performed in the same manner as in Example 8. The results are shown in Table 4.
[0056]
[Comparative Example 5]
Using the powder used in Comparative Example 4, kneading, granulation and evaluation were performed in the same manner as in Example 8. The results are shown in Table 4.
[0057]
[Comparative Example 6]
To 100 parts by weight of polypropylene powder, 0.1 parts by weight of an antioxidant (manufactured by Ciba Specialty Chemicals, Irganox 1010) and 0.2 parts by weight of a processing stabilizer (Irgaphos 168) are dry blended with a mixer. Thereafter, kneading, granulation and evaluation were performed in the same manner as in Example 8. The results are shown in Table 4.
[0058]
[Table 3]
[0059]
[Table 4]
[0060]
【The invention's effect】
According to the present invention, it is possible to obtain a deodorant excellent in performance of removing bad odors and bad tastes of aldehyde-based substances and acid-based substances. This deodorizer can be blended into a thermoplastic resin substrate such as a polyolefin resin, and a thermoplastic resin composition blended with the deodorizer can provide a deodorized molded product and an aldehyde adsorbent molded product. It is useful for food packaging materials. Moreover, since the thermoplastic resin composition containing the deodorizing agent has an action of adsorbing odor that may be generated in a small amount during molding, it contributes to deodorization of the atmosphere in which the molding process is performed.
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FI122914B (en) * | 2005-04-01 | 2012-08-31 | Biohit Oyj | Food composition for binding of acetaldehyde in the mouth and in the digestive tract and process for the preparation of the composition |
JP5159026B2 (en) * | 2005-04-04 | 2013-03-06 | 共栄社化学株式会社 | Ionic substance adsorbent in aqueous solution |
JP4909549B2 (en) * | 2005-09-02 | 2012-04-04 | 株式会社シナネンゼオミック | Deodorant and deodorized article |
JP2007238902A (en) * | 2006-03-13 | 2007-09-20 | Bridgestone Corp | Deodorant for natural rubber, deodorated natural rubber composition, and method for producing the same |
JP5101829B2 (en) * | 2006-03-28 | 2012-12-19 | 共栄社化学株式会社 | Resin reinforcing agent and resin composite material containing the same |
JP5854753B2 (en) * | 2011-10-13 | 2016-02-09 | 旭化成ホームプロダクツ株式会社 | Deodorant composition |
JP2021054490A (en) * | 2019-09-30 | 2021-04-08 | 大日本印刷株式会社 | Gas absorbing film |
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JPH0295436A (en) * | 1988-09-30 | 1990-04-06 | Titan Kogyo Kk | Deodorizing thermoplastic resin composition, deodorizing thermoplastic resin film and sheet |
JPH02124949A (en) * | 1988-11-02 | 1990-05-14 | Suzuki Sogyo Kk | Plastic molding |
JPH11293034A (en) * | 1998-04-13 | 1999-10-26 | Dainichiseika Color & Chem Mfg Co Ltd | Deordorizing resin composition |
JP2001120649A (en) * | 1999-10-26 | 2001-05-08 | Toagosei Co Ltd | Deodorant for aldehyde gas of unsaturated hydrocarbon |
JP2002306582A (en) * | 2001-04-17 | 2002-10-22 | Toyota Central Res & Dev Lab Inc | Liquid composition for deodorization and deodorant article to which this composition is applied |
JP2002336693A (en) * | 2001-05-14 | 2002-11-26 | Mitsubishi Gas Chem Co Inc | Oxygen absorbent composition |
JP2003093872A (en) * | 2001-09-21 | 2003-04-02 | Toyobo Co Ltd | Adsorbent and its preparing method |
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Patent Citations (7)
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JPH0295436A (en) * | 1988-09-30 | 1990-04-06 | Titan Kogyo Kk | Deodorizing thermoplastic resin composition, deodorizing thermoplastic resin film and sheet |
JPH02124949A (en) * | 1988-11-02 | 1990-05-14 | Suzuki Sogyo Kk | Plastic molding |
JPH11293034A (en) * | 1998-04-13 | 1999-10-26 | Dainichiseika Color & Chem Mfg Co Ltd | Deordorizing resin composition |
JP2001120649A (en) * | 1999-10-26 | 2001-05-08 | Toagosei Co Ltd | Deodorant for aldehyde gas of unsaturated hydrocarbon |
JP2002306582A (en) * | 2001-04-17 | 2002-10-22 | Toyota Central Res & Dev Lab Inc | Liquid composition for deodorization and deodorant article to which this composition is applied |
JP2002336693A (en) * | 2001-05-14 | 2002-11-26 | Mitsubishi Gas Chem Co Inc | Oxygen absorbent composition |
JP2003093872A (en) * | 2001-09-21 | 2003-04-02 | Toyobo Co Ltd | Adsorbent and its preparing method |
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