JP3618223B2 - Antibacterial-containing masterbatch and method for producing the same - Google Patents
Antibacterial-containing masterbatch and method for producing the same Download PDFInfo
- Publication number
- JP3618223B2 JP3618223B2 JP14179898A JP14179898A JP3618223B2 JP 3618223 B2 JP3618223 B2 JP 3618223B2 JP 14179898 A JP14179898 A JP 14179898A JP 14179898 A JP14179898 A JP 14179898A JP 3618223 B2 JP3618223 B2 JP 3618223B2
- Authority
- JP
- Japan
- Prior art keywords
- carbonate
- fluorine
- antifoggant
- weight
- film
- 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.)
- Expired - Fee Related
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
- B65D1/0223—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by shape
- B65D1/023—Neck construction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
- B65D1/0223—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by shape
- B65D1/0261—Bottom construction
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/25—Greenhouse technology, e.g. cooling systems therefor
Landscapes
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Mechanical Engineering (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Greenhouses (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Protection Of Plants (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、防霧剤含有マスターバッチ、その製造方法および該防霧剤含有マスターバッチを用いた農業用フィルムの製造方法に関する。さらに詳しくは、農業用ビニルハウスとして使用した際にフィルム内面近傍における霧発生現象を抑制する能力（防霧性） および、その防霧性を長時間にわたって発揮する能力（防霧持続性） を有する、塩素原子を含まない農業用フィルムの製造方法と、原料である防霧剤含有マスターバッチおよびその製造方法に関する。
【０００２】
【従来の技術】
近年、有用植物の生産性、市場価値を高めるために、農業用フィルムによる被覆下に、有用植物を促成、半促成、または抑制栽培する、いわゆるハウス栽培やトンネル栽培が盛んに行われている。
この農業用フィルムとして現在塩化ビニル系樹脂が使用されている。フィルム内表面における水滴の流下を促進し、日光の入射量を多くするために、この農業用フィルムは界面活性剤の一種である防曇剤（ソルビタン脂肪酸エステルなど）を含んでいる。このような防曇剤を含むフィルムによる被覆下では内外での温度差が大きくなり、内表面近傍において霧が発生するため、含フッ素防霧剤を添加して防霧性を付与している。
【０００３】
しかし、塩化ビニル系樹脂は塩素原子を有するため、低温での燃焼では猛毒のダイオキシンが発生し、廃棄の際は特別な高温燃焼処理設備で処理しなければならない。
塩化ビニル系樹脂以外の樹脂で上記の性能を有する農業用フィルムも検討されているが、樹脂を変えるだけでは、いくつかの問題があり実用化されていない。例えばポリエチレン樹脂や酢酸ビニル樹脂等のような塩素原子を含まない熱可塑性樹脂を用いる場合、溶融成形しうる温度が塩化ビニル系樹脂と比べて高い（１５０〜２３０℃）ため、高温での混練溶融、ペレット化および製膜加工を要する。
【０００４】
現在塩化ビニル系樹脂フィルムに使用されている含フッ素防霧剤としては、フルオロアルキル基含有エポキシ化合物とオキシエチレン基含有化合物とをルイス酸触媒下で開環付加して合成した含フッ素防霧剤（特開昭５９−９３７３９、特開昭６１−１３３２４４、特開昭６１−１５２７４５、特開昭６４−１４７、特開昭６４−１４２６３、特開平１−２１６９４７、特開平１−２４６２３７等に記載。）がある。
【０００５】
ルイス酸触媒としては、反応性の面から三フッ化ホウ素（ＢＦ３ ）またはその錯体が使用されているが、これらの方法で合成した含フッ素防霧剤は、酸分および少量のＢＦ３ が残存している。このＢＦ３ は、空気中の水分および残存する酸分等により分解してフッ酸（ＨＦ）ガスを発生する性質がある。この性質は高温では特に顕著であり、溶融成形しうる温度が塩化ビニル系樹脂と比べて高い塩素原子を含まない熱可塑性樹脂を用いる場合の問題となる。
【０００６】
この問題を解決するために、含フッ素防霧剤中にＢＦ３ が残存せず、酸分を腐食性のない状態まで減らす方法を検討した。この腐食性をなくすには、酸分がＨＦ換算で１ｐｐｍ未満でなければならず、０．１ｐｐｍ未満であることがさらに望まれる。
【０００７】
含フッ素防霧剤中のＢＦ３ などの酸分を水洗により除去する方法は、含フッ素防霧剤が界面活性剤であるため、水に溶解、乳化または均一分散し、水との分離が困難であり実用には適さない。
【０００８】
含フッ素防霧剤中のＢＦ３ などの酸分を混合溶剤による洗浄により除去する方法（特公昭６１−４５９７３）では、含フッ素防霧剤が配位性の高いエーテル性酸素原子を多く含んでいるためＢＦ３ と一部配位しており、完全には除去できない。同様の理由で２３０℃未満の温度で減圧除去しても完全には除去できない。２３０℃以上では、配位しているＢＦ３ の触媒作用が活発となり、含フッ素防霧剤のオキシエチレン部分の環化反応によるジオキサンの発生や分解反応を引き起こし、防霧性が低下し、また着色により光透過性が低下する。
【０００９】
反応に使用するＢＦ３ 錯体の量を減らす方法もあるが、反応を進行させるためには、原料であるフルオロアルキル基含有エポキシ化合物に対して０．１重量％以上のＢＦ３ 錯体が必要であり、これ以下への減量はできない。
以上のように、含フッ素防霧剤中のＢＦ３ の残存量を減らすことも、酸分を除去することも困難である。
【００１０】
上記のＢＦ３ が残存し酸分を含むフッ素系防霧剤を、塩素原子を含まない熱可塑性樹脂に使用した場合、１５０℃以上の高温下で混練溶融をするため、残存するＢＦ３ が分解しＨＦガスが発生する。そのため設備には酸性ガスの除害設備が必要となり作業性、コスト面で問題がある。特に防霧剤含有マスターバッチにおいては、含フッ素防霧剤の含有量が多いため、ＢＦ３ が分解したＨＦガスの発生が激しく問題が大きい。また、発生したＨＦガスの一部は防霧剤含有マスターバッチ中に残存し成形、製膜加工時にＨＦガスが発生するため、成形、製膜設備として酸に腐食されやすい軟鋼等を使用できず、材質がハステロイやチタン等の高価なものに制約される。また製品であるフィルム中にも酸分が残存するおそれがあり、環境汚染の問題もある。
【００１１】
【発明が解決しようとする課題】
本発明の目的は、農業用フィルム製造時にＢＦ３ などに基づく酸分の発生を伴わない、塩素原子を含まない熱可塑性樹脂を用いた防霧剤含有マスターバッチ、およびそれを用いた農業用フィルムの製造方法、さらに、ＢＦ３ などに基づく酸分の発生を伴わない防霧剤含有マスターバッチの製造方法、の提供にある。
【００１２】
【課題を解決するための手段】
本発明は、１５０〜２３０℃で溶融成形しうる塩素原子を含まない熱可塑性樹脂と、前記熱可塑性樹脂１００重量部に対して、ＢＦ３またはその錯体を用いて合成したことによりＢＦ３が残存する含フッ素防霧剤１〜７０重量部と、炭酸塩（炭酸ナトリウム、炭酸カリウム、炭酸カルシウム、炭酸リチウム、炭酸マグネシウム、炭酸カリウムナトリウム、炭酸バリウム）０．０１〜１４重量部と、を溶融混合してなる防霧剤含有マスターバッチを提供する。
また、押し出し成形機を用いて１５０〜２３０℃で混練溶融することを特徴とする上記防霧剤含有マスターバッチの製造方法を提供する。
また、上記防霧剤含有マスターバッチと塩素原子を含まない熱可塑性樹脂とを混合して製膜加工することを特徴とする農業用フィルムの製造方法を提供する。
【００１３】
【発明の実施の形態】
本発明の防霧剤含有マスターバッチは、１５０〜２３０℃で溶融成形しうる塩素原子を含まない熱可塑性樹脂と、前記熱可塑性樹脂１００重量部に対して、ＢＦ３またはその錯体を用いて合成したことによりＢＦ３が残存する含フッ素防霧剤１〜７０重量部と、炭酸塩（炭酸ナトリウム、炭酸カリウム、炭酸カルシウム、炭酸リチウム、炭酸マグネシウム、炭酸カリウムナトリウム、炭酸バリウム）０．０１〜１４重量部と、を溶融混合してなる。溶融混合の方法としては、混合したのち混練溶融する方法が挙げられる。
【００１４】
防霧剤含有マスターバッチを得るための原料の割合としては、熱可塑性樹脂１００重量部に対して、含フッ素防霧剤は１〜７０重量部、特に５〜５０重量部、が好ましく、炭酸塩（炭酸ナトリウム、炭酸カリウム、炭酸カルシウム、炭酸リチウム、炭酸マグネシウム、炭酸カリウムナトリウム、炭酸バリウム）は０．０１〜１４重量部、特に０．０５〜５重量部が好ましい。
【００１５】
含フッ素防霧剤が７０重量部超では、ヘンシェルミキサー等を用いた混合時にべたつきが生じ、押し出し成形機に搬入しづらく、樹脂と相溶できる限界を超えるため均一性が乏しくなる。また１重量部未満では防霧性能が低下する。
炭酸塩（炭酸ナトリウム、炭酸カリウム、炭酸カルシウム、炭酸リチウム、炭酸マグネシウム、炭酸カリウムナトリウム、炭酸バリウム）が０．０１重量部未満では酸分除去が充分にできず、１４重量部超では成形がしづらくなる。
含フッ素防霧剤に対する炭酸塩（炭酸ナトリウム、炭酸カリウム、炭酸カルシウム、炭酸リチウム、炭酸マグネシウム、炭酸カリウムナトリウム、炭酸バリウム）の重量比としては、０．００５〜０．２が好ましく、０．０１〜０．１が特に好ましい。
【００１６】
炭酸塩は炭酸ナトリウム、炭酸カリウム、炭酸カルシウム、炭酸リチウム、炭酸マグネシウム、炭酸カリウムナトリウム、炭酸バリウムであり、炭酸カルシウム、炭酸バリウム、炭酸マグネシウムが好ましい。
【００２０】
炭酸塩（炭酸ナトリウム、炭酸カリウム、炭酸カルシウム、炭酸リチウム、炭酸マグネシウム、炭酸カリウムナトリウム、炭酸バリウム）は、含フッ素防霧剤中に含まれる酸分、加熱時に発生する酸分等を中和するためには、粒子径は小さいほどよく、０．１〜１０μｍ、特に０．１〜２μｍ、が好ましい。粒子径が０．１μｍ未満では粉末が舞いやすく、均一分散させる作業が困難である。１０μｍ超では、表面積が小さく添加量を増やす必要があり、フィルムにした際に光の透過率が５％以上低下する。
これらの炭酸塩（炭酸ナトリウム、炭酸カリウム、炭酸カルシウム、炭酸リチウム、炭酸マグネシウム、炭酸カリウムナトリウム、炭酸バリウム）は、１種単独で使用してもよく、２種以上を併用してもよい。
【００２１】
１５０〜２３０℃で溶融成形しうる塩素原子を含まない熱可塑性樹脂は、透明性、加工の容易さ、耐久性からポリオレフィン系樹脂および／またはエチレン−酢酸ビニル系樹脂を合量で８０重量％以上含有するものが好ましく、特に１００重量％が好ましい。エチレン−酢酸ビニル系樹脂（ＥＶＡ）は、寒冷地での耐久性がよく好ましい。
【００２２】
ポリオレフィン系樹脂の具体例としては、以下に示す樹脂が挙げられる。
単独重合体の樹脂としては、ポリエチレン樹脂が好ましく、特に好ましいのはフィルム加工性のよい低密度ポリエチレン樹脂（略称：ＬＤＰＥ）である。共重合体の樹脂としては、エチレン−プロピレン樹脂、エチレン−ブチレン樹脂が好ましい。
【００２３】
また、樹脂の流動性としてはＪＩＳ−Ｋ７２１０によるメルトインデックス（ＭＩ値）が２〜１００（ｇ／１０分） の範囲のものが好ましく、特に５〜２０（ｇ／１０分） のものが好ましい。
【００２４】
現在、ＬＤＰＥは、住友化学、三井化学、旭化成工業、東ソー、昭和電工、三菱化学、日本ユニカー、三井デュポンポリケミカルズをはじめ多数の会社から、ＭＩ値の異なる製品が市販されている。また樹脂の形状も粉末、ペレットおよび塊状のものがある。ＥＶＡも同様にポリエチレンメーカーから多数の製品が市販されている。
【００２５】
また、本発明において、塩素原子を含まない熱可塑性樹脂として上述のポリオレフィン系樹脂、ＥＶＡの代わりに、または上述のポリオレフィン系樹脂、ＥＶＡに加えて使用できる樹脂としては、プロピレン−酢酸ビニル樹脂、エチレン−酢酸ビニル−プロピレン樹脂、スチレン樹脂、エチレン−スチレン樹脂、カーボネート樹脂、ＡＢＳ樹脂、アクリル樹脂、エチレンテレフタレート樹脂、フッ素樹脂、ナイロン樹脂、ウレタン樹脂等が挙げられる。ただし、溶融成形しうる温度が１５０〜２３０℃の塩素原子を含まない熱可塑性樹脂に限る。
【００２６】
本発明における含フッ素防霧剤としては、下記式２または式３で表されるフッ素化合物が好ましい。
【００２７】
【化２】
Ｒｆａ−Ｒ１ −Ｏ（Ｃ２ Ｈ４ Ｏ）ｈ −Ｒ２ −Ｒｆｂ・・・・・式２
Ｒｆｃ−Ｒ３ −Ｏ（Ｃ２ Ｈ４ Ｏ）ｉ −（ＣＯ）ｊ −Ｒ４ ・・式３
【００２８】
ただし、式２、式３中の記号は下記の意味を示す。
Ｒ１ 、Ｒ２ 、Ｒ３ ：それぞれ独立して、炭素−炭素間に酸素原子が挿入されていてもよい炭素数２〜１２の２価の脂肪族炭化水素基で、該基中の水素原子がアセトキシ基等のアシルオキシ基または水酸基に置換されていてもよい。
Ｒ４ ：水素原子、フェニル基、グリシジル基、または、炭素−炭素間に酸素原子が挿入されていてもよく２重結合を含有してもよい炭素数２〜１６の１価の脂肪族炭化水素基。
Ｒｆａ、Ｒｆｂ、Ｒｆｃ：それぞれ独立して、炭素−炭素間に酸素原子が挿入されていてもよい炭素数４〜１６のポリフルオロアルキル基。
ｈ、 ｉ：それぞれ独立して、２〜３０の数。
ｊ：０または１。
【００２９】
Ｒ１ 、Ｒ２ 、Ｒ３ としては炭素−炭素間に酸素原子が挿入されていてもよい炭素数が３〜５の２価の脂肪族炭化水素基が好ましい。水素原子が置換された基としては、水素原子の一つがアセトキシ基または水酸基に置換されているものが好ましい。Ｒ４ は水素原子または炭素数が１〜５のアルキル基が好ましい。
【００３０】
ポリフルオロアルキル基を以下Ｒｆ 基と記す。Ｒｆ 基は、アルキル基の２個以上の水素原子がフッ素原子に置換された基である。Ｒｆ 基の炭素数は４〜１６が好ましい。Ｒｆ 基は、直鎖構造が好ましく、フッ素原子の数は、［（Ｒｆ 基中のフッ素原子数）／（同一炭素数の対応するアルキル基中に含まれる水素原子数）］×１００（％）で表現した場合、６０％以上が好ましく、８０％以上が特に好ましい。
含フッ素防霧剤としては、具体的には下記の化合物が好ましい。式中、Ｐｈはフェニル基、Ｇはグリシジル基を示す。
【００３１】
【化３】
【化４】
これらの化合物は、フルオロアルキル基含有エポキシ化合物と、分子内に１個以上の水酸基を有する化合物とをＢＦ３ またはそのエーテルやアルコールとの錯体、硫酸、ＮａＨＳＯ４ などの酸触媒存在下で反応させることにより合成できる（特公昭６１−４５９７３等）。また、含フッ素アルコールと分子内に１個以上のグリシジル基を有する化合物とを前述の酸触媒存在下で反応させることで合成できる。これらの触媒中、ＢＦ３ 錯体が反応速度が速く、副生成物の少ない利点があり最も使用されている。上記の製造方法で合成される含フッ素防霧剤には酸分が１ｐｐｍ以上残存するとともに、ＢＦ３ が残存している。
【００３４】
本発明の防霧剤含有マスターバッチは、含フッ素防霧剤としてさらに下記式４で表されるモノマに基づく重合単位を含む防霧性能を有する共重合体を含有してもよい。この共重合体を含有することにより防霧持続性が向上し好ましい。
Ｒｆｄ−Ｑ−ＯＣＯＣＲ５ ＝ＣＨ２ ・・・式４
ただし、式４中における記号は以下の意味を示す。
Ｒｆｄ：炭素数４〜１６のポリフルオロアルキル基。
Ｑ：単結合または２価連結基。
Ｒ５ ：水素原子またはメチル基。
【００３５】
式４で表されるモノマに基づく重合単位を含む共重合体は、１５０℃以上での溶融混練時に、含フッ素防霧剤中に残存するＢＦ３により架橋反応が起こり、急激に粘度が上昇するが、炭酸塩（炭酸ナトリウム、炭酸カリウム、炭酸カルシウム、炭酸リチウム、炭酸マグネシウム、炭酸カリウムナトリウム、炭酸バリウム）の添加により、この架橋反応を抑えることができる。
【００３６】
Ｒｆｄは、前述のＲｆ 基と同様のものであり、炭素数は６〜１０が特に好ましい。
式４で表されるモノマとしては、以下のものが好ましい。
【００３７】
【化５】
式４で表されるモノマに基づく重合単位を含む共重合体は、式４で表されるモノマと、これと共重合しうる化合物との共重合オリゴマ（特開昭５９−８０４６８等）が好ましく、数平均分子量が１千〜５万の範囲のものが好ましい。
【００３９】
式４で表されるモノマと共重合しうる化合物としては、エチレン、酢酸ビニル、フッ化ビニル、スチレン、α−メチルスチレン、ｐ−メチルスチレン、（メタ）アクリル酸、（メタ）アクリル酸アルキルエステル、ポリ（オキシアルキレン）（メタ）アクリレート、（メタ）アクリルアミド、ジアセトン（メタ）アクリルアミド、Ｎ−メチロール（メタ）アクリルアミド、ビニルアルキルエーテル、ビニルアルキルケトン、ブタジエン、イソプレン、グリシジル（メタ）アクリレート、ベンジル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、無水マレイン酸、アジリジニル（メタ）アクリレート、Ｎ−ビニルカルバゾールが例示できる。上記共重合オリゴマは、これらの化合物の１種または２種以上と式４で表されるモノマとを共重合させた含フッ素共重合オリゴマである。
なお本明細書では、アクリレ−トおよびメタクリレートを総称して（メタ）アクリレートという。他の（メタ）アクリル酸等の表記も同様とする。
【００４０】
現在市販されている含フッ素防霧剤としては、旭硝子社製サーフロン「ＫＣ−２０」、サーフロン「ＫＣ−４０」、「ＡＦ−ＥＰ−５」、ダイキン工業社製ユニダイン「ＤＳ−４０１」、 ユニダイン「ＤＳ−４０３」、ネオス社製フタージェント「２５１」、大日本インキ化学工業社製メガファック「Ｆ−１４２Ｄ」等がある。なお、表２ではこれら市販含フッ素防霧剤を上記「 」内の表示で略記した。
【００４１】
本発明の防霧剤含有マスターバッチの製造方法は、押し出し成形機を用いて１５０〜２３０℃で混練溶融することを特徴とする。具体例としては、ヘンシェルミキサーやリボンミキサー等の各種混合機を用いて、塩素原子を含まない熱可塑性樹脂と、含フッ素防霧剤と炭酸塩（炭酸ナトリウム、炭酸カリウム、炭酸カルシウム、炭酸リチウム、炭酸マグネシウム、炭酸カリウムナトリウム、炭酸バリウム）とを混合し、それを２軸押し出し成形機、スクリュー押出機、ロール式混練機に代表される混練機で１５０〜２３０℃で混練溶融することで、容易に防霧剤含有マスターバッチを製造できる。この防霧剤含有マスターバッチは、通常、所定形状に成形される。
【００４２】
防霧剤含有マスターバッチの形状としては、製膜加工時に仕込み等の作業性の良いペレット状が好ましい。塊状では仕込みにくく、粉末では舞うので作業性が悪くなる。ペレット状に成形する具体例としては、糸状のストランドとし、ペレタイザーで切断する方法が挙げられる。
【００４３】
さらに、これらの防霧剤含有マスターバッチと塩素原子を含まない熱可塑性樹脂とを混合し製膜加工することにより、製膜加工時にＨＦガスの発生を伴うことなく農業用フィルムを製造できる。この際に用いられる塩素原子を含まない熱可塑性樹脂としては特に限定されないが、作業性から防霧剤含有マスターバッチに含まれる熱可塑性樹脂と同一のものが好ましい。このフィルムは防霧性能を有し、農業用フィルムとして有用であり、廃棄時に環境への影響も少ない。
【００４４】
以上のように、炭酸塩（炭酸ナトリウム、炭酸カリウム、炭酸カルシウム、炭酸リチウム、炭酸マグネシウム、炭酸カリウムナトリウム、炭酸バリウム）の添加により、ＨＦ等の酸性ガスの発生がない方法で防霧剤含有マスターバッチ、防霧性能を有する農業用フィルムの製造ができる。
【００４５】
【実施例】
例１〜３は含フッ素防霧剤の合成例、例４〜１４および例２５〜２７は実施例、例１５〜２４および例２８は比較例である。
【００４６】
［例１］化合物（Ａ）の合成
１００ｍｌガラス製反応フラスコに、３−パーフルオロオクチル−１，２−エポキシプロパン（ダイキン工業社製）４７．６ｇ（０．１０モル）、ポリオキシエチレングリコール（日本油脂社製、商品名：ＰＥＧ１０００）５１．１ｇ（０．０５モル）およびＢＦ３ エーテル錯体０．４ｇを仕込み、６０℃に制御された湯浴上で撹拌しながら４時間反応を行い、未精製の化合物（Ａ）を得た。得られた未精製の化合物（Ａ）を試料１とする。分析のため、未精製の化合物（Ａ）の一部を（ＣＨ３ ）３ ＳｉＣｌでシリル化し、ガスクロマトグラフィー（ＧＣ）分析した結果、エポキシドの全量の消費とポリオキシエチレングリコールの９２．６％の消費を確認した。
【００４７】
［例２］化合物（Ａ）の減圧処理
例１で得られた未精製の化合物（Ａ）を温度８０℃、圧力２ｍｍＨｇに３時間保持する減圧処理をした。減圧処理の前後の酸分は、それぞれ１７２０ｐｐｍ、６２ｐｐｍであった。この減圧処理後の化合物（Ａ）を試料２とする。
【００４８】
［例３］
２００ｍｌガラス製反応フラスコにパーフルオロオクチルエチルアクリレート２５ｇ、（ポリオキシアルキレン）アクリレート（日本油脂社製、商品名：ＰＥ−２００）２５ｇ、酢酸エチル５０ｇ、メルカプタン系分子量調節剤２．５ｇ、および重合開始剤（ＡＩＢＮ：アゾビスイソブチルニトリル）０．５ｇを仕込み、７０℃で１０時間反応を行った。室温まで冷却後、ＧＣ分析により、モノマの全量の消費を確認した。得られた反応液を減圧乾燥で溶媒を除去し、淡黄色粘稠液体状の共重合物を得た。ゲル浸透クロマトグラフィ（ＧＰＣ）分析した結果、得られた共重合物の平均分子量はスチレン換算で５０００であった。この共重合物と試料１を同重量の比率で混合し試料３とした。
【００４９】
［例４〜２４］
以下の（１）〜（３）の３成分を、表２に示す配合比にてヘンシェルミキサーで混合し、２軸押し出し成形機を用いて、温度１７０〜２００℃で混練溶融、成形しペレット状の防霧剤含有マスターバッチを得た。以下、ペレット状の防霧剤含有マスターバッチをペレットと記す。得られたペレットのそれぞれについて、以下に示す方法で酸分、腐食性評価、ＨＦの発生の有無を測定した。結果を表２に示す。
【００５０】
（１）含フッ素防霧剤（試料１、２、３または市販含フッ素防霧剤）。
（２）炭酸塩（炭酸ナトリウム、炭酸カリウム、炭酸カルシウム、炭酸リチウム、炭酸マグネシウム、炭酸カリウムナトリウム、炭酸バリウム）またはその比較例としてのトリ（ｎ−ブチル）アミン［Ｂｕ３Ｎ］。
（３）熱可塑性樹脂（ＬＤＰＥ：ＭＩ値が８の三菱化学社製、商品名ＬＪ−６０５。ＥＶＡ：ＥＶＡの粉末）。
【００５１】
分析の精度が高いため、酸分の測定にはフッ素イオン濃度を用いた。ＨＦ以外の酸の存在も考えられるが、市販品を含めて含フッ素防霧剤すべてにホウ素が５０〜４００ｐｐｍ検出されたため、合成時の触媒としてＢＦ３ またはＢＦ３ 錯体が使用されていると判断し、発生する酸分の大部分はＨＦであると考え、フッ素イオン濃度から計算したＨＦ量を酸分の量とした。
【００５２】
測定方法としては、フッ素樹脂容器に一定量のペレットを入れ、窒素気流下で１５０℃まで昇温（溶融）させ、窒素に同伴する酸分をイオン交換水に吸収した。酸性ガスが認められなくなるまでその操作を継続後、吸収させた水溶液を０．１規定ＫＯＨ水溶液で中和し、含まれるフッ素イオン濃度を、フッ素イオン選択電極で測定した。測定値よりペレット中に含まれる酸分を算出した。
【００５３】
［腐食性評価］
ペレットを軟鋼板にあて、１８０〜２００℃の温度下の５００時間後の軟鋼板表面の腐食性の度合いを外観評価した。評価基準としては腐食の度合いを表１の基準で目視評価し５点満点で数値化した。
【００５４】
【表１】
［ＨＦガスの発生の有無］
２軸押し出し成形機により、１７０〜２００℃で混練溶融する際に発生するガス中のＨＦガスの有無を、成形機のベント口部分で検知管で測定した。
【００５６】
【表２】
表２の結果のとおり、炭酸塩（炭酸ナトリウム、炭酸カリウム、炭酸カルシウム、炭酸リチウム、炭酸マグネシウム、炭酸カリウムナトリウム、炭酸バリウム）を添加することで、押し出し成形機での溶融混練時のＨＦガスの発生を防止でき、酸分を含まない防霧剤含有マスターバッチを製造できることが確認された。またペレットは酸分を含まないため、製膜加工する際の金属材料に対する腐食の心配もない。また、炭酸塩（炭酸ナトリウム、炭酸カリウム、炭酸カルシウム、炭酸リチウム、炭酸マグネシウム、炭酸カリウムナトリウム、炭酸バリウム）の代わりにトリ（ｎ−ブチル）アミンを用いた場合、ＨＦの発生を防止できないこともわかった。
【００５８】
［例２５〜２８］
例１２〜１４の配合比および製造方法で製造されたペレット３点を表３の配合比で混合し製膜加工してフィルムとした（それぞれ例２５〜２７）。比較例として、ペレットを添加しない以外同様にしてフィルムとした（例２８）。作成したフィルムのフィルム外観、防霧性を下記の方法により評価した結果を表４に示す。
【００５９】
【表３】
［フィルム外観］
ペレットを含有しないフィルムと比較して、フィルムの透明性、着色の有無について、差異がないか目視で確認した。
【００６１】
［防霧性評価］
フィルムよりビニルハウスを作成して屋外に設置した。観測期間は１ヶ月（平成１０年２〜３月）、観測頻度は朝、夕各１回で、目視で霧が発生しているかを確認し、霧の発生した回数をカウントした。
【００６２】
【表４】
表４に示すとおり、本発明の防霧剤含有マスターバッチを含有することによる、フィルム外観への影響はなく、良好な防霧性を示すことが確認された。
【００６４】
【発明の効果】
本発明の防霧剤含有マスターバッチの製造方法によれば、混練溶融時にＨＦをはじめとする酸性ガスの発生を防止し、作業環境の低下を防止できる。得られる防霧剤含有マスターバッチは、酸分および腐食性もなく、取り扱いも容易なため、農業用ビニルハウス向けの塩素原子を含まない熱可塑性樹脂からなる防霧性能を有する農業用フィルムの原料として優れている。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an antifoggant-containing masterbatch, a method for producing the same, and a method for producing an agricultural film using the antifoggant-containing masterbatch. More specifically, when used as an agricultural vinyl house, it has the ability to suppress the occurrence of fog near the inner surface of the film (anti-fogging property) and the ability to exert its anti-fogging property for a long time (fog-proof durability) The present invention relates to a method for producing an agricultural film containing no chlorine atom, an antifoggant-containing masterbatch that is a raw material, and a method for producing the same.
[0002]
[Prior art]
In recent years, in order to increase the productivity and market value of useful plants, so-called house cultivation and tunnel cultivation in which useful plants are promoted, semi-encouraged, or inhibited under an agricultural film are actively performed.
Currently, vinyl chloride resins are used as agricultural films. In order to promote the flow of water droplets on the inner surface of the film and increase the amount of incident sunlight, this agricultural film contains an antifogging agent (such as sorbitan fatty acid ester) which is a kind of surfactant. Under the coating with such a film containing an antifogging agent, the temperature difference between inside and outside becomes large and fog is generated in the vicinity of the inner surface. Therefore, a fluorine-containing antifogging agent is added to impart antifogging properties.
[0003]
However, since vinyl chloride resin has chlorine atoms, highly toxic dioxins are generated when it is burned at a low temperature, and it must be treated with a special high-temperature combustion treatment facility when it is discarded.
Agricultural films having the above performance with resins other than vinyl chloride resins are also being studied, but simply changing the resin has some problems and has not been put into practical use. For example, when a thermoplastic resin that does not contain chlorine atoms, such as polyethylene resin or vinyl acetate resin, is used, the temperature at which it can be melt-molded is higher than that of vinyl chloride resin (150-230 ° C). , Pelletization and film formation are required.
[0004]
The fluorine-containing antifogging agent currently used for vinyl chloride resin films is a fluorine-containing antifogging agent synthesized by ring-opening addition of a fluoroalkyl group-containing epoxy compound and an oxyethylene group-containing compound under a Lewis acid catalyst. (Described in JP-A-59-93739, JP-A-61-133244, JP-A-61-152745, JP-A-64-147, JP-A-64-14263, JP-A-1-216947, JP-A-1-246237, etc. .)
[0005]
As the Lewis acid catalyst, boron trifluoride (BF 3 ) or a complex thereof is used from the viewpoint of reactivity, but the fluorine-containing antifogging agent synthesized by these methods has an acid content and a small amount of BF 3. Remains. This BF 3 has the property of being decomposed by moisture in the air and the remaining acid content to generate hydrofluoric acid (HF) gas. This property is particularly noticeable at high temperatures, and becomes a problem when a thermoplastic resin containing no chlorine atom is used, which has a higher temperature at which melt molding is possible than vinyl chloride resin.
[0006]
In order to solve this problem, a method was examined in which BF 3 does not remain in the fluorine-containing anti-fogging agent and the acid content is reduced to a non-corrosive state. In order to eliminate this corrosiveness, the acid content must be less than 1 ppm in terms of HF, and more desirably less than 0.1 ppm.
[0007]
The method of removing acid content such as BF 3 in the fluorine-containing antifogging agent by washing with water is difficult to separate from water because the fluorine-containing antifogging agent is a surfactant, so that it is dissolved, emulsified or uniformly dispersed in water. It is not suitable for practical use.
[0008]
In a method of removing by washing acid content, such as BF 3 in the fluorine-containing anti-fogging agent with a mixed solvent (Akira Japanese public 61-45973), a fluorine-containing anti-fogging agent contains more coordination highly etheric oxygen atom Therefore, it is partially coordinated with BF 3 and cannot be completely removed. For the same reason, even if it is removed under reduced pressure at a temperature of less than 230 ° C., it cannot be completely removed. Above 230 ° C., the catalytic action of coordinated BF 3 becomes active, causing generation and decomposition reaction of dioxane due to cyclization reaction of the oxyethylene portion of the fluorine-containing anti-fogging agent, resulting in a decrease in fog prevention. The light transmittance decreases due to coloring.
[0009]
There is a method of reducing the amount of BF 3 complex used in the reaction, but in order to proceed the reaction, 0.1% by weight or more of BF 3 complex is required with respect to the fluoroalkyl group-containing epoxy compound as a raw material. , You can not reduce the weight below this.
As described above, it is difficult to reduce the residual amount of BF 3 in the fluorine-containing antifogging agent and to remove the acid content.
[0010]
When the above-mentioned fluorinated anti-fogging agent containing BF 3 and containing an acid content is used for a thermoplastic resin containing no chlorine atom, the remaining BF 3 is decomposed because it is kneaded and melted at a high temperature of 150 ° C. or higher. HF gas is generated. For this reason, the facility requires an acid gas abatement facility, which is problematic in terms of workability and cost. In particular, in an antifoggant-containing masterbatch, since the content of the fluorine-containing antifoggant is large, generation of HF gas in which BF 3 is decomposed is serious and the problem is great. In addition, some of the generated HF gas remains in the antibacterial agent-containing masterbatch, and HF gas is generated during molding and film-forming. Therefore, it is not possible to use mild steel that is easily corroded by acid as molding and film-forming equipment. The material is limited to expensive materials such as Hastelloy and titanium. Moreover, there is a possibility that acid content may remain in the film as a product, and there is a problem of environmental pollution.
[0011]
[Problems to be solved by the invention]
An object of the present invention is to provide an antifoggant-containing masterbatch using a thermoplastic resin that does not contain chlorine atoms and does not generate an acid content based on BF 3 or the like during the production of an agricultural film, and an agricultural film using the same And a method for producing an antifoggant-containing masterbatch without generation of an acid content based on BF 3 or the like.
[0012]
[Means for Solving the Problems]
The present invention includes a thermoplastic resin containing no chlorine atom that can be melt-molded at 150 to 230 ° C., with respect to the thermoplastic resin 100 parts by weight, BF 3 left by prepared using BF 3 or its complex 1 to 70 parts by weight of a fluorine-containing antifogging agent and 0.01 to 14 parts by weight of carbonate (sodium carbonate, potassium carbonate, calcium carbonate, lithium carbonate, magnesium carbonate, sodium potassium carbonate, barium carbonate) An antifoggant-containing masterbatch is provided.
Moreover, the manufacturing method of the said antifoggant containing masterbatch characterized by kneading | melting at 150-230 degreeC using an extrusion molding machine is provided.
Moreover, the manufacturing method of the film for agriculture characterized by mixing the said antifoggant containing masterbatch and the thermoplastic resin which does not contain a chlorine atom, and forming into a film is provided.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
The antibacterial agent-containing masterbatch of the present invention is synthesized using BF 3 or a complex thereof with respect to 100 parts by weight of the thermoplastic resin not containing chlorine atoms that can be melt-molded at 150 to 230 ° C. and 100 parts by weight of the thermoplastic resin. 1 to 70 parts by weight of a fluorine-containing antifoggant in which BF 3 remains and carbonate (sodium carbonate, potassium carbonate, calcium carbonate, lithium carbonate, magnesium carbonate, sodium potassium carbonate, barium carbonate) 0.01 to 14 A part by weight is melt-mixed. Examples of the melt mixing method include a method of kneading and melting after mixing.
[0014]
The proportion of the raw materials for obtaining the anti-fogging agent containing master batch, relative to 100 parts by weight of the thermoplastic resin, fluorine-containing Bokirizai 1 to 70 parts by weight, particularly 5 to 50 parts by weight, preferably the carbonate (Sodium carbonate, potassium carbonate, calcium carbonate, lithium carbonate, magnesium carbonate, sodium potassium carbonate, barium carbonate) is preferably 0.01 to 14 parts by weight, particularly 0.05 to 5 parts by weight.
[0015]
If the fluorine-containing antifogging agent is more than 70 parts by weight, stickiness occurs during mixing using a Henschel mixer or the like, and it is difficult to carry into an extrusion molding machine, and the uniformity exceeding the limit compatible with the resin becomes poor. Moreover, if it is less than 1 weight part, fog prevention performance will fall.
If the amount of carbonate (sodium carbonate, potassium carbonate, calcium carbonate, lithium carbonate, magnesium carbonate, sodium potassium carbonate, barium carbonate) is less than 0.01 parts by weight, acid content cannot be sufficiently removed, and if it exceeds 14 parts by weight, molding is not possible. It becomes difficult.
The weight ratio of carbonate (sodium carbonate, potassium carbonate, calcium carbonate, lithium carbonate, magnesium carbonate, sodium potassium carbonate, barium carbonate) to the fluorine-containing antifogging agent is preferably 0.005 to 0.2, 0.01 -0.1 is particularly preferred.
[0016]
Carbonate sodium carbonate, potassium carbonate, calcium carbonate, lithium carbonate, magnesium carbonate, sodium potassium carbonate, and barium carbonate, calcium carbonate, barium carbonate, magnesium carbonate good preferable.
[0020]
Carbonates (sodium carbonate, potassium carbonate, calcium carbonate, lithium carbonate, magnesium carbonate, sodium potassium carbonate, barium carbonate) neutralize the acid content in the fluorine-containing anti-fogging agent and the acid content generated during heating. For this purpose, the smaller the particle diameter, the better, and 0.1 to 10 μm, particularly 0.1 to 2 μm is preferable. When the particle size is less than 0.1 μm, the powder is likely to be blown, and the work of uniformly dispersing is difficult. If it exceeds 10 μm, it is necessary to increase the amount of addition because the surface area is small, and when it is formed into a film, the light transmittance decreases by 5% or more.
These carbonates (sodium carbonate, potassium carbonate, calcium carbonate, lithium carbonate, magnesium carbonate, sodium potassium carbonate, barium carbonate) may be used alone or in combination of two or more.
[0021]
Thermoplastic resin containing no chlorine atom that can be melt-molded at 150 to 230 ° C. is 80% by weight or more in total of polyolefin resin and / or ethylene-vinyl acetate resin from transparency, ease of processing, and durability. What is contained is preferable, and 100% by weight is particularly preferable. Ethylene-vinyl acetate resin (EVA) is preferable because of its good durability in cold regions.
[0022]
Specific examples of the polyolefin resin include the following resins.
The homopolymer resin is preferably a polyethylene resin, and particularly preferably a low density polyethylene resin (abbreviation: LDPE) having good film processability. The copolymer resin is preferably an ethylene-propylene resin or an ethylene-butylene resin.
[0023]
Further, the fluidity of the resin preferably has a melt index (MI value) according to JIS-K7210 of 2 to 100 (g / 10 minutes), particularly 5 to 20 (g / 10 minutes).
[0024]
Currently, LDPE products with different MI values are commercially available from many companies including Sumitomo Chemical, Mitsui Chemicals, Asahi Kasei Kogyo, Tosoh, Showa Denko, Mitsubishi Chemical, Nihon Unicar, and Mitsui DuPont Polychemicals. Also, the shape of the resin includes powders, pellets and lumps. A number of products of EVA are also commercially available from polyethylene manufacturers.
[0025]
Further, in the present invention, as a thermoplastic resin not containing chlorine atoms, a resin that can be used in place of or in addition to the above-mentioned polyolefin resin, EVA, or in addition to the above-mentioned polyolefin resin, EVA, includes propylene-vinyl acetate resin, ethylene -Vinyl acetate-propylene resin, styrene resin, ethylene-styrene resin, carbonate resin, ABS resin, acrylic resin, ethylene terephthalate resin, fluororesin, nylon resin, urethane resin and the like. However, it is limited to a thermoplastic resin that does not contain chlorine atoms having a melt molding temperature of 150 to 230 ° C.
[0026]
The fluorine-containing antifogging agent in the present invention is preferably a fluorine compound represented by the following formula 2 or formula 3.
[0027]
[Chemical formula 2]
R fa —R 1 —O (C 2 H 4 O) h —R 2 —R fb Formula 2
R fc —R 3 —O (C 2 H 4 O) i — (CO) j —R 4.
[0028]
However, the symbols in Formula 2 and Formula 3 have the following meanings.
R 1 , R 2 , R 3 : each independently a divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms in which an oxygen atom may be inserted between carbon and carbon, and a hydrogen atom in the group May be substituted with an acyloxy group such as an acetoxy group or a hydroxyl group.
R 4 : a hydrogen atom, a phenyl group, a glycidyl group, or a monovalent aliphatic hydrocarbon having 2 to 16 carbon atoms in which an oxygen atom may be inserted between carbon and carbon and a double bond may be contained Group.
R fa , R fb , R fc : each independently a C 4-16 polyfluoroalkyl group in which an oxygen atom may be inserted between carbon and carbon.
h, i: each independently a number of 2 to 30.
j: 0 or 1.
[0029]
R 1 , R 2 and R 3 are preferably a divalent aliphatic hydrocarbon group having 3 to 5 carbon atoms in which an oxygen atom may be inserted between carbon and carbon. The group in which a hydrogen atom is substituted is preferably a group in which one of the hydrogen atoms is substituted with an acetoxy group or a hydroxyl group. R 4 is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
[0030]
The polyfluoroalkyl group is hereinafter referred to as R f group. The R f group is a group in which two or more hydrogen atoms of an alkyl group are substituted with fluorine atoms. As for carbon number of Rf group, 4-16 are preferable. The R f group preferably has a linear structure, and the number of fluorine atoms is [(number of fluorine atoms in the R f group) / (number of hydrogen atoms contained in the corresponding alkyl group having the same carbon number)] × 100 ( %) Is preferably 60% or more, particularly preferably 80% or more.
Specifically, the following compounds are preferred as the fluorine-containing antifogging agent. In the formula, Ph represents a phenyl group, and G represents a glycidyl group.
[0031]
[Chemical 3]
[Formula 4]
These compounds react a fluoroalkyl group-containing epoxy compound with a compound having one or more hydroxyl groups in the molecule in the presence of an acid catalyst such as BF 3 or its ether or alcohol complex, sulfuric acid, NaHSO 4 or the like. It can be synthesized by (Akira Japanese public 61-45973, etc.). Moreover, it is compoundable by making a fluorine-containing alcohol and the compound which has a 1 or more glycidyl group in a molecule | numerator react in the presence of the above-mentioned acid catalyst. Among these catalysts, the BF 3 complex is most used because it has a high reaction rate and less by-products. The fluorine-containing antifogging agent synthesized by the above production method has an acid content of 1 ppm or more and BF 3 remaining.
[0034]
The anti-fogging agent-containing masterbatch of the present invention may further contain a copolymer having anti-fogging performance including a polymer unit based on a monomer represented by the following formula 4 as a fluorine-containing anti-fogging agent. By containing this copolymer, the antifogging durability is improved, which is preferable.
R fd -Q-OCOCR 5 = CH 2 ... Formula 4
However, the symbol in Formula 4 shows the following meaning.
R fd : a polyfluoroalkyl group having 4 to 16 carbon atoms.
Q: a single bond or a divalent linking group.
R 5 : a hydrogen atom or a methyl group.
[0035]
A copolymer containing a polymer unit based on a monomer represented by Formula 4 undergoes a crosslinking reaction due to BF 3 remaining in the fluorine-containing anti-fogging agent when melt-kneaded at 150 ° C. or higher, and the viscosity rapidly increases. However, the addition of carbonate (sodium carbonate, potassium carbonate, calcium carbonate, lithium carbonate, magnesium carbonate, sodium potassium carbonate, barium carbonate) can suppress this crosslinking reaction.
[0036]
R fd is the same as the aforementioned R f group, and the number of carbon atoms is particularly preferably 6 to 10.
As the monomer represented by Formula 4, the following are preferable.
[0037]
[Chemical formula 5]
The copolymer containing a polymerization unit based on a monomer represented by formula 4 is preferably a copolymer oligomer (such as JP-A-59-80468) of a monomer represented by formula 4 and a compound copolymerizable therewith. The number average molecular weight is preferably in the range of 1,000 to 50,000.
[0039]
Compounds that can be copolymerized with the monomer represented by Formula 4 include ethylene, vinyl acetate, vinyl fluoride, styrene, α-methylstyrene, p-methylstyrene, (meth) acrylic acid, and (meth) acrylic acid alkyl ester. , Poly (oxyalkylene) (meth) acrylate, (meth) acrylamide, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, vinyl alkyl ether, vinyl alkyl ketone, butadiene, isoprene, glycidyl (meth) acrylate, benzyl ( Examples include meth) acrylate, cyclohexyl (meth) acrylate, maleic anhydride, aziridinyl (meth) acrylate, and N-vinylcarbazole. The copolymer oligomer is a fluorine-containing copolymer oligomer obtained by copolymerizing one or more of these compounds and a monomer represented by Formula 4.
In the present specification, acrylate and methacrylate are collectively referred to as (meth) acrylate. The same applies to other notations such as (meth) acrylic acid.
[0040]
As fluorine-containing antifogging agents currently on the market, Surflon “KC-20”, Surflon “KC-40”, “AF-EP-5” manufactured by Asahi Glass Co., Ltd., Unidyne “DS-401” manufactured by Daikin Industries, Ltd., Unidyne There are "DS-403", Neos's footagent "251", Dainippon Ink & Chemicals, Inc. MegaFuck "F-142D" and the like. In Table 2, these commercially available fluorine-containing anti-fogging agents are abbreviated by the indications in the above “”.
[0041]
The method for producing an antifoggant-containing masterbatch of the present invention is characterized by kneading and melting at 150 to 230 ° C. using an extrusion molding machine. As specific examples, using various mixers such as a Henschel mixer and a ribbon mixer, a thermoplastic resin containing no chlorine atom, a fluorine-containing antifoggant and a carbonate (sodium carbonate, potassium carbonate, calcium carbonate, lithium carbonate, Easy mixing by mixing with magnesium carbonate, potassium carbonate, barium carbonate) and kneading and melting at 150-230 ° C with a kneader represented by a twin screw extruder, screw extruder, and roll kneader. An antifoggant-containing masterbatch can be produced. This antifoggant-containing masterbatch is usually formed into a predetermined shape.
[0042]
The shape of the antibacterial agent-containing masterbatch is preferably a pellet shape with good workability such as preparation during film forming. It is difficult to prepare in the lump form, and the workability deteriorates because it flies in powder. A specific example of forming into a pellet is a method of forming a strand of yarn and cutting with a pelletizer.
[0043]
Furthermore, by mixing these antifoggant-containing master batches with a thermoplastic resin containing no chlorine atom and forming a film, an agricultural film can be produced without generating HF gas during the film forming process. Although it does not specifically limit as a thermoplastic resin which does not contain the chlorine atom used in this case, The same thing as the thermoplastic resin contained in a fog prevention agent containing masterbatch is preferable from workability | operativity. This film has antifogging performance, is useful as an agricultural film, and has little environmental impact when discarded.
[0044]
As described above, the addition of carbonates (sodium carbonate, potassium carbonate, calcium carbonate, lithium carbonate, magnesium carbonate, sodium potassium carbonate, barium carbonate) prevents the generation of acidic gases such as HF, and the like contains an antifoggant master. Agricultural film with batch and anti-fog performance can be manufactured.
[0045]
【Example】
Examples 1 to 3 are synthesis examples of fluorine-containing antifogging agents, Examples 4 to 14 and Examples 25 to 27 are Examples, and Examples 15 to 24 and Example 28 are Comparative Examples.
[0046]
Example 1 Synthesis of Compound (A) In a 100 ml glass reaction flask, 47.6 g (0.10 mol) of 3-perfluorooctyl-1,2-epoxypropane (produced by Daikin Industries), polyoxyethylene glycol ( Nihon Yushi Co., Ltd., trade name: PEG1000) 51.1 g (0.05 mol) and BF 3 ether complex 0.4 g were charged and reacted for 4 hours with stirring in a hot water bath controlled at 60 ° C. The purified compound (A) was obtained. The obtained unpurified compound (A) is designated as sample 1. For analysis, a part of the crude compound (A) was silylated with (CH 3 ) 3 SiCl and analyzed by gas chromatography (GC). As a result, the total consumption of epoxide and 92.6% of polyoxyethylene glycol were analyzed. Confirmed consumption.
[0047]
[Example 2] Decompression treatment of compound (A) The unpurified compound (A) obtained in Example 1 was subjected to a decompression treatment in which the temperature was maintained at 80 ° C and a pressure of 2 mmHg for 3 hours. The acid contents before and after the decompression treatment were 1720 ppm and 62 ppm, respectively. The compound (A) after this reduced pressure treatment is designated as sample 2.
[0048]
[Example 3]
In a 200 ml glass reaction flask, 25 g of perfluorooctylethyl acrylate, 25 g of (polyoxyalkylene) acrylate (manufactured by NOF Corporation, trade name: PE-200), 50 g of ethyl acetate, 2.5 g of a mercaptan molecular weight regulator, and polymerization start 0.5 g of an agent (AIBN: azobisisobutylnitrile) was charged and reacted at 70 ° C. for 10 hours. After cooling to room temperature, consumption of the entire amount of monomer was confirmed by GC analysis. The obtained reaction solution was dried under reduced pressure to remove the solvent to obtain a pale yellow viscous liquid copolymer. As a result of gel permeation chromatography (GPC) analysis, the average molecular weight of the obtained copolymer was 5000 in terms of styrene. This copolymer and Sample 1 were mixed at the same weight ratio to obtain Sample 3.
[0049]
[Examples 4 to 24]
The following three components (1) to (3) were mixed with a Henschel mixer at the blending ratio shown in Table 2, and kneaded, melted and molded at a temperature of 170 to 200 ° C. using a biaxial extrusion molding machine. An antifoggant-containing masterbatch was obtained. Hereinafter, the pellet-shaped antifoggant-containing master batch is referred to as a pellet. About each of the obtained pellet, the presence or absence of generation | occurrence | production of acid content, corrosivity evaluation, and HF was measured by the method shown below. The results are shown in Table 2.
[0050]
(1) Fluorine-containing antifogging agent (samples 1, 2, 3 or commercially available fluorine-containing antifogging agent).
(2) Carbonate (sodium carbonate, potassium carbonate, calcium carbonate, lithium carbonate, magnesium carbonate, sodium potassium carbonate, barium carbonate) or tri (n-butyl) amine [Bu 3 N] as a comparative example .
(3) Thermoplastic resin (LDPE: trade name LJ-605, manufactured by Mitsubishi Chemical Corporation with MI value of 8; EVA: EVA powder).
[0051]
Since the accuracy of analysis is high, the fluoride ion concentration was used for the measurement of acid content. The presence of acids other than HF is also considered, but it was judged that BF 3 or BF 3 complex was used as a catalyst at the time of synthesis because boron was detected in all fluorine-containing anti-fogging agents including commercial products in an amount of 50 to 400 ppm. Then, most of the generated acid content was considered to be HF, and the HF amount calculated from the fluorine ion concentration was taken as the acid content.
[0052]
As a measuring method, a certain amount of pellets was put in a fluororesin container, and the temperature was raised (melted) to 150 ° C. under a nitrogen stream, and the acid content accompanying nitrogen was absorbed in ion-exchanged water. The operation was continued until no acidic gas was observed, and then the absorbed aqueous solution was neutralized with a 0.1 N KOH aqueous solution, and the fluorine ion concentration contained was measured with a fluorine ion selective electrode. The acid content contained in the pellet was calculated from the measured value.
[0053]
[Corrosion evaluation]
The pellets were applied to a mild steel plate, and the degree of corrosivity on the surface of the mild steel plate after 500 hours at a temperature of 180 to 200 ° C. was evaluated. As the evaluation criteria, the degree of corrosion was visually evaluated according to the criteria shown in Table 1, and was converted into a numerical value with a maximum of 5 points.
[0054]
[Table 1]
[Presence or absence of HF gas generation]
The presence or absence of HF gas in the gas generated when kneading and melting at 170 to 200 ° C. was measured with a detector tube at the vent port portion of the molding machine using a biaxial extrusion molding machine.
[0056]
[Table 2]
As shown in Table 2, by adding carbonate (sodium carbonate, potassium carbonate, calcium carbonate, lithium carbonate, magnesium carbonate, sodium potassium carbonate, barium carbonate) , HF gas during melt kneading in an extrusion molding machine Generation | occurrence | production can be prevented and it was confirmed that the fog prevention agent containing masterbatch which does not contain an acid content can be manufactured. Further, since the pellet does not contain an acid content, there is no concern about corrosion of the metal material during film formation. In addition, when tri (n-butyl) amine is used instead of carbonate (sodium carbonate, potassium carbonate, calcium carbonate, lithium carbonate, magnesium carbonate, sodium potassium carbonate, barium carbonate) , generation of HF may not be prevented. all right.
[0058]
[Examples 25 to 28]
Three pellets produced by the blending ratio of Examples 12 to 14 and the production method were mixed at the blending ratio of Table 3 to form a film (Examples 25 to 27, respectively). As a comparative example, a film was prepared in the same manner except that no pellet was added (Example 28). Table 4 shows the results of evaluating the film appearance and fog resistance of the prepared film by the following methods.
[0059]
[Table 3]
[Film appearance]
As compared with a film not containing pellets, it was visually confirmed whether there was a difference in transparency and coloring of the film.
[0061]
[Anti-fogging evaluation]
A vinyl house was created from the film and installed outdoors. The observation period was 1 month (February to March 1998), the observation frequency was once in the morning and evening, and it was confirmed visually that fog had occurred, and the number of occurrences of fog was counted.
[0062]
[Table 4]
As shown in Table 4, it was confirmed that containing the antibacterial agent-containing masterbatch of the present invention had no effect on the film appearance and showed good antifogging properties.
[0064]
【The invention's effect】
According to the method for producing an antifoggant-containing masterbatch of the present invention, it is possible to prevent the generation of acidic gas including HF during kneading and melting, and to prevent the working environment from being lowered. The resulting antibacterial agent-containing masterbatch has no acid content, no corrosive properties, and is easy to handle. Therefore, it is a raw material for agricultural films having antifogging properties made of a thermoplastic resin that does not contain chlorine atoms for agricultural vinyl houses. As excellent.
Claims (4)
炭酸塩：炭酸ナトリウム、炭酸カリウム、炭酸カルシウム、炭酸リチウム、炭酸マグネシウム、炭酸カリウムナトリウム、炭酸バリウム。Fluorine-containing prevention in which BF 3 remains as a result of synthesis using BF 3 or a complex thereof with respect to 100 parts by weight of the thermoplastic resin that does not contain chlorine atoms that can be melt-molded at 150 to 230 ° C. An antifoggant-containing masterbatch obtained by melt-mixing 1 to 70 parts by weight of an atomizing agent and 0.01 to 14 parts by weight of the following carbonate.
Carbonate: sodium carbonate, potassium carbonate, calcium carbonate, lithium carbonate, magnesium carbonate, potassium potassium carbonate, barium carbonate.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14179898A JP3618223B2 (en) | 1998-05-22 | 1998-05-22 | Antibacterial-containing masterbatch and method for producing the same |
| KR1019990018222A KR100591055B1 (en) | 1998-05-22 | 1999-05-20 | Masterbatch containing antifoaming agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14179898A JP3618223B2 (en) | 1998-05-22 | 1998-05-22 | Antibacterial-containing masterbatch and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11335568A JPH11335568A (en) | 1999-12-07 |
| JP3618223B2 true JP3618223B2 (en) | 2005-02-09 |
Family
ID=15300393
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14179898A Expired - Fee Related JP3618223B2 (en) | 1998-05-22 | 1998-05-22 | Antibacterial-containing masterbatch and method for producing the same |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP3618223B2 (en) |
| KR (1) | KR100591055B1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100716586B1 (en) * | 2005-11-16 | 2007-05-09 | 부경대학교 산학협력단 | Method for processing of polyethylene for agriculture film having antifogging |
| JP2011201967A (en) * | 2010-03-24 | 2011-10-13 | C I Kasei Co Ltd | Master batch pellet and method for producing the same |
| KR102522084B1 (en) * | 2021-05-13 | 2023-04-14 | 연세대학교 산학협력단 | Agricultural film absorbing infrared ray with excellent anti-fogging and manufacturing method of the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3396303B2 (en) * | 1994-09-22 | 2003-04-14 | 住友化学工業株式会社 | Masterbatch for polyolefin film and composition for polyolefin film |
| US6087446A (en) * | 1996-03-20 | 2000-07-11 | Hercules Incorporated | Masterbatch formulations for polyolefin applications |
| KR100197902B1 (en) * | 1996-03-27 | 1999-06-15 | 남창우 | Compounding compositions for airing film |
-
1998
- 1998-05-22 JP JP14179898A patent/JP3618223B2/en not_active Expired - Fee Related
-
1999
- 1999-05-20 KR KR1019990018222A patent/KR100591055B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11335568A (en) | 1999-12-07 |
| KR19990088438A (en) | 1999-12-27 |
| KR100591055B1 (en) | 2006-06-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1120184C (en) | Vinyl alcohol polymer and its composition | |
| JP2016079379A (en) | Soluble material for three-dimensional molding | |
| JPS6164707A (en) | Production of vinylidene fluoride-containing fluoroelastomer | |
| JP3933392B2 (en) | Near infrared absorbing agent and near infrared absorbing synthetic resin composition | |
| CN101228117A (en) | Fluorosulfonyl group-containing compound, method for its production and polymer thereof | |
| CN104781312B (en) | Method for preparing fluoropolymer heterozygosis composite | |
| JP2000313721A (en) | New hydroxy group-containing copolymer and its production | |
| JP3618223B2 (en) | Antibacterial-containing masterbatch and method for producing the same | |
| CN1886475A (en) | Cationically curable composition | |
| CN1268651C (en) | Additive for rendering inert acidic or halogen-containing compounds contained in olefin polymers | |
| EP3746497B1 (en) | Hyperbranched polylactide resin compositions | |
| JP6691641B2 (en) | Modified vinyl alcohol polymer and method for producing the same | |
| CN102482487B (en) | Novel nonionic surfactant and fog-preventive agent | |
| WO2016059987A1 (en) | Soluble material for three-dimensional molding | |
| CN112759887A (en) | Sound-insulation polystyrene and preparation method thereof | |
| CN109999716B (en) | Nonionic fluorine-containing surfactant and preparation method and application thereof | |
| CN103611570B (en) | Preparation method of resin catalyst for synthesis of difluoromethyl ether | |
| JP2003138120A (en) | Aromatic polycarbonate resin composition | |
| CN108485144A (en) | The method for preparing biomass-based stabilizer using forest and agricultural biomass | |
| CN114957524B (en) | Polymer for transparent super-hydrophilic anti-fog coating and preparation method thereof | |
| CN112142931A (en) | Ammonium salt antibacterial polyethylene material and preparation method thereof | |
| CN108699230A (en) | The manufacturing method of high molecular aromatic polycarbonate resin | |
| JPH11152383A (en) | Agricultural vinyl chloride-based resin film | |
| JP3261825B2 (en) | Polyethylene resin composition having excellent transparency and method for producing the same | |
| JP3363413B2 (en) | Resin composition for agricultural film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20040511 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040701 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20040824 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040903 |
|
| A911 | Transfer of reconsideration by examiner before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20041015 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20041109 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20041109 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20071119 Year of fee payment: 3 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101119 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101119 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131119 Year of fee payment: 9 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |