JPH10330625A - Antimicrobial packaging material and its production - Google Patents
Antimicrobial packaging material and its productionInfo
- Publication number
- JPH10330625A JPH10330625A JP9152948A JP15294897A JPH10330625A JP H10330625 A JPH10330625 A JP H10330625A JP 9152948 A JP9152948 A JP 9152948A JP 15294897 A JP15294897 A JP 15294897A JP H10330625 A JPH10330625 A JP H10330625A
- Authority
- JP
- Japan
- Prior art keywords
- antibacterial
- packaging material
- poly
- resin
- glycerin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Packages (AREA)
- Apparatus For Disinfection Or Sterilisation (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、食品や産業資材な
どの包装に使用される抗菌性包装材料およびその製造方
法に関する。さらに詳しくは、特定の（ポリ）グリセリ
ン脂肪酸エステルまたは銀系抗菌剤等を特定量含んでな
る抗菌性包装材料およびその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial packaging material used for packaging food and industrial materials, and a method for producing the same. More specifically, the present invention relates to an antibacterial packaging material containing a specific amount of a specific (poly) glycerin fatty acid ester or a silver-based antimicrobial agent, and a method for producing the same.
【０００２】[0002]
【従来の技術】食品や産業資材等の包装材料に抗菌性を
付与することが望まれている。熱可塑性樹脂に抗菌性を
付与する技術には、有機系と無機系の抗菌剤を単独また
は併用して使用することが行われている。 金、銀、亜
鉛などの金属化合物、金属粒子や金属イオンが抗菌性を
示すことは古くから知られている。また、金属超微粒子
を用いた抗菌性材料も提案されている。例えば、特開平
０６−２９３６１１号公報には、母材に、平均粒径が２
００ｎｍ未満の金属超微粒子が０．１ｐｐｍ以上分散し
ている抗菌性材料が提案されている。金属粒子が細かく
なると表面積が増え、抗菌活性は増えるが、金属微粒子
が凝集し、取り扱い難くなると共に、使用対象物への均
一な分散がし難くなる。特開平０７−１７３０２２号公
報には担体に金属微粒子を担持させた抗菌性材料が提案
されている。これらの抗菌性材料は、金属微粒子を含む
塗工液を母材の表面に塗布する方法、金属微粒子を含む
マスターバッチを母材樹脂に添加し、母材樹脂中に金属
微粒子を分散させる方法により得ることが開示されてい
る。特開平８−２８９７６９号公報では、乳酸菌ラクト
パチルス・ロイテリによって産生された抗菌性物質ロイ
テリンとグリセリン脂肪酸エステル等との食品用乳化剤
を含有する食品保存剤の提案がある。特開平６−３１６
６４１号公報では、添加剤としてポリグリセリンステア
リン酸エステルが、樹脂に対し０．１〜３．０重量％含
有されている肉剥離性の良好な塩化ビニリデン系樹脂フ
ィルムの提案がある。2. Description of the Related Art It is desired to impart antibacterial properties to packaging materials such as foods and industrial materials. As a technique for imparting antibacterial properties to a thermoplastic resin, use of an organic or inorganic antibacterial agent alone or in combination is performed. It has long been known that metal compounds such as gold, silver and zinc, metal particles and metal ions exhibit antibacterial properties. Antibacterial materials using ultrafine metal particles have also been proposed. For example, Japanese Patent Application Laid-Open No. 06-293611 discloses that a base material has an average particle size of 2%.
An antibacterial material in which ultrafine metal particles having a diameter of less than 00 nm are dispersed by 0.1 ppm or more has been proposed. When the metal particles become finer, the surface area increases and the antibacterial activity increases, but the metal fine particles aggregate, making it difficult to handle, and making it difficult to uniformly disperse them in the object to be used. Japanese Patent Application Laid-Open No. 07-173022 proposes an antibacterial material in which metal fine particles are supported on a carrier. These antibacterial materials are prepared by applying a coating liquid containing fine metal particles to the surface of the base material, adding a master batch containing fine metal particles to the base resin, and dispersing the fine metal particles in the base resin. It is disclosed to obtain. Japanese Patent Application Laid-Open No. Hei 8-289969 proposes a food preservative containing a food emulsifier such as an antibacterial substance reuterin produced by lactic acid bacteria Lactobacillus reuteri and glycerin fatty acid ester. JP-A-6-316
Japanese Patent No. 641 proposes a vinylidene chloride-based resin film having good flaking properties in which polyglycerin stearate is contained as an additive in an amount of 0.1 to 3.0% by weight based on the resin.
【０００３】このようにグリセリン脂肪酸エステルを食
品にその乳剤として添加すること、肉剥離性の改良のた
めにフィルム樹脂層に添加することは知られている。し
かしながら、特定の（ポリ）グリセリン脂肪酸エステル
を抗菌剤として塗布或いは合成樹脂に添加することは知
られていない。It is known that glycerin fatty acid esters are added to foods as emulsions as described above, and that they are added to film resin layers to improve meat peelability. However, it has not been known that a specific (poly) glycerin fatty acid ester is applied as an antibacterial agent or added to a synthetic resin.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、熱可
塑性樹脂と特定抗菌剤とからなる押出加工性に優れた抗
菌性包装材料およびその製造方法を提供することにあ
る。また、本発明の目的は、インフレーション成形方法
による新規な抗菌性樹脂フィルムの製造方法を提供する
ことにある。SUMMARY OF THE INVENTION It is an object of the present invention to provide an antibacterial packaging material comprising a thermoplastic resin and a specific antibacterial agent and having excellent extrusion processability, and a method for producing the same. Another object of the present invention is to provide a novel method for producing an antibacterial resin film by an inflation molding method.
【０００５】[0005]
【課題を解決するための手段】本発明者等は、前記課題
を達成するために鋭意検討した結果、熱可塑性樹脂に抗
菌剤、特にグリセリン脂肪酸エステル等の有機系抗菌剤
を特定量添加することにより抗菌性付与と、押出後のロ
ール状に巻かれたフィルムを取出し易くして、バッグや
パウチ等の二次加工する際のトラブルを少なくすること
を見出した。また、抗菌剤の過剰添加による押出加工性
の低下を防ぐとともに、粘着剤、粘着付与剤が包装材料
中に存在すると添加した抗菌剤濃度が包装材料表面で高
くなり、少量の抗菌剤の塗布、添加であっても効果的に
抗菌性を高めることを見出し、本発明を完成するに至っ
た。また、本発明者らは、インフレーションフィルムの
製造工程中、予備円筒状成形体の内側と抗菌剤を含有す
る塗布液とを接触させることにより予備円筒状成形体の
内側に抗菌剤を塗工できることを見い出し、本発明を完
成するに至った。Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a specific amount of an antibacterial agent, particularly an organic antibacterial agent such as glycerin fatty acid ester, is added to a thermoplastic resin. Thus, the present inventors have found that imparting antibacterial properties and facilitating removal of a film wound into a roll after extrusion can reduce troubles in secondary processing of bags, pouches and the like. In addition, while preventing extrusion processability from being reduced due to excessive addition of an antibacterial agent, if an adhesive or tackifier is present in the packaging material, the concentration of the added antibacterial agent increases on the surface of the packaging material. The present inventors have found that the antibacterial property is effectively improved even with the addition, and have completed the present invention. In addition, the present inventors are able to apply an antimicrobial agent to the inside of the preliminary cylindrical molded article by contacting the inside of the preliminary cylindrical molded article with a coating solution containing an antimicrobial agent during the process of manufacturing the blown film. And completed the present invention.
【０００６】即ち、本発明は液状助剤１０重量部未満と
熱可塑性樹脂１００重量部に、脂肪酸の炭素数６〜１０
の（ポリ）グリセリン脂肪酸エステルが０．０５〜１．
５０重量部含有されてなる押出加工性の優れた抗菌性包
装材料を提供する。また、塩化ビニリデン系樹脂中に添
加剤として親水性/親油性バランス（ＨＬＢ）が５．５
〜８の範囲にあり、脂肪酸の炭素数６〜１０の（ポリ）
グリセリン脂肪酸モノ（ジ）エステルが含有されてなる
抗菌性包装材料を提供する。さらに、本発明は平均重合
度１１００〜２５００の塩化ビニル樹脂中に添加剤とし
て親水性/親油性バランス（ＨＬＢ）が５．５〜８の範
囲にあり、脂肪酸の炭素数６〜１０の（ポリ）グリセリ
ン脂肪酸モノ（ジ）エステルが含有されてなる押出加工
性に優れた抗菌性包装材料を提供する。That is, according to the present invention, less than 10 parts by weight of a liquid auxiliary and 100 parts by weight of a thermoplastic resin contain 6 to 10 carbon atoms of a fatty acid.
(Poly) glycerin fatty acid ester is 0.05-1.
An antibacterial packaging material containing 50 parts by weight and having excellent extrudability is provided. The vinylidene chloride-based resin has an hydrophilic / lipophilic balance (HLB) of 5.5 as an additive.
~ 8, the fatty acid has 6 to 10 carbon atoms (poly)
Provided is an antibacterial packaging material containing glycerin fatty acid mono (di) ester. Furthermore, the present invention has a hydrophilic / lipophilic balance (HLB) in the range of 5.5 to 8 as an additive in a vinyl chloride resin having an average degree of polymerization of 1100 to 2500, and a fatty acid having 6 to 10 carbon atoms (poly). ) To provide an antibacterial packaging material containing glycerin fatty acid mono (di) ester and having excellent extrudability.
【０００７】本発明は、１価または多価アルコール、グ
リセリン系またはソルビタン系非イオン界面活性剤と有
機抗菌剤を用いることおよび多価アルコール、グリセリ
ン系またはソルビタン系非イオン界面活性剤と無機系抗
菌剤を用いることを特徴とする抗菌性包装材料の製造方
法を提供する。The present invention uses a monohydric or polyhydric alcohol, glycerin or sorbitan nonionic surfactant and an organic antibacterial agent, and uses a polyhydric alcohol, glycerin or sorbitan nonionic surfactant and an inorganic antibacterial agent. A method for producing an antibacterial packaging material, characterized by using an agent.
【０００８】さらに、本発明は、溶融状態の樹脂を環状
ダイで円筒状に押出して予備円筒状成形体とし、冷却
し、次いで前記予備円筒状成形体（本発明では予備円筒
状成形体がインフレーションされる迄をパリソンと呼
ぶ）を延伸するインフレーションフィルムの製造方法に
おいて、ダイ出口を経て予備円筒状成形体が延伸される
迄の区間で、予備円筒成形体の内側を抗菌剤を含む塗布
液により塗工することを特徴とする抗菌性樹脂フィルム
の製造方法を提供する。Further, the present invention provides a pre-cylindrical molded article formed by extruding a molten resin into a cylindrical shape with an annular die and cooling the pre-cylindrical molded article. Until the preliminary cylindrical molded body is stretched through the die outlet, the inside of the preliminary cylindrical molded body is coated with a coating solution containing an antibacterial agent. Provided is a method for producing an antibacterial resin film, which is characterized by being coated.
【０００９】また、本発明は前記発明の樹脂が塩化ビニ
リデン系樹脂である抗菌性樹脂フィルムの製造方法を提
供する。さらに、前記発明において、抗菌剤が銀系超微
粒子の無機系抗菌剤または有機系抗菌剤である抗菌性樹
脂フィルムの製造方法を提供する。The present invention also provides a method for producing an antibacterial resin film in which the resin of the invention is a vinylidene chloride resin. Further, the present invention provides a method for producing an antibacterial resin film in which the antibacterial agent is an inorganic antibacterial agent or an organic antibacterial agent of silver-based ultrafine particles.
【００１０】[0010]
【発明の実施の形態】以下、本発明を詳しく説明する。
本発明で、押出加工性が良いとは、樹脂の未溶融物の流
出およびフローマークの発生が少なく、押出量が安定
し、フィルムやシートに成形加工した時に厚み斑を生じ
難いこと、あるいは押出後のロールに巻かれたフィルム
やシートが二次加工する際取り出し易いことを意味す
る。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
In the present invention, good extrusion processability means that there is little outflow of unmelted resin and occurrence of flow marks, the extrusion amount is stable, and thickness unevenness hardly occurs when formed into a film or sheet, or This means that a film or sheet wound on a later roll can be easily taken out during secondary processing.
【００１１】本発明のフィルムの材料として用いられる
樹脂としては、熱可塑性樹脂、具体的には、ポリエステ
ル系樹脂、含ハロゲン系樹脂、ポリアミド系樹脂、ポリ
オレフィン系樹脂等が含まれる。特に、産業上有用なも
のとして、ポリエステル系樹脂では、ポリブチレンテレ
フタレート、ポリ乳酸、ポリグリコール酸、ポリエチレ
ンテレフタレート等、とりわけテレフタール酸、イソフ
タール酸などのジカルボン酸成分とジオール成分の共重
合ポリエステルである。含ハロゲン系樹脂では、ポリフ
ッ化ビニリデンおよびその共重合体、ポリ塩化ビニー
ル、ポリ塩化ビニリデンおよびその共重合体等、ポリア
ミド系樹脂では、ナイロン６、ナイロン６−６６、ナイ
ロンＭＸＤ６，ポリオレフィン系樹脂では、ポリエチレ
ン、ポリプロピレンおよびその共重合体、ポリ−４メチ
ルペンテンー１、これらのうち熱可塑性樹脂、厚みを薄
くする等して、柔軟なものが好まれる。特に、ラップフ
ィルムに適当である。The resin used as the material of the film of the present invention includes a thermoplastic resin, specifically, a polyester resin, a halogen-containing resin, a polyamide resin, a polyolefin resin and the like. Particularly useful as industrial materials are polyester resins, such as polybutylene terephthalate, polylactic acid, polyglycolic acid, polyethylene terephthalate, etc., and especially a copolymerized polyester of a dicarboxylic acid component such as terephthalic acid and isophthalic acid and a diol component. In the halogen-containing resin, polyvinylidene fluoride and its copolymer, polyvinyl chloride, polyvinylidene chloride and its copolymer, and in the polyamide resin, nylon 6, nylon 6-66, nylon MXD6, and in the polyolefin resin, Polyethylene, polypropylene and copolymers thereof, poly-4-methylpentene-1, a thermoplastic resin, and a flexible resin such as a thinner one are preferred. Particularly, it is suitable for a wrap film.
【００１２】塩化ビニル樹脂としては、平均重合度 １
１００〜２５００、フィルムやシートの押出加工には、
好ましくは１１００〜１８００のものを用いる。平均重
合度は、押出加工性と液状助剤、抗菌剤の保持力とのバ
ランスから選択される。ポリオレフィン系樹脂は、フィ
ルムやシートの押出加工にはＭＦＲ（メルトフローレー
ト）が好ましくは０．５〜４．０、さらに好ましくは
１，０〜２．５であることが少ない抗菌剤の添加で抗菌
性が発揮できる観点から好ましい。The vinyl chloride resin has an average degree of polymerization of 1
100 to 2500, for the extrusion of films and sheets,
Preferably, those having 1100 to 1800 are used. The average polymerization degree is selected from the balance between the extrudability and the holding power of the liquid auxiliary agent and the antibacterial agent. The polyolefin-based resin has an MFR (melt flow rate) of preferably 0.5 to 4.0, more preferably 1,0 to 2.5 for extrusion of a film or sheet. It is preferable from the viewpoint that antibacterial properties can be exhibited.
【００１３】塩化ビニリデン系樹脂としては、塩化ビニ
リデンを主成分としてこれと共重合し得る単量体（単
に、コモノマーと云うことがある）との共重合体であ
り、樹脂組成として塩化ビニリデン含有率６５〜９８重
量％であることが好ましい。塩化ビニリデンの含有率が
６５重量％未満であると酸素ガスバリア性が悪くなり、
酸素ガス透過度が大きくなる。塩化ビニリデンの含有率
が９８重量％を越えると、樹脂溶融温度と樹脂分解温度
との差が小さくなって押出し加工性が悪くなるからであ
る。また、塩化ビニリデンと共重合し得る単量体として
は、例えば塩化ビニル、アクリルニトリル、スチレン、
炭素数が１〜１８のアクリル酸アルキルエステル、炭素
数が１〜１８のメタクリル酸アルキルエステル、イタコ
ン酸、イタコン酸のアルキルエステル、マレイン酸、マ
レイン酸のアルキルエステル、酢酸ビニル等の不飽和単
量体からなる１種以上より選ばれた共重合体を例示でき
る。共重合性、酸素ガスバリア性、押出加工性の観点か
ら、特には塩化ビニルまたはアクリル酸メチルエステル
との共重合体が好ましい。塩化ビニリデン系共重合体の
押出し加工性を良くするために、必要に応じて該共重合
体に対して約３重量％以下の二塩基性脂肪酸エステル系
等の可塑剤、エポキシ系等の熱安定剤を添加することが
好ましい。これらの塩化ビニリデン系樹脂のうち、還元
粘度が少なくとも０．０３５、好ましくは０．０３９〜
０．０７０のものは、抗菌剤添加による押出加工性の維
持および少ない抗菌剤の添加で抗菌性が発揮できる等の
観点から好ましく用いられる。The vinylidene chloride resin is a copolymer of vinylidene chloride as a main component and a monomer copolymerizable therewith (sometimes simply referred to as a comonomer). It is preferably from 65 to 98% by weight. When the content of vinylidene chloride is less than 65% by weight, the oxygen gas barrier property deteriorates,
Oxygen gas permeability increases. If the content of vinylidene chloride exceeds 98% by weight, the difference between the resin melting temperature and the resin decomposition temperature becomes small, and the extrudability deteriorates. Further, as a monomer copolymerizable with vinylidene chloride, for example, vinyl chloride, acrylonitrile, styrene,
C1-C18 alkyl acrylate, C1-C18 alkyl methacrylate, itaconic acid, alkyl esters of itaconic acid, maleic acid, alkyl esters of maleic acid, unsaturated monomers such as vinyl acetate Examples thereof include copolymers selected from one or more of a copolymer. From the viewpoints of copolymerizability, oxygen gas barrier properties, and extrudability, a copolymer with vinyl chloride or methyl acrylate is particularly preferred. In order to improve the extrusion processability of the vinylidene chloride-based copolymer, if necessary, about 3% by weight or less based on the copolymer of a plasticizer such as a dibasic fatty acid ester or a heat-stable epoxy. It is preferable to add an agent. Among these vinylidene chloride resins, the reduced viscosity is at least 0.035, preferably 0.039 to
The one with 0.070 is preferably used from the viewpoints of maintaining the extrusion processability by adding an antibacterial agent and exhibiting antibacterial properties by adding a small amount of an antibacterial agent.
【００１４】本発明に用いられる液状助剤とは、ＤＢＳ
（ジブチルセバケート）などの二塩基性脂肪酸エステ
ル、ＡＴＢＣ（アセチルトリブチルシトレート）、ジア
セチル化モノグリセライド（炭素数酸１２および１６）
およびポリエステル系可塑剤等の可塑剤類、エポキシ化
大豆油、エポキシ化亜麻仁油、エポキシ化ステアリン酸
オクチル、エポキシ化ポリブタジエンおよびエポキシヘ
キサヒドロフタル酸エステルなどのエポキシ化合物であ
り、必要に応じて、ピロリン酸ナトリウム、リン酸ナト
リウム、（ＥＤＴＡ−２Ｎａ）エチレンジアミン４酢酸
２ナトリウム、クエン酸、クエン酸３ナトリウム、クエ
ン酸３ナトリウム、クエン酸カリウム、酸化マグネシウ
ムおよび水酸化マグネシウムなどの熱安定剤、フェノー
ル系のＶＥ（ビタミンＥ）、イルガノックス２４５、硫
黄系のＤＳＴＤＰ（ジステアリルチオジプロピオネー
ト）、ＤＬＴＤＰ（ジラウリルチオジプロピオネート）
などの酸化防止剤、ステアリン酸アマイド（脂肪酸アミ
ド）、グリセリン脂肪酸エステル、各種脂肪酸エステ
ル、ポリエチレンワックスおよび酸化ポリエチレンなど
の滑剤、二酸化珪素、炭酸カルシウム、タルク、ゼオラ
イトなどの粗面化剤、ベンゾトリアゾール系、ベンゾフ
ェノン系およびザロール系の紫外線吸収剤（光安定
剤）、アゾ系、縮合アゾ系、ベンゾイミダゾロン系、ジ
アリライド系、キナクリドン系、ジオキサジン系、イソ
インドリノン系およびフタロシアニン系等の有機顔料、
酸化チタン、アルミナ、カーボンブラックおよび硫酸バ
リウムなどの無機顔料、アクリル酸系ポリマー、グリシ
ジル系ポリマー、ポリアミド系ポリマーおよびポリエス
テル系ポリマーなどの肉密着性付与剤、ＥＶＡ（エチレ
ン−酢酸ビニル共重合体）、アクリル系加工助剤、アク
リル/スチレン系加工助剤などの高分子添加剤等が含ま
れる。特に、塩素系樹脂の押出加工性の向上のために用
いられる。熱可塑性樹脂１００重量部に対し１０重量部
以下、好ましくは０〜７重量部の範囲で用いられる。The liquid auxiliary used in the present invention is DBS
Dibasic fatty acid esters such as (dibutyl sebacate), ATBC (acetyl tributyl citrate), diacetylated monoglyceride (acids having 12 and 16 carbon atoms)
And plasticizers such as polyester plasticizers, epoxidized soybean oil, epoxidized linseed oil, epoxidized octyl stearate, epoxy compounds such as epoxidized polybutadiene and epoxy hexahydrophthalic acid ester. Heat stabilizers such as sodium citrate, sodium phosphate, (EDTA-2Na) disodium ethylenediaminetetraacetate, citric acid, trisodium citrate, trisodium citrate, potassium citrate, magnesium oxide and magnesium hydroxide; VE (vitamin E), Irganox 245, sulfur-based DSTDP (distearylthiodipropionate), DLTDP (dilaurylthiodipropionate)
Antioxidants such as stearic acid amide (fatty acid amide), glycerin fatty acid ester, various fatty acid esters, lubricants such as polyethylene wax and polyethylene oxide, silicon dioxide, calcium carbonate, talc, zeolite and other surface roughening agents, benzotriazoles Benzophenone-based and zarol-based ultraviolet absorbers (light stabilizers), azo-based, condensed azo-based, benzimidazolone-based, diarylide-based, quinacridone-based, dioxazine-based, isoindolinone-based and phthalocyanine-based organic pigments,
Inorganic pigments such as titanium oxide, alumina, carbon black and barium sulfate; meat adhesion imparting agents such as acrylic acid polymers, glycidyl polymers, polyamide polymers and polyester polymers; EVA (ethylene-vinyl acetate copolymer); Polymer additives such as acrylic processing aids and acrylic / styrene processing aids are included. In particular, it is used for improving the extrudability of a chlorine-based resin. It is used in an amount of 10 parts by weight or less, preferably 0 to 7 parts by weight based on 100 parts by weight of the thermoplastic resin.
【００１５】塩化ビニリデン系樹脂を用いた場合、安定
剤および/または可塑剤の液状助剤を樹脂１００重量部
に対してそれぞれ０．５〜７．０重量部、さらには２〜
６重量部添加した抗菌性包装材料が好ましく用いられ
る。液状助剤が多いと樹脂の分解を抑制し押出加工性が
安定するが、ガスバリヤー性が低下する。また、少量の
抗菌剤の添加で抗菌性の効果を得るのが難しい。抗菌剤
を多く添加すると抗菌性は得られるが押出量の変動が大
きくなって押出加工性が不安定となり易い。さらにフィ
ルムの透明性も低下する。粘着剤としてはポリブテン、
ポリブタジエン、ポリイソブチレン、ポリプロピレン等
を挙げることができる。これらのうち、ポリブテン、ポ
リイソブチレンが包装材料の変色防止の観点から好まし
い。粘着付与剤としては、常温で液状であるポリエチレ
ングリコール、流動パラフィン、プロピレングリコール
等を挙げることができる。粘着剤、粘着付与剤はそれら
を組み合わせて用いることができる。熱可塑性樹脂１０
０重量部に対してそれぞれ３重量部以下、さらには０．
０１〜１．０重量部含有されていることが好ましい。When a vinylidene chloride resin is used, 0.5 to 7.0 parts by weight, preferably 2 to 2 parts by weight, of a liquid auxiliary of a stabilizer and / or a plasticizer is added to 100 parts by weight of the resin.
An antibacterial packaging material added with 6 parts by weight is preferably used. When the amount of the liquid auxiliary is large, the decomposition of the resin is suppressed and the extrudability is stabilized, but the gas barrier property is reduced. Further, it is difficult to obtain an antibacterial effect by adding a small amount of an antibacterial agent. When a large amount of an antibacterial agent is added, the antibacterial property can be obtained, but the fluctuation of the extruded amount is large and the extrudability is likely to be unstable. Further, the transparency of the film is reduced. Polybutene as an adhesive,
Examples thereof include polybutadiene, polyisobutylene, and polypropylene. Among these, polybutene and polyisobutylene are preferred from the viewpoint of preventing discoloration of the packaging material. Examples of the tackifier include polyethylene glycol, liquid paraffin, and propylene glycol which are liquid at normal temperature. An adhesive and a tackifier can be used in combination. Thermoplastic resin 10
3 parts by weight or less, more preferably 0.
It is preferably contained in an amount of from 0.01 to 1.0 part by weight.
【００１６】本発明に用いる抗菌剤としては、無機系抗
菌剤および有機系抗菌剤を使用できる。有機系抗菌剤と
しては、炭素数６〜１０個を持つ脂肪酸の（ポリ）グリ
セリンエステルを主成分とするものを云う。炭素数が６
個の（ポリ）グリセリンカプロン酸モノエステル、炭素
数が８個の飽和脂肪酸である（ポリ）グリセリンカプリ
ル酸モノエステル、炭素数１０個の飽和脂肪酸である
（ポリ）グリセリンカプリン酸モノエステルが特に好ま
しい。As the antibacterial agent used in the present invention, an inorganic antibacterial agent and an organic antibacterial agent can be used. As the organic antibacterial agent, one containing a (poly) glycerin ester of a fatty acid having 6 to 10 carbon atoms as a main component is used. 6 carbon atoms
(Poly) glycerin caproic acid monoester, (poly) glycerin caprylic acid monoester which is a saturated fatty acid having 8 carbon atoms, and (poly) glycerin capric acid monoester which is a saturated fatty acid having 10 carbon atoms are particularly preferred. .
【００１７】遊離脂肪酸、高級脂肪酸モノグリセライド
と比較して低級脂肪酸モノグリセライドは水に対する親
和性が高く、液相中で均一分布し易く、微生物が取り込
み易い状態であり、低級脂肪酸モノグリセライドの中で
は炭素数の大きいものほど親油性が高く、細胞脂質に対
する親和性が増して、細胞内への取り込みが速くなる。
オキシ酸、多価カルボン酸では、親水性が高いので細胞
内への取り込みが遅くなる。側鎖のある脂肪酸は代謝さ
れ難く、蓄積効果がなく抗菌効果が弱い。脂肪酸の炭素
数８〜１０個のグリセリンエステルを主体とし、これら
の単独、またはそれらの組み合わせ、およびこれらと脂
肪酸の炭素数１２〜２２のグリセリンエステルから選ば
れた少なくとも１種の組み合わせ等が好ましい。Compared with free fatty acids and higher fatty acid monoglycerides, lower fatty acid monoglycerides have a higher affinity for water, are more easily distributed in the liquid phase, are easier to take up by microorganisms, and have a lower carbon number among lower fatty acid monoglycerides. Larger ones are more lipophilic, have higher affinity for cellular lipids, and have faster uptake into cells.
In the case of oxyacids and polycarboxylic acids, their uptake into cells is slow because of their high hydrophilicity. Fatty acids with side chains are not easily metabolized, have no accumulation effect, and have a weak antibacterial effect. A glycerin ester having 8 to 10 carbon atoms of a fatty acid as a main component is preferably used alone, or a combination thereof, or a combination of at least one selected from glycerin esters having 12 to 22 carbon atoms with a fatty acid.
【００１８】抗菌性包装材表面または包装材中の有機系
抗菌剤の量は、熱可塑性樹脂１００重量部に対し、０．
０５〜１．５０重量部、さらに好ましくは０．１０〜
１．０重量部、最も好ましくは０．１〜０．７重量部で
ある。含有量が１．５０を超えると押出加工性が低下す
ることがあり、未溶融樹脂の流出、フローマークの発
生、押出量の変動、モーター負荷の変動等が発生し易く
なる。また、０．０５重量部以下では十分な抗菌性が発
現しない。The amount of the organic antibacterial agent on the surface of the antibacterial packaging material or in the packaging material is 0.1 to 100 parts by weight of the thermoplastic resin.
0.5 to 1.50 parts by weight, more preferably 0.10 to
1.0 parts by weight, most preferably 0.1 to 0.7 parts by weight. If the content exceeds 1.50, the extrusion processability may decrease, and the outflow of unmelted resin, the occurrence of flow marks, the variation of the extrusion amount, the variation of the motor load, and the like are likely to occur. If the amount is less than 0.05 parts by weight, sufficient antibacterial properties are not exhibited.
【００１９】熱可塑性樹脂が塩化ビニリデン系樹脂また
は平均重合度が１１００〜２５００の塩化ビニル樹脂の
場合、抗菌剤としてＨＬＢが５．５〜８、好ましくは６
〜８の範囲にある脂肪酸の炭素数６〜１０の（ポリ）グ
リセリン脂肪酸モノ（ジ）エステルを含有した抗菌性包
装材料を本発明の好ましいものとして挙げることができ
る。ＨＬＢが小さ過ぎると食品との親和性に乏しく、包
装材料の表面に抗菌剤がブリードし難くなり、一方、大
き過ぎると押出加工された包装材料が発泡し易くなり、
良好な製品となり難い。When the thermoplastic resin is a vinylidene chloride resin or a vinyl chloride resin having an average degree of polymerization of 1100 to 2500, HLB is 5.5 to 8, preferably 6 as an antibacterial agent.
Antibacterial packaging materials containing (poly) glycerin fatty acid mono (di) esters having 6 to 10 carbon atoms of fatty acids in the range of from 8 to 8 can be mentioned as preferred examples of the present invention. If the HLB is too small, the affinity with food is poor, and the antibacterial agent does not easily bleed on the surface of the packaging material. On the other hand, if the HLB is too large, the extruded packaging material tends to foam,
It is hard to be a good product.
【００２０】無機系抗菌剤では、金属超微粒子を用い
銀、銅、亜鉛、鉄から選ばれた少なくとも１種の金属種
を含む金属超微粒子が用いられる。これらのうち銀系、
銀と亜鉛の混合無機抗菌剤が好ましい。銀系無機抗菌剤
の抗菌のメカニズムは、まだ完全に解明されてはいない
が、抗菌剤から出る銀イオンと、銀の触媒作用によって
活性イオンが生じ抗菌性を発現するものと考えられてい
る。使用の形態としては好ましくは平均粒径２００ｎｍ
未満、さらに好ましくは１００ｎｍ未満、最も好ましく
は５０ｎｍ未満である。通常１〜２０ｎｍの範囲のもの
が使用される。As the inorganic antibacterial agent, ultrafine metal particles are used, and ultrafine metal particles containing at least one metal species selected from silver, copper, zinc and iron are used. Of these, silver-based,
A mixed inorganic antibacterial agent of silver and zinc is preferred. The antibacterial mechanism of the silver-based inorganic antibacterial agent has not been completely elucidated yet, but it is considered that silver ions emitted from the antibacterial agent and active ions are generated by the catalytic action of silver to exhibit antibacterial properties. The form of use is preferably 200 nm in average particle size.
Less than 100 nm, more preferably less than 50 nm. Usually, those having a range of 1 to 20 nm are used.
【００２１】通常、前記金属の超微粒子をＴｉＯ2（酸
化チタン）、ＳｉＯ2・Ａｌ2Ｏ3・ＭｇＯ（メタ珪酸ア
ルミン酸マグネシウム）などに担持させ、コロイド分散
液の形態で用いられる。例えば、ＴｉＯ2に銀微粒子を
５重量％担持させる分散媒としては通常、水、アルコー
ル等が用いられ、ＡｔｏｍｙＢａｌｌ（触媒化成工業
（株）社製などが市販されている。Usually, the ultrafine particles of the metal are supported on TiO 2 (titanium oxide), SiO 2 · Al 2 O 3 · MgO (magnesium aluminate metasilicate) or the like, and used in the form of a colloidal dispersion. For example, water, alcohol or the like is usually used as a dispersion medium for supporting 5% by weight of silver fine particles on TiO 2 , and AtomyBall (manufactured by Catalyst Chemical Industry Co., Ltd.) is commercially available.
【００２２】本発明の抗菌性包装材料の製造方法は、１
価または多価アルコール、グリセリン系またはソルビタ
ン系非イオン界面活性剤から選ばれた溶媒に抗菌剤を混
合した塗布液を塗工することを特徴とする製造方法であ
る。抗菌剤塗布液が油性でないので簡単且つ有効に塗布
できる。塗布の対象は熱可塑性樹脂、無機系蒸着膜を有
するフィルム、合成紙、紙、不織布、骨付き肉用のボー
ンガードと呼ばれる食品用繊維製品、肉汁吸収剤等を挙
げることができる。ここで、塗工とは、コーター、印刷
機、噴霧等を含む。熱可塑性樹脂に特定の（ポリ）グリ
セリン脂肪酸エステルが添加されていると成形品表面の
表面張力が低下し、さらに抗菌剤を塗布し易くなる。紙
に、抗菌剤を塗布（噴霧)したもの、紙と抗菌性を付与
された熱可塑性樹脂からなる抗菌性包装材料等が含まれ
る。The method for producing the antibacterial packaging material of the present invention comprises:
This is a production method characterized by applying a coating solution obtained by mixing an antibacterial agent with a solvent selected from a polyhydric or polyhydric alcohol, a glycerin-based or sorbitan-based nonionic surfactant. Since the antibacterial agent coating solution is not oily, it can be easily and effectively applied. Examples of the application target include thermoplastic resins, films having an inorganic vapor-deposited film, synthetic paper, paper, nonwoven fabrics, fiber products for food called bone guards for meat with bone, and gravy absorbents. Here, the coating includes a coater, a printing machine, a spray, and the like. When a specific (poly) glycerin fatty acid ester is added to the thermoplastic resin, the surface tension of the surface of the molded article is reduced, and the antibacterial agent is easily applied. An antibacterial agent is applied (sprayed) to paper, and an antibacterial packaging material made of paper and a thermoplastic resin having antibacterial properties is included.
【００２３】１価または多価アルコール、グリセリン系
またはソルビタン系非イオン界面活性剤から選ばれた溶
媒としては、エチルアルコール、イソプロピルアルコー
ル等を挙げることができる。これらのうちエチルアルコ
ール、イソプロピルアルコール、ポリオキシエチレンソ
ルビタン脂肪酸エステルの水溶液等が好ましく用いられ
る。Examples of the solvent selected from monohydric or polyhydric alcohols, glycerin-based or sorbitan-based nonionic surfactants include ethyl alcohol and isopropyl alcohol. Of these, aqueous solutions of ethyl alcohol, isopropyl alcohol, and polyoxyethylene sorbitan fatty acid ester are preferably used.
【００２４】本発明のもう一つの製造方法は、公知のイ
ンフレーション装置および方法を用いてなされる。塩化
ビニリデン樹脂からなる抗菌性フィルムを例としてフィ
ルムの製造方法を図１を用いて説明するが、本発明はこ
れに限定されるものではない。インフレーション成形用
に配合された樹脂組成物を単軸または多軸のスクリュウ
を備えた押出機（図示せず）に一定供給量で供給し、樹
脂温度１７０〜２００℃で溶融樹脂を環状ダイを通して
下方に押し出す。このときダイから出た予備円筒状成形
体（パリソン）は、塩化ビニリデンの結晶化を防ぐため
に４〜１０℃の水あるいは空気で急冷（図示せず）され
る。パリソン下方で開口性維持のため４〜１０℃の第１
浴槽を通り、第１浴槽内のロールでパリソンの内側同士
が接触して、開口性が悪くなるのを防ぐためにダイ中央
部から注入されるパイル液をためた状態となる。パイル
剤は通常ポリオキシエチレンソルビタン脂肪酸エステル
原液または水溶液、プロピレングリコール原液または水
溶液、グリセリン原液または水溶液、ジグリセリンラウ
レート原液または水溶液、ポリグリセリンラウレート原
液または水溶液あるいはこれらの混合物等を使用する。
このパイル液に抗菌剤塗布液を混合してもよいし、パイ
ル液に替えて抗菌剤塗布液を単独に用いてもよい。次い
で扁平になったパリソンは第２ロール（Ａ），（Ｂ）間
で不活性ガス、例えば空気を封入されると同時に延伸操
作を行い易くするために第２浴槽で１０〜３０℃に加熱
され第２ロール（Ｂ）を経る。その後、圧縮不活性ガス
を封入されフィルムの幅方向、縦方向の２軸に延伸され
る。本発明で云う「ダイ出口を経て予備円筒状成形体が
延伸される迄の区間で」とは環状ダイの出口から第２ロ
ール（Ｂ）を経てフィルムが延伸のため膨張される直前
迄の区間を云う。Another production method of the present invention is performed using a known inflation apparatus and method. A method for producing a film will be described with reference to FIG. 1 using an antimicrobial film made of vinylidene chloride resin as an example, but the present invention is not limited to this. The resin composition compounded for inflation molding is supplied to an extruder (not shown) equipped with a single-screw or multi-screw at a constant supply rate, and the molten resin is passed through an annular die at a resin temperature of 170 to 200 ° C. Extrude. At this time, the pre-cylindrical molded product (parison) that has exited from the die is quenched (not shown) with water or air at 4 to 10 ° C. in order to prevent crystallization of vinylidene chloride. First at 4-10 ° C to maintain openness below the parison
After passing through the bathtub, the inside of the parison contacts each other with the rolls in the first bathtub, and the pile liquid injected from the center of the die is stored in order to prevent the opening property from being deteriorated. As the pile agent, a polyoxyethylene sorbitan fatty acid ester stock solution or aqueous solution, propylene glycol stock solution or aqueous solution, glycerin stock solution or aqueous solution, diglycerin laurate stock solution or aqueous solution, polyglycerin laurate stock solution or aqueous solution, or a mixture thereof is used.
The pile liquid may be mixed with an antibacterial agent coating liquid, or the antibacterial agent coating liquid may be used alone instead of the pile liquid. Next, the flattened parison is filled with an inert gas, for example, air, between the second rolls (A) and (B), and is heated to 10 to 30 ° C. in the second bath to facilitate the stretching operation. It passes through the second roll (B). Thereafter, the film is filled with a compressed inert gas and stretched biaxially in the width and length directions of the film. In the present invention, "the section before the preliminary cylindrical molded body is stretched through the die outlet" means the section from the outlet of the annular die to immediately before the film is expanded for stretching through the second roll (B). I say
【００２５】抗菌剤塗布液は第２ロール（Ａ），（Ｂ）
の間に封入してもよい。また、抗菌剤塗布液が前記の様
にパリソンの内側から塗工されている限りにおいてパリ
ソンの外側からも塗工してもよい。塗布液の濃度は好ま
しくは有機系抗菌剤の場合６０〜１００重量％、無機系
抗菌剤の場合、塗布液の銀の含有量が０．５〜３．５ｍ
ｇ/ｍｌの範囲である。さらに、前記のように塗布液を
パリソンの内側に塗工するには塗布液の粘度が取り扱
い、塗工性等の観点から有機系抗菌剤の場合０．０１０
〜０．２００Ｐａ・ｓ、無機系抗菌剤の場合０．００１
〜０．００２Ｐａ・ｓの範囲に調整するとよい。The antimicrobial agent coating solution is a second roll (A), (B)
It may be enclosed between. Further, as long as the antibacterial agent application liquid is applied from the inside of the parison as described above, it may be applied from the outside of the parison. The concentration of the coating solution is preferably 60 to 100% by weight in the case of an organic antibacterial agent, and the silver content of the coating solution is 0.5 to 3.5 m in the case of an inorganic antibacterial agent.
g / ml. Further, as described above, in order to apply the coating solution to the inside of the parison, the viscosity of the coating solution is handled, and in the case of an organic antibacterial agent, 0.010
~ 0.200 Pa · s, 0.001 for inorganic antibacterial agents
It may be adjusted to the range of 0.002 Pa · s.
【００２６】ここで、抗菌剤塗布液の調製については、
特別な制限はないが、前記の１価または多価アルコー
ル、グリセリン系またはソルビタン系非イオン界面活性
剤から選ばれた溶媒に抗菌剤を混合した塗布液を用いる
ことも好ましい。また、必要に応じて有機系抗菌剤と無
機系抗菌剤とを併用しても良い。Here, with respect to the preparation of the antibacterial agent coating solution,
Although there is no particular limitation, it is also preferable to use a coating solution obtained by mixing an antibacterial agent with a solvent selected from the above-mentioned monohydric or polyhydric alcohols, glycerin-based or sorbitan-based nonionic surfactants. Moreover, you may use together an organic antibacterial agent and an inorganic antibacterial agent as needed.
【００２７】また、別の方法としては、抗菌剤を樹脂中
に練り込む方法がある。練り込む方法としては、他の添
加剤、液状助剤と共に樹脂に直接所定量の抗菌剤或いは
抗菌剤成分を添加し均一に混合する方法、予め高濃度の
抗菌剤を含むマスターバッチを調製しておき、これを樹
脂に添加し所定量の抗菌剤を含む包装材料を得る方法等
がある。抗菌剤の種類、性質により選択して使用でき
る。As another method, there is a method of kneading an antibacterial agent into a resin. As a method of kneading, a method in which a predetermined amount of an antibacterial agent or an antibacterial agent component is directly added to a resin together with other additives and liquid auxiliaries and uniformly mixed, and a master batch containing a high concentration of an antibacterial agent in advance is prepared. There is a method of adding this to a resin to obtain a packaging material containing a predetermined amount of an antibacterial agent. It can be selected and used depending on the type and properties of the antibacterial agent.
【００２８】インフレーション工程で縦２．５〜４．５
倍、横４〜６．５倍に延伸され巻き取られたチューブ状
フィルムは、使用に適した幅にスリットされる。得られ
た抗菌性フィルムはラップ、ソーセージや生肉等の包装
材料の用途に用いられる。フィルムの厚みとして抗菌剤
を練り込む場合、好ましくは５〜６０μｍ、より好まし
くは８〜３０μｍが抗菌性をよく発揮できる。In the inflation process, the length is 2.5 to 4.5.
The tube-shaped film stretched twice and stretched 4 to 6.5 times in width is slit into a width suitable for use. The resulting antibacterial film is used for packaging materials such as wraps, sausages and raw meat. When kneading an antibacterial agent as the thickness of the film, preferably 5 to 60 μm, more preferably 8 to 30 μm can exhibit good antibacterial properties.
【００２９】[0029]
【実施例】以下、実施例により本発明を具体的に説明す
るが、本発明はこれらに限定されるものではない。EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples.
【００３０】（抗菌フィルムの評価）銀等無機抗菌剤研
究会が定めた「抗菌加工製品の抗菌力試験法１（１９９
５年度版）−フィルム密着法」に準拠した。 方法：対照区として無菌ＰＥフィルム、無加工区として
ブランク、抗菌加工区として本発明の製造方法により得
られたフィルムを用いた。(Evaluation of antibacterial film) "Testing method for antibacterial activity of antibacterial products 1 (199
5th edition) -Film adhesion method ". Method: A sterile PE film was used as a control group, a blank was used as a non-processed group, and a film obtained by the production method of the present invention was used as an antibacterial group.
【００３１】（パリソン開口性）パリソンが容易に開口
し、塗布液やインフレーションするための空気をを封入
し易くする。パリソンの開口性が悪いと折り畳み部にピ
ンチ筋（筋状の厚みの厚い部分など）が残り、インフレ
ーションの破裂や塗り斑等の原因となる。 ○：手で容易に開口できる。 ×：容易に開口しない。(Parison Opening Property) The parison is easily opened so that a coating liquid or air for inflation can be easily enclosed. If the openness of the parison is poor, pinch streaks (thick streaks, etc.) remain in the folded portions, causing rupture of inflation and spotting. ：: The opening can be easily made by hand. ×: Does not open easily.
【００３２】（押出加工性） ○：押出量が安定し、樹脂の未溶融物が流出しない。 △：フィルムの厚み斑を生じ、二次加工の製袋、充填が
悪い。（ロール状に巻かれたフィルムが抗菌剤、液状助
剤のブリードでベタ付きが発生し、取り出し難く、ま
た、厚み斑のためロール状に凹凸が生じている）(Extrusion processability) ：: The extrusion amount is stable, and the unmelted resin does not flow out. Δ: Uneven thickness of the film was generated, and secondary processing bag making and filling were poor. (The film wound in a roll form becomes sticky due to the bleeding of the antibacterial agent and the liquid auxiliary, making it difficult to take out, and unevenness in the roll shape due to uneven thickness.)
【００３３】（実施例１〜７、比較例１）塩化ビニリデ
ン共重合体（ＶＤ/ＶＣ＝８８．０/１２．０重量比）１
００重量部、アセチルモノブチルサイトレート５．０重
量部、エポキシ化亜麻仁油２．０重量部からなる塩化ビ
ニリデン系樹脂配合物を、２０Ｌヘンシェルミキサーに
入れ、これに常温でグリース状の抗菌剤を一旦約５０℃
に加熱溶解し、表１に示した量それぞれ計量し添加混合
し、その後温度を７０℃迄昇温し、冷却したものを押出
に供した。押出条件は押出機４０ｍｍφ、Ｌ/Ｄ＝２
２，押出シリンダー温度を１１０℃、１２５℃、１４５
℃、１７５℃、単軸スクリュウ使用、環状ダイス（２
４．０×２５．５ｍｍφ）温度１７０℃、押出量１４０
ｇ/ｍｉｎ．であった。このとき押し出された延伸前の
パリソンを５．０℃の第１浴槽に導き、次いで第２ロー
ル（Ａ）を経て延伸性をよくするための予熱浴である第
２浴槽を通し第２ロール（Ｂ）に導いた。第２ロール
（Ｂ）を通過した未延伸パリソンは引取速度を変えた第
２ロール（Ｂ）と第３ロールの間で圧縮空気を封入しイ
ンフレーション成形により縦３．５倍、横５．７倍に延
伸し、シングル厚み約２０μｍの２枚のフィルムに折り
畳みワインダーによりロール状に巻き取った。環状ダイ
と第１浴槽のピンチロール間のパリソンの中に、パリソ
ンが押し合わされた時、粘着して開口しなくなるのを防
止するための開口剤としてプロピレングリコールを使用
した。各々の実施例に用いた抗菌剤は抗菌剤（ＯＡ）は
グリセリンカプリン酸モノエステル約８０重量％とグリ
セリンミリスチン酸モノエステル約２０重量％、抗菌剤
（ＯＢ）はグリセリンカプリン酸モノエステル約８０重
量％と他のグリセリンオレイン酸モノエステル約２０重
量％である。これらのフィルムについて、「抗菌加工製
品の抗菌力試験法１（１９９５年度版）−フィルム密着
法」に準拠した抗菌性の評価を行い結果を表１に示し
た。尚、比較例１は抗菌性の評価をしなかった。(Examples 1 to 7, Comparative Example 1) Vinylidene chloride copolymer (VD / VC = 88.0 / 12.0 weight ratio) 1
A vinylidene chloride-based resin composition consisting of 00 parts by weight, 5.0 parts by weight of acetyl monobutyl citrate, and 2.0 parts by weight of epoxidized linseed oil was placed in a 20 L Henschel mixer, and a grease-like antibacterial agent was added thereto at room temperature. About 50 ℃ once
The mixture was heated and dissolved, and the amounts shown in Table 1 were measured and added and mixed. Thereafter, the temperature was raised to 70 ° C., and the cooled product was subjected to extrusion. Extrusion conditions are extruder 40mmφ, L / D = 2
2. Extrusion cylinder temperature 110 ° C, 125 ° C, 145
° C, 175 ° C, using a single screw, annular die (2
4.0 × 25.5 mmφ) temperature 170 ° C., extrusion amount 140
g / min. Met. At this time, the extruded parison, which was extruded, was guided to a first bath at 5.0 ° C., and then passed through a second roll (A), passed through a second bath which was a preheating bath for improving stretchability, and then passed through a second roll ( B). The unstretched parison that has passed through the second roll (B) is filled with compressed air between the second roll (B) and the third roll whose take-up speed has been changed, and is 3.5 times long and 5.7 times wide by inflation molding. The film was folded into two films having a single thickness of about 20 μm and wound up into a roll by a winder. Propylene glycol was used as an opening agent to prevent the parison from sticking and opening when the parison was pressed into the parison between the annular die and the pinch roll in the first bathtub. The antibacterial agent (OA) used in each example was about 80% by weight of glycerin capric acid monoester and about 20% by weight of glycerin myristic acid monoester, and the antibacterial agent (OB) was about 80% by weight of glycerin capric acid monoester. % And about 20% by weight of other glycerin oleic acid monoester. These films were evaluated for antibacterial properties in accordance with "Testing Methods for Antibacterial Activity of Antibacterial Products 1 (1995 Edition) -Film Adhesion Method", and the results are shown in Table 1. Comparative Example 1 was not evaluated for antibacterial properties.
【００３４】（実施例８〜１２および比較例２〜５）塩
化ビニリデン共重合体（ＶＤ/ＶＣ＝８８．０/１２．０
重量比）１００重量部、アセチルモノブチルサイトレー
ト５．０重量部、エポキシ化亜麻仁油２．０重量部、ポ
リブテン０．１重量部からなる塩化ビニリデン樹脂配合
物を図１に示した工程により実施例１〜７と同様にイン
フレーション成形し、チューブ状フィルムを得た。押出
条件は押出機４０ｍｍφ、Ｌ/Ｄ＝２２，押出シリンダ
ー温度を１１０℃、１２５℃、１４５℃、１７５℃、単
軸スクリュウ使用、環状ダイス（２６．０×２７．５ｍ
ｍφ）温度１７０℃、押出量１１４ｇ/ｍｉｎ．であっ
た。第１浴槽温度８．０℃、第２浴槽温度２５．７℃で
あった。このとき、第２ロール（Ａ）と（Ｂ）の間でパ
リソン内にダスティング剤注入器を用いて表２に示した
濃度の各抗菌剤液を注入した。さらに第２ロール（Ｂ）
上にサラシ綿布を巻き、その上に内側抗菌剤塗布液と同
濃度の各抗菌剤液を滴下し外側へ間接塗布した。各々の
実施例に用いた抗菌剤は抗菌剤（Ａ）は５ｎｍ超微粒子
コロイド分散液Ａｇ/ＴｉＯ2（銀成分として約５００μ
ｇ/ｍｌ）の原液を水で希釈し、ポリオキシエチレンソ
ルビタンモノオレートをそれぞれ添加して用いた。抗菌
剤（Ｂ）は１０ｎｍ超微粒子コロイド分散液Ａｇ/Ｔｉ
Ｏ2の原液を水で希釈し（表２では×で希釈倍率を示
す）、ポリオキシエチレンソルビタンモノオレートをそ
れぞれ添加して用いた。抗菌剤（ＯＡ）は、実施例１か
ら３のものを使用した。延伸倍率は縦/横＝３．５/５．
７であった。得られたチューブフィルムは、折り畳み幅
９０ｍｍ、厚み（シングル）２０μｍであった。第２ロ
ール（Ｂ）から出たパリソンについてパリソン開口性を
評価し、表２に示した。(Examples 8 to 12 and Comparative Examples 2 to 5) Vinylidene chloride copolymer (VD / VC = 88.0 / 12.0)
A vinylidene chloride resin composition comprising 100 parts by weight, 5.0 parts by weight of acetyl monobutyl citrate, 2.0 parts by weight of epoxidized linseed oil and 0.1 part by weight of polybutene was carried out according to the process shown in FIG. Inflation molding was performed in the same manner as in Examples 1 to 7 to obtain a tubular film. The extrusion conditions were as follows: extruder 40 mmφ, L / D = 22, extrusion cylinder temperature 110 ° C., 125 ° C., 145 ° C., 175 ° C., use of a single screw, annular die (26.0 × 27.5 m)
mφ) Temperature 170 ° C., extrusion rate 114 g / min. Met. The first bath temperature was 8.0 ° C and the second bath temperature was 25.7 ° C. At this time, each antibacterial agent solution having the concentration shown in Table 2 was injected into the parison between the second rolls (A) and (B) using a dusting agent injector. Further, the second roll (B)
A silk cotton cloth was wound on the top, and each antibacterial agent solution having the same concentration as that of the inner antibacterial agent coating solution was dropped thereon and indirectly applied to the outer side. The antibacterial agent (A) used in each example was a 5 nm ultrafine particle colloidal dispersion Ag / TiO 2 (about 500 μm as a silver component).
g / ml) was diluted with water, and polyoxyethylene sorbitan monooleate was added and used. Antibacterial agent (B) is 10 nm ultrafine particle colloidal dispersion Ag / Ti
The O 2 stock solution was diluted with water (in Table 2, the dilution ratio is indicated by x), and polyoxyethylene sorbitan monooleate was added and used. The antibacterial agents (OA) used were those of Examples 1 to 3. The stretching ratio is 3.5 / 5.
It was 7. The obtained tube film had a folding width of 90 mm and a thickness (single) of 20 μm. The parison opening from the second roll (B) was evaluated for parison opening properties, and the results are shown in Table 2.
【００３５】（実施例１３〜１５）市販のダイレクト・
ブロー成形機でインフレーションフィルムを作成し抗菌
剤を外側と内側に塗布して得たチューブ状フィルム（厚
さ２０μｍ）を用い、抗菌性の評価を行った。抗菌剤と
して、実施例１３ではＯＡ１重量部とエタノール８０/
２０（重量比）の混合液をパリソンに注入して塗布液と
して用い、実施例１４ではＯＢ１重量部とエタノールの
８０/２０（重量比）混合液をパリソンに注入して塗布
液として用い、実施例１５では前記Ａｔｏｍｙ Ｂａｌ
ｌ（ｓ）の原液に０．０２重量％のポリオキシエチレン
ソルビタンモノオレートを加えパリソンに注入して塗布
した。これらのフィルムについて、「抗菌加工製品の抗
菌力試験法１（１９９５年度版）−フィルム密着法」に
準拠した抗菌性の評価を行い、結果を表３に示した。表
３の中で、接種直後対照区（Ａ）は無菌ポリエチレンフ
ィルムに菌を接種直後のものの菌数の測定値（３サンプ
ルの平均値）であり、対照区（Ｂ）は無菌ポリエチレン
フィルムに菌を接種後温度３５±１℃、相対湿度湿度９
０％以上で２４時間保存したものの菌数の測定値（３サ
ンプルの平均値）であり、無加工試験区（Ｃ）は抗菌剤
を塗布していない実施例と同質の塩化ビニリデンフィル
ムに菌を接種後温度３５±１℃、相対湿度湿度９０％以
上で２４時間保存したものの菌数の測定値（３サンプル
の平均値）であり、抗菌加工試験（Ｄ）は実施例のフィ
ルムに菌を接種後温度３５±１℃、相対湿度湿度９０％
以上で２４時間保存したものの菌数の測定値（３サンプ
ルの平均値）である。(Examples 13 to 15)
An anti-bacterial property was evaluated using a tubular film (thickness: 20 μm) obtained by forming an inflation film with a blow molding machine and applying an antibacterial agent to the outside and inside. In Example 13, OA1 part by weight and ethanol 80 /
In Example 14, a mixture of 20 parts (by weight) was injected into a parison and used as a coating liquid. In Example 14, an 80/20 (weight ratio) mixture of 1 part by weight of OB and ethanol was injected into a parison and used as a coating liquid. In Example 15, the Atomy Bal
0.02% by weight of polyoxyethylene sorbitan monooleate was added to 1 (s) of the stock solution, and the mixture was injected into a parison and coated. These films were evaluated for antibacterial properties in accordance with "Testing Methods for Antibacterial Activity of Antibacterial Products 1 (1995 Version) -Film Adhesion Method", and the results are shown in Table 3. In Table 3, the control section immediately after inoculation (A) shows the measured value of the number of bacteria immediately after the inoculation of the bacteria on the sterile polyethylene film (average value of three samples), and the control section (B) shows the bacteria on the sterile polyethylene film. After inoculation, temperature 35 ± 1 ° C, relative humidity and humidity 9
It is a measured value of the number of bacteria (average value of three samples) of those stored for 24 hours at 0% or more, and the non-processed test plot (C) shows the bacteria on the vinylidene chloride film of the same quality as the example without the antibacterial agent applied. It is a measured value of the number of bacteria (average value of three samples) of the samples stored for 24 hours at a temperature of 35 ± 1 ° C. and a relative humidity and humidity of 90% or more after inoculation. After temperature 35 ± 1 ℃, relative humidity 90%
This is the measured value of the number of bacteria (average value of three samples) stored for 24 hours.
【００３６】[0036]
【表１】 [Table 1]
【００３７】[0037]
【表２】 [Table 2]
【００３８】[0038]
【表３】 [Table 3]
【発明の効果】液状助剤、抗菌剤、熱可塑性樹脂の組み
合わせにより、押出加工性の優れた抗菌性を有する包装
材料が得られる。抗菌剤をパリソンの内側から塗工する
ことによって、塗工工程を別途設けることなく通常のイ
ンフレーション成形工程内で塗布が可能となった。得ら
れた抗菌性フィルムは実施例で示した如く優れた抗菌性
を有している。According to the present invention, a combination of a liquid auxiliary agent, an antibacterial agent, and a thermoplastic resin can provide a packaging material having excellent extrudability and antibacterial properties. By applying the antimicrobial agent from the inside of the parison, it became possible to apply the antibacterial agent in a normal inflation molding process without separately providing a coating process. The obtained antibacterial film has excellent antibacterial properties as shown in the examples.
【図１】抗菌性フィルムの製造工程略図である。FIG. 1 is a schematic view of a manufacturing process of an antibacterial film.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０８Ｋ 5/10 Ｃ０８Ｋ 5/10 Ｃ０８Ｌ 23/00 Ｃ０８Ｌ 23/00 27/08 27/08 Ｃ２３Ｃ 24/00 Ｃ２３Ｃ 24/00 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI C08K 5/10 C08K 5/10 C08L 23/00 C08L 23/00 27/08 27/08 C23C 24/00 C23C 24/00
Claims (21)
００重量部に、脂肪酸の炭素数６〜１０の（ポリ）グリ
セリン脂肪酸エステルが０．０５〜１．５０重量部含有
されてなる押出加工性の優れた抗菌性包装材料。(1) less than 10 parts by weight of a liquid auxiliary and thermoplastic resin (1)
An antibacterial packaging material excellent in extrusion processability, wherein (00) parts by weight of a fatty acid (poly) glycerin fatty acid ester having 6 to 10 carbon atoms is contained in an amount of 0.05 to 1.50 parts by weight.
リ）グリセリンカプロン酸モノ（ジ）エステル、（ポ
リ）グリセリンカプリル酸モノ（ジ）エステルおよび
（ポリ）グリセリンカプリン酸モノ（ジ）エステルの群
から選ばれた少なくとも１種である請求項１記載の抗菌
性包装材料。2. The (poly) glycerin fatty acid ester is selected from the group consisting of (poly) glycerol caproic acid mono (di) ester, (poly) glycerin caprylic acid mono (di) ester and (poly) glycerin capric acid mono (di) ester. The antibacterial packaging material according to claim 1, which is at least one selected from the group consisting of:
る請求項２記載の抗菌性包装材料。3. The antibacterial packaging material according to claim 2, wherein the thermoplastic resin is a vinylidene chloride resin.
水性/親油性バランス（ＨＬＢ）が５．５〜８の範囲で
あって、少なくとも脂肪酸の炭素数６〜１０の（ポリ）
グリセリン脂肪酸モノ（ジ）エステルが含有されてなる
抗菌性包装材料。4. An additive in a vinylidene chloride resin having a hydrophilic / lipophilic balance (HLB) in the range of 5.5 to 8 and at least a fatty acid having 6 to 10 carbon atoms (poly).
An antibacterial packaging material containing glycerin fatty acid mono (di) ester.
も１種の液状助剤が該塩化ビニリデン系樹脂１００重量
部に対して０．５〜７．０重量部含有されてなる請求項
４記載の抗菌性包装材料。5. The composition according to claim 4, wherein at least one liquid auxiliary selected from a stabilizer and a plasticizer is contained in an amount of 0.5 to 7.0 parts by weight based on 100 parts by weight of the vinylidene chloride resin. Antibacterial packaging material.
とも０．０３９である請求項４記載の抗菌性包装材料。6. The antibacterial packaging material according to claim 4, wherein the reduced viscosity of the vinylidene chloride resin is at least 0.039.
る請求項２記載の抗菌性包装材料。7. The antibacterial packaging material according to claim 2, wherein the thermoplastic resin is a polyolefin resin.
ローレート）が０．５〜４．０の範囲にある請求項７記
載の抗菌性包装材料。8. The antibacterial packaging material according to claim 7, wherein the polyolefin resin has an MFR (melt flow rate) in the range of 0.5 to 4.0.
ル樹脂中に添加剤として親水性/親油性バランス（ＨＬ
Ｂ）が５．５〜８の範囲であって、少なくとも脂肪酸の
炭素数６〜１０の（ポリ）グリセリン脂肪酸モノ（ジ）
エステルが含有されてなる押出加工性に優れた抗菌性包
装材料。9. A hydrophilic / lipophilic balance (HL) as an additive in a vinyl chloride resin having an average degree of polymerization of 1100 to 2500.
B) is in the range of 5.5 to 8, and at least 6 to 10 carbon atoms of the fatty acid (poly) glycerin fatty acid mono (di)
An antibacterial packaging material containing an ester and having excellent extrudability.
温で液状であり、熱可塑性樹脂１００重量部に対して粘
着剤または粘着付与剤の少なくとも１種を３重量部以下
含有してなる請求項４，７および９のいずれかに記載の
抗菌性包装材料。10. An additive, wherein at least the tackifier is liquid at room temperature, and contains at least one kind of the pressure-sensitive adhesive or the tackifier with respect to 100 parts by weight of the thermoplastic resin. , 7 and 9.
レンから選ばれ、粘着付与剤がポリエチレングリコー
ル、流動パラフィン、プロピレングリコールの群から選
ばれた粘着剤または粘着付与剤の少なくとも１種を含む
請求項１０記載の抗菌性包装材料。11. The adhesive according to claim 10, wherein the adhesive is selected from polybutene or polyisobutylene, and the tackifier comprises at least one of an adhesive selected from the group consisting of polyethylene glycol, liquid paraffin, and propylene glycol. Antibacterial packaging material.
系またはソルビタン系の非イオン界面活性剤から選ばれ
た溶媒と、（ポリ）グリセリンカプロン酸モノ（ジ）エ
ステル、（ポリ）グリセリンカプリル酸モノ（ジ）エス
テルおよび（ポリ）グリセリンカプリン酸モノ（ジ）エ
ステルの群から選ばれた少なくとも１種の（ポリ）グリ
セリン脂肪酸エステルを用いることを特徴とする抗菌性
包装材料の製造方法。12. A solvent selected from monohydric or polyhydric alcohols, glycerin-based or sorbitan-based nonionic surfactants, (poly) glycerin caproic acid mono (di) ester, (poly) glycerin caprylic acid mono ( A method for producing an antibacterial packaging material, comprising using at least one (poly) glycerin fatty acid ester selected from the group consisting of di) esters and (poly) glycerin capric acid mono (di) ester.
ルビタン系の非イオン界面活性剤から選ばれた溶媒と、
銀系超微粒子の抗菌剤を用いることを特徴とする抗菌性
包装材料の製造方法。13. A solvent selected from polyhydric alcohols, glycerin-based or sorbitan-based nonionic surfactants,
A method for producing an antibacterial packaging material, comprising using an antibacterial agent of silver-based ultrafine particles.
とを特徴とする請求項１２または１３記載の抗菌性包装
材料の製造方法。14. A method for producing an antibacterial packaging material according to claim 12, wherein a coating solution of an antibacterial agent is applied to the packaging material.
出して予備円筒状成形体とし、冷却し、次いで前記予備
円筒状成形体を延伸してなるインフレーションフィルム
の製造方法において、ダイ出口を経て予備円筒状成形体
が延伸される迄の区間で、予備円筒成形体の内側を抗菌
剤を含む塗布液により塗工することを特徴とする抗菌性
樹脂フィルムの製造方法。15. A method for producing a blown film, comprising extruding a resin in a molten state into a cylindrical shape by using an annular die to form a preliminary cylindrical molded product, cooling, and then stretching the preliminary cylindrical molded product. A method for producing an antibacterial resin film, comprising coating the inside of the preliminary cylindrical molded body with a coating solution containing an antibacterial agent in a section until the preliminary cylindrical molded body is stretched.
リセリン系またはソルビタン系の非イオン界面活性剤か
ら選ばれた溶媒のうち少なくとも１種と抗菌剤を混合し
たものである請求項１２または１５記載の抗菌性樹脂フ
ィルムの製造方法。16. The coating liquid according to claim 12, wherein the antimicrobial agent is mixed with at least one solvent selected from monohydric or polyhydric alcohols, glycerin-based or sorbitan-based nonionic surfactants. The method for producing the antibacterial resin film according to the above.
項１２、１３または１５のいずれかに記載の抗菌性包装
材料の製造方法。17. The method for producing an antibacterial packaging material according to claim 12, wherein the resin is a vinylidene chloride resin.
リ）グリセリン脂肪酸モノ（ジ）エステルまたは銀系超
微粒子から選ばれた少なくとも１種の抗菌剤である請求
項１５〜１７のいずれかに記載の抗菌性包装材料の製造
方法。18. The antibacterial agent according to any one of claims 15 to 17, wherein the antibacterial agent is at least one selected from (poly) glycerin fatty acid mono (di) ester having 6 to 10 carbon atoms of fatty acid and silver-based ultrafine particles. A method for producing an antibacterial packaging material according to the above.
ｇ/ｍｌである請求項１８記載の抗菌性包装材料の製造
方法。19. The coating solution has a silver content of 0.5 to 3.5 m.
The method for producing an antibacterial packaging material according to claim 18, wherein the amount is g / ml.
Ｐａ・ｓである請求項１２，１４，１５および１７のい
ずれかに記載の抗菌性包装材料の製造方法。20. A coating solution having a viscosity of 0.010 to 0.200.
The method for producing an antibacterial packaging material according to any one of claims 12, 14, 15, and 17, which is Pa · s.
Ｐａ・ｓである請求項１３，１４，１５および１７のい
ずれかに記載の抗菌性包装材料の製造方法。21. A coating solution having a viscosity of 0.001 to 0.002.
The method for producing an antibacterial packaging material according to any one of claims 13, 14, 15, and 17, which is Pa · s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9152948A JPH10330625A (en) | 1997-05-27 | 1997-05-27 | Antimicrobial packaging material and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9152948A JPH10330625A (en) | 1997-05-27 | 1997-05-27 | Antimicrobial packaging material and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10330625A true JPH10330625A (en) | 1998-12-15 |
Family
ID=15551668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9152948A Pending JPH10330625A (en) | 1997-05-27 | 1997-05-27 | Antimicrobial packaging material and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10330625A (en) |
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