JP2008297416A - Surface modified polyamide film and its manufacturing method - Google Patents
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Abstract
Description
本発明は表面改質されたポリアミドフィルムおよびその製造方法に関し、特にコロナ放電処理によって表面改質された高分子フィルムおよびその製造方法に関する。 The present invention relates to a surface-modified polyamide film and a method for producing the same, and more particularly to a polymer film surface-modified by corona discharge treatment and a method for producing the same.
高分子フィルムは、その表面に文字や絵柄などを印刷することが頻繁に行われており、表面の印刷性が要求される。ところが、一般に高分子フィルムの表面は撥水性を示すものが多く、このため、高分子フィルムを表面処理することによって、その表面の改質が行われている。 The polymer film is frequently printed with characters, pictures, etc. on its surface, and the surface printability is required. However, in general, the surface of a polymer film often exhibits water repellency. Therefore, the surface of the polymer film is modified by surface treatment.
従来からの高分子フィルムの表面処理法として、プラズマ放電処理、コロナ放電処理などの放電処理や、火炎処理などによって、表面に親水性を付与して印刷性を向上させる方法が挙げられる。あるいは、フィルム表面に親水基を有した薬剤皮膜を形成させる方法などが挙げられる。この中でも、プラズマ放電処理、コロナ放電処理は、処理スピードが速く、効果が高いことから、工業的に有用で広く利用されている。 Conventional surface treatment methods for polymer films include methods for imparting hydrophilicity to the surface and improving printability by discharge treatment such as plasma discharge treatment and corona discharge treatment, and flame treatment. Or the method etc. which form the chemical | medical agent film | membrane which has a hydrophilic group on the film surface are mentioned. Among these, plasma discharge treatment and corona discharge treatment are industrially useful and widely used because of their high processing speed and high effect.
しかし、従来のコロナ放電処理では、微小な処理ムラが発生しており、条件の厳しい近年の半調印刷においては印刷抜けが発生するなどの問題がある。 However, in the conventional corona discharge treatment, minute processing unevenness occurs, and there is a problem that printing omission occurs in recent semi-tone printing under severe conditions.
ポリアミドフィルムを均一に表面処理する方法として、特許文献１〜３には、プラズマ放電処理、コロナ放電処理を行うことが提案されている。特許文献１には、ウエブを搬送するアースロールまたはロール電極の金属ロール表面に、高誘電率物質を含有する絶縁性被覆層を形成して、ウエブに均一に帯電するようにしたコロナ放電方法が開示されている。特許文献２には、高分子フィルムの表面にコロナ放電処理・プラズマ放電処理等の放電処理を施した後、続いて少なくとも放電処理された表面を水または水溶性液と接触させて高分子フィルムの表面処理を行うことにより、フィルム表面に高い親水性を付与し、かつ経時の親水性の低下を少なくすることが開示されている。さらに、特許文献３には、連続フィルムシートをコロナ放電処理または大気圧プラズマ放電処理する表面予備処理工程と、その表面予備処理工程に連続してそのフィルムシートを大気圧プラズマ放電処理する表面本処理工程とを備えることで、所望の官能基を均質にかつ確実に導入する方法が開示されている。 As a method for uniformly surface-treating a polyamide film, Patent Documents 1 to 3 propose performing plasma discharge treatment and corona discharge treatment. Patent Document 1 discloses a corona discharge method in which an insulating coating layer containing a high dielectric constant material is formed on the surface of an earth roll for conveying a web or a metal roll of a roll electrode so that the web is uniformly charged. It is disclosed. In Patent Document 2, the surface of the polymer film is subjected to a discharge treatment such as corona discharge treatment or plasma discharge treatment, and then at least the surface subjected to the discharge treatment is brought into contact with water or a water-soluble liquid. By performing the surface treatment, it has been disclosed to impart high hydrophilicity to the film surface and to reduce the decrease in hydrophilicity over time. Further, Patent Document 3 discloses a surface pretreatment process in which a continuous film sheet is subjected to corona discharge treatment or atmospheric pressure plasma discharge treatment, and a main surface treatment in which the film sheet is subjected to atmospheric pressure plasma discharge treatment in succession to the surface pretreatment process. And a method for introducing a desired functional group uniformly and reliably.
しかし、高い電界強度によりウエブに電荷を帯電させてその帯電量を均一化すると、ウエブの帯電量の絶対値が大きくなって、ブロッキングやスパークなどの静電気障害が起こりやすいという問題がある。また、水または水溶液と接触させる方法では、装置が複雑になり工業的に不利である。さらに、プラズマ放電処理は、コロナ放電処理に比べて取り扱いが難しいという欠点がある。このように、近年の厳しい条件の半調印刷に適応可能で、簡便で、しかも均一な表面改質を行う方法は、これまで提案されていない。
本発明は、上記課題を解決し、ポリアミドフィルムの表面改質をするにあたって、簡便で、静電気障害が発生しにくく、かつ、微小な処理ムラがなくフィルム全体に均一なコロナ放電処理する方法と、その方法によって得られる表面改質されたポリアミドフィルムとを提供することを目的とする。 The present invention solves the above-mentioned problems, and is a method for surface treatment of a polyamide film. It is an object of the present invention to provide a surface-modified polyamide film obtained by the method.
本発明者は、鋭意研究を重ねた結果、ポリアミドフィルムを弱い電界強度でコロナ放電処理することで、ブロッキングやスパークなどの静電気障害の発生を抑え、さらに、その弱い電界強度で２回またはそれより多い回数のコロナ放電処理を行うことで、微小な処理ムラがなくフィルム全体に均一なコロナ放電処理することが可能となり、さらに、処理面の微小範囲かつ処理面全体において均一な濡れ性を有するポリアミドフィルムを得られることを見出し、本発明に至ったのである。 As a result of extensive research, the present inventor conducted corona discharge treatment on the polyamide film with a weak electric field intensity to suppress the occurrence of electrostatic disturbances such as blocking and sparks, and further, twice or more with the weak electric field intensity. By performing a large number of corona discharge treatments, it becomes possible to perform uniform corona discharge treatment on the entire film without any minute processing unevenness, and furthermore, polyamide having uniform wettability over a small range of the treated surface and the entire treated surface The inventors have found that a film can be obtained and have reached the present invention.
すなわち、本発明の要旨は、以下のとおりである。
（１）ポリアミドフィルムの幅方向に１０ｃｍ間隔で測定ポイントをとり、水に対する前記ポリアミドフィルムの接触角を、前記測定ポイントを中心として前記ポリアミドフィルムの幅方向に２ｍｍ間隔で１０点の測定点で測定したときの最大値をθ１ｍａｘ、最小値をθ１ｍｉｎ、平均値をθ１ａｖとし、さらに、すべての測定ポイントにおけるθ１ａｖの最大値をθ２ｍａｘ、最小値をθ２ｍｉｎとしたとき、すべての測定ポイントにおいて以下の（式１）および（式２）を満たし、かつ以下の（式３）を満たすことを特徴とする表面改質されたポリアミドフィルム。
That is, the gist of the present invention is as follows.
(1) Measurement points are taken at 10 cm intervals in the width direction of the polyamide film, and the contact angle of the polyamide film with water is measured at 10 measurement points at intervals of 2 mm in the width direction of the polyamide film with the measurement point as the center. When the maximum value is θ1max, the minimum value is θ1min, the average value is θ1av, the maximum value of θ1av at all measurement points is θ2max, and the minimum value is θ2min, the following (formula A surface-modified polyamide film satisfying 1) and (Formula 2) and satisfying the following (Formula 3):
θ１ｍａｘ−θ１ｍｉｎ ≦ ５ｄｅｇ． （式１）
４５ｄｅｇ． ≦ θ１ａｖ ≦ ５５ｄｅｇ． （式２）
θ２ｍａｘ−θ２ｍｉｎ ≦ ５ｄｅｇ． （式３）
θ1max−θ1min ≦ 5 deg. (Formula 1)
45 deg. ≦ θ1av ≦ 55 deg. (Formula 2)
θ2max−θ2min ≦ 5 deg. (Formula 3)
（２）上記（１）の表面改質されたポリアミドフィルムを製造するに際し、２回またはそれより多い回数のコロナ放電処理を施すことを特徴とする表面改質されたポリアミドフィルムの製造方法。 (2) A method for producing a surface-modified polyamide film, wherein the surface-modified polyamide film (1) is subjected to corona discharge treatment twice or more times.
（３） 平均電界強度が１〜５０ｋＶ／ｃｍの高電圧電界により発生させたコロナ放電により処理を施すことを特徴とする（２）の表面改質されたポリアミドフィルムの製造方法。 (3) The method for producing a surface-modified polyamide film according to (2), wherein the treatment is performed by corona discharge generated by a high voltage electric field having an average electric field strength of 1 to 50 kV / cm.
本発明の方法によれば、ポリアミドフィルムの表面改質をするにあたって、簡便で、静電気障害が発生しにくく、微小な処理ムラがなくフィルム全体に均一なコロナ放電処理をすることが可能である。さらに、その表面処理によって、処理面の微小範囲かつ処理面全体において均一な濡れ性を有するポリアミドフィルムを得ることができる。 According to the method of the present invention, when modifying the surface of a polyamide film, it is simple and hardly causes electrostatic damage, and it is possible to perform a uniform corona discharge treatment on the entire film without causing minute processing unevenness. Furthermore, by the surface treatment, it is possible to obtain a polyamide film having uniform wettability over a small range of the treated surface and the entire treated surface.
本発明では、表面改質したポリアミドフィルムの幅方向に１０ｃｍ間隔で測定ポイントをとり、水に対する前記ポリアミドフィルムの接触角を、前記測定ポイントを中心として前記ポリアミドフィルムの幅方向に２ｍｍ間隔で１０点の測定点で測定したときの最大値をθ１ｍａｘ、最小値をθ１ｍｉｎ、平均値をθ１ａｖとし、さらに、すべての測定ポイントにおけるθ１ａｖの最大値をθ２ｍａｘ、最小値をθ２ｍｉｎとしたとき、すべての測定ポイントにおいて以下の（式１）および（式２）を満たし、かつ以下の（式３）を満たすことが必要である。 In the present invention, measurement points are taken at 10 cm intervals in the width direction of the surface-modified polyamide film, and the contact angle of the polyamide film with respect to water is set at 10 points at intervals of 2 mm in the width direction of the polyamide film centering on the measurement points. When measuring at the measurement points, the maximum value is θ1max, the minimum value is θ1min, the average value is θ1av, and the maximum value of θ1av at all measurement points is θ2max, and the minimum value is θ2min. It is necessary to satisfy the following (formula 1) and (formula 2) and satisfy the following (formula 3).
θ１ｍａｘ−θ１ｍｉｎ ≦ ５ｄｅｇ． （式１）
４５ｄｅｇ． ≦ θ１ａｖ ≦ ５５ｄｅｇ． （式２）
θ２ｍａｘ−θ２ｍｉｎ ≦ ５ｄｅｇ． （式３）
θ1max−θ1min ≦ 5 deg. (Formula 1)
45 deg. ≦ θ1av ≦ 55 deg. (Formula 2)
θ2max−θ2min ≦ 5 deg. (Formula 3)
式１に関し、好ましくは θ１ｍａｘ−θ１ｍｉｎ ≦ ３ｄｅｇ．であり、さらに好ましくは θ１ｍａｘ−θ１ｍｉｎ ≦ ２ｄｅｇ．である。θ１ｍａｘ−θ１ｍｉｎ ＞ ５ｄｅｇ.となる測定ポイントがある場合は、表面改質したフィルム表面の微小範囲で処理ムラが発生しているため、半調印刷において印刷抜けが発生する恐れがある。 Regarding Equation 1, preferably θ1max−θ1min ≦ 3 deg. And more preferably θ1max−θ1min ≦ 2 deg. It is. When there is a measurement point satisfying θ1max−θ1min> 5 deg., processing unevenness occurs in a minute range on the surface of the film that has been surface-modified.
式２に関し、好ましくは ４５ｄｅｇ． ≦ θ１ａｖ ≦ ５０ｄｅｇ．であり、さらに好ましくは ４５ｄｅｇ． ≦ θ１ａｖ ≦ ４８ｄｅｇ．である。θ１ａｖ＜４５ｄｅｇ．の場合は、フィルム表面の処理度合いが強すぎるため、ブロッキングやスパークなどの静電気障害を引き起こす恐れがある。θ１ａｖ＞５５ｄｅｇ．の場合は、フィルム表面の処理不足で、濡れ性が低く、印刷に問題が生じる恐れがある。 For Equation 2, preferably 45 deg. ≦ θ1av ≦ 50 deg. And more preferably 45 deg. ≦ θ1av ≦ 48 deg. It is. θ1av <45 deg. In this case, since the degree of treatment on the film surface is too strong, there is a risk of causing static electricity damage such as blocking or sparking. θ1av> 55 deg. In this case, the film surface is insufficiently processed, the wettability is low, and there is a possibility that a problem may occur in printing.
式３に関し、好ましくは θ２ｍａｘ−θ２ｍｉｎ ≦ ３ｄｅｇ．であり、さらに好ましくは θ２ｍａｘ−θ２ｍｉｎ ≦ ２ｄｅｇ．である。θ２ｍａｘ−θ２ｍｉｎ ＞ ５ｄｅｇ.であると、表面改質したフィルム表面全体で処理ムラが発生しているため、印刷の濃淡ムラの恐れがある。 Regarding Equation 3, preferably θ2max−θ2min ≦ 3 deg. And more preferably θ2max−θ2min ≦ 2 deg. It is. If θ2max−θ2min> 5 deg., processing unevenness occurs on the entire surface of the surface-modified film, and thus there is a risk of uneven printing density.
さらに、すべての測定ポイントについてのθ１ａｖの平均値をθ２ａｖとすると、式２を満たしていれば必然的に ４５ｄｅｇ． ≦ θ２ａｖ ≦ ５５ｄｅｇ．となる。この場合は、フィルム全体での処理度合が適当である。好ましくは ４５ｄｅｇ． ≦ θ２ａｖ ≦ ４９ｄｅｇ．であり、さらに好ましくは ４５ｄｅｇ． ≦ θ２ａｖ ≦ ４８ｄｅｇ．である。 Furthermore, if the average value of θ1av for all measurement points is θ2av, it is inevitably 45 deg. ≦ θ2av ≦ 55 deg. It becomes. In this case, the processing degree in the whole film is appropriate. Preferably 45 deg. ≦ θ2av ≦ 49 deg. And more preferably 45 deg. ≦ θ2av ≦ 48 deg. It is.
本発明に関わるコロナ放電処理装置の一態様を図１に示す。ここで、１、２は高圧電源、３、４は放電電極、５、６は対極ロール、７はガイドロールである。８がコロナ放電処理されるポリアミドフィルムである。いずれの部材も基本的には公知のコロナ放電処理装置のものを使用することができる。 One embodiment of a corona discharge treatment apparatus according to the present invention is shown in FIG. Here, 1 and 2 are high-voltage power supplies, 3 and 4 are discharge electrodes, 5 and 6 are counter electrode rolls, and 7 is a guide roll. 8 is a polyamide film to be subjected to corona discharge treatment. As for any member, those of a known corona discharge treatment apparatus can be basically used.
本発明の製造方法では、ポリアミドフィルムに２回またはそれより多い回数のコロナ放電処理を行うことが必要である。２回または３回行うことが好ましい。コロナ放電処理を４回以上行っても、フィルムの表面改質の効果は飽和してほとんど変わらず、装置が大型化してしまう。なお、コロナ放電処理は、放電電極内の放電針を高密度で設置しても完全に均一なコロナ放電を発生させることが困難であるため、１回のコロナ放電処理では微小範囲で処理ムラが生じやすい。 In the production method of the present invention, it is necessary to perform corona discharge treatment twice or more times on the polyamide film. It is preferable to carry out twice or three times. Even if the corona discharge treatment is performed four or more times, the effect of surface modification of the film is saturated and hardly changed, and the apparatus becomes large. In the corona discharge treatment, it is difficult to generate a completely uniform corona discharge even if the discharge needles in the discharge electrode are installed at a high density. Prone to occur.
本発明に用いるコロナ放電装置は、図示のように放電電極３、４を２つまたはそれよりも多く有している形態、好ましくは２つまたは３つ有している形態でも良く、もしくは、放電装置を２台以上有している形態、好ましくは２台または３台有している形態でも良い。 The corona discharge device used in the present invention may have a form having two or more discharge electrodes 3, 4 as shown in the figure, preferably a form having two or three, or a discharge The form which has 2 or more apparatuses, Preferably the form which has 2 or 3 units | sets may be sufficient.
本発明においては、全てのコロナ放電処理について、コロナ放電の印加電圧／極間距離で表される平均電界強度を、１〜５０ｋＶ／ｃｍに設定するのが好ましい。さらに好ましくは２０〜４０ｋＶ／ｃｍである。平均電界強度が１ｋＶ／ｃｍ未満では、有効なコロナ放電が発生し難く、表面処理効果が乏しくなる。反対に平均電界強度が５０ｋＶ／ｃｍを超えると、ブロッキングやスパークなどの静電気障害が発生しやすくなる。 In the present invention, for all corona discharge treatments, it is preferable to set the average electric field strength represented by the applied voltage of corona discharge / distance between electrodes to 1 to 50 kV / cm. More preferably, it is 20-40 kV / cm. When the average electric field strength is less than 1 kV / cm, effective corona discharge hardly occurs and the surface treatment effect becomes poor. On the other hand, when the average electric field strength exceeds 50 kV / cm, electrostatic disturbances such as blocking and sparking tend to occur.
本発明において、ポリアミドフィルムは、以下のポリアミド樹脂を主成分とするフィルムであることが好ましい。すなわち、ポリアミド樹脂としては、３員環以上のラクタム、重合可能なω−アミノ酸、二塩基酸とジアミンなどの重縮合によって得られるポリアミド樹脂を用いることができる。具体的には、ε−カプロラクタム、アミノカプロン酸、エナントラクタム、７−アミノヘプタン酸、１１−アミノウンデカン酸、９−アミノノナン酸、α−ピロリドン、α−ピペリドンなどの重合体や；ヘキサメチレンジアミン、ノナメチレンジアミン、ウンデカメチレンジアミン、ドデカメチレンジアミン、メタキシリレンジアミンなどのジアミンと、テレフタル酸、イソフタル酸、アジピン酸、セバチン酸、ドデカン二塩基酸、グルタール酸などのジカルボン酸との塩を重縮合せしめて得られる重合体や；これらの共重合体が挙げられる。例えば、ナイロン４、６、７、８、１１、１２、６・６、６・１０、６・１１、６・１２、６Ｔ、６／６・６、６／１２、６／６Ｔ、６Ｉ／６Ｔなどが挙げられる。機械的特性や熱的特性に優れる点から、特に包装用途に供する場合は、ナイロン６を主成分とするのが好適である。
In the present invention, the polyamide film is preferably a film mainly composed of the following polyamide resin. That is, as the polyamide resin, a polyamide resin obtained by polycondensation of a lactam having a three or more member ring, a polymerizable ω-amino acid, a dibasic acid and a diamine can be used. Specifically, polymers such as ε-caprolactam, aminocaproic acid, enanthractam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9-aminononanoic acid, α-pyrrolidone, α-piperidone; hexamethylenediamine, nona Polycondensation of diamines such as methylenediamine, undecamethylenediamine, dodecamethylenediamine, and metaxylylenediamine with dicarboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, sebacic acid, dodecane dibasic acid, and glutaric acid Examples thereof include polymers obtained by caulking, and copolymers thereof. For example,
さらに必要に応じて、通常配合される各種の添加剤および改質剤、例えば、滑材、耐熱安定剤、紫外線吸収剤、光安定剤、酸化防止剤、帯電防止剤、粘着性付与剤、シール性改良剤、防曇剤、結晶核剤、離型剤、可塑剤、架橋剤、難燃剤および着色剤（顔料、染料など）などを配合してもよい。 Furthermore, various additives and modifiers that are usually blended as necessary, for example, lubricants, heat stabilizers, UV absorbers, light stabilizers, antioxidants, antistatic agents, tackifiers, seals A property improver, an antifogging agent, a crystal nucleating agent, a mold release agent, a plasticizer, a crosslinking agent, a flame retardant, and a colorant (pigment, dye, etc.) may be added.
本発明において、表面改質を目的としてコロナ処理を施すためのポリアミドフィルムは、公知の製造方法で製造することができる。たとえば、Ｔダイから溶融ポリマーを押出後、キャスティングロールで冷却して未延伸シートを作成し、これを同時２軸延伸、または、逐次２軸延伸する。延伸後のフィルムは、寸法安定性を良くするために、２００℃前後の温度で短時間の熱処理を施す。 In the present invention, the polyamide film for performing corona treatment for the purpose of surface modification can be produced by a known production method. For example, after extruding a molten polymer from a T-die, it is cooled with a casting roll to produce an unstretched sheet, which is simultaneously biaxially stretched or sequentially biaxially stretched. The stretched film is subjected to a short heat treatment at a temperature of around 200 ° C. in order to improve dimensional stability.
この熱処理の後、ポリアミドフィルムを巻き取るまでの工程で、コロナ処理を施すのが好ましい。あるいは、いったん巻き取った後に巻き戻しを行いながら実施するスリット工程で、コロナ処理を施すことも可能である。両方の工程でコロナ処理を施すことも可能である。 After this heat treatment, corona treatment is preferably performed in a process until the polyamide film is wound up. Or it is also possible to give a corona treatment in the slit process implemented while winding up once and winding up. Corona treatment can be applied in both steps.
また、フィルムに機能性を付与するために、表面処理に影響を与えない範囲で、インラインコート延伸技法を用いて、未延伸のポリアミドフィルムに、帯電防止剤、接着性改良組成物、バリア性樹脂等をコートした後に、延伸することもできる。 In addition, in order to impart functionality to the film, an anti-strength agent, an adhesion improving composition, and a barrier resin are applied to an unstretched polyamide film using an in-line coat stretching technique as long as the surface treatment is not affected. It is also possible to stretch the film after coating.
また、ポリアミドフィルムは、単層フィルムであってもよいし、表層がポリアミドであれば共押出の積層フィルムであってもよい。 The polyamide film may be a single layer film or a coextruded laminated film if the surface layer is polyamide.
以下、実施例を挙げて本発明を説明する。ただし、本発明は、その要旨を逸脱しない限り、下記の実施例に限定されるものではない。なお、フィルムの各物性は、以下に示す方法によって求めた。 Hereinafter, the present invention will be described with reference to examples. However, the present invention is not limited to the following examples without departing from the gist thereof. In addition, each physical property of the film was calculated | required by the method shown below.
（１）接触角：ＪＩＳ Ｒ３２５７ に記載の静滴法に従って測定した。ただし、測定箇所は次のとおりした。すなわち、幅４ｍのポリアミドフィルムに対して、幅方向に沿ったフィルムの端から幅方向に１０ｃｍ間隔で計３９箇所の測定ポイントをとり、各々の測定ポイントについて、水に対する表面改質面の接触角を、測定ポイントを中心としてフィルムの幅方向に２ｍｍ間隔で１０点について測定した。１０点の測定点で測定した接触角の最大値をθ１ｍａｘ、最小値をθ１ｍｉｎ、平均値をθ１ａｖとした。さらに、３９箇所の測定ポイントについてのθ１ａｖの最大値をθ２ｍａｘ、最小値をθ２ｍｉｎとした。 (1) Contact angle: Measured according to the sessile drop method described in JIS R3257. However, the measurement location was as follows. That is, for a polyamide film having a width of 4 m, a total of 39 measurement points were taken at 10 cm intervals in the width direction from the end of the film along the width direction, and for each measurement point, the contact angle of the surface modified surface with water Was measured at 10 points at 2 mm intervals in the width direction of the film with the measurement point as the center. The maximum value of the contact angle measured at 10 measurement points was θ1max, the minimum value was θ1min, and the average value was θ1av. Further, the maximum value of θ1av for 39 measurement points was θ2max, and the minimum value was θ2min.
（２）濡れ張力：ＪＩＳ Ｋ６７６８に従って測定した。 (2) Wetting tension: measured according to JIS K6768.
（３）半調印刷性：グラビアロール（スクリーン１５０線×３０μｍ×３０％）で印刷を施したフィルムの表面に発生した印刷抜けを、ライトスコープを用い、倍率３０倍で２７ｃｍ２の面積について観察することで、１ｃｍ２当たりの個数で判定した。評価基準は、次のとおりとした。 (3) Semi-tone printability: Observed printing loss occurring on the surface of a film printed with a gravure roll (screen 150 lines × 30 μm × 30%) using a light scope at an area of 27 cm 2 at a magnification of 30 times. Thus, the number of pieces per 1 cm 2 was determined. The evaluation criteria were as follows.
◎：１ｃｍ２当たりの印刷抜け数が０〜１個
○：１ｃｍ２当たりの印刷抜け数が２〜５個
△：１ｃｍ２当たりの印刷抜け数が６〜１０個
×：１ｃｍ２当たりの印刷抜け数が１０個より多い
◎ 1 to 2 printing omissions per 1 cm 2 ○ 2 to 5 printing omissions per 1 cm 2 △ 6 to 10 printing omissions per 1 cm 2 × 1 printing omission per 1 cm 2 More than 10
実施例１
添加剤として平均粒径１．５μｍのシリカ粒子０．２質量％とエチレンビスステアロアミド０．０５質量％と含有するナイロン６原料を準備し、押出機およびＴダイを用いて溶融押出しした。これをキャスティング・ドラムに巻き付けて冷却固化することで、未延伸シートを作製した。この未延伸シートを７０℃に温調した温水槽に送り、１分間の調湿処理を施した。その後、幅方向に沿ったシート端部をフラット式同時２軸延伸機のクリップに把持させ、１９５℃の条件下、縦３．０倍、横３．３倍の延伸倍率で同時２軸延伸を施した。次いで、横方向の弛緩率を５％として、２００℃で３秒間の熱処理を施し、冷却工程を経て、幅４ｍ、厚さ１５μｍの、２軸延伸ポリアミドフィルム原反を得た。このフィルム原反を図１に示したコロナ放電処理装置に供給して、対極ロール５、６に密着させ、放電電極３、４のコロナ放電場に通過させて、同ポリアミドフィルムの片面を２回コロナ放電処理した。このとき、平均電界強度は１５ｋＶ／ｃｍとし、フィルム走行速度は５０ｍ／ｍｉｎとした。
Example 1
A nylon 6 raw material containing 0.2% by mass of silica particles having an average particle diameter of 1.5 μm and 0.05% by mass of ethylene bisstearamide as an additive was prepared and melt-extruded using an extruder and a T die. This was wound around a casting drum and solidified by cooling to produce an unstretched sheet. This unstretched sheet was sent to a hot water tank whose temperature was adjusted to 70 ° C., and subjected to a humidity conditioning treatment for 1 minute. Thereafter, the end of the sheet along the width direction is held by a clip of a flat simultaneous biaxial stretching machine, and simultaneously biaxially stretched at a stretching ratio of 3.0 times in length and 3.3 times in width at 195 ° C. gave. Next, heat treatment was performed at 200 ° C. for 3 seconds with a lateral relaxation rate of 5%, and a biaxially stretched polyamide film original having a width of 4 m and a thickness of 15 μm was obtained through a cooling process. The original film is supplied to the corona discharge treatment apparatus shown in FIG. 1, is brought into close contact with the counter electrode rolls 5, 6, and is passed through the corona discharge field of the discharge electrodes 3, 4. Corona discharge treatment was performed. At this time, the average electric field strength was 15 kV / cm, and the film running speed was 50 m / min.
得られたポリアミドフィルムの処理表面の水に対する接触角、濡れ張力、半調印刷性を、表１に示す。なお、表１において、θ１ｍａｘ−θ１ｍｉｎの値と、θ１ａｖの値とについては、上述の３９箇所の測定ポイントについての最小値から最大値までの範囲を記載した。 Table 1 shows the water contact angle, wetting tension, and halftone printability of the treated surface of the obtained polyamide film. In Table 1, for the value of θ1max−θ1min and the value of θ1av, the range from the minimum value to the maximum value for the 39 measurement points described above is described.
実施例２〜４および比較例１〜５
実施例１に比べ、コロナ処理回数、平均電界強度を変化させた。それ以外は実施例１と同様にして、表面改質されたポリアミドフィルムを得た。得られたフィルムについての測定結果を表１に示す。なお、コロナ放電処理の回数が１回の場合は、図１における放電電極４を使用せずにコロナ放電処理を施した。コロナ放電処理の回数が３回の場合は、実施例１と同様に２回処理した後、放電電極４を使用せずに、さらにもう１回コロナ放電処理を施した。
Examples 2-4 and Comparative Examples 1-5
Compared to Example 1, the number of corona treatments and the average electric field strength were changed. Other than that was carried out similarly to Example 1, and obtained the surface-modified polyamide film. The measurement results for the obtained film are shown in Table 1. In addition, when the frequency | count of the corona discharge process was 1 time, the corona discharge process was performed without using the discharge electrode 4 in FIG. In the case where the number of corona discharge treatments was 3, after treatment twice as in Example 1, the corona discharge treatment was performed one more time without using the discharge electrode 4.
表１に示される測定結果によれば、コロナ放電処理を複数回行うことでθ１ｍａｘとθ１ｍｉｎとの差が小さくなった。これは、微小範囲での処理ムラが少ないことを表している。濡れ張力の評価を見ると、いずれの条件も差異がほとんど見られないことから、この微小範囲の処理ムラ評価においては、従来の濡れ張力評価では不十分であることが分かる。 According to the measurement results shown in Table 1, the difference between θ1max and θ1min was reduced by performing the corona discharge treatment a plurality of times. This indicates that there is little processing unevenness in the minute range. Looking at the evaluation of the wetting tension, almost no difference is observed in any of the conditions, so that it can be seen that the conventional wetting tension evaluation is insufficient for evaluating the processing unevenness in this minute range.
θ１ａｖについては、コロナ処理を複数回行うことで、θ１ａｖの最小値（θ２ｍｉｎ）と、その最大値（θ２ｍａｘ）との差（θ２ｍａｘ−θ２ｍｉｎ）が小さくなった。これより、コロナ放電処理を１回だけしか行わない場合に比べて、複数回処理することで、フィルム全体でより均一な表面改質ができることが分かった。 For θ1av, the corona treatment was performed a plurality of times, and the difference (θ2max−θ2min) between the minimum value (θ2min) of θ1av and the maximum value (θ2max) was reduced. From this, it was found that, by performing the treatment a plurality of times as compared with the case where the corona discharge treatment is performed only once, a more uniform surface modification can be performed on the entire film.
つまり、実施例１〜実施例４のものは、いずれも、すべての測定ポイントにおいて（式１）および（式２）を満たし、かつ（式３）を満たすものであった。これに対し、比較例１〜比較例５では、実施例１〜実施例４のものと相違して、すべての測定ポイントにおいて（式１）および（式２）を満たし、かつ（式３）を満たすというものは無かった。 That is, all of Examples 1 to 4 satisfied (Expression 1) and (Expression 2) at all measurement points, and also satisfied (Expression 3). On the other hand, in Comparative Example 1 to Comparative Example 5, unlike those of Examples 1 to 4, the (Equation 1) and (Equation 2) are satisfied at all measurement points, and (Equation 3) is satisfied. There was nothing to satisfy.
比較例５は、コロナ放電処理を１回だけしか行わなかったものであるが、平均電界強度が高過ぎた影響でブロッキングが発生しており、半調印刷性は評価できなかった。 In Comparative Example 5, the corona discharge treatment was performed only once, but blocking occurred due to the influence of the average electric field strength being too high, and the halftone printability could not be evaluated.
１、２ 高圧電源
３、４ 放電電極
５、６ 対極ロール
７ ガイドロール
８ ポリアミドフィルム
1, 2 High voltage power supply 3, 4
Claims (3)
θ１ｍａｘ−θ１ｍｉｎ ≦ ５ｄｅｇ． （式１）
４５ｄｅｇ． ≦ θ１ａｖ ≦ ５５ｄｅｇ． （式２）
θ２ｍａｘ−θ２ｍｉｎ ≦ ５ｄｅｇ． （式３） When measuring points are taken at intervals of 10 cm in the width direction of the polyamide film, and the contact angle of the polyamide film with respect to water is measured at 10 measuring points at intervals of 2 mm in the width direction of the polyamide film with the measurement point as the center. When the maximum value is θ1max, the minimum value is θ1min, the average value is θ1av, and the maximum value of θ1av at all measurement points is θ2max and the minimum value is θ2min, the following (Equation 1) and A surface-modified polyamide film characterized by satisfying (Expression 2) and satisfying (Expression 3) below.
θ1max−θ1min ≦ 5 deg. (Formula 1)
45 deg. ≦ θ1av ≦ 55 deg. (Formula 2)
θ2max−θ2min ≦ 5 deg. (Formula 3)
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| JP2008297416A true JP2008297416A (en) | 2008-12-11 |
| JP5147292B2 JP5147292B2 (en) | 2013-02-20 |
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| JP2007144296A Active JP5147292B2 (en) | 2007-05-31 | 2007-05-31 | Surface-modified polyamide film and method for producing the same |
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| JP (1) | JP5147292B2 (en) |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016047416A1 (en) * | 2014-09-26 | 2016-03-31 | 大日本印刷株式会社 | Batrery packaging material |
| JP2016072211A (en) * | 2014-09-26 | 2016-05-09 | 大日本印刷株式会社 | Battery packaging material |
| JP2016184478A (en) * | 2015-03-25 | 2016-10-20 | 大日本印刷株式会社 | Battery packaging material |
| JP2016184477A (en) * | 2015-03-25 | 2016-10-20 | 大日本印刷株式会社 | Battery packaging material |
| JP2016186871A (en) * | 2015-03-27 | 2016-10-27 | 大日本印刷株式会社 | Battery packaging material |
| US10396316B2 (en) | 2015-03-25 | 2019-08-27 | Dai Nippon Printing Co., Ltd. | Cell packaging material and cell |
| US10581033B2 (en) | 2014-09-26 | 2020-03-03 | Dai Nippon Printing Co., Ltd. | Battery packaging material |
| JPWO2021149815A1 (en) * | 2020-01-24 | 2021-07-29 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107090113A (en) * | 2017-05-04 | 2017-08-25 | 湖州长园特发科技有限公司 | A kind of slim foam of novel radiation crosslinked polyethylene and preparation method thereof |
| CN113665145B (en) * | 2021-07-23 | 2023-08-25 | 山东双健新材料有限公司 | Corona treatment device for film preparation |
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| JPH01193331A (en) * | 1988-01-29 | 1989-08-03 | Kasuga Denki Kk | Apparatus for surface-treatment by corona discharge |
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| EP1124136A1 (en) * | 2000-02-10 | 2001-08-16 | Sumitomo Wiring Systems, Ltd. | Electrical connection testing device and method for connector terminals |
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2007
- 2007-05-31 JP JP2007144296A patent/JP5147292B2/en active Active
- 2007-07-09 CN CN2007101280832A patent/CN101074293B/en active Active
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2008
- 2008-01-17 HK HK08100613.9A patent/HK1106947A1/en not_active IP Right Cessation
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| JPS579085A (en) * | 1980-06-20 | 1982-01-18 | Fuji Photo Film Co Ltd | Corona discharge processing electrode |
| JPS6441186A (en) * | 1987-08-07 | 1989-02-13 | Oji Paper Co | Corona discharge processor |
| JPH01193331A (en) * | 1988-01-29 | 1989-08-03 | Kasuga Denki Kk | Apparatus for surface-treatment by corona discharge |
| JPH08258232A (en) * | 1995-03-23 | 1996-10-08 | Kohjin Co Ltd | Easily bondable polyamide film |
| JPH10195674A (en) * | 1996-12-27 | 1998-07-28 | Japan Vilene Co Ltd | Treatment of total surface and treatment apparatus for total surface |
| JPH10241827A (en) * | 1996-12-27 | 1998-09-11 | Nippon Paint Co Ltd | Corona discharge generator |
| JP2000246091A (en) * | 1998-12-29 | 2000-09-12 | Konica Corp | Method and apparatus for surface treatment of substrate and surface-treated substrate |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016047416A1 (en) * | 2014-09-26 | 2016-03-31 | 大日本印刷株式会社 | Batrery packaging material |
| JP2016072211A (en) * | 2014-09-26 | 2016-05-09 | 大日本印刷株式会社 | Battery packaging material |
| US10581033B2 (en) | 2014-09-26 | 2020-03-03 | Dai Nippon Printing Co., Ltd. | Battery packaging material |
| JP2016184478A (en) * | 2015-03-25 | 2016-10-20 | 大日本印刷株式会社 | Battery packaging material |
| JP2016184477A (en) * | 2015-03-25 | 2016-10-20 | 大日本印刷株式会社 | Battery packaging material |
| US10396316B2 (en) | 2015-03-25 | 2019-08-27 | Dai Nippon Printing Co., Ltd. | Cell packaging material and cell |
| JP2016186871A (en) * | 2015-03-27 | 2016-10-27 | 大日本印刷株式会社 | Battery packaging material |
| JPWO2021149815A1 (en) * | 2020-01-24 | 2021-07-29 | ||
| CN115003735A (en) * | 2020-01-24 | 2022-09-02 | 尤尼吉可股份有限公司 | Method for producing polyamide resin film |
| JP7137808B2 (en) | 2020-01-24 | 2022-09-15 | ユニチカ株式会社 | Method for producing polyamide resin film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5147292B2 (en) | 2013-02-20 |
| HK1106947A1 (en) | 2008-03-20 |
| CN101074293B (en) | 2010-10-06 |
| CN101074293A (en) | 2007-11-21 |
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