JP5441843B2 - Contents adhesion prevention lid material and manufacturing method thereof - Google Patents
Contents adhesion prevention lid material and manufacturing method thereof Download PDFInfo
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- JP5441843B2 JP5441843B2 JP2010154457A JP2010154457A JP5441843B2 JP 5441843 B2 JP5441843 B2 JP 5441843B2 JP 2010154457 A JP2010154457 A JP 2010154457A JP 2010154457 A JP2010154457 A JP 2010154457A JP 5441843 B2 JP5441843 B2 JP 5441843B2
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- Laminated Bodies (AREA)
Description
本発明は、主として食品類の包装用容器に適用されるヒートシール蓋材、更に具体的には、ヨーグルト、ゼリー、プリン、ジャム等の包装用のカップ状容器に適用される内容物付着防止性を備えた蓋材およびその製造方法に関する。 The present invention relates to a heat-sealing lid material mainly applied to containers for packaging foods, and more specifically, to prevent adhesion of contents applied to cup-shaped containers for packaging such as yogurt, jelly, pudding, jam, etc. And a manufacturing method thereof.
この種の熱封緘用の蓋材は、一般に基材フィルムとアルミニウム箔との積層からなる基材層のアルミ箔面側に、中間樹脂層を介してヒートシール層、即ち熱封緘層を設けたものとなされ、ヨーグルト等の被包装物を充填したカップ状の容器本体の上面開口に被せて、周縁部を容器本体の上縁フランジ部上に熱融着することによって密封包装物を形成する。 This type of heat sealing lid material is generally provided with a heat sealing layer, that is, a heat sealing layer, on an aluminum foil surface side of a base material layer made of a laminate of a base material film and an aluminum foil via an intermediate resin layer. A sealed package is formed by covering the upper opening of a cup-shaped container body filled with an object to be packaged such as yogurt and heat-sealing the peripheral part on the upper edge flange part of the container body.
従って、かかる蓋材においては、良好なヒートシール性、密封性と、開封時のための適当な易剥離性が求められるのと同時に、内容物の非付着性、即ち容器の内面側の蓋材裏面に内容物が付着するのを防止しうるものであることが望まれる。蓋材の裏面に内容物が付着すると、開封時に手指や衣服、あるいは周辺を汚すおそれがあると共に、内容物の棄損による無駄を生じ、あるいは付着物を剥がし取る手間がかかり、更には不潔感を催す等の不利益を生じるためである。 Therefore, in such a lid material, good heat-sealing property, sealing property, and appropriate easy peelability for opening are required, and at the same time, the non-adhesiveness of the contents, that is, the lid material on the inner surface side of the container It is desired that the contents can be prevented from adhering to the back surface. If the contents adhere to the back of the lid, fingers, clothes, or the surrounding area may be soiled when opened, resulting in waste due to the loss of the contents, or time and effort to peel off the contents, and an unclean feeling. This is to cause a disadvantage such as hosting.
そこで、従来、内容物付着防止性能を備えた蓋材について、下記特許文献１〜６に示されるような種々の提案がなされてきた。
Therefore, conventionally, various proposals as shown in
上記特許文献１〜３に示す先行技術は、基材の片面の熱封緘層に、付着防止効果を有する非イオン界面活性剤又は疎水性添加物、あるいはワックス等を添加するものであり、熱封緘層そのものに付着防止性能を付与しようとするものであるが、いずれも未だ所期する内容物付着防止効果の点で不満足なものでしかなかった。
The prior arts shown in
また、特許文献４〜５の先行技術は、熱封緘層の外面（容器側の面）に、別途内容物付着防止層を付加形成するというものであり、該付着防止層をワックスと、その中に分散された固体微粒子充填剤との組成物で構成するものである。これらの先行技術は、前記特許文献１〜３の先行技術に比べると内容物付着防止効果は一段と改善されるが、それでも未だ十分とはいえないのに加えて、ワックス中に充填剤を分散させているものであるため、熱封緘層のヒートシール性に悪影響を及ぼして密封性が不安定なものになりやすい懸念があった。
Further, the prior arts of
更に、特許文献６に示される先行技術は、熱封緘層の外面に、内容物付着防止層として、微細な疎水性シリカ等の疎水性酸化物微粒子による三次元網目状構造の多孔質層を形成するというものである。この付着防止層の形成は、一次粒子平均径が３〜１００ｎｍの極めて微細な酸化物微粒子を用い、これをエタノール等の分散媒中に分散させた分散液を塗布したのち、乾燥させることにより、乾燥後の上記微粒子の付着量が０．０１〜１０ｇ／ｍ２、好ましくは０．２〜１．５ｇ／ｍ２、最適には０．３〜１ｇ／ｍ２で、厚みが０．１〜０．５μｍ、好ましくは０．２〜２．５μｍの多孔質層とするというものである。
Furthermore, in the prior art disclosed in
この先行提案技術は、内容物付着防止効果の点では非常に優れた効果を奏し得る。 This prior proposal technique can have a very excellent effect in terms of the content adhesion preventing effect.
ところが反面、蓋材の容器本体に対するヒートシール部において、無機微粒子による多孔質層が夾雑物となってヒートシール性を阻害する。このため、概してシール強度が低下し、良好な密封性、所要の耐剥離強度を保持し難いものとなり易い難点があった。とりわけ、疎水性微粒子をエタノールやメタノール等の溶媒に分散して、グラビアコート方式やスプレーコート方式で塗工する場合、液だれを起こし易く、疎水性微粒子を均一に塗布することが難しい。このため、疎水性微粒子が過剰に存在する部分が発生し易く、益々シール不良を生じるおそれが増大する。一方、塗布量の分布の均一化をはかるため、疎水性微粒子分散液の濃度を高くし、粘度を高め、塗布し易くすることも考えられるが、この場合、結果的に塗布量が多くなり、付着防止性は良好でも熱封緘性が低下することになる。 On the other hand, in the heat seal portion of the lid material with respect to the container body, the porous layer made of inorganic fine particles becomes a contaminant and inhibits heat sealability. For this reason, the sealing strength is generally lowered, and it is difficult to maintain good sealing properties and required peel strength. In particular, when hydrophobic fine particles are dispersed in a solvent such as ethanol or methanol and applied by a gravure coating method or a spray coating method, dripping easily occurs and it is difficult to uniformly apply the hydrophobic fine particles. For this reason, it is easy to generate a portion where the hydrophobic fine particles are excessively present, and the possibility of causing a sealing failure increases. On the other hand, in order to make the distribution of the coating amount uniform, it is possible to increase the concentration of the hydrophobic fine particle dispersion, increase the viscosity, and make it easier to apply, but in this case, the coating amount increases as a result, Even if the adhesion preventing property is good, the heat sealing property is lowered.
このような難点を払拭するための１つの手段として、熱封緘層自体のシール強度をその組成面で高めに設計し、疎水性微粒子層の介在によるシール強度の低下を補うようにすることが考慮される。しかしながら、このような手段によれば、塗工時に生じることの多い疎水性微粒子の塗布量のばらつきにも起因して、特に塗布量の少ない部分でシール強度が大きくなり過ぎて易剥離性が損なわれるおそれが大である。 As one means for wiping out such difficulties, it is considered that the sealing strength of the heat-sealing layer itself is designed to be high in terms of its composition to compensate for the decrease in sealing strength due to the inclusion of the hydrophobic fine particle layer. Is done. However, according to such means, due to the variation in the amount of hydrophobic fine particles that often occurs during coating, the seal strength becomes too large particularly in a portion where the amount of application is small, and the easy peelability is impaired. There is a great risk of being caught.
一方、塗布量を少なくすることでシール強度の低下を抑制することも当然考慮される。しかしながら、この場合、疎水性微粒子の分散濃度の低い分散液を用いることになるため、乾燥後の微粒子分布において部分的にほとんど微粒子層を有しない部分を生じ易く、結果として、良好な付着防止性能が得られないのみならず、全周に安定した均一な封止強度、耐剥離強度を得難く、シール強度の弱い部分から不本意に内容物が漏出するおそれがあるとか、逆にシール強度の過度に強い部分で蓋材を強く引っ張って開けようとした場合に、内容物が飛び散るおそれがあるなどの問題を生じる。 On the other hand, it is naturally considered that the decrease in the seal strength is suppressed by reducing the coating amount. However, in this case, since a dispersion having a low dispersion concentration of hydrophobic fine particles is used, a portion having almost no fine particle layer is easily formed in the fine particle distribution after drying, and as a result, good adhesion prevention performance Not only can be obtained, it is difficult to obtain a stable and uniform sealing strength and peel strength on the entire circumference, and the contents may leak unintentionally from areas where the sealing strength is weak, or conversely When an attempt is made to open the cover member with an excessively strong portion, the content may scatter.
本発明は、従来技術における上記のような諸問題に鑑み、それらの更なる改善をはかること、具体的には、安定した良好なヒートシール性能を維持しつつ、内容物の付着防止性能に優れ、しかも該付着防止効果を発現する疎水性微粒子の熱封緘層に対する安定付着性を高めて上記内容物付着防止効果の安定持続性を担保しうる新たな改善技術を提供することを目的とする。 In view of the above-described problems in the prior art, the present invention is intended to make further improvements thereof, specifically, while maintaining stable and good heat sealing performance, it is excellent in content adhesion prevention performance. And it aims at providing the new improvement technique which can improve the stable adhesiveness with respect to the heat sealing layer of the hydrophobic fine particle which expresses this adhesion prevention effect, and can ensure the stability persistence of the said content adhesion prevention effect.
本発明は、上記の目的を達成する手段として、先ず内容物付着防止蓋材について次の［１］〜［９］項の手段を提示する。 In order to achieve the above object, the present invention first presents the following means [1] to [9] for the content adhesion preventing lid.
［１］ 少なくとも基材層と熱封緘層とを有する蓋材において、
前記熱封緘層の外面に、高さ１００μｍ以下の多数の微小突起が全面に亘って密に設けられると共に、
この突起を有する前記外面に、付着防止層が形成され、
該付着防止層は、疎水性微粒子からなり、その付着量が０．０５ｇ／ｍ２以上でかつ多くとも前記微小突起の頂端面を僅かに覆う量以下に設定されていることを特徴とする内容物付着防止蓋材。
[1] In a lid having at least a base material layer and a heat sealing layer,
On the outer surface of the heat sealing layer, a large number of microprojections having a height of 100 μm or less are densely provided over the entire surface,
An adhesion preventing layer is formed on the outer surface having the protrusions,
The adhesion preventing layer is made of hydrophobic fine particles, and its adhesion amount is set to 0.05 g / m 2 or more and at most set to an amount that slightly covers the top end surface of the microprotrusions. Material adhesion prevention lid.
［２］前記微小突起は、高さ１μｍ以上、直径（相当直径を含む）５０〜５００μｍであり、かつその配設ピッチが１００〜１０００μｍに設定されている前記［１］に記載の内容物付着防止蓋材。 [2] The content attachment according to [1], wherein the minute protrusion has a height of 1 μm or more, a diameter (including an equivalent diameter) of 50 to 500 μm, and an arrangement pitch of 100 to 1000 μm. Prevention lid material.
［３］前記微小突起は、円柱状または角柱状である前記［１］または［２］に記載の内容物付着防止蓋材。 [3] The content adhesion preventing lid member according to [1] or [2], wherein the minute protrusions are columnar or prismatic.
［４］前記微小突起は、縦断面形状が円錐台または角錐台形状である前記［１］または［２］に記載の内容物付着防止蓋材。 [4] The content adhesion preventing lid member according to [1] or [2], wherein the minute protrusion has a truncated cone shape or a truncated pyramid shape.
［５］前記微小突起は、頂端面が凸球面に形成されている前記［３］または［４］に記載の内容物付着防止蓋材。 [5] The content adhesion preventing lid member according to [3] or [4], wherein the minute protrusion has a top end surface formed into a convex spherical surface.
［６］前記付着防止層は、疎水性微粒子の付着量が、乾燥後重量において１．０ｇ／ｍ２以下に設定されている前記［１］〜［５］のいずれか１項に記載の内容物付着防止蓋材。 [6] The content according to any one of [1] to [5], wherein the adhesion preventing layer has a hydrophobic fine particle adhesion amount set to 1.0 g / m 2 or less in terms of weight after drying. Material adhesion prevention lid.
［７］前記疎水性微粒子は、平均粒径１ｎｍ〜５，０００ｎｍである前記［１］〜［６］のいずれか１項に記載の内容物付着防止蓋材。 [7] The content adhesion preventing lid material according to any one of [1] to [6], wherein the hydrophobic fine particles have an average particle diameter of 1 nm to 5,000 nm.
［８］前記疎水性微粒子が、疎水性シリカである前記［１］〜［７］のいずれか１項に記載の内容物付着防止蓋材。 [8] The content adhesion preventing lid material according to any one of [1] to [7], wherein the hydrophobic fine particles are hydrophobic silica.
［９］前記熱封緘層が、ワックス、及びエチレン−不飽和エステル共重合体を主成分として含むホットメルト樹脂組成物からなる前記［１］〜［８］のいずれか１項に記載の内容物付着防止蓋材。 [9] The content according to any one of [1] to [8], wherein the heat sealing layer is formed of a hot melt resin composition containing a wax and an ethylene-unsaturated ester copolymer as main components. Adhesion prevention lid.
本発明はまた、上記内容物付着防止蓋材の製造方法について、下記［１０］〜［１６］項の手段を提示する。 The present invention also provides means of the following items [10] to [16] for the method for producing the content adhesion preventing lid material.
［１０］少なくとも基材層と熱封緘層とを有する蓋材の前記熱封緘層の外面に高さ１００μｍ以下の多数の微小突起を全面に亘って形成し、
次いで、この微小突起を形成した前記外面に、有機溶媒に疎水性微粒子を分散した分散液を塗布し、
この塗布層の表面側の過剰分散液をドクターナイフで掻き取り除去したのち、乾燥することにより、前記外面に、前記疎水性微粒子からなり、その付着量が０．０５ｇ／ｍ２以上でかつ多くとも前記微小突起の頂端面を僅かに覆う量以下に設定された付着防止層を形成することを特徴とする内容物付着防止蓋材の製造方法。
[10] A large number of microprojections having a height of 100 μm or less are formed over the entire outer surface of the heat sealing layer of the lid member having at least a base material layer and a heat sealing layer,
Next, a dispersion liquid in which hydrophobic fine particles are dispersed in an organic solvent is applied to the outer surface on which the fine protrusions are formed,
The excess dispersion on the surface side of the coating layer is scraped off with a doctor knife and then dried, so that the outer surface is composed of the hydrophobic fine particles, and the adhesion amount is 0.05 g / m 2 or more and much. A method for producing a content adhesion preventing lid material, characterized in that an adhesion preventing layer set to an amount that slightly covers the top end surface of the microprojections is formed.
［１１］前記熱封緘層の外面の微小突起は、該熱封緘層を塗工形成するグラビアロールの表面に微小な対応形状の凹部を形成したグラビアロールを用いて、熱封緘層の塗工工程時に同時形成する前記［１０］に記載の内容物付着防止蓋材の製造方法。 [11] A microprojection on the outer surface of the heat-sealing layer is a step of applying a heat-sealing layer using a gravure roll in which a concave portion having a minute corresponding shape is formed on the surface of the gravure roll on which the heat-sealing layer is formed. The method for producing a content adhesion preventing lid material according to [10], which is sometimes formed at the same time.
［１２］前記微小突起は、高さ１μｍ以上、直径（相当直径を含む）１００〜５００μｍであり、かつその配設ピッチを１００〜１０００μｍに設定する前記［１０］または［１１］に記載の内容物付着防止蓋材の製造方法。 [12] The content according to [10] or [11], wherein the microprojections have a height of 1 μm or more, a diameter (including an equivalent diameter) of 100 to 500 μm, and an arrangement pitch of 100 to 1000 μm. A method for manufacturing an object adhesion prevention lid.
［１３］前記微小突起は、円柱状または角柱状に形成する前記［１０］〜［１２］のいずれか１項に記載の内容物付着防止蓋材の製造方法。 [13] The method for manufacturing a content adhesion preventing lid material according to any one of [10] to [12], wherein the minute protrusions are formed in a columnar shape or a prismatic shape.
［１４］前記微小突起は、縦断面形状が円錐台または角錐台形状である前記［１０］〜［１２］のいずれか１項に記載の内容物付着防止蓋材の製造方法。 [14] The manufacturing method of the content adhesion preventing lid member according to any one of [10] to [12], wherein the minute protrusion has a truncated cone shape or a truncated pyramid shape.
［１５］前記微小突起は、頂端面を凸球面に形成する前記［１３］または［１４］に記載の内容物付着防止蓋材の製造方法。 [15] The method for manufacturing a content adhesion prevention lid member according to [13] or [14], wherein the minute protrusion has a top end surface formed into a convex spherical surface.
［１６］前記乾燥工程を、温度８０〜１４０℃、時間５〜３０秒の乾燥条件で行う前記［１０］〜［１５］のいずれか１項に記載の内容物付着防止蓋材の製造方法。 [16] The method for producing a content adhesion preventing lid material according to any one of [10] to [15], wherein the drying step is performed under drying conditions of a temperature of 80 to 140 ° C. and a time of 5 to 30 seconds.
本発明の前記［１］に記載の構成を有する蓋材は、先ず、その疎水性微粒子からなる付着防止層が、熱封緘層の外面の全面に亘って高さ１００μｍ以下の多数の微小突起が形成された凹凸面に対して、疎水性微粒子を付与することによって形成されたものとなされている。従って、疎水性微粒子の分散液の塗布工程において、上記微小突起により分散液の面上流動、液だれを防止して微粒子分布の均一な付着防止層を容易に形成することができる。即ち、疎水性微粒子の過剰な部分とか、逆に極端に少ない部分等の分布の偏在を効果的に防止できる。しかも、その上で、疎水性微粒子の付着量が少なくとも０．０５ｇ／ｍ２以上のものとなされていることにより、付着防止層を全面に亘って良好な内容物付着防止効果を有するものとなしうる。 In the lid material having the configuration described in [1] of the present invention, first, the adhesion preventing layer made of the hydrophobic fine particles has a large number of minute protrusions having a height of 100 μm or less over the entire outer surface of the heat sealing layer. It is formed by applying hydrophobic fine particles to the formed uneven surface. Therefore, in the step of applying the dispersion of hydrophobic fine particles, the fine protrusions can prevent the dispersion from flowing on the surface and dripping, thereby easily forming an adhesion preventing layer having a uniform fine particle distribution. That is, it is possible to effectively prevent uneven distribution of an excessive portion of the hydrophobic fine particles or an extremely small portion of the reverse. In addition, since the amount of hydrophobic fine particles attached is at least 0.05 g / m 2 or more, the anti-adhesion layer has a good content adhesion preventing effect over the entire surface. sell.
しかも、付着防止層における疎水性微粒子の付着量は、多くても前記のような高さの低い微小突起の頂端面を薄く覆う程度以下のものとなされていることにより、付着防止層は、微小突起の存在する部分において熱封緘層が点状に露出しているかまたは疎水性微粒子層の極めて薄い部分となって、これらの部分が面上に点状に密な分布で存在する。従って、ヒートシール部において疎水性微粒子層が夾雑物となってヒートシール性を大きく阻害するということがなく、シール強度、密封性を良好に維持しうると共に、該シール強度を全周に亘って均一なものとすることができ、ひいては開封時の安定した易剥離性をも向上しうる。一方、付着防止層は、少ない量の疎水性微粒子群で構成されるにも拘わらず、後掲の実施例と比較例との対比によっても判るように、全体に亘って疎水性微粒子が均一に分布したものとなるため、全面に安定した必要かつ十分な程度の内容物付着防止効果を発現せしめ得る。しかも、付着防止層中に点在する微小突起が、蓋材の取扱い時及び使用中における不本意な微粒子の脱落や剥落を防止し、更には外部の干渉物との摩擦による白化痕の発生を防止して、長期に亘り安定した内容物付着防止効果の維持と共に遜色ない外観の維持に貢献する。 In addition, the adhesion amount of the hydrophobic fine particles in the adhesion preventing layer is not more than the extent that it covers the top end surface of the microprojection with a low height as described above at most, so that the adhesion preventing layer has a minute amount. The heat-sealing layer is exposed in the form of dots in the portions where the protrusions are present, or the portions of the hydrophobic fine particle layer are extremely thin, and these portions are present in a dense distribution in the form of dots on the surface. Therefore, the hydrophobic fine particle layer does not become a contaminant in the heat seal portion, and the heat seal performance is not greatly hindered, and the seal strength and the sealability can be maintained well, and the seal strength can be maintained over the entire circumference. It can be made uniform, and as a result, the stable easy peelability at the time of opening can be improved. On the other hand, despite the fact that the anti-adhesion layer is composed of a small amount of hydrophobic fine particle groups, the hydrophobic fine particles are uniformly distributed throughout the whole, as can be seen from the comparison between Examples and Comparative Examples described later. Since it is distributed, the necessary and sufficient content adhesion preventing effect can be expressed on the entire surface. In addition, the minute protrusions scattered in the adhesion preventing layer prevent unintentional fine particles from falling off and peeling off during handling and use of the lid material, and further, whitening marks are generated due to friction with external interferences. This contributes to the maintenance of the appearance that is inferior with the maintenance of the content adhesion prevention effect that is stable over a long period of time.
また、前記［２］〜［５］項に記載の構成は、熱封緘層の外面に形成する微小突起の最も好ましい設計条件を提示するものであり、これらの充足により前記［１］項の効果をより一層良好にかつ確実に達成することができる。 Moreover, the structure of said [2]-[5] item | presents the most preferable design conditions of the microprotrusion formed in the outer surface of a heat sealing layer, The effect of said [1] item | term is satisfy | filled by these satisfaction. Can be achieved even better and reliably.
また、前記［６］項に記載の構成は、微小突起の前記のような好ましい設計条件との対応関係において、疎水性微粒子の好ましい付与量の上限値を提示するものであり、前記［１］項に記載の下限値との組合せによる０．０５〜１．０ｇ／ｍ２の付着量に設定することにより、シール強度の低下が少なくしかも内容物の付着防止効果が良好であるという、両要請を同時にバランス良く調和させた蓋材を提供することができる。 In addition, the configuration described in the above item [6] presents an upper limit value of the preferable amount of the hydrophobic fine particles in the correspondence relationship with the preferable design conditions as described above for the fine protrusions. Both requests that the adhesive strength of 0.05 to 1.0 g / m 2 by the combination with the lower limit value described in the section is set to be low, and the effect of preventing the adhesion of the contents is good. Can be provided at the same time in a balanced manner.
また、前記［７］項に記載の構成では、市場から入手しやすい比較的安価な疎水性微粒子材料を用いて、内容物付着防止効果に優れたものとすることができる。 Further, in the configuration described in [7] above, it is possible to use a relatively inexpensive hydrophobic fine particle material that is easily available from the market and to have an excellent content adhesion preventing effect.
また、前記［８］項に記載のように疎水性微粒子に疎水性シリカと選択使用するときは、愈々市場から入手しやすい安価な材料を用いて、内容物付着防止効果に優れたものとすることができる。 In addition, as described in the above item [8], when the hydrophobic fine particles are selectively used with hydrophobic silica, an inexpensive material easily available from the market is often used, and the content adhesion preventing effect is excellent. be able to.
更にまた、前記［９］項に記載のように、ホットメルト樹脂組成物からなる、熱封緘層を有する蓋材に前記［１］〜［８］項に記載の構成を適用することにより、
それらの作用効果を一層良好に、確実に達成しうる。
Furthermore, as described in the above item [9], by applying the configuration described in the items [1] to [8] to a lid member having a heat sealing layer made of a hot melt resin composition,
These effects can be achieved better and reliably.
本発明はまた、前記［１０］項に記載の製造方法の発明において、熱封緘層の外面の全面に高さの低い微小突起を形成させ、その上に疎水性微粒子分散液をグラビアコート方式やスプレーコート方式等で塗布し、過剰な分散液をドクターナイフで掻き取り除去したのち、乾燥して、前記［１］項に記載のような疎水性微粒子の付着量の少ない付着防止層を形成するものであるから、全面に密に分布する上記微小突起の存在と、塗工後のドクターナイフによる過剰微粒子の掻き取り除去とによって、全面に薄くて均一な付着防止層を形成できる。しかも該付着防止層は、前述のように微小突起が存在する部分において、熱封緘層の樹脂組成物が部分的に点状に露出しているかまたは疎水性微粒子層の極めて薄い部分となって、それらの部分が点状の密な分布で存在することになる。従って、熱封緘層上に別途疎水性微粒子による付着防止層を設けるものでありながらそれがヒートシール性を大きく阻害することがなく、シール強度を、付着防止層を形成しない蓋材に較べてもほとんど低下しない、あるいは低下しても低下率が２０％以下であるような密封性能に優れた蓋材を得ることができる。 The present invention also provides the manufacturing method according to the above item [10], wherein fine protrusions having a low height are formed on the entire outer surface of the heat sealing layer, and a hydrophobic fine particle dispersion is formed on the fine protrusions by a gravure coating method. Apply by spray coating, etc., scrape and remove the excess dispersion with a doctor knife, and then dry to form an adhesion prevention layer with a small amount of hydrophobic fine particles as described in [1] above. Therefore, a thin and uniform anti-adhesion layer can be formed on the entire surface by the presence of the fine protrusions densely distributed over the entire surface and the removal and removal of excess fine particles by a doctor knife after coating. Moreover, in the portion where the microprotrusions are present as described above, the adhesion preventing layer is partially exposed in the form of a dot of the resin composition of the heat sealing layer or becomes an extremely thin portion of the hydrophobic fine particle layer, Those portions exist in a dense dot distribution. Accordingly, although an adhesion preventing layer made of hydrophobic fine particles is separately provided on the heat sealing layer, it does not significantly impair the heat sealing property, and the sealing strength is compared with a lid material that does not form an adhesion preventing layer. It is possible to obtain a lid material excellent in sealing performance that hardly decreases or even if it decreases, the reduction rate is 20% or less.
また、前記［１１］項に記載のような手法で微小突起を形成することにより、蓋材本体への熱封緘層の塗工形成工程において同時に、何ら格別の作業工程を付加することなく微小突起の形成を簡単かつ正確に行うことができ、生産性、製造コストの面で有利である。 Further, by forming the microprotrusions by the method as described in the above item [11], the microprotrusions can be performed at the same time in the heat sealing layer coating forming process on the lid body without adding any special work process. Can be easily and accurately formed, which is advantageous in terms of productivity and manufacturing cost.
また、前記［１２］〜［１５］項に記載のような微小突起の形状、寸法及び配置の設定とすることにより、前記［１０］［１１］項の効果をより一層良好にかつ確実に達成できる。特に前記［１５］項のように、微小突起の頂端面を凸球形のものとする場合には、疎水性微粒子の塗工後ドクターナイフで過剰塗布分を掻き取るに際し、微小突起の頂点で掻き取り量を正確に制限することができるので、愈々疎水性微粒子分布が均一で薄い付着防止層の形成を容易に行うことができる。 In addition, by setting the shape, size, and arrangement of the minute protrusions as described in the above items [12] to [15], the effect of the items [10] and [11] can be achieved more satisfactorily and reliably. it can. In particular, as described in [15] above, when the top end surface of the microprotrusions has a convex spherical shape, when the excess coating is scraped off with a doctor knife after applying the hydrophobic fine particles, the tops of the microprotrusions are scraped. Since the amount taken can be accurately limited, it is possible to easily form a thin anti-adhesion layer with a uniform hydrophobic fine particle distribution.
更にまた、前記［１６］項に記載の乾燥条件を採用することにより、疎水性微粒子に最も有利な疎水性シリカを用いる場合にあっても、それのもつ疎水性、撥水性を損なうことなく、残存塗層を短時間で能率良く乾燥させることができる。 Furthermore, by adopting the drying conditions described in the above item [16], even when using the most advantageous hydrophobic silica for the hydrophobic fine particles, without impairing its hydrophobicity and water repellency, The remaining coating layer can be efficiently dried in a short time.
図１は、本発明に係る内容物付着防止蓋材の積層構成の一例を示す。該蓋材は、基材フィルム層（２）と金属箔層（３）との積層からなる基材層（１）と、該基材層（１）の金属箔（３）側の外面、即ち施蓋使用時に容器本体の内部に向く側の面に中間樹脂層（４）を介して熱封緘層（５）が設けられている。上記の積層構成は従来の蓋材のそれと同様であり、基材層（１）と熱封緘層（５）とを含む積層体をここでは「蓋材本体」と呼称することとする。 FIG. 1 shows an example of a laminated structure of a content adhesion preventing lid according to the present invention. The lid material includes a base material layer (1) composed of a laminate of a base film layer (2) and a metal foil layer (3), and an outer surface of the base material layer (1) on the metal foil (3) side, A heat sealing layer (5) is provided on the surface facing the inside of the container body when the lid is used via an intermediate resin layer (4). The above laminated structure is the same as that of the conventional lid, and the laminated body including the base material layer (1) and the heat sealing layer (5) will be referred to as a “lid body” here.
本発明に係る内容物付着防止蓋材は、上記蓋材本体の熱封緘層（５）の外面に、更に付加的に付着防止層（６）を有する。 The content adhesion prevention lid according to the present invention further has an adhesion prevention layer (6) on the outer surface of the heat sealing layer (5) of the lid body.
基材フィルム層（２）は、包装容器の表側に配置されるもので、その材料としては、ポリエステル、ポリエチレン、ポリプロピレン、ポリアミド、ポリカーボネート、ポリ塩化ビニル、セルロースアセテート、セロハンなどの単層または複合フィルム、あるいはこれらのフィルムを紙などにラミネートしたものなどを例示することができる。基材フィルム層（２）は通常適宜印刷（７）が施されて意匠性が付与される。 The base film layer (2) is disposed on the front side of the packaging container, and the material thereof is a single layer or composite film such as polyester, polyethylene, polypropylene, polyamide, polycarbonate, polyvinyl chloride, cellulose acetate, cellophane, etc. Or what laminated these films on paper etc. can be illustrated. The base film layer (2) is usually appropriately printed (7) to impart design properties.
金属箔層（３）は、ガスバリヤ性、遮光性などを付与するものであり、多くはアルミニウム箔が用いられる。特にヨーグルトの容器用の蓋材にあっては、遮光性、軽量性を満足するものとして厚さ５〜５０μｍ程度のアルミニウム箔が好適に用いられる。また、基材フィルム層（２）との積層接着には一般的な接着剤が用いられる。 The metal foil layer (3) imparts gas barrier properties, light shielding properties, etc., and aluminum foil is often used. In particular, in the case of a lid for a yogurt container, an aluminum foil having a thickness of about 5 to 50 μm is preferably used in order to satisfy light shielding properties and light weight. Moreover, a general adhesive agent is used for lamination | stacking adhesion | attachment with a base film layer (2).
なお、基材層（１）として、金属箔層（３）を使用せずに、シリカやアルミナ等の金属を基材フィルム層（２）に蒸着した金属蒸着フィルムを使用することも可能である。 In addition, as a base material layer (1), it is also possible to use the metal vapor deposition film which vapor-deposited metals, such as a silica and an alumina, to the base film layer (2), without using a metal foil layer (3). .
中間樹脂層（４）は、基材層（１）と熱封緘層（５）との間に介在して、蓋材に所定の剛性やヒートシール時のクッション性を付与するものであり、適宜必要に応じて設けられる。一般的には厚さ５〜４０μｍのポリエチレン、ポリプロピレン、エチレン（メタ）アクリル酸共重合体、エチレン（メタ）アクリル酸エステル共重合体等のオレフィン樹脂、ポリアミド、ポリエステル、ポリカーボネート、ポリ塩化ビニル等が用いられる。 The intermediate resin layer (4) is interposed between the base material layer (1) and the heat sealing layer (5), and imparts a predetermined rigidity and cushioning property at the time of heat sealing to the lid material. Provided as needed. Generally, olefin resin such as polyethylene, polypropylene, ethylene (meth) acrylic acid copolymer, ethylene (meth) acrylic acid ester copolymer, polyamide, polyester, polycarbonate, polyvinyl chloride, etc. having a thickness of 5 to 40 μm Used.
熱封緘層（５）は、中間樹脂層（４）および容器側との接着性が良好なものであれば、その材料は、特に限定されない。例えば、ホットメルト接着剤のほか、ラッカータイプ接着剤あるいは公知のシーラントフィルムを用いることもできる。特にヨーグルト包装用容器の蓋材にあっては、ホットメルト接着剤を用いるのが一般的であり、なかでもワックスと、エチレン−不飽和エステル共重合体とを主成分として含み、上記エチレン−不飽和エステル共重合体を３０重量％以上の割合で含むホットメルト樹脂組成物からなるものを用いるのが好適である。その理由は、後述の方法による付着防止層の形成において、疎水性微粒子の付着安定性を良好なものとなし得て、熱封緘層（５）に対する付着防止層（６）の密着性を良好なものとなし得ることによる。また、熱封緘層の厚みは特に限定されるものではないが、コスト、密封性、生産性等の点から、微小突起（８）を除く部分において厚さ３〜１００μｍ程度とするのが一般的であり、好適には、１０〜５０μｍの範囲とするのが良い。 The material of the heat sealing layer (5) is not particularly limited as long as it has good adhesion to the intermediate resin layer (4) and the container side. For example, besides a hot melt adhesive, a lacquer type adhesive or a known sealant film can also be used. In particular, a hot melt adhesive is generally used for a lid for a container for yogurt packaging, and includes a wax and an ethylene-unsaturated ester copolymer as main components, and the ethylene-unsaturated material. It is preferable to use a hot melt resin composition containing a saturated ester copolymer in a proportion of 30% by weight or more. The reason is that in the formation of the adhesion preventing layer by the method described later, the adhesion stability of the hydrophobic fine particles can be made good, and the adhesion of the adhesion preventing layer (6) to the heat sealing layer (5) is good. By what can be done. The thickness of the heat sealing layer is not particularly limited, but it is generally set to about 3 to 100 μm in the portion excluding the minute projections (8) from the viewpoint of cost, sealing performance, productivity, and the like. Preferably, the range is 10 to 50 μm.
ところで、本発明はその実施において、先ず重要なことの１つとして、図１に示すように、上記熱封緘層（５）の外面の全面に、高さの低い多数の微小突起（８）を、望ましくは縦横に規則的な配列状態で、密に設けたものとなされる。 By the way, in the practice of the present invention, as one of the first important matters, as shown in FIG. 1, a large number of small protrusions (8) having a low height are formed on the entire outer surface of the heat sealing layer (5). Preferably, they are densely arranged in a regular arrangement in the vertical and horizontal directions.
この微小突起（８）の形状は、特に限定されるものではないが、シール強度の確実な確保の上から、円柱状または角柱状のものとすることが最も好ましいが、外周面に若干のテーパーないし傾斜を付与した円錐台または角錐台の縦断面形状を有するものとしても良い。その他円錐形、角錐形のものであっても良い。更には、不規則、不定型な凸部形状によるものであっても良い。 The shape of the microprotrusions (8) is not particularly limited, but is most preferably cylindrical or prismatic in order to ensure the sealing strength, but the outer peripheral surface is slightly tapered. Or it is good also as what has the longitudinal cross-sectional shape of the truncated cone or the truncated pyramid which provided the inclination. Other cones and pyramids may also be used. Furthermore, it may be an irregular or irregular convex shape.
また、微小突起（８）の頂端面は、後述のドクターナイフによる掻き取り作業の円滑な遂行及び残存微粒子量の正確な制御のために、上方に円弧状をなす凸球面に形成したものとすることが好ましい。 Further, the top end surface of the microprojection (8) is formed as a convex spherical surface having an arc shape upward in order to smoothly perform a scraping operation with a doctor knife described later and to accurately control the amount of remaining fine particles. It is preferable.
また、この微小突起（８）の寸法設定、配置設定は、図３に示すように高さＨにおいて最大高さＨを１００μｍ以下とすることを必須とすることのほか、最低高さＨを１μｍ以上とし、直径Ｄを５０〜５００μｍ、配設ピッチＰを１００〜１０００μｍに設定することが望ましい。 In addition, as shown in FIG. 3, in setting the dimensions and arrangement of the micro-projections (8), it is essential that the maximum height H is 100 μm or less at the height H, and the minimum height H is 1 μm. It is preferable to set the diameter D to 50 to 500 μm and the arrangement pitch P to 100 to 1000 μm.
尚、微小突起（８）の「直径」は、突起形状が断面円形以外の多角形等である場合、４Ａ／Ｌ（Ａ：断面積、Ｌ：断面長）で定義される「相当直径」を含むものとする。 The “diameter” of the microprotrusion (8) is an “equivalent diameter” defined by 4 A / L (A: cross-sectional area, L: cross-sectional length) when the shape of the protrusion is a polygon other than a circular cross section. Shall be included.
微小突起（８）の高さＨが１００μｍを超える高いものとすると、疎水性微粒子の少量の付着量のもとで十分な付着防止効果を得ることができない。逆に、１μｍ未満の低すぎるものであるときは、疎水性微粒子の塗布量（付着量）の均一化をはかり難いだけでなく、良好なシール性の確保も困難なものとなり、本発明の効果を満足に達成することができない。本発明の実施における微小突起（８）の好ましい高さＨは、概ね３０〜８０μｍの範囲である。 If the height H of the microprotrusions (8) is higher than 100 μm, a sufficient adhesion preventing effect cannot be obtained under a small amount of hydrophobic fine particles. On the other hand, if it is too low, less than 1 μm, it is difficult not only to make the coating amount (adhesion amount) of the hydrophobic fine particles uniform, but also it is difficult to ensure good sealing properties. Can not be achieved satisfactorily. The preferred height H of the microprotrusions (8) in the practice of the present invention is generally in the range of 30-80 μm.
また、微小突起（８）の直径Ｄは、該突起（８）の最大径を有する部分の直径として定義されるものであり、これが５０μｍ未満の突起はその形成が困難である。 Further, the diameter D of the fine protrusion (8) is defined as the diameter of the portion having the maximum diameter of the protrusion (8), and it is difficult to form a protrusion having a diameter of less than 50 μm.
逆に、直径が５００μｍを超える太さの大きいものとするときは、概して全面に均一な付着防止効果を達成することが困難になる。本発明の実施における好ましい直径Ｄの範囲は、概ね１００〜３００μｍである。 On the contrary, when the diameter is larger than 500 μm, it is generally difficult to achieve a uniform adhesion preventing effect on the entire surface. A preferable range of the diameter D in the practice of the present invention is approximately 100 to 300 μm.
更にまた、微小突起（８）の配設ピッチＰ、即ち隣接する突起同士の中心間距離は、これが１００μｍ未満では良好な付着防止効果を達成することができず、逆に１０００μｍを超えるときは、良好なシール性、シール強度の確保が困難になる。好ましい配設ピッチＰの範囲は、概ね２００〜４５０μｍである。 Furthermore, when the arrangement pitch P of the fine protrusions (8), that is, the distance between the centers of adjacent protrusions is less than 100 μm, a good adhesion preventing effect cannot be achieved, and conversely when it exceeds 1000 μm, It becomes difficult to ensure good sealing performance and sealing strength. A preferable range of the arrangement pitch P is approximately 200 to 450 μm.
熱封緘層（５）の外面への上記微小突起（８）の形成手段は、本発明において特に限定されるものではないが、熱封緘層（５）の形成を上記のようなホットメルト樹脂組成物を用いたグラビアコート方式での塗工によって行うものとし、その際、図２に示すように、グラビアロール（１０）としてその外周面に上記微小突起（８）の形状と配置に対応した多数の微小凹部（１０ａ）を彫刻したものを用いることによって、熱封緘層（５）の塗工形成と同時にその表面に微小突起（８）を形成せしめるものとするのが最も有利である。その他の微小突起（８）の形成手段としては、例えば熱封緘層（５）の形成後に、別途、微小凹部を有する型押しロールあるいはプレス金型を用いて、熱プレス成形する方法を採用しても良い。 The means for forming the microprotrusions (8) on the outer surface of the heat sealing layer (5) is not particularly limited in the present invention, but the formation of the heat sealing layer (5) may be performed as described above. In this case, as shown in FIG. 2, many gravure rolls (10) corresponding to the shape and arrangement of the fine protrusions (8) are formed on the outer peripheral surface. It is most advantageous to form a microprotrusion (8) on the surface of the heat-sealing layer (5) at the same time as the application of the heat-sealing layer (5) by using a sculpture of the microrecesses (10a). As another means for forming the microprotrusions (8), for example, after the heat sealing layer (5) is formed, a method of separately performing hot press molding using a press roll or press mold having micro concave portions is employed. Also good.
本発明の実施において、もう１つの重要な事項の１つは、微小突起（８）を全面に形成した上記熱封緘層（５）の外面に、更に別途、所定範囲の少量の疎水性微粒子からなる厚さが薄くて均一な、付着防止層（６）を形成することである。 In the practice of the present invention, another important matter is that, on the outer surface of the heat sealing layer (5) having the fine protrusions (8) formed on the entire surface, a small amount of hydrophobic fine particles in a predetermined range are separately provided. This is to form an adhesion prevention layer (6) that is thin and uniform.
具体的には、付着防止層（６）における疎水性微粒子の付着量（残存塗布量）を０．０５ｇ／ｍ２以上に設定すると共に、多くとも前記微小突起（８）の頂端面を薄く僅かに覆う程度の量以下に設定することである。このような付着量の上限を数値で表せば、概ね１．０ｇ／ｍ２である。疎水性微粒子の付着量が上記の下限値０．０５ｇ／ｍ２未満であると、良好な内容物付着防止効果を得ることができない。逆にそれらが上限値の１．０ｇ／ｍ２を超えるときは、内容物付着防止効果に優れるものの、付着防止層（６）が熱封緘層（５）のヒートシール性を阻害し、具体的には付着防止層（６）を有しない場合に較べてシール強度（耐剥離強度）が２０％以上も低下し、安定した良好な容器の密封性が損なわれるおそれがある。 Specifically, the adhesion amount (remaining coating amount) of the hydrophobic fine particles in the adhesion preventing layer (6) is set to 0.05 g / m 2 or more, and at the most, the top end surface of the microprojections (8) is thin and slightly thin. It is to set below the quantity of the extent which covers. If the upper limit of such an adhesion amount is expressed by a numerical value, it is approximately 1.0 g / m 2 . When the adhesion amount of the hydrophobic fine particles is less than the above lower limit of 0.05 g / m 2 , a good content adhesion preventing effect cannot be obtained. On the contrary, when they exceed the upper limit of 1.0 g / m 2 , although the content adhesion preventing effect is excellent, the adhesion preventing layer (6) hinders the heat sealing property of the heat sealing layer (5), specifically The seal strength (peeling resistance) is reduced by 20% or more as compared with the case where the anti-adhesion layer (6) is not provided, and there is a possibility that the stable and good sealing performance of the container is impaired.
上記の付着防止層（６）を構成する疎水性微粒子は、蓋材の内容物付着防止性能の支配的役割を担うものであり、２０ｍＮ／ｍ以上の表面エネルギーを有する疎水性物質からなるものであればその材料は特に限定されない。具体的に例示すれば、疎水性のシリカ、アルミナ、酸化カルシウム、炭酸カルシウム、硫酸カルシウム、ケイ酸カルシウム等を挙げることができる。なかでも、疎水性能、コスト、超微粒子材料の市場からの入手のし易さ等の観点から、疎水性シリカやアルミナの使用が好適である。 The hydrophobic fine particles constituting the adhesion preventing layer (6) play a dominant role in the content adhesion preventing performance of the lid, and are made of a hydrophobic substance having a surface energy of 20 mN / m or more. If there is, the material is not particularly limited. Specific examples include hydrophobic silica, alumina, calcium oxide, calcium carbonate, calcium sulfate, calcium silicate, and the like. Of these, the use of hydrophobic silica or alumina is preferred from the viewpoint of hydrophobic performance, cost, availability of ultrafine particle materials from the market, and the like.
疎水性微粒子の一次粒子における平均粒径は、１〜５，０００ｎｍの範囲のものを用いるべきである。平均粒径１ｎｍの未満の超微粒子は、市場からの入手が困難であり、またコストの面からも不利である。他方、平均粒径５，０００ｎｍを超えるものでは、ヒートシール性を阻害するおそれが増大すると共に、付着防止効果が低下するおそれがあるため不適である。好ましい平均直径は３〜３０００ｎｍ、特に好ましくは３〜１０００ｎｍの範囲である。 The average particle diameter of primary particles of hydrophobic fine particles should be in the range of 1 to 5,000 nm. Ultrafine particles having an average particle size of less than 1 nm are difficult to obtain from the market and are disadvantageous in terms of cost. On the other hand, if the average particle size exceeds 5,000 nm, the risk of hindering heat sealability increases, and the adhesion preventing effect may be reduced, which is not suitable. A preferred average diameter is in the range of 3 to 3000 nm, particularly preferably 3 to 1000 nm.
本発明に係る蓋材の製造において、上記付着防止層（６）の形成方法もまた、蓋材の内容物付着防止性能、及びヒートシール性に重大な影響をもつ。 In the production of the lid according to the present invention, the method for forming the adhesion preventing layer (6) also has a significant influence on the contents adhesion preventing performance and heat sealability of the lid.
本発明による蓋材の製造方法において、付着防止層（６）の形成は、微小突起（８）を形成した熱封緘層（５）の外面への疎水性微粒子の適正量の塗工（塗布）と乾燥のみによって行うものとしても良いが、好適な方法としては、疎水性微粒子の過剰量の塗工（塗布）、その直後のドクターナイフによる過剰な疎水性微粒子の掻き取り除去、そして最後に乾燥の各工程の順次実施によって行うものとする。 In the method for producing a lid material according to the present invention, the adhesion preventing layer (6) is formed by applying (applying) an appropriate amount of hydrophobic fine particles to the outer surface of the heat sealing layer (5) on which the fine protrusions (8) are formed. However, the preferred method is to apply an excessive amount of hydrophobic fine particles (coating), remove the excess hydrophobic fine particles with a doctor knife immediately after that, and finally dry. It shall be performed by carrying out each of these steps sequentially.
次に、これらの各工程の詳細について説明する。 Next, details of each of these steps will be described.
［疎水性微粒子の塗工］
先ず、有機溶媒中に所定濃度に疎水性微粒子を分散した分散液を調製し、これを蓋材本体における熱封緘層（５）の外面の多数の微小突起（８）を有する面に塗布する。
[Coating of hydrophobic fine particles]
First, a dispersion in which hydrophobic fine particles are dispersed in a predetermined concentration in an organic solvent is prepared, and this is applied to the surface having a large number of microprojections (8) on the outer surface of the heat sealing layer (5) in the lid body.
分散液の調製に用いる溶媒は、下地の熱封緘層（５）に対する疎水性微粒子の定着性、付着性を確保するために有機溶媒を用いるべきであり、特に極性基を有する有機溶媒を用いるのが好ましい。なかでもアルコール類の使用が好適であり、特にコスト、安全性、撥水性の発現効果等の面からエタノールやメタノールの使用が好適である。 The solvent used for the preparation of the dispersion should be an organic solvent in order to ensure the fixability and adhesion of the hydrophobic fine particles to the underlying heat-sealing layer (5). In particular, an organic solvent having a polar group is used. Is preferred. Of these, the use of alcohols is preferred, and ethanol and methanol are particularly preferred from the standpoints of cost, safety, water repellency and the like.
分散液中の微粒子の分散濃度は、採用する塗工手段との関係を考慮して、２〜１０％程度の範囲で任意に設定しうるが、好適な分散濃度は概ね３〜６％程度である。 The dispersion concentration of the fine particles in the dispersion can be arbitrarily set in the range of about 2 to 10% in consideration of the relationship with the coating means to be employed, but the preferable dispersion concentration is about 3 to 6%. is there.
分散液の塗工手段は、公知の任意の方法を採用しうる。例えばグラビアコート法、吹き付け、バーコート法等を任意に採用しうる。 Any known method can be adopted as means for applying the dispersion. For example, a gravure coating method, spraying, a bar coating method, etc. can be arbitrarily adopted.
ここに重要なことは、分散液の実質的な塗布量である。即ち、塗布後の分散液に含まれる疎水性微粒子の乾燥後重量が、付着防止層（６）に求める付着量を超えるような過剰な量として塗布すべきである。次工程のドクターナイフによる過剰微粒子の掻き取り除去によって、全面に薄くて微粒子分布の均一な付着防止層（６）を確実に形成せしめるものとするためである。このような塗工工程時における分散液の塗布量は、固形分量すなわち分散液に含まれる疎水性微粒子の重量において概ね０．１〜１．２ｇ／ｍ２の範囲に設定すべきである。 What is important here is a substantial coating amount of the dispersion. That is, it should be applied in an excessive amount such that the weight after drying of the hydrophobic fine particles contained in the dispersion liquid after application exceeds the adhesion amount required for the adhesion preventing layer (6). This is because, by removing the excessive fine particles with a doctor knife in the next step, an adhesion prevention layer (6) that is thin and has a uniform fine particle distribution can be surely formed on the entire surface. The coating amount of the dispersion during such a coating process should be set in a range of about 0.1 to 1.2 g / m 2 in terms of the solid content, that is, the weight of the hydrophobic fine particles contained in the dispersion.
［ドクターナイフによる掻き取り］
上記分散液の塗工後、なるべくその直後において、図４に示すように塗布層（６ａ）の面上にゴム製等の柔軟なドクターナイフ（１２）を軽く押し当てるようにしながら該面を摺擦し、塗布層（６ａ）の面を平坦に均すと共に、過剰に塗布された分散液を掻き取り除去する。ここに、ドクターナイフ（１２）の刃先の設定位置の調節、即ち微小突起（８）の頂端面との間の距離の調節により、残存分散液の量を自在にコントロールすることができる。従って、形成しようとする付着防止層（６）の疎水性微粒子の付着量の設計標準値に対応してそれを任意に調節する。
[Scraping with a doctor knife]
As soon as possible after application of the dispersion, the surface is slid while gently pressing a soft doctor knife (12) made of rubber or the like on the surface of the coating layer (6a) as shown in FIG. By rubbing, the surface of the coating layer (6a) is flattened, and the excessively applied dispersion is scraped off and removed. Here, the amount of the remaining dispersion can be freely controlled by adjusting the setting position of the cutting edge of the doctor knife (12), that is, adjusting the distance from the top end surface of the microprojection (8). Therefore, it is arbitrarily adjusted according to the design standard value of the adhesion amount of the hydrophobic fine particles of the adhesion preventing layer (6) to be formed.
［乾燥］
次いで、上記の分散液の塗工及び掻き取り除去工程後、蓋材本体を乾燥工程に供し、分散液中の有機溶媒を揮散させて、所期する付着防止層（６）を形成する。この乾燥は自然乾燥で行っても良いが、作業効率及び疎水性微粒子（１０）の定着性の向上のためには強制的な加熱乾燥で行うことが望ましい。このときの加熱条件は特に限定されるものではないが、温度８０〜１４０℃、好ましくは１００〜１２０℃、時間５〜３０秒、好ましくは１０〜２０秒程度に設定すべきである。温度が上記下限値８０℃より低いと乾燥工程に時間がかかり、時間が５秒未満では乾燥が不十分なものとなり、その後の取扱いにおいて付着防止層の部分的剥離や脱落を生じ易い。反面、乾燥温度を１４０℃を超える高い温度に設定したり、あるいは時間を３０秒を超える時間に設定すると、殊に疎水性微粒子に疎水性シリカを用いている場合、それがもつ疎水性、撥水性が損なわれるおそれがある。
[Dry]
Next, after the above-described dispersion liquid coating and scraping removal process, the lid body is subjected to a drying process, and the organic solvent in the dispersion liquid is volatilized to form the desired anti-adhesion layer (6). Although this drying may be performed by natural drying, it is desirable to perform by forced heating drying in order to improve work efficiency and fixability of the hydrophobic fine particles (10). The heating conditions at this time are not particularly limited, but should be set to a temperature of 80 to 140 ° C., preferably 100 to 120 ° C., a time of 5 to 30 seconds, and preferably about 10 to 20 seconds. If the temperature is lower than the lower limit of 80 ° C., the drying process takes time, and if the time is less than 5 seconds, the drying becomes insufficient, and the adhesion preventing layer is likely to be partially peeled off or dropped during subsequent handling. On the other hand, when the drying temperature is set to a high temperature exceeding 140 ° C., or the time is set to a time exceeding 30 seconds, especially when hydrophobic silica is used for the hydrophobic fine particles, the hydrophobicity and repellent property of the hydrophobic fine particles. There is a risk that the aqueous properties may be impaired.
上記の乾燥工程により、塗工分散液中に含まれる溶媒のアルコール類は蒸発し、除去されるので、残留する疎水性微粒子によって形成される付着防止層（６）は、微小突起（８）による凹凸面に沿った形で表面凹凸状に形成される。しかも微視的には、隣接する微小突起（８）（８）間の谷部ないし凹部において厚さが厚く、微小突起（８）部分において相対的に薄い層として形成される。 By the above drying step, the alcohols of the solvent contained in the coating dispersion are evaporated and removed, so that the adhesion preventing layer (6) formed by the remaining hydrophobic fine particles is formed by the fine protrusions (8). Surface irregularities are formed along the irregular surface. In addition, microscopically, it is formed as a relatively thin layer in the valley or recess between the adjacent microprotrusions (8) and (8) and is relatively thin in the microprotrusion (8).
更にまた、上記により形成された付着防止層（６）は、熱封緘層（５）の表面に接触している下層部分の疎水性微粒子が該熱封緘層に付着一体化して定着している一方、層（６）の全体が微小突起（８）による拘束作用を受けて成層状態を安定に保持したものとなる。このため疎水性粒子の不本意な脱落、剥落のおそれが少なく、良好な密着性を保有する付着防止層（６）が形成される。 Furthermore, in the adhesion preventing layer (6) formed as described above, the hydrophobic fine particles in the lower layer part in contact with the surface of the heat sealing layer (5) are adhered and integrated to the heat sealing layer and fixed. The entire layer (6) is subjected to the restraining action by the microprotrusions (8) and stably maintains the stratified state. For this reason, there is little possibility of unintentional dropping and peeling of hydrophobic particles, and an adhesion preventing layer (6) having good adhesion is formed.
次に、本発明の効果を確認するために、その各種の実施例を比較例との対比において示す。 Next, in order to confirm the effect of the present invention, various examples will be shown in comparison with comparative examples.
（蓋材本体の作製）
基材フィルム（２）として厚さ１２μｍのポリエチレンテレフタレートフィルムを用い、その片面に厚さ３０μｍのアルミニウム箔（３）をポリウレタン系ドライラミネート接着剤により貼合わせ、基材層（１）とした。
(Preparation of lid body)
A polyethylene terephthalate film having a thickness of 12 μm was used as the substrate film (2), and an aluminum foil (3) having a thickness of 30 μm was bonded to one surface thereof with a polyurethane-based dry laminate adhesive to obtain a substrate layer (1).
次に、上記基材層（１）のアルミニウム箔（３）側の表面に上記同様の接着剤により、厚さ２０μｍのポリエチレンフィルムを積層接着して中間樹脂層（４）を形成し、更にその外側にグラビアコート法により熱封緘層（５）を形成した。これによって得られた基材層（１）／中間樹脂層（４）／熱封緘層（５）の積層体をもって蓋材本体とした。 Next, an intermediate resin layer (4) is formed by laminating and bonding a 20 μm thick polyethylene film to the surface of the base material layer (1) on the aluminum foil (3) side using the same adhesive as described above. A heat sealing layer (5) was formed on the outside by a gravure coating method. The laminate of the base material layer (1) / intermediate resin layer (4) / heat sealing layer (5) obtained in this way was used as the lid body.
ここに、上記熱封緘層（５）としては、ワックス：４０重量部、エチレン-酢酸ビニル共重合体：５４重量部、ロジン：５重量部、シリコンオイル：１重量部、からなる組成のホットメルト樹脂組成物を用い、塗布量１８ｇ／ｍ２の割合でグラビアコート法により塗工形成するものとした。 Here, as the heat sealing layer (5), a hot melt having a composition comprising wax: 40 parts by weight, ethylene-vinyl acetate copolymer: 54 parts by weight, rosin: 5 parts by weight, and silicon oil: 1 part by weight. The resin composition was used and applied by gravure coating at a coating rate of 18 g / m 2 .
また、実施例の各種試料のものについては、上記グラビアコート法による塗工に用いるグラビアロールに、下記の微小突起の各種設計仕様に対応した凹刻部を外周面の全面に設けたものを使用し、それによって熱封緘層（５）の形成と同時にその外面に、高さＨと直径Ｄ及び配設ピッチＰを互いに異にした下記Ｉ、II、III、IVの４種類の短円柱状微小突起（８）を形成するものとした。
Ｉ： Ｈ３０μｍ×Ｄ２００μｍ×Ｐ３００μｍ
II： Ｈ５０μｍ×Ｄ１００μｍ×Ｐ２００μｍ
III： Ｈ８０μｍ×Ｄ３００μｍ×Ｐ４５０μｍ
IV： Ｈ１５０μｍ×Ｄ１，０００μｍ×Ｐ１，５００μｍ
Also, for the various samples of the examples, the gravure roll used for coating by the above gravure coating method uses a concave portion corresponding to various design specifications of the following microprotrusions provided on the entire outer peripheral surface. Thus, at the same time as the formation of the heat-sealing layer (5), the following four types of short cylindrical micros of I, II, III, and IV having different heights H, diameters D and arrangement pitches P are provided on the outer surface. A protrusion (8) was formed.
I: H30 μm × D200 μm × P300 μm
II: H50 μm × D100 μm × P200 μm
III: H80μm × D300μm × P450μm
IV: H 150 μm × D 1,000 μm × P 1,500 μm
（疎水性微粒子の塗工）
疎水性微粒子として、下記Ａ，Ｂの２種類を用意した。
Ａ：疎水性シリカ 一次粒子平均粒径 ７ｎｍ
（商品名：アロエジルＲ８１２Ｓ）
Ｂ：疎水性シリカ 平均粒径 ３０００ｎｍ
（商品名：サイロホービック１００）
(Coating of hydrophobic fine particles)
The following two types A and B were prepared as hydrophobic fine particles.
A: Hydrophobic silica Primary particle
(Product name: Aloe Gil R812S)
B: Hydrophobic silica average particle diameter 3000 nm
(Product name: Silo Hovic 100)
そして、上記Ａ，Ｂの各疎水性シリカを、エタノール溶媒及びメタノール溶媒の各有機溶媒中に表１に示す分散濃度で分散させて各種の分散液を調製した。 Then, each of the hydrophobic silicas A and B was dispersed in the organic solvents such as ethanol solvent and methanol solvent at the dispersion concentrations shown in Table 1 to prepare various dispersions.
次いで、これらの各種分散液を、蓋材本体の前記熱封緘層（５）の外面にスプレーコート法により表１に示す各種の塗布量のもとに塗布した。表１に示す分散液の塗布量は、いずれも分散液中に含まれる疎水性微粒子の重量をもって示すものである。 Next, these various dispersions were applied to the outer surface of the heat sealing layer (5) of the lid body by the spray coating method under various application amounts shown in Table 1. The coating amount of the dispersion shown in Table 1 is shown by the weight of the hydrophobic fine particles contained in the dispersion.
（塗膜の均整処理：ドクターナイフによる掻き取り）
上記分散液の塗布直後に、塗工工程の一貫として、塗布層の表面にドクターナイフを当接させこれを相対移動させることにより、塗布層の表面部の過剰な分散液を掻き取り除去すると共に、塗布層の表面を平坦状に均して、分散液が所期する厚みで残存した塗工済シートを得た。
(Coating of the coating film: scraping with a doctor knife)
Immediately after the application of the dispersion, as a part of the coating process, a doctor knife is brought into contact with the surface of the coating layer and moved relatively to scrape and remove the excess dispersion on the surface of the coating layer. Then, the surface of the coating layer was leveled to obtain a coated sheet that remained with the desired thickness of the dispersion.
（乾燥）
次いで、上記塗工済みシートを表１に示す乾燥条件で強制乾燥し、熱封緘層（５）上に疎水性微粒子が表１に示すような付着量で残存付着した内容物付着防止層（６）を形成した。
(Dry)
Next, the coated sheet was forcibly dried under the drying conditions shown in Table 1, and the content adhesion preventing layer (6) in which hydrophobic fine particles remained on the heat-sealing layer (5) in an adhesion amount as shown in Table 1. ) Was formed.
尚、表1に示す各種の試料中、実施例及び比較例のNo．１〜５は前記Ｉの微小突起を形成したものである。同様にNo．９〜１１はIIの微小突起を、No．１４〜１６はIIIの微小突起を、比較例のNo．６〜８はIVの微小突起を形成したものであり、比較例のNo．１２，１３は微小突起を有しない熱封緘層面上に付着防止層を形成したものである。 Of the various samples shown in Table 1, Nos. Of Examples and Comparative Examples. 1 to 5 are formed with the I minute protrusions. Similarly, no. Nos. 9 to 11 are II microprotrusions. Nos. 14 to 16 are III microprotrusions, No. Nos. 6 to 8 were formed with IV microprotrusions. Nos. 12 and 13 are formed by forming an adhesion preventing layer on the surface of the heat sealing layer having no microprotrusions.
以上により、表１に示す実施例及び比較例の各種試料を得た。そして、各試料について下記の評価試験を行った。結果を図1に併記する。 Thus, various samples of Examples and Comparative Examples shown in Table 1 were obtained. And the following evaluation test was done about each sample. The results are also shown in FIG.
（評価試験）
（１）付着防止性能
各試料Ｎｏ．１〜１５の蓋材の裏面、即ち付着防止層の外面上に、アロエヨーグルト（森永乳業株式会社製 商標「森永アロエヨーグルト」）を約０．５ｃｃの液滴として滴下し、試料をゆっくりと傾けたときに上記液滴が「転がりはじめたときの傾斜角度」を測定して、次の基準で判定評価した。
(Evaluation test)
(1) Anti-adhesion performance Each sample No. Aloe yogurt (Trademark “Morinaga Aloe Yogurt” manufactured by Morinaga Milk Industry Co., Ltd.) is dropped on the back of the lid material 1-15, that is, on the outer surface of the anti-adhesion layer, and the sample is slowly tilted. When the above-mentioned droplet was measured, the “inclination angle when it started to roll” was measured and evaluated according to the following criteria.
◎・・・３０度以下
○・・・３１度以上６０度以下
△・・・６１度以上９０度以下
×・・・９０度以上
◎ ・ ・ ・ 30 degrees or less ○ ・ ・ ・ 31 degrees or more and 60 degrees or less △ ・ ・ ・ 61 degrees or more and 90 degrees or less × ・ ・ ・ 90 degrees or more
（２）シール性
試料Ｎｏ．１〜１５の蓋材を、１２０〜１８０℃×０．２ＭＰａ×１．０ｓｅｃの熱圧シール条件で容器本体（紙／ポリエチレン製容器）のフランジ面上にヒートシールした。
(2) Sealability Sample No. 1-15 cover materials were heat-sealed on the flange surface of a container main body (paper / polyethylene container) under hot-pressure sealing conditions of 120-180 ° C. × 0.2 MPa × 1.0 sec.
そして、付着防止層を設けていない蓋材本体のままの蓋材におけるシール強度（蓋材の耐剥離強度・密封性）を基準値として、シール強度の低下率を下記の基準で判定評価した。
◎・・・付着防止層なしのものとほぼ同等
○・・・強度低下２０％未満
×・・・強度低下２０％以上
Then, the seal strength (peeling resistance / sealing strength of the lid material) in the lid material as it is without the adhesion preventing layer was used as a reference value, and the rate of decrease in the seal strength was judged and evaluated according to the following criteria.
◎ ... Almost the same as the one without adhesion prevention layer ○ ... Less than 20% strength reduction ×… More than 20% strength reduction
（３）密着性
試料Ｎｏ．１〜１５の各蓋材の付着防止層の面に、黒い布を巻き付けた重り（５００ｇ）を垂直に載せ、ゆっくりと長さ２００ｍｍ擦り、布に付着したシリカを目視で確認した。
(3) Adhesion Sample No. A weight (500 g) wrapped with a black cloth was placed vertically on the surface of the adhesion preventing layer of each of the
そして、黒い布における疎水性微粒子及び付着防止層の転移付着量（剥離量）を目視検査し、下記の評価基準で評価した。
◎・・・ほとんど付着なし
○・・・許容範囲と認められる僅かな付着あり
×・・・明らかに多くの付着あり
上記（１）〜（３）の各評価試験の結果を、表１に併記して示す。
And the transfer adhesion amount (peeling amount) of the hydrophobic fine particles and the adhesion preventing layer in the black cloth was visually inspected and evaluated according to the following evaluation criteria.
◎ ・ ・ ・ No adhesion ○ ・ ・ ・ Slight adhesion that is recognized as an acceptable range × ・ ・ ・ Clearly much adhesion The results of each of the evaluation tests (1) to (3) are shown in Table 1. And show.
表１の「付着防止の性能」試験の結果に示すように、本発明による内容物付着防止蓋材においては、試料を僅かに傾けるだけでヨーグルト液滴が転がり移動を始める。このことは、ヨーグルト、プリン、ゼリー等の粘稠な液体成分を含むような内容物に対し、蓋材裏面への該内容物の付着防止効果に優れたものであることを示す。しかも「シール性」試験の結果に示すように、付着防止層の存在によってヒートシール性がほとんど損なわれることなく、良好な密封性を維持しつつ、上記付着防止性能を付与しうる。加えて、「密着性」試験の結果に見られるように、疎水性粒子からなる付着防止層の密着性が良好で、不本意な疎水性微粒子の分離脱落、付着防止層の部分剥離等のおそれがなく、長期に亘って内容物付着防止性能を安定に維持しうると共に、容器内への異物混入のおそれもない。 As shown in the results of the “adhesion prevention performance” test in Table 1, in the content adhesion prevention lid material according to the present invention, the yogurt droplet starts rolling and moving only by slightly tilting the sample. This indicates that the contents containing viscous liquid components such as yogurt, pudding, and jelly are excellent in the effect of preventing the contents from adhering to the back surface of the lid. In addition, as shown in the results of the “sealability” test, the presence of the adhesion preventing layer hardly impairs the heat sealability, and the above adhesion prevention performance can be imparted while maintaining good sealing performance. In addition, as shown in the results of the “adhesion” test, the adhesion of the anti-adhesion layer made of hydrophobic particles is good, and there is a risk of unintentional separation and dropping of hydrophobic fine particles, partial peeling of the anti-adhesion layer, etc. In addition, the content adhesion prevention performance can be stably maintained over a long period of time, and there is no possibility of foreign matter entering the container.
１・・・基材層
２・・・基材フィルム層
３・・・金属箔層
４・・・中間樹脂層
５・・・熱封緘層
６・・・付着防止層
８・・・微小突起
１０・・グラビアロール
１０ａ・微小凹部
１１・・バックアップロール
Ｈ・・・微小突起の高さ
Ｄ・・・微小突起の直径
Ｐ・・・微小突起の配設ピッチ
DESCRIPTION OF
Claims (16)
前記熱封緘層の外面に、高さ１００μｍ以下の多数の微小突起が全面に亘って密に設けられると共に、
この突起を有する前記外面に、付着防止層が形成され、
該付着防止層は、疎水性微粒子からなり、その付着量が０．０５ｇ／ｍ２以上でかつ多くとも前記微小突起の頂端面を僅かに覆う量以下に設定されていることを特徴とする内容物付着防止蓋材。 In a lid having at least a base material layer and a heat sealing layer,
On the outer surface of the heat sealing layer, a large number of microprojections having a height of 100 μm or less are densely provided over the entire surface,
An adhesion preventing layer is formed on the outer surface having the protrusions,
The adhesion preventing layer is made of hydrophobic fine particles, and its adhesion amount is set to 0.05 g / m 2 or more and at most set to an amount that slightly covers the top end surface of the microprotrusions. Material adhesion prevention lid.
次いで、この微小突起を形成した前記外面に、有機溶媒に疎水性微粒子を分散した分散液を塗布し、
この塗布層の表面側の過剰分散液をドクターナイフで掻き取り除去したのち、乾燥することにより、前記外面に、前記疎水性微粒子からなり、その付着量が０．０５ｇ／ｍ２以上でかつ多くとも前記微小突起の頂端面を僅かに覆う量以下に設定された付着防止層を形成することを特徴とする内容物付着防止蓋材の製造方法。 A large number of microprojections having a height of 100 μm or less are formed over the entire surface of the outer surface of the heat sealing layer of the lid member having at least a base material layer and a heat sealing layer,
Next, a dispersion liquid in which hydrophobic fine particles are dispersed in an organic solvent is applied to the outer surface on which the fine protrusions are formed,
The excess dispersion on the surface side of the coating layer is scraped off with a doctor knife and then dried, so that the outer surface is composed of the hydrophobic fine particles, and the adhesion amount is 0.05 g / m 2 or more and much. A method for producing a content adhesion preventing lid material, characterized in that an adhesion preventing layer set to an amount that slightly covers the top end surface of the microprojections is formed.
The manufacturing method of the content adhesion prevention lid | cover material of any one of Claims 10-15 which performs the said drying process on the drying conditions of temperature 80-140 degreeC and time 5 to 30 second.
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| JP5995463B2 (en) * | 2012-02-29 | 2016-09-21 | 東洋アルミニウム株式会社 | Packaging material and manufacturing method thereof |
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| JP5994338B2 (en) * | 2012-03-30 | 2016-09-21 | 凸版印刷株式会社 | Heat-sealable film and method for producing heat-sealable film |
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| JP5962362B2 (en) * | 2012-09-12 | 2016-08-03 | 凸版印刷株式会社 | Lid material |
| JP6015318B2 (en) * | 2012-10-02 | 2016-10-26 | 凸版印刷株式会社 | Heat sealable film |
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