JP2004082727A - Receiving paper for use in thermal transfer recording - Google Patents
Receiving paper for use in thermal transfer recording Download PDFInfo
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Abstract
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本発明は、熱溶融性のインク層を有する熱転写記録媒体と組み合わせて使用される熱転写記録用受容紙に関する。このような熱転写記録用受容紙は、熱転写記録用ラベルに好適に用いられる。 The present invention relates to a thermal transfer recording receiving paper used in combination with a thermal transfer recording medium having a heat-meltable ink layer. Such a receiving paper for thermal transfer recording is suitably used for a label for thermal transfer recording.
従来、種々の熱転写記録方式が公知であるが、それらの中で熱溶融性のインク層を有する熱転写記録媒体を用い、インク受容層を設けた紙やプラスティックフィルム等のラベルに様々な情報、画像を形成する方法が提案されている。特に産業分野においてバーコードを記録し銘板、工程管理、物流管理等の用途に広く用いられている。上記用途においては記録画像の耐有機溶剤性、耐水性、耐摩擦性、耐薬品性が要求されるため、受像体としてポリエステル、ポリプロピレン、ポリエチレン等のプラスティックフィルム、または合成紙等が広く用いられ、記録媒体としてそれらに耐え得るよう設計された熱可塑性高分子化合物を主成分とするインク層を有する熱転写記録媒体が一般的に使われている。
しかし、プラスティックフィルムを受容体として用いた場合は価格が高価であり使用範囲が限定されてしまうという問題が生じており、また上質紙、中質紙などの天然繊維紙を受像体として用いたラベルは、熱可塑性高分子化合物を主成分とするインク層を有する熱転写記録媒体を用いたときにはインクの熱転写性、定着性が悪いという問題がある。
Conventionally, various thermal transfer recording methods are known. Among them, a thermal transfer recording medium having a heat-meltable ink layer is used, and various information and images are printed on a label such as paper or a plastic film provided with an ink receiving layer. Have been proposed. In particular, in the industrial field, barcodes are recorded and widely used for applications such as nameplates, process management, and distribution management. In the above applications, the organic solvent resistance of the recorded image, water resistance, friction resistance, chemical resistance is required, polyester, polypropylene, plastic film such as polyethylene, or synthetic paper is widely used as the image receiving member, As a recording medium, a thermal transfer recording medium having an ink layer mainly composed of a thermoplastic polymer compound designed to withstand them is generally used.
However, when a plastic film is used as a receiver, there is a problem that the price is expensive and the range of use is limited, and a label using a natural fiber paper such as a high-quality paper or a medium-quality paper as an image receiver. However, when a thermal transfer recording medium having an ink layer containing a thermoplastic polymer compound as a main component is used, there is a problem that the thermal transferability and fixability of the ink are poor.
これに対し、天然繊維紙を支持体に用い熱転写性の向上を目的とし、支持体上に熱溶融インクの受理性の良い受容層を設けた受容体の提案が多くされている。
しかし、これらの方法を用いた場合、充分な記録画像の耐有機溶剤性、耐摩擦性、耐水性が得られず、また、これらの方法で得られた受容体の裏面に粘着剤層を設けラベルとして使用した場合は、支持体、受容層が有機溶剤、水に対するバリアー性を有さないため、有機溶剤や水により裏面の粘着付与層の粘着性が低下してしまいラベルとしての機能をなくしてしまうという問題がある。
On the other hand, there have been many proposals for receivers provided with a receiving layer having good receptivity for hot-melt ink on the support for the purpose of improving thermal transferability using natural fiber paper as the support.
However, when these methods are used, sufficient organic solvent resistance, rub resistance, and water resistance of a recorded image cannot be obtained, and a pressure-sensitive adhesive layer is provided on the back surface of the receptor obtained by these methods. When used as a label, since the support and the receiving layer do not have a barrier property against organic solvents and water, the adhesiveness of the tackifying layer on the back surface is reduced by the organic solvent and water, and the function as a label is lost. Problem.
これに対して、特許文献１には、インク層のバインダー樹脂と受容層の主成分のバインダー樹脂が同一種類でＳＰ値を規定した技術が開示されている。この技術では、記録画像の耐有機溶剤性、耐摩擦性、耐水性には優れるものの、インクと受容体をセットとして使用しなければならず、使用範囲が極めて限定されてしまうため、ユーザーでの使い勝手が低下してしまう。
また、層の耐溶剤性を得るために、特許文献２には支持体と受容層の間に重合度５０〜４５０のポリビニールアルコールの中間層を設けることが提案されており、また、特許文献３には１８〜８０モル％の疎水基を有するポリビニールアルコールの中間層を設けるものが提案されている。
On the other hand, Patent Literature 1 discloses a technique in which the binder resin of the ink layer and the binder resin of the main component of the receiving layer are of the same type and the SP value is defined. In this technology, although the recorded image is excellent in organic solvent resistance, rub resistance, and water resistance, the ink and the receptor must be used as a set, and the range of use is extremely limited. Usability will be reduced.
Further, in order to obtain the solvent resistance of the layer, Patent Document 2 proposes to provide an intermediate layer of polyvinyl alcohol having a degree of polymerization of 50 to 450 between the support and the receiving layer. No. 3 proposes providing an intermediate layer of polyvinyl alcohol having a hydrophobic group of 18 to 80 mol%.
しかし、重合度５０〜４５０のポリビニールアルコールの中間層を設ける方法においては、重合度が低いため成膜性が不充分であり充分な耐有機溶剤性が得られず、また使用材料の水に対する溶解性が良いため、水に接触することで中間層が溶解し層剥離がおこり、受容紙の耐水性を得ることができないといった問題がある。また、低重合のため塗膜のタック性が強く、塗工時の搬送ロール等への粘着が発生し生産性の低下を起こすといった問題がある。
また、１８〜８０モル％の疎水基を有するポリビニールアルコールの中間層を設ける方法においては、その疎水基の含有量が多くなるつれ耐有機溶剤性が低下し、含有量が少ないと耐水性が低下するという欠点があり、この方法では充分な耐有機溶剤性と耐水性を得ることができないという問題がある。
However, in the method of providing an intermediate layer of polyvinyl alcohol having a degree of polymerization of 50 to 450, the degree of polymerization is low, so that the film-forming properties are insufficient, sufficient organic solvent resistance cannot be obtained, and the material used with respect to water Because of its good solubility, there is a problem that the contact with water causes the dissolution of the intermediate layer and the delamination, which makes it impossible to obtain the water resistance of the receiving paper. In addition, there is a problem that the tackiness of the coating film is strong due to low polymerization, and adhesion to a transport roll or the like at the time of coating occurs to lower productivity.
In the method of providing a polyvinyl alcohol intermediate layer having a hydrophobic group of 18 to 80 mol%, the organic solvent resistance decreases as the content of the hydrophobic group increases, and the water resistance decreases as the content of the hydrophobic group decreases. However, this method has a problem that sufficient organic solvent resistance and water resistance cannot be obtained by this method.
本発明の課題は、本発明の熱転写記録用ラベルを使用することにより、前記の従来技術の欠点である記録画像の耐有機溶剤性、耐水性、耐摩擦性と、受容紙の裏面に粘着付与層を設けたラベルとして用いる場合の耐有機溶剤性、耐水性を解消し、かつ、安価な熱転写記録用ラベルおよび熱転写記録方法を提供することにある。 The object of the present invention is to use the label for thermal transfer recording of the present invention to provide an organic solvent-resistant, water-resistant, and abrasion-resistant recording image, which is a drawback of the above-mentioned prior art, and to provide an adhesive on the back surface of the receiving paper. An object of the present invention is to provide an inexpensive label for thermal transfer recording and a thermal transfer recording method, which eliminate organic solvent resistance and water resistance when used as a label provided with a layer, and are inexpensive.
上記課題は、本発明の（１）「支持体紙上に熱により溶融または軟化したインクを受容する受容層を有し、これとは反対面に粘着付与層を設けた熱転写記録用受容紙の製造方法において、エマルジョン樹脂を含有する受容層形成液を支持体紙上に塗工し、該受容層液塗工面の温度を前記エマルジョン樹脂のＭＦＴ（最低造膜温度）以上とする工程を含むことを特徴とする熱転写記録用受容紙の製造方法」、（２）「ガラス転移温度が４５℃以上であるエマルジョン樹脂を少なくとも含有する受容層形成液を用いることを特徴とする前記第（１）項に記載の熱転写記録用受容紙の製造方法」、（３）「前記エマルジョン樹脂として、少なくともポリエステル系、ウレタン系から選ばれる１種類以上のエマルジョン樹脂を含有する受容層形成液を用いることを特徴とする前記第（１）項又は第（２）項に記載の熱転写記録用受容紙の製造方法」、（４）「前記インク受容層中に中空率が５０％以上である中空粒子を含有することを特徴とする前記第（１）項乃至第（３）項のいずれかに記載の熱転写記録用受容紙の製造方法」、（５）「前記受容層表面が王研式平滑度５００秒以上であることを特徴とする前記第（１）項乃至第（４）項のいずれかに記載の熱転写記録用受容紙の製造方法」、（６）「前記支持体紙と受容層の間、又は支持体紙と粘着付与層との間に、水性樹脂とその硬化剤とを主成分とする中間層を設ける工程を含むことを特徴とする前記第（１）項乃至第（５）項のいずれかに記載の熱転写記録用受容紙の製造方法」、（７）「前記中間層の水性樹脂がポリビニールアルコール／または変性ポリビニールアルコール樹脂であることを特徴とする前記第（６）項に記載の熱転写記録用受容紙の製造方法」により達成される。
また上記課題は、本発明の（８）「支持体紙上に熱により溶融または軟化したインクを受容する受容層を有し、これとは反対面に粘着付与層を設けた熱転写記録用受容紙において、受容層形成液中にエマルジョン樹脂を含有し、該受容層を形成する製造工程において、受容層形成液を支持体紙上に塗工後、受容層液塗工面の温度を前記エマルジョン樹脂のＭＦＴ（最低造膜温度）以上とする工程を設けて製造されることを特徴とする熱転写記録用受容紙」、（９）「ガラス転移温度が４５℃以上であるエマルジョン樹脂を少なくとも受容層形成液中に含有することを特徴とする前記第（８）項に記載の熱転写記録用受容紙」、（１０）「前記エマルジョン樹脂として、少なくともポリエステル系、ウレタン系から選ばれる１種類以上のエマルジョン樹脂を受容層中に含有することを特徴とする前記第（８）項又は第（９）項に記載の熱転写記録用受容紙」、（１１）「前記インク受容層中に中空率が５０％以上である中空粒子を含有することを特徴とする前記第（８）項乃至第（１０）項のいずれかに記載の熱転写記録用受容紙」、（１２）「前記受容層表面が王研式平滑度５００秒以上であることを特徴とする前記第（８）項乃至（１１）項のいずれかに記載の熱転写記録用受容紙」、（１３）「前記支持体紙と受容層の間、又は支持体紙と粘着付与層との間に、水性樹脂とその硬化剤とを主成分とする中間層を設けたことを特徴とする前記第（８）項乃至第（１２）項のいずれかに記載の熱転写記録用受容紙」、（１４）「前記中間層の水性樹脂がポリビニールアルコール／または変性ポリビニールアルコール樹脂であることを特徴とする前記第（１３）項に記載の熱転写記録用受容紙」により達成される。
The object of the present invention is to provide (1) the production of a thermal transfer recording receiving paper having a receiving layer for receiving ink melted or softened by heat on a support paper and having a tackifier layer on the opposite surface. The method comprises a step of applying a receiving layer forming liquid containing an emulsion resin onto a support paper, and adjusting the temperature of the receiving layer liquid coated surface to MFT (minimum film forming temperature) of the emulsion resin or higher. (2) A method for producing a receiving paper for thermal transfer recording, wherein (2) a receiving layer forming liquid containing at least an emulsion resin having a glass transition temperature of 45 ° C. or higher is used. (3) A method for producing a receiving layer for a thermal transfer recording paper, and (3) a liquid for forming a receiving layer containing at least one emulsion resin selected from the group consisting of polyester and urethane as the emulsion resin. (4) The method for producing a thermal transfer recording receiving paper according to the above (1) or (2), wherein (4) the hollow having a hollow ratio of 50% or more in the ink receiving layer. (5) The method for producing a thermal transfer recording receiving paper according to any one of the above (1) to (3), wherein the surface of the receiving layer is smooth by Oken type. The method for producing a thermal transfer recording receiving paper according to any one of the above items (1) to (4), wherein the temperature is 500 seconds or more, and (6) “the support paper and the receiving layer”. (1) to (5), including a step of providing an intermediate layer mainly composed of an aqueous resin and a curing agent thereof between the support paper and the tackifier layer. (7) The method for producing a thermal transfer recording receiving paper according to any one of (1) to (7), wherein the aqueous resin of the intermediate layer is polyvinyl It is achieved by the first (6) for thermal transfer recording receiving sheet manufacturing method according to claim ", which is a alcohol / or modified polyvinyl alcohol resin.
Another object of the present invention is to provide (8) a thermal transfer recording receiving paper according to the present invention, wherein the support paper has a receiving layer for receiving ink melted or softened by heat, and a tackifier layer provided on the opposite surface. In a manufacturing step of forming an emulsion layer in a receiving layer forming liquid and forming the receiving layer, after coating the receiving layer forming liquid on a support paper, the temperature of the receiving layer liquid coating surface is adjusted to the MFT of the emulsion resin. (Receiving paper for thermal transfer recording characterized by being provided with a step of not lower than the minimum film forming temperature) ”, (9)“ Emulsion resin having a glass transition temperature of 45 ° C. or higher, at least in the receiving layer forming liquid. (8) The receiving paper for thermal transfer recording according to the item (8), wherein the emulsion resin comprises at least one emulsion selected from at least polyester and urethane. (7) The receiving paper for thermal transfer recording according to the above (8) or (9), wherein the ink receiving layer contains a hollow resin in the ink receiving layer. (12) The receiving paper for thermal transfer recording according to any one of the above (8) to (10), wherein the receiving layer contains 50% or more of hollow particles. The thermal transfer recording receiving paper according to any one of the above items (8) to (11), wherein the polishing paper has a grinding smoothness of 500 seconds or more. (8) to (12), wherein an intermediate layer mainly composed of an aqueous resin and its curing agent is provided between the support paper and the tackifier layer. (14) The aqueous resin of the intermediate layer is polyvinyl alcohol / It is achieved by the second (13) thermal transfer recording receiving sheet according to claim ", characterized in that is modified polyvinyl alcohol resin.
本発明の熱転写記録用ラベルを用いることで、受容層の転写のない良好な印字が得られ、更には耐ブロッキング性にも優れ、しかも印字画像の耐有機溶剤性、耐水性、耐摩擦性と、ラベルの耐有機溶剤性、耐水性とに優れた熱転写記録を提供することができる。 By using the label for thermal transfer recording of the present invention, good printing without transfer of the receiving layer is obtained, furthermore, excellent in anti-blocking property, and furthermore, organic solvent resistance, water resistance, and abrasion resistance of the printed image. In addition, it is possible to provide a thermal transfer recording excellent in organic solvent resistance and water resistance of the label.
本発明の最も基本的な熱転写記録媒体としては、支持体紙上に熱により溶融または軟化したインクを受容する受容層を有し、これとは反対面に粘着付与層を設けた熱転写記録用ラベルである。
本発明において、支持体紙に好ましく用いられる原紙は、木材パルプと填料を主成分として構成される。木材パルプとしては、ＬＢＫＰ、ＮＢＫＰ等の化学パルプ、ＧＰ、ＰＧＷ、ＲＭＰ、ＴＭＰ、ＣＴＭＰ、ＣＭＰ、ＣＧＰ等の機械パルプ、ＤＩＰ等の古紙パルプ等のパルプを含み、必要に応じて従来公知の顔料やバインダー及びサイズ剤や定着剤、歩留まり向上剤、カチオン化剤、紙力増強剤等の各種添加剤を１種以上用いて混合し、長網抄紙機、円網抄紙機、ツインワイヤ抄紙機等の各種装置で支持体の製造が可能であり、酸性、中性、アルカリ性で抄造できる。また、該原紙は、金属ロールと合成樹脂ロールからなるカレンダー装置をオンマシン処理しても良い。その際、オフマシン処理しても良く、処理後に、更にマシンカレンダー、スーパーカレンダー等でカレンダー処理を施して平坦性をコントロールしても良い。
The most basic thermal transfer recording medium of the present invention is a thermal transfer recording label having a receiving layer for receiving ink melted or softened by heat on a support paper, and a tackifier layer provided on the opposite surface. is there.
In the present invention, the base paper preferably used for the support paper is composed mainly of wood pulp and filler. Wood pulp includes chemical pulp such as LBKP, NBKP, etc., mechanical pulp such as GP, PGW, RMP, TMP, CTMP, CMP, CGP, and pulp such as waste paper pulp such as DIP. , Binders, sizing agents, fixing agents, retention aids, cationizing agents, paper strength enhancers, etc., and mixing using one or more of these additives. Fourdrinier paper machine, circular net paper machine, twin wire paper machine, etc. The support can be manufactured with any of the various types of apparatuses described above, and the paper can be formed under acidic, neutral, or alkaline conditions. In addition, the base paper may be subjected to on-machine processing of a calender device including a metal roll and a synthetic resin roll. At this time, off-machine processing may be performed, and after the processing, flatness may be controlled by further performing calendar processing using a machine calendar, a super calendar, or the like.
支持体紙の裏面に設ける粘着付与層は、本発明においてはとくに耐有機溶剤性を必要としないため、通常のラベルに用いられる粘着剤が使用可能であるが、一般的にはアクリル系樹脂のエマルションが用いられる。
また、離型紙を必要としない熱活性タイプの粘着剤、例えば熱可塑性樹脂と固体可塑剤とからなる粘着付与層を設けることも可能である。
The tackifier layer provided on the back side of the support paper does not particularly require organic solvent resistance in the present invention, and therefore, a pressure-sensitive adhesive used for ordinary labels can be used. Emulsions are used.
Further, it is also possible to provide a heat-active type pressure-sensitive adhesive that does not require release paper, for example, a tackifier layer composed of a thermoplastic resin and a solid plasticizer.
本発明では受容層形成液中にエマルジョン樹脂を含有する。この受容層を形成する製造工程において、受容層形成液を支持体紙上に塗工後、受容層液塗工面の温度を前記エマルジョン樹脂のＭＦＴ以上とする工程を設けて製造することを特徴とする。なお、ＭＦＴ（Ｍｉｎｉｍｕｍ Ｆｉｌｍｉｎｇ Ｔｅｍｐｅｒａｔｕｒｅ）とは最低造膜温度のことであり、この温度以上でエマルジョン樹脂は連続的な皮膜を形成する。この温度以下では、たとえエマルジョンの溶媒を蒸発させても、樹脂は連続的な皮膜とはならない。この特性は、受容層を形成する製造工程においても同様な特性を示すと考えられ、受容層形成液を支持体紙上に塗工後、乾燥によりエマルジョンの溶媒を蒸発させただけでは、エマルジョン樹脂は不連続なままで層形成される。そこで、受容層液塗工面の温度を前記エマルジョン樹脂のＭＦＴ以上とする工程を設けて製造することで、連続皮膜が形成される。なお、製造工程としては、乾燥（エマルジョン溶媒の蒸発）工程の後に直ちにエマルジョン樹脂のＭＦＴ以上とする工程を設けると、製造工程の簡略化ができる。 で は In the present invention, an emulsion resin is contained in the receiving layer forming liquid. In the manufacturing process of forming the receiving layer, after the receiving layer forming liquid is applied on the support paper, a step of setting the temperature of the coated surface of the receiving layer liquid to MFT or higher of the emulsion resin is provided. . Note that MFT (Minimum Filming Temperature) is the minimum film forming temperature, and above this temperature the emulsion resin forms a continuous film. Below this temperature, the resin does not form a continuous film, even if the solvent of the emulsion is evaporated. It is considered that this property shows the same property in the manufacturing process of forming the receiving layer, and the emulsion resin is simply formed by applying the receiving layer forming liquid on the support paper and then evaporating the solvent of the emulsion by drying. The layer is formed in a discontinuous state. Therefore, a continuous film is formed by providing a step of setting the temperature of the coating surface of the receiving layer liquid to be equal to or higher than the MFT of the emulsion resin. The manufacturing process can be simplified by providing a process of making the emulsion resin MFT or more immediately after the drying (evaporation of the emulsion solvent) process.
このエマルジョン樹脂のＭＦＴ以上とする工程を設ける効果であるが、受容層中で樹脂が連続層になることで、不連続層の場合と比べて、記録画像の耐有機溶剤性、耐水性、耐摩擦性および、受容紙の裏面に粘着付与層を設けたラベルとして用いる場合の耐有機溶剤性、耐水性が優れるようになる。これは、連続層となることで受容層の機械的強度が増し、また後述する範囲の温度に過熱した後に放冷することにより受容層組織が緻密化され、さらには有機溶剤、水に対する溶解性が低下し、また特定エマルジョン樹脂を用いることで有機溶剤、水に対する耐久性が一層向上し、かつ表面平滑化の実効が上がるためと考えられる。 The effect of providing a step of making the emulsion resin MFT or more is that the resin becomes a continuous layer in the receiving layer, so that compared with the case of a discontinuous layer, the organic solvent resistance, water resistance, and water resistance of the recorded image are improved. The abrasion resistance and the organic solvent resistance and water resistance when used as a label having a tackifier layer on the back surface of the receiving paper are improved. This is because the mechanical strength of the receiving layer increases by becoming a continuous layer, and the structure of the receiving layer is densified by being allowed to cool after being heated to a temperature in the range described later, and further, the solubility in an organic solvent and water. It is considered that the use of the specific emulsion resin further improves the durability against an organic solvent and water and increases the effectiveness of surface smoothing.
記録画像の耐有機溶剤性、耐水性は、受容層樹脂が有機溶剤や水にわずかでも溶解することで低下する。また耐摩擦性は受容層の機械的強度が弱いと低下する。さらには、ラベルとして用いる場合、受容層樹脂が有機溶剤や水に溶解することで、受容紙裏面の粘着付与層まで有機溶剤、水が浸透しやすく、この結果、粘着付与層の粘着機能が低下してしまうためと考える。ところが、連続層とすることでこのような作用が起き難くなる。 (4) The organic solvent resistance and water resistance of the recorded image are lowered by the resin of the receiving layer being slightly dissolved in the organic solvent or water. Further, the friction resistance is reduced when the mechanical strength of the receiving layer is weak. Furthermore, when used as a label, by dissolving the receiving layer resin in an organic solvent or water, the organic solvent and water easily penetrate to the tackifying layer on the back surface of the receiving paper, and as a result, the adhesive function of the tackifying layer is reduced. I think that it would be. However, such an action is less likely to occur by forming a continuous layer.
なお、受容層液塗工面の温度が前記エマルジョン樹脂のＭＦＴを超えさらに高くなると乾燥が進み、含有水分の低下および樹脂の軟化が起こり、塗工面が粗れてくる現象が発生する。このような現象は塗工面の温度が前記エマルジョン樹脂のＭＦＴより５０℃以上高くなると発生しやすくなる。このため塗工面の温度はＭＦＴより５０℃以上は高くしないほうが望ましい。なお、塗工面が粗れてくると熱転写記録媒体で印字した場合に、細かい文字や線がかすれるといった印字性能の低下が見られる。この塗工面の粗れはキャレンダー処理を行なっても、なお印字性能に影響を及ぼす性質を有することが多いので塗工面温度の管理は重要である。 (4) When the temperature of the receiving layer liquid coated surface exceeds the MFT of the emulsion resin and becomes higher, the drying proceeds, and the water content decreases and the resin softens, causing a phenomenon that the coated surface becomes rough. Such a phenomenon tends to occur when the temperature of the coating surface is higher than the MFT of the emulsion resin by 50 ° C. or more. For this reason, it is desirable that the temperature of the coated surface is not higher than the MFT by 50 ° C. or more. When the coated surface becomes rough, when printing is performed on a thermal transfer recording medium, printing performance such as blurring of fine characters and lines is observed. Since the roughness of the coated surface often has the property of affecting the printing performance even after the calendering treatment, it is important to control the temperature of the coated surface.
ここで用いるエマルジョン樹脂は、ガラス転移温度が４５℃以上である樹脂を含有させることで耐ブロッキング性を向上させられる。ここでいうブロッキング性とは、巻取り状態で保管される場合に受容層とこれと接する面との間の接着現象を指す。前記、エマルジョン樹脂のＭＦＴ以上とする工程を設けて製造することで、記録画像の耐有機溶剤性、耐水性、耐摩擦性、および受容紙の裏面に粘着付与層を設けたラベルとして用いる場合の耐有機溶剤性、耐水性を向上させようとする発明に対して、製造工程を容易にする目的で、ＭＦＴの低いエマルジョン樹脂を採用することが提案される。しかし、ＭＦＴの低いエマルジョン樹脂は、乾燥、造膜後も接する面との間に接着力を有する場合が多く、耐ブロッキング性が低下しやすい。これに対してガラス転移温度が４５℃以上である樹脂を含有させることで耐ブロッキング性が向上できる。この４５℃という温度であるが、巻取り状態で保管する際の条件として、この温度以下である場合がほとんどであり、保管温度以上のガラス転移温度を有するエマルジョン樹脂を用いることで、保管時には接着力が発現しないためと考えられる。 エ マ ル ジ ョ ン The emulsion resin used here can improve blocking resistance by containing a resin having a glass transition temperature of 45 ° C or higher. Here, the blocking property refers to an adhesive phenomenon between the receiving layer and a surface in contact with the receiving layer when stored in a wound state. By providing a step of making the emulsion resin MFT or more, the organic solvent resistance of the recorded image, water resistance, abrasion resistance, and when used as a label provided with a tackifier layer on the back surface of the receiving paper. In order to improve the organic solvent resistance and water resistance, it is proposed to employ an emulsion resin having a low MFT for the purpose of facilitating the production process. However, an emulsion resin having a low MFT often has an adhesive force with a surface that is in contact even after drying and film formation, and the blocking resistance tends to decrease. In contrast, by including a resin having a glass transition temperature of 45 ° C. or higher, blocking resistance can be improved. Although the temperature is 45 ° C., most of the conditions for storage in a rolled state are lower than this temperature, and by using an emulsion resin having a glass transition temperature higher than the storage temperature, adhesion during storage is performed. This is probably because no force was developed.
なお、エマルジョン樹脂の種類としては、スチレン／ブタジエン共重合体、スチレン／ブタジエン／アクリル系共重合体などのラテックス類や、酢酸ビニル樹脂、酢酸ビニル／アクリル系共重合体、塩化ビニル樹脂、塩化ビニリデン樹脂、スチレン／アクリル酸エステル共重合体、アクリル酸エステル樹脂、ポリウレタン樹脂などのエマルジョンが挙げられる。これらを単独あるいは２種類以上を混合して用いることができる。
この中でもポリエステル系、ウレタン系を用いると、記録画像の耐有機溶剤性、耐水性、および受容紙の裏面に粘着付与層を設けたラベルとして用いる場合の耐有機溶剤性、耐水性が格段に優れるようになる。これはポリエステル系、ウレタン系樹脂は、有機溶剤、水に対する溶解度が極めて小さいためと考えられる。
ポリエステル系、ウレタン系樹脂の使用量は、層中樹脂の３０〜１００重量％が好ましく、より好ましくは４０重量％以上である。
The types of emulsion resin include latexes such as styrene / butadiene copolymer and styrene / butadiene / acrylic copolymer, vinyl acetate resin, vinyl acetate / acrylic copolymer, vinyl chloride resin, vinylidene chloride Emulsions such as resins, styrene / acrylate copolymers, acrylate resins, and polyurethane resins are exemplified. These can be used alone or in combination of two or more.
Among these, polyester-based and urethane-based organic solvent resistance of recorded images, water resistance, and organic solvent resistance when used as a label provided with a tackifier layer on the back side of the receiving paper, water resistance is extremely excellent. Become like This is presumably because the polyester and urethane resins have extremely low solubility in organic solvents and water.
The amount of the polyester-based or urethane-based resin used is preferably 30 to 100% by weight of the resin in the layer, and more preferably 40% by weight or more.
更に、受容層中に中空率が５０％以上の中空粒子を含有することで、記録画像の耐有機溶剤性、耐水性、耐摩擦性がより優れる。これは中空粒子を含有することで、層のクッション性、断熱性が向上でき、印字時のインク受理性が向上するために、受容層とインク成分との接着力が増すためと考えられる。このため有機溶剤、水を接触させたり、摩擦した場合でも、インク成分が剥がれにくくなる。なお、受容層中に単に中空粒子を含有させることは従来技術の範囲であるが、本発明のごとく、受容層液塗工面の温度を前記エマルジョン樹脂のＭＦＴ以上とする工程を設けて製造することで、受容層の皮膜強度が向上できたことで、中空粒子を含有させる発明が効果を持つようになった。
すなわち、皮膜強度が低い状態で中空粒子を含有させた場合には、印刷時のインク受理後の剥離過程で、受容層の成分が熱転写記録媒体側にもっていかれてしまう現象がみられた。さらにはこれを防ぐために受容層中に樹脂成分の含有量を増やそうとすると、中空粒子の含有量を少なくしなければならず、中空粒子を含有させる効果が少なくなってしまうといったことが起こった。しかし、受容層液塗工面の温度を前記エマルジョン樹脂のＭＦＴ以上とする工程を設けて製造することで、受容層の皮膜強度が向上でき、中空粒子を充分量含有させても、副作用のない印字が可能となった。なお、中空粒子の主成分はアクリル、スチレン、アクリル−スチレン、塩化ビニリデン等の耐有機溶剤性の高い樹脂から構成されることが好ましいが、これらに限定されるものではない。
Further, when the receiving layer contains hollow particles having a hollow ratio of 50% or more, the organic solvent resistance, water resistance, and rub resistance of the recorded image are further improved. This is considered to be because the inclusion of the hollow particles can improve the cushioning property and the heat insulating property of the layer, improve the ink receptivity during printing, and increase the adhesive force between the receiving layer and the ink component. Therefore, even when the organic solvent or water is brought into contact with or rubbed with the organic solvent or water, the ink components are not easily peeled off. It is to be noted that simply including hollow particles in the receiving layer is within the range of the prior art. However, as in the present invention, the receiving layer is manufactured by providing a step of setting the temperature of the liquid coating surface of the receiving layer to MFT or higher of the emulsion resin. By improving the film strength of the receiving layer, the invention containing the hollow particles became effective.
That is, when the hollow particles were contained in a state where the film strength was low, a phenomenon was observed in which the components of the receiving layer were transferred to the thermal transfer recording medium side during the peeling process after receiving the ink at the time of printing. Further, if an attempt is made to increase the content of the resin component in the receiving layer in order to prevent this, the content of the hollow particles must be reduced, and the effect of including the hollow particles is reduced. However, by providing a process in which the temperature of the liquid coating surface of the receiving layer is set to be equal to or higher than the MFT of the emulsion resin, the film strength of the receiving layer can be improved, and even if a sufficient amount of hollow particles are contained, printing without side effects can be achieved. Became possible. The main component of the hollow particles is preferably composed of a resin having high organic solvent resistance such as acryl, styrene, acryl-styrene, and vinylidene chloride, but is not limited thereto.
また、受容層表面が王研式平滑度５００秒以上であると、記録画像の耐有機溶剤性、耐水性、耐摩擦性がより優れる。これは王研式平滑度を５００秒以上とすることで、受容層面と熱転写記録媒体との接触の確率が大きくなるため、印字時のインク受理性が向上し、受容層とインク成分との接着力が増すためと考えられる。この発明も、受容層液塗工面の温度を前記エマルジョン樹脂のＭＦＴ以上とする工程を設けて製造することで、受容層の皮膜強度が向上できたことで、王研式平滑度を５００秒以上とする発明が効果を持つようになった。
受像層には、筆記性を良好にする、地肌の黄変を防止する、耐ブロッキング性を向上させるなどを目的として、顔料、蛍光増白剤、退色剤防止剤、滑剤などを添加しても構わない。
When the surface of the receiving layer has an Oken type smoothness of 500 seconds or more, the organic solvent resistance, water resistance and rub resistance of the recorded image are more excellent. This is because the probability of contact between the receiving layer surface and the thermal transfer recording medium is increased by setting the Oken type smoothness to 500 seconds or more, so that ink receptivity at the time of printing is improved, and adhesion between the receiving layer and the ink component is improved. It is thought that power is increasing. The present invention also provides a process in which the temperature of the receiving layer liquid coating surface is set to be equal to or higher than the MFT of the emulsion resin, thereby improving the film strength of the receiving layer. Invention came to have an effect.
In the image receiving layer, for the purpose of improving the writability, preventing the yellowing of the background, improving the anti-blocking property, etc., a pigment, a fluorescent whitening agent, an anti-fading agent, a lubricant and the like may be added. I do not care.
更に本発明では、支持体紙と受容層の間、又は支持体紙と粘着付与層との間に、水性樹脂とその硬化剤とを主成分とする中間層を設けてなる構成が提示される。この作用であるが、中間層がいわゆる有機溶剤、水に対するバリヤー層の機能を発現するために、受容紙の裏面に粘着付与層を設けたラベルとして用いる場合の耐有機溶剤性、耐水性が格段に優れるようになる。 Further, in the present invention, there is provided a configuration in which an intermediate layer mainly composed of an aqueous resin and a curing agent thereof is provided between the support paper and the receiving layer or between the support paper and the tackifier. . With this function, in order for the intermediate layer to exhibit the function of a barrier layer against so-called organic solvents and water, the organic solvent resistance and water resistance when used as a label having a tackifier layer on the back surface of the receiving paper are remarkably improved. To become better.
また、本発明の一つの特徴である中間層は水性樹脂と硬化剤とを主成分とするが水性樹脂は一般的な水溶性樹脂または疎水性樹脂の水性エマルションが使用できるが、特に好ましいものはポリビニールアルコールまたはカルボキシ、アセトアセチル、メチロール、エポキシ、アルコキシ等の変性ポリビニールアルコール等を挙げることができる。また、これら樹脂の重合度、ケン化度は成膜性に大きく影響し、成膜性が低下するとバリアー性機能の発現が低下し充分な耐有機溶剤性、耐水性を得ることができなくなるため、重合度は８００以上が好しく、ケン化度は８５％以上が好ましい。重合度があまり大きかったり、ケン化度が高すぎると塗布液の粘度が上昇し、生産性の低下または塗膜の成膜性に低下を起こす場合があるため、生産設備等を考慮して選択する必要がある。 Further, the intermediate layer, which is one feature of the present invention, is mainly composed of an aqueous resin and a curing agent, and the aqueous resin can be an aqueous emulsion of a general water-soluble resin or a hydrophobic resin. Examples thereof include polyvinyl alcohol or modified polyvinyl alcohol such as carboxy, acetoacetyl, methylol, epoxy, and alkoxy. In addition, the degree of polymerization of these resins, the degree of saponification greatly affects the film formability, and when the film formability is reduced, the expression of the barrier function is reduced and sufficient organic solvent resistance and water resistance cannot be obtained. The degree of polymerization is preferably 800 or more, and the degree of saponification is preferably 85% or more. If the degree of polymerization is too large or the degree of saponification is too high, the viscosity of the coating solution will increase, which may cause a decrease in productivity or a decrease in the film formability of the coating film. There is a need to.
硬化剤としてはグリシジル、グリシジルアミン、メチロールアミン、エポキシ、エピクロ、アルキレンイミン、イソシアネート、アルデヒド等の反応活性基を有する硬化剤が好ましい。また、中間層のバリアー性を効率良く発現するには、硬化剤を前記樹脂と混合して使用することが好ましく、樹脂と硬化剤を別々の層とすると充分な効果を得ることができなくなる。ポリビニールアルコールまたは変性ポリビニールアルコールと硬化剤の使用比率は９：１〜５：５が好ましい。中間層の塗布量としては１ｇ／ｍ２以上必要であり、それ以下では充分なバリアー性が得られない。 As the curing agent, a curing agent having a reactive group such as glycidyl, glycidylamine, methylolamine, epoxy, epichloro, alkyleneimine, isocyanate, or aldehyde is preferable. In order to efficiently exhibit the barrier properties of the intermediate layer, it is preferable to use a curing agent mixed with the resin, and if the resin and the curing agent are formed as separate layers, a sufficient effect cannot be obtained. The use ratio of polyvinyl alcohol or modified polyvinyl alcohol to the curing agent is preferably from 9: 1 to 5: 5. The coating amount of the intermediate layer is required to be 1 g / m 2 or more, and below this, sufficient barrier properties cannot be obtained.
なお中間層には任意に無機および／または有機フィラーを添加することができ、その具体例としては炭酸カルシウム、シリカ、酸化チタン、水酸化アルミニウム、硫酸バリウム、クレー、タルク、および尿素−ホルマリン樹脂、スチレン−アクリル樹脂、ポリスチレン樹脂等の微粉末を挙げることができる。また、これら無機および／または有機フィラーの吸油量は１００ｍｌ／１００ｇ以下が好ましく、それ以上になると塗布膜の平滑性、バリアー性が低下する。 In addition, an inorganic and / or organic filler can be arbitrarily added to the intermediate layer. Specific examples thereof include calcium carbonate, silica, titanium oxide, aluminum hydroxide, barium sulfate, clay, talc, and urea-formalin resin. Fine powder such as styrene-acrylic resin and polystyrene resin can be used. Further, the oil absorption of these inorganic and / or organic fillers is preferably 100 ml / 100 g or less, and if it is more than that, the smoothness and barrier properties of the coating film decrease.
以下、本発明を実施例により具体的に説明する。ここで、部及び％はともに重量基準である。
実施例１
基材として、坪量６６ｇ／ｍ２の上質紙を用い、下記組成の受容層液をワイヤーバーコーティングにより乾燥後の塗布量が４．５ｇ／ｍ２となるように塗布、乾燥した。このときの受容層液塗工面の温度は最高で４５℃であった。この後、キャレンダー処理を行ない表面受容層紙を得た。この表面の平滑度は３００秒だった。
次いで、基材として表面にシリコン系離型剤を塗布してある坪量６０ｇ／ｍ２のグラシン紙に下記組成の粘着付与層液をワイヤーバーコーティングにより乾燥後の塗布量が１８．０ｇ／ｍ２となるように塗布、乾燥した後、粘着付与層と上記の表面受容層紙の裏面と張り合わせ実施例１の熱転写記録用ラベルを得た。
受容層液
スチレン−アクリル共重合樹脂水系エマルション ５０部
（固形分３０％、ＭＦＴ３５℃、Ｔｇ４０℃）
シリカ ５部
水 ２０部
粘着付与層液
アクリル酸エステル共重合体水系エマルション（５０％） １００部
Hereinafter, the present invention will be described specifically with reference to examples. Here, both parts and% are based on weight.
Example 1
A high quality paper having a basis weight of 66 g / m 2 was used as a substrate, and a receiving layer solution having the following composition was applied by wire bar coating so that the applied amount after drying was 4.5 g / m 2, and dried. At this time, the temperature of the receiving layer liquid coated surface was 45 ° C. at the maximum. Thereafter, a calendering treatment was performed to obtain a surface receiving layer paper. The smoothness of this surface was 300 seconds.
Next, a tackifier layer solution having the following composition was dried on a glassine paper having a basis weight of 60 g / m 2 having a surface coated with a silicone-based release agent as a base material by wire bar coating to obtain a coating amount of 18.0 g / m 2. After coating and drying to obtain No. 2 , the tackifier layer and the back surface of the above-mentioned surface receiving layer paper were adhered to each other to obtain a thermal transfer recording label of Example 1.
Receptive layer liquid Styrene-acrylic copolymer resin aqueous emulsion 50 parts (solid content 30%, MFT 35 ° C, Tg 40 ° C)
Silica 5 parts Water 20 parts Tackifier layer liquid Acrylic ester copolymer aqueous emulsion (50%) 100 parts
実施例２
基材として、坪量６６ｇ／ｍ２の上質紙を用い、下記組成の受容層液をワイヤーバーコーティングにより乾燥後の塗布量が４．５ｇ／ｍ２となるように塗布、乾燥した。このときの受容層液塗工面の温度は最高で５０℃であった。この後、キャレンダー処理を行ない表面受容層紙を得た。この表面の平滑度は２５０秒だった。
次いで、実施例１と同様の方法で、グラシン紙に粘着付与層液を塗布、乾燥した後、粘着付与層と上記の表面受容層紙の裏面と張り合わせ実施例２の熱転写記録用ラベルを得た。
受容層液
アクリル酸−メタクリル酸共重合樹脂水系エマルション ４０部
（固形分４０％、ＭＦＴ４０℃、Ｔｇ５５℃）
シリカ ５部
水 ２０部
Example 2
A high quality paper having a basis weight of 66 g / m 2 was used as a substrate, and a receiving layer solution having the following composition was applied by wire bar coating so that the applied amount after drying was 4.5 g / m 2, and dried. At this time, the temperature of the receiving layer liquid coated surface was 50 ° C. at the maximum. Thereafter, a calendering treatment was performed to obtain a surface receiving layer paper. The smoothness of this surface was 250 seconds.
Next, in the same manner as in Example 1, a tackifier layer solution was applied to glassine paper and dried, and then the tackifier layer was bonded to the back surface of the surface receiving layer paper to obtain a thermal transfer recording label of Example 2. .
Receptor layer liquid Acrylic acid-methacrylic acid copolymer resin aqueous emulsion 40 parts (solid content 40%, MFT 40 ° C, Tg 55 ° C)
Silica 5 parts Water 20 parts
実施例３
基材として、坪量６６ｇ／ｍ２の上質紙を用い、下記組成の受容層液をワイヤーバーコーティングにより乾燥後の塗布量が４．５ｇ／ｍ２となるように塗布、乾燥した。このときの受容層液塗工面の温度は最高で６５℃であった。この後、キャレンダー処理を行ない表面受容層紙を得た。この表面の平滑度は２５０秒だった。
次いで、実施例１と同様の方法で、グラシン紙に粘着付与層液を塗布、乾燥した後、粘着付与層と上記の表面受容層紙の裏面と張り合わせ実施例３の熱転写記録用ラベルを得た。
受容層液
スチレン−アクリル共重合樹脂水系エマルション ２０部
（固形分４５％、ＭＦＴ０℃、Ｔｇ５℃）
ポリエステル樹脂水系エマルション ２０部
（固形分４０％、ＭＦＴ４０℃、Ｔｇ５２℃）
シリカ ５部
水 ２０部
Example 3
A high quality paper having a basis weight of 66 g / m 2 was used as a substrate, and a receiving layer solution having the following composition was applied by wire bar coating so that the applied amount after drying was 4.5 g / m 2, and dried. At this time, the temperature of the receiving layer liquid coated surface was 65 ° C. at the maximum. Thereafter, a calendering treatment was performed to obtain a surface receiving layer paper. The smoothness of this surface was 250 seconds.
Next, in the same manner as in Example 1, the tackifier layer solution was applied to glassine paper and dried, and then the tackifier layer and the back surface of the above-mentioned surface receiving layer paper were laminated to obtain a thermal transfer recording label of Example 3. .
Receptor layer liquid Styrene-acrylic copolymer resin aqueous emulsion 20 parts (solid content 45%, MFT 0 ° C, Tg 5 ° C)
20 parts of polyester resin aqueous emulsion (solid content 40%, MFT 40 ° C, Tg 52 ° C)
Silica 5 parts Water 20 parts
実施例４
基材として、坪量６６ｇ／ｍ２の上質紙を用い、下記組成の受容層液をワイヤーバーコーティングにより乾燥後の塗布量が４．５ｇ／ｍ２となるように塗布、乾燥した。このときの受容層液塗工面の温度は最高で９５℃であった。この後、キャレンダー処理を行ない表面受容層紙を得た。この表面の平滑度は４００秒だった。
次いで、実施例１と同様の方法で、グラシン紙に粘着付与層液を塗布、乾燥した後、粘着付与層と上記の表面受容層紙の裏面と張り合わせ実施例４の熱転写記録用ラベルを得た。
受容層液
アクリル酸−メタクリル酸共重合樹脂水系エマルション ２０部
（固形分４５％、ＭＦＴ７９℃、Ｔｇ８５℃）
中空粒子 ５部
（固形分５０％、中空率５０％、コア剤はスチレン−アクリル共重合体）
シリカ ５部
水 ２０部
Example 4
A high quality paper having a basis weight of 66 g / m 2 was used as a substrate, and a receiving layer solution having the following composition was applied by wire bar coating so that the applied amount after drying was 4.5 g / m 2, and dried. At this time, the temperature of the receiving layer liquid coated surface was 95 ° C. at the maximum. Thereafter, a calendering treatment was performed to obtain a surface receiving layer paper. The smoothness of this surface was 400 seconds.
Next, in the same manner as in Example 1, a tackifier layer solution was applied to glassine paper and dried, and then the tackifier layer and the back surface of the surface receiving layer paper were laminated to obtain a thermal transfer recording label of Example 4. .
Receiving layer liquid Acrylic acid-methacrylic acid copolymer resin aqueous emulsion 20 parts (solid content 45%, MFT 79 ° C, Tg 85 ° C)
5 parts of hollow particles (solid content 50%, hollow ratio 50%, core agent is styrene-acrylic copolymer)
Silica 5 parts Water 20 parts
実施例５
基材として、坪量６６ｇ／ｍ２の上質紙を用い、下記組成の受容層液をワイヤーバーコーティングにより乾燥後の塗布量が４．５ｇ／ｍ２となるように塗布、乾燥した。このときの受容層液塗工面の温度は最高で９５℃であった。この後、キャレンダー処理を行ない表面受容層紙を得た。この表面の平滑度は８００秒だった。
次いで、実施例１と同様の方法で、グラシン紙に粘着付与層液を塗布、乾燥した後、粘着付与層と上記の表面受容層紙の裏面と張り合わせ実施例５の熱転写記録用ラベルを得た。
受容層液
アクリル酸−メタクリル酸共重合樹脂水系エマルション １５部
（固形分４５％、ＭＦＴ７９℃、Ｔｇ８５℃）
ポリウレタン樹脂水系エマルション １５部
（固形分４０％、ＭＦＴ１３℃、Ｔｇ２６℃）
中空粒子 ５部
（固形分５０％、中空率５０％ コア剤はスチレン−アクリル共重合体）
シリカ ５部
水 ２０部
Example 5
A high quality paper having a basis weight of 66 g / m 2 was used as a substrate, and a receiving layer solution having the following composition was applied by wire bar coating so that the applied amount after drying was 4.5 g / m 2, and dried. At this time, the temperature of the receiving layer liquid coated surface was 95 ° C. at the maximum. Thereafter, a calendering treatment was performed to obtain a surface receiving layer paper. The smoothness of this surface was 800 seconds.
Then, in the same manner as in Example 1, a tackifier layer solution was applied to glassine paper and dried, and then the tackifier layer and the back surface of the surface receiving layer paper were laminated to obtain a thermal transfer recording label of Example 5. .
Receiving layer liquid Acrylic acid-methacrylic acid copolymer resin aqueous emulsion 15 parts (solid content 45%, MFT 79 ° C, Tg 85 ° C)
Polyurethane resin aqueous emulsion 15 parts (solid content 40%, MFT 13 ° C, Tg 26 ° C)
5 parts of hollow particles (solid content 50%, hollow ratio 50%, core agent is styrene-acrylic copolymer)
Silica 5 parts Water 20 parts
実施例６
基材として、坪量６６ｇ／ｍ２の上質紙を用い、表面に下記組成の中間層液をワイヤーバーコーティングにより乾燥後の塗布量が３．０ｇ／ｍ２となるように塗布、乾燥した。次いで、中間層上に下記組成の受容層液をワイヤーバーコーティングにより乾燥後の塗布量が４．５ｇ／ｍ２となるように塗布、乾燥した。このときの受容層液塗工面の温度は最高で９５℃であった。この後、キャレンダー処理を行ない表面受容層紙を得た。この表面の平滑度は１２００秒だった。
次いで、実施例１と同様の方法で、グラシン紙に粘着付与層液を塗布、乾燥した後、粘着付与層と上記の表面受容層紙の裏面と張り合わせ実施例６の熱転写記録用ラベルを得た。
中間層液
ジアルデヒドデンプン（５％水溶液） ２０部
グリオキザール ５部
水酸化アルミニウム粉末 ２部
水 ７３部
受容層液
アクリル酸−メタクリル酸共重合樹脂水系エマルション １５部
（固形分４５％、ＭＦＴ７９℃、Ｔｇ８５℃）
ポリウレタン樹脂水系エマルション １５部
（固形分４０％、ＭＦＴ１３℃、Ｔｇ２６℃）
中空粒子 １０部
（固形分４０％、中空率９０％、
コア剤は塩化ビニリデン−メタクリル酸メチル共重合体）
シリカ ５部
水 ２０部
Example 6
Using a high-quality paper having a basis weight of 66 g / m 2 as a base material, an intermediate layer solution having the following composition was applied to the surface by wire bar coating so that the coating amount after drying was 3.0 g / m 2 , followed by drying. Next, a receiving layer liquid having the following composition was applied onto the intermediate layer by wire bar coating so that the coating amount after drying was 4.5 g / m 2, and the coating was dried. At this time, the temperature of the receiving layer liquid coated surface was 95 ° C. at the maximum. Thereafter, a calendering treatment was performed to obtain a surface receiving layer paper. The smoothness of this surface was 1200 seconds.
Then, in the same manner as in Example 1, a tackifier layer solution was applied to glassine paper and dried, and then the tackifier layer and the back surface of the surface receiving layer paper were laminated to obtain a thermal transfer recording label of Example 6. .
Intermediate layer liquid Dialdehyde starch (5% aqueous solution) 20 parts Glyoxal 5 parts Aluminum hydroxide powder 2 parts Water 73 parts Reception layer liquid Acrylic acid-methacrylic acid copolymer resin aqueous emulsion 15 parts (solid content 45%, MFT 79 ° C, Tg 85) ℃)
Polyurethane resin aqueous emulsion 15 parts (solid content 40%, MFT 13 ° C, Tg 26 ° C)
10 parts of hollow particles (solid content 40%, hollow ratio 90%,
The core agent is vinylidene chloride-methyl methacrylate copolymer)
Silica 5 parts Water 20 parts
実施例７
基材として、坪量６６ｇ／ｍ２の上質紙を用い、表面に下記組成の中間層液をワイヤーバーコーティングにより乾燥後の塗布量が３．０ｇ／ｍ２となるように塗布、乾燥した。この乾燥物を４０℃環境下に３時間放置し中間層を得た。次いで、中間層上に実施例６と同じ組成の受容層液をワイヤーバーコーティングにより乾燥後の塗布量が４．５ｇ／ｍ２となるように塗布、乾燥した。このときの受容層液塗工面の温度は最高で１０５℃であった。この後、キャレンダー処理を行ない表面受容層紙を得た。この表面の平滑度は７００秒だった。
次いで、実施例１と同様の方法で、グラシン紙に粘着付与層液を塗布、乾燥した後、粘着付与層と上記の表面受容層紙の裏面と張り合わせ実施例７の熱転写記録用ラベルを得た。
中間層液
カルボキシ基変性ポリビニールアルコール（１０％水溶液） ５０部
ポリアミドエピクロヒドリン樹脂（１２．５％水溶液） １０部
水酸化アルミニウム粉末 ２部
水 ８１部
Example 7
Using a high-quality paper having a basis weight of 66 g / m 2 as a base material, an intermediate layer solution having the following composition was applied to the surface by wire bar coating so that the coating amount after drying was 3.0 g / m 2 , followed by drying. This dried product was left under an environment of 40 ° C. for 3 hours to obtain an intermediate layer. Next, a receiving layer liquid having the same composition as in Example 6 was applied onto the intermediate layer by wire bar coating so that the coating amount after drying was 4.5 g / m 2, and the coating was dried. At this time, the temperature of the receiving layer liquid coated surface was 105 ° C. at the maximum. Thereafter, a calendering treatment was performed to obtain a surface receiving layer paper. The smoothness of this surface was 700 seconds.
Next, in the same manner as in Example 1, the tackifier layer solution was applied to glassine paper and dried, and then the tackifier layer was bonded to the back surface of the surface receiving layer paper to obtain a thermal transfer recording label of Example 7. .
Intermediate layer liquid Carboxy group-modified polyvinyl alcohol (10% aqueous solution) 50 parts Polyamide epichlorohydrin resin (12.5% aqueous solution) 10 parts Aluminum hydroxide powder 2 parts Water 81 parts
実施例８
基材として、坪量６６ｇ／ｍ２の上質紙を用い、表面に下記組成の中間層液をワイヤーバーコーティングにより乾燥後の塗布量が３．０ｇ／ｍ２となるように塗布、乾燥した。この乾燥物を４０℃環境下に３時間放置し中間層を得た。次いで、中間層上に以下組成の受容層液をワイヤーバーコーティングにより乾燥後の塗布量が４．５ｇ／ｍ２となるように塗布、乾燥した。このときの受容層液塗工面の温度は最高で１０５℃であった。この後、キャレンダー処理を行ない表面受容層紙を得た。この表面の平滑度は７００秒だった。
次いで、実施例１と同様の方法で、グラシン紙に粘着付与層液を塗布、乾燥した後、粘着付与層と上記の表面受容層紙の裏面と張り合わせ実施例８の熱転写記録用ラベルを得た。
中間層液
カルボキシ基変性ポリビニールアルコール（１０％水溶液） ５０部
ポリアミドエピクロヒドリン樹脂（１２．５％水溶液） １０部
水酸化アルミニウム粉末 ２部
水 ８１部
受容層液
アクリル酸−メタクリル酸共重合樹脂水系エマルション １９部
（固形分４５％、ＭＦＴ７９℃、Ｔｇ８５℃）
ポリウレタン樹脂水系エマルション １１部
（固形分４０％、ＭＦＴ１３℃、Ｔｇ２６℃）
中空粒子 １０部
（固形分４０％、中空率９０％、
コア剤は塩化ビニリデン−メタクリル酸メチル共重合体）
シリカ ５部
水 ２０部
Example 8
Using a high-quality paper having a basis weight of 66 g / m 2 as a base material, an intermediate layer solution having the following composition was applied to the surface by wire bar coating so that the coating amount after drying was 3.0 g / m 2 , followed by drying. This dried product was left under an environment of 40 ° C. for 3 hours to obtain an intermediate layer. Next, a receiving layer solution having the following composition was applied onto the intermediate layer by wire bar coating so that the coating amount after drying was 4.5 g / m 2, and dried. At this time, the temperature of the receiving layer liquid coated surface was 105 ° C. at the maximum. Thereafter, a calendering treatment was performed to obtain a surface receiving layer paper. The smoothness of this surface was 700 seconds.
Then, in the same manner as in Example 1, a tackifier layer solution was applied to glassine paper and dried, and then the tackifier layer and the back surface of the surface receiving layer paper were laminated to obtain a thermal transfer recording label of Example 8. .
Intermediate layer liquid Carboxy group-modified polyvinyl alcohol (10% aqueous solution) 50 parts Polyamide epichlorohydrin resin (12.5% aqueous solution) 10 parts Aluminum hydroxide powder 2 parts Water 81 parts Reception layer liquid Acrylic acid-methacrylic acid copolymer 19 parts of resin-based emulsion (solid content 45%, MFT 79 ° C, Tg 85 ° C)
Polyurethane resin aqueous emulsion 11 parts (solid content 40%, MFT 13 ° C, Tg 26 ° C)
10 parts of hollow particles (solid content 40%, hollow ratio 90%,
The core agent is vinylidene chloride-methyl methacrylate copolymer)
Silica 5 parts Water 20 parts
比較例１
基材として、坪量６６ｇ／ｍ２の上質紙を用い、下記組成の受容層液をワイヤーバーコーティングにより乾燥後の塗布量が４．５ｇ／ｍ２となるように塗布、乾燥した。このときの受容層液塗工面の温度は最高で４５℃であった。この後、キャレンダー処理を行ない表面受容層紙を得た。この表面の平滑度は３５０秒だった。
次いで、実施例１と同様の方法で、グラシン紙に粘着付与層液を塗布、乾燥した後、粘着付与層と上記の表面受容層紙の裏面と張り合わせ比較例１の熱転写記録用ラベルを得た。
受容層液
アクリル酸−メタクリル酸共重合樹脂水系エマルション １５部
（固形分４５％、ＭＦＴ７９℃、Ｔｇ８５℃）
シリカ ５部
水 ２０部
Comparative Example 1
A high quality paper having a basis weight of 66 g / m 2 was used as a substrate, and a receiving layer solution having the following composition was applied by wire bar coating so that the applied amount after drying was 4.5 g / m 2, and dried. At this time, the temperature of the receiving layer liquid coated surface was 45 ° C. at the maximum. Thereafter, a calendering treatment was performed to obtain a surface receiving layer paper. The smoothness of this surface was 350 seconds.
Then, in the same manner as in Example 1, a tackifier layer solution was applied to glassine paper and dried, and then the tackifier layer and the back surface of the above-described surface receiving layer paper were laminated to obtain a thermal transfer recording label of Comparative Example 1. .
Receiving layer liquid Acrylic acid-methacrylic acid copolymer resin aqueous emulsion 15 parts (solid content 45%, MFT 79 ° C, Tg 85 ° C)
Silica 5 parts Water 20 parts
比較例２
基材として、坪量６６ｇ／ｍ２の上質紙を用い、下記組成の受容層液をワイヤーバーコーティングにより乾燥後の塗布量が４．５ｇ／ｍ２となるように塗布、乾燥した。このときの受容層液塗工面の温度は最高で４８℃であった。この後、キャレンダー処理を行ない表面受容層紙を得た。この表面の平滑度は３５０秒だった。
次いで、実施例１と同様の方法で、グラシン紙に粘着付与層液を塗布、乾燥した後、粘着付与層と上記の表面受容層紙の裏面と張り合わせ比較例２の熱転写記録用ラベルを得た。
受容層液
ポリ塩化ビニリデン樹脂水系エマルション ２０部
（固形分４２％、ＭＦＴ５３℃、Ｔｇ６５℃）
中空粒子 ５部
（固形分５０％、中空率５０％ コア剤はスチレン−アクリル共重合体）
シリカ ５部
水 ２０部
Comparative Example 2
A high quality paper having a basis weight of 66 g / m 2 was used as a substrate, and a receiving layer solution having the following composition was applied by wire bar coating so that the applied amount after drying was 4.5 g / m 2, and dried. At this time, the temperature of the receiving layer liquid coated surface was 48 ° C. at the maximum. Thereafter, a calendering treatment was performed to obtain a surface receiving layer paper. The smoothness of this surface was 350 seconds.
Then, in the same manner as in Example 1, a tackifier layer solution was applied to glassine paper and dried, and then the tackifier layer and the back surface of the above-described surface receiving layer paper were laminated to obtain a thermal transfer recording label of Comparative Example 2. .
Reception layer liquid Polyvinylidene chloride resin aqueous emulsion 20 parts (solid content 42%, MFT 53 ° C, Tg 65 ° C)
5 parts of hollow particles (solid content 50%, hollow ratio 50%, core agent is styrene-acrylic copolymer)
Silica 5 parts Water 20 parts
比較例３
基材として、坪量６６ｇ／ｍ２の上質紙を用い、表面に下記組成の中間層液をワイヤーバーコーティングにより乾燥後の塗布量が３．０ｇ／ｍ２となるように塗布、乾燥した。次いで中間層上に下記組成の受容層液をワイヤーバーコーティングにより乾燥後の塗布量が４．５ｇ／ｍ２となるように塗布、乾燥した。このときの受容層液塗工面の温度は最高で３５℃であった。この後、キャレンダー処理を行ない表面受容層紙を得た。この表面の平滑度は８００秒だった。
次いで、実施例１と同様の方法で、グラシン紙に粘着付与層液を塗布、乾燥した後、粘着付与層と上記の表面受容層紙の裏面と張り合わせ比較例３の熱転写記録用ラベルを得た。
中間層液
ジアルデヒドデンプン（５％水溶液） ２０部
グリオキザール ５部
水酸化アルミニウム粉末 ２部
水 ７３部
受容層液
アクリル酸−メタクリル酸共重合樹脂水系エマルション １５部
（固形分４５％、ＭＦＴ３８℃、Ｔｇ４２℃）
中空粒子 １０部
（固形分４０％、中空率９０％、
コア剤は塩化ビニリデン−メタクリル酸メチル共重合体）
シリカ ５部
水 ２０部
Comparative Example 3
Using a high-quality paper having a basis weight of 66 g / m 2 as a base material, an intermediate layer solution having the following composition was applied to the surface by wire bar coating so that the coating amount after drying was 3.0 g / m 2 , followed by drying. Next, a receiving layer solution having the following composition was applied onto the intermediate layer by wire bar coating so that the coating amount after drying was 4.5 g / m 2, and dried. At this time, the temperature of the receiving layer liquid coated surface was 35 ° C. at the maximum. Thereafter, a calendering treatment was performed to obtain a surface receiving layer paper. The smoothness of this surface was 800 seconds.
Next, in the same manner as in Example 1, the tackifier layer solution was applied to glassine paper, and dried, and then the tackifier layer and the back surface of the surface receiving layer paper were laminated to obtain a thermal transfer recording label of Comparative Example 3. .
Intermediate layer liquid Dialdehyde starch (5% aqueous solution) 20 parts Glyoxal 5 parts Aluminum hydroxide powder 2 parts Water 73 parts Reception layer liquid Acrylic acid-methacrylic acid copolymer resin aqueous emulsion 15 parts (solid content 45%, MFT 38 ° C, Tg 42) ℃)
10 parts of hollow particles (solid content 40%, hollow ratio 90%,
The core agent is vinylidene chloride-methyl methacrylate copolymer)
Silica 5 parts Water 20 parts
＜評価項目と評価方法＞
評価に用いた熱転写記録媒体の作成
片面に耐熱滑性層を設けた厚さ４．５μｍのＰＥＴフィルムを基材とし、この基材の耐熱滑性層を設けた側とは反対の側に下記組成の剥離層液をワイヤーバーコーティングにより、乾燥後の塗布量が０．５ｇ／ｍ２となるように塗布、乾燥し剥離層済シートを得た。次いで下記組成のインク層液を、剥離層済シートの剥離層上に乾燥後の塗布量が１．２ｇ／ｍ２となるように塗布、乾燥し、熱転写記録媒体を作成した。
剥離層液
ポリエチレンワックス １０部
（ポリワックス８５０、東洋ペトロライト社製）
ブタジエンゴム １０部
（トルエン５％溶液、ボンＲＩ−１、コニシ社製）
エチレン・酢酸ビニル樹脂 ０．２部
（エバフレックスＥＶ２５０、三井デュポン社製）
トルエン ７９．８部
インク層液
カーボンブラック ５部
ポリエステル系樹脂 １０部
（ニチゴーポリエスターＴＰ２９５、日本合成化学社製）
カルナバワックス ４部
メチルエチルケトン ８１部
<Evaluation items and evaluation methods>
Preparation of Thermal Transfer Recording Medium Used for Evaluation A 4.5 μm-thick PET film provided with a heat-resistant slip layer on one side was used as a base material, and the following side of the base material opposite to the side provided with the heat-resistant slip layer was The release layer liquid having the composition was applied by wire bar coating so that the applied amount after drying was 0.5 g / m 2, and dried to obtain a release layer-completed sheet. Subsequently, an ink layer liquid having the following composition was applied onto the release layer of the release layer-coated sheet so that the applied amount after drying was 1.2 g / m 2, and dried to prepare a thermal transfer recording medium.
Release layer liquid Polyethylene wax 10 parts (Polywax 850, manufactured by Toyo Petrolite)
Butadiene rubber 10 parts (5% solution in toluene, Bon RI-1, manufactured by Konishi)
0.2 parts of ethylene / vinyl acetate resin (Evaflex EV250, manufactured by Mitsui DuPont)
Toluene 79.8 parts Ink layer liquid Carbon black 5 parts Polyester resin 10 parts (Nichigo Polyester TP295, manufactured by Nippon Synthetic Chemical Company)
Carnauba wax 4 parts Methyl ethyl ketone 81 parts
１．印字画像の評価
熱転写記録用ラベルについて、以下の条件で印字を行なった。
印字条件
サーマルヘッド：部分グレーズ薄膜ヘッド（８ｄｏｔ／ｍｍ）
プラテン圧：１５０ｇ／ｃｍ
記録媒体の引き剥がし角度：３０°
引き剥がしトルク：２００ｇ
印字速度：１００ｍｍ／ｓ
1. Evaluation of Printed Image Printing was performed on the thermal transfer recording label under the following conditions.
Printing conditions Thermal head: Partial glaze thin film head (8 dots / mm)
Platen pressure: 150g / cm
Peeling angle of recording medium: 30 °
Peeling torque: 200g
Printing speed: 100mm / s
１−１．受容層の転写
印字後の熱転写記録媒体を観察し、受容層成分が熱転写記録用ラベル側から転写していないかどうかを目視にて確認した。
1-1. Transfer of Receptive Layer The thermal transfer recording medium after printing was observed, and it was visually confirmed whether or not the components of the receiving layer were transferred from the label for thermal transfer recording.
１−２．画像耐性（耐エタノール性）
上記印字条件にて印字エネルギーは熱感度の印字エネルギー＋１．０ｍｊ／ｍｍ２で（２・５）パラレルバーコードを印字して印字サンプルを得た。
その印字画像上にエタノールを充分滴下し、荷重２００ｇ／ｍ２にて対物に綿布を用い１００回擦り、その印字画像を下記の評価を行ない印字画像の耐エタノール性とした。
○：画像の破損が全くない
△：一部画像の破損がある
×：全体に画像の破損がある
1-2. Image resistance (ethanol resistance)
A printing sample was obtained by printing a (2.5) parallel bar code at a printing energy of +1.0 mj / mm 2 under the printing conditions described above.
Ethanol was sufficiently dropped on the printed image and rubbed 100 times with a cotton cloth at a load of 200 g / m 2 as an object. The printed image was evaluated as follows to obtain the ethanol resistance of the printed image.
：: no image damage Δ: partial image damage ×: entire image damage
１−３．画像耐性（耐水性）
２−２と同様の方法で印字サンプルを得た。
その印字サンプルを２４時間水中に浸漬した後、印字画像を指で１０回擦り、その印字画像を下記の評価を行ない印字画像の耐水性とした。
○：画像の破損が全くない
△：一部画像の破損がある
×：全体に画像の破損がある
1-3. Image resistance (water resistance)
A print sample was obtained in the same manner as in 2-2.
After the printed sample was immersed in water for 24 hours, the printed image was rubbed with a finger 10 times, and the printed image was evaluated as follows to determine the water resistance of the printed image.
：: no image damage Δ: partial image damage ×: entire image damage
１−４．画像耐性（耐摩擦性）
２−２と同様の方法で印字サンプルを得た。そのサンプルの印字画像部を約１ｋｇの荷重を掛けたペンスキャナーで、５０ｃｍ／ｓｅｃの速度で１０００回擦り、印字画像の破損の有無にて印字画像の耐摩擦性とした。
1-4. Image resistance (rub resistance)
A print sample was obtained in the same manner as in 2-2. The printed image portion of the sample was rubbed 1,000 times at a speed of 50 cm / sec with a pen scanner with a load of about 1 kg applied thereto, and the printed image was evaluated for the abrasion resistance based on whether or not the printed image was damaged.
２．耐ブロッキング性
熱転写記録用ラベルを３インチ外径の紙管に巻き付け、この巻き付けたものを４０℃で８０％Ｒ．Ｈ．環境下に２４時間保管した後、巻取りをほどき受容層面と接するグラシン紙との間に貼り付きがないかどうかを観察した。
○：貼り付きなし
△：ゆるやかな貼り付きあり。（手で引き剥がすことが容易にでき、引き剥がした跡が残らない）
×：貼り付きあり。（手で引き剥がすと引き剥がした跡が残る。）
2. Blocking resistance A label for thermal transfer recording was wrapped around a 3-inch outer diameter paper tube, and the wrapped product was baked at 40 ° C. and 80% R.D. H. After being stored for 24 hours in an environment, the film was unwound and observed for sticking between the receiving layer surface and the glassine paper in contact with the receiving layer surface.
○: No sticking △: Loose sticking (It can be easily peeled off by hand, leaving no trace of peeling)
×: There is sticking. (When peeled off by hand, traces of peeling remain.)
３．熱転写記録用ラベルの粘着力
実施例１〜８、比較例１〜３で得られた熱転写記録用ラベルについて、粘着力の評価を行なった。
３−１．初期粘着力
熱転写記録用ラベルを２．５ｃｍ×１０ｃｍにカットし、裏面の離型紙を剥がし被着体（アルミニウム板）に貼り付けて、剥離角度１８０°、剥離速度３００ｍｍ／ｍｉｎの条件で剥離させる。そのときの抵抗値を測定し初期接着力とした。
3. Adhesive Strength of Thermal Transfer Recording Label The adhesive strength of the thermal transfer recording labels obtained in Examples 1 to 8 and Comparative Examples 1 to 3 was evaluated.
3-1. Initial adhesive strength The label for thermal transfer recording is cut into 2.5 cm x 10 cm, the release paper on the back is peeled off, and the label is peeled off and adhered to an adherend (aluminum plate) at a peeling angle of 180 ° and a peeling speed of 300 mm / min. . The resistance value at that time was measured and used as the initial adhesive strength.
３−２．接着力の耐エチルアルコール性
熱転写記録用ラベルを２．５ｃｍ×１０ｃｍにカットし、裏面の離型紙を剥がし、被着体（アルミニウム板）に貼り付けて、受容層表面にエチルアルコールを滴下して、２分後に３−１の方法と同様にして接着力を測定し、接着力の耐エチルアルコール性とした。
3-2. Ethyl alcohol resistance of adhesive strength The label for thermal transfer recording is cut into 2.5 cm x 10 cm, the release paper on the back is peeled off, it is stuck on the adherend (aluminum plate), and ethyl alcohol is dropped on the surface of the receiving layer. After 2 minutes, the adhesive force was measured in the same manner as in the method of 3-1 to determine the adhesive force as ethyl alcohol-resistant.
３−３．接着力の耐ガソリン性
３−２のエタノールをガソリンにかえて同様にして接着力を測定し、接着力の耐ガソリン性とした。
3-3. Gasoline Resistance of Adhesive Strength Adhesive strength was measured in the same manner as in 3-2 except that ethanol was replaced by gasoline, and the gasoline resistance of adhesive strength was determined.
３−４．接着力の耐水性
３−２のエタノールを水にかえて同様にして接着力を測定し、接着力の耐水性とした。
3-4. Water Resistance of Adhesive Force Adhesive force was measured in the same manner except that ethanol of 3-2 was replaced with water, and the water resistance of the adhesive force was determined.
Claims (7)
7. The thermal transfer recording receiving paper according to claim 6, wherein the aqueous resin of the intermediate layer is a polyvinyl alcohol / modified polyvinyl alcohol resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003284943A JP4204411B2 (en) | 2002-08-05 | 2003-08-01 | Receptive paper for thermal transfer recording |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002227690 | 2002-08-05 | ||
| JP2003284943A JP4204411B2 (en) | 2002-08-05 | 2003-08-01 | Receptive paper for thermal transfer recording |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004082727A true JP2004082727A (en) | 2004-03-18 |
| JP4204411B2 JP4204411B2 (en) | 2009-01-07 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP2003284943A Expired - Fee Related JP4204411B2 (en) | 2002-08-05 | 2003-08-01 | Receptive paper for thermal transfer recording |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7479470B2 (en) | 2004-08-04 | 2009-01-20 | Ricoh Company, Ltd. | Thermal transfer receiver, method for producing the same, method for recording image, and recorded image |
| JP2014198417A (en) * | 2013-03-29 | 2014-10-23 | 大日本印刷株式会社 | Thermal transfer image receiving sheet and manufacturing method thereof |
-
2003
- 2003-08-01 JP JP2003284943A patent/JP4204411B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7479470B2 (en) | 2004-08-04 | 2009-01-20 | Ricoh Company, Ltd. | Thermal transfer receiver, method for producing the same, method for recording image, and recorded image |
| JP2014198417A (en) * | 2013-03-29 | 2014-10-23 | 大日本印刷株式会社 | Thermal transfer image receiving sheet and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4204411B2 (en) | 2009-01-07 |
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