JP5686375B2 - Reversible thermosensitive recording material - Google Patents
Reversible thermosensitive recording material Download PDFInfo
- Publication number
- JP5686375B2 JP5686375B2 JP2011155941A JP2011155941A JP5686375B2 JP 5686375 B2 JP5686375 B2 JP 5686375B2 JP 2011155941 A JP2011155941 A JP 2011155941A JP 2011155941 A JP2011155941 A JP 2011155941A JP 5686375 B2 JP5686375 B2 JP 5686375B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- thermosensitive recording
- reversible thermosensitive
- recording material
- polysiloxane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Landscapes
- Thermal Transfer Or Thermal Recording In General (AREA)
Description
本発明は、感熱記録層の温度による可逆的な透明度変化を利用して、画像の記録及び消去を何度も繰り返すことを可能にした、記録の書き換えができる可逆性感熱記録材料に関する。 The present invention relates to a reversible thermosensitive recording material capable of rewriting a recording, which makes it possible to repeatedly record and erase an image by utilizing a reversible change in transparency depending on the temperature of a thermosensitive recording layer.
交通機関の定期券、催し会場や建物への入場許可証、各種プリペイドカード等において、種々の情報を記録して格納しておくことができる磁気カードやＩＣカードが使用されている。しかし、これらのカードでは、格納されている記録内容を直接目視することができないため、支払い金額や残高を簡単にチェックすることができず、使用者に対して、格納された情報の内容保証を明確にするといった観点からは問題があった。このような問題に対し、従来、これらのカードを記録媒体とし、該カード類に目視可能な記録を行い、また記録を消去し、さらには格納される情報の変更に伴って当該記録を適宜に書き換えることができる方法が提案されている（特許文献１〜４参照）。例えば、感熱記録材料において、その感熱記録層を可逆性感熱記録塗料で構成することで、該感熱記録層を、サーマルヘッド等の外部からの熱を加えた時に、その温度に応じて透明な状態から白濁状態までの範囲でその光透過性を変え、一方、冷却後にはその状態を保持する性質を持つものにする方法がある。このような感熱記録層を利用することで、文字や画像を、書き換え可能に書き込むことができるようになる。この技術は、上記したような格納される情報の内容が変更されることを前提としたカード類に、目視可能な記録を行い、その変更された情報の内容を随時、目視可能に表示していく方法として極めて有用である。 Magnetic cards and IC cards that can record and store various kinds of information are used in commuter pass tickets for transportation, admission permits to event venues and buildings, and various prepaid cards. However, with these cards, it is not possible to directly check the contents of the stored records, so it is not possible to easily check the payment amount or balance, and guarantee the contents of the stored information to the user. There was a problem in terms of clarity. Conventionally, with respect to such problems, these cards are used as recording media, and visual recording is performed on the cards, the recording is erased, and the recording is appropriately performed according to the change of stored information. Methods that can be rewritten have been proposed (see Patent Documents 1 to 4). For example, in a heat-sensitive recording material, the heat-sensitive recording layer is composed of a reversible heat-sensitive recording paint so that the heat-sensitive recording layer is transparent according to the temperature when heat is applied from the outside such as a thermal head. There is a method of changing the light transmittance in a range from a cloudy state to a cloudy state while maintaining the state after cooling. By using such a heat-sensitive recording layer, characters and images can be written in a rewritable manner. This technology performs visual recording on cards that are premised on the contents of stored information being changed as described above, and displays the contents of the changed information in a visible manner as needed. It is extremely useful as a way to go.
しかしながら、このような感熱記録層を構成する可逆性感熱記録材料は、画像の形成及び消去を繰り返し行うと、サーマルヘッドなどによる度重なる圧力や加熱によって生じる、可逆性感熱記録材料表面のキズや摩耗により画像の形成ができなくなるという問題がある。そこで、感熱記録層の耐久性を向上させるために耐熱性の保護層を設けることが検討されている。例えば、感熱記録層の上に、熱可塑性樹脂や熱硬化性樹脂よりなる保護層を設けたり、紫外線硬化樹脂や電子線硬化樹脂よりなる保護層を設けることが提案されている（特許文献５〜７参照）。しかし、保護層を形成しても、サーマルヘッドで削られた滓がサーマルヘッドに付着し、このことが原因して画像の形成や消去が不十分となるといった問題もある。そのため、形成した保護層に滑性を付与してヘッド滓の発生を防止するため、保護層の形成材料に、硬化性樹脂にシリコーンオイルを添加することや、硬化性シリコーン樹脂やシリコーン変性樹脂を使用することなどが検討されている（特許文献８〜１０参照）。 However, the reversible thermosensitive recording material constituting such a thermosensitive recording layer has scratches and abrasions on the surface of the reversible thermosensitive recording material caused by repeated pressure or heating by a thermal head or the like when image formation and erasure are repeated. This makes it impossible to form an image. Therefore, it has been studied to provide a heat-resistant protective layer in order to improve the durability of the thermosensitive recording layer. For example, it has been proposed to provide a protective layer made of a thermoplastic resin or a thermosetting resin or a protective layer made of an ultraviolet curable resin or an electron beam curable resin on the thermosensitive recording layer (Patent Documents 5 to 5). 7). However, even if the protective layer is formed, wrinkles cut by the thermal head adhere to the thermal head, which causes a problem that image formation and erasure become insufficient. Therefore, in order to impart lubricity to the formed protective layer and prevent the occurrence of head wrinkles, it is necessary to add silicone oil to the curable resin or to add a curable silicone resin or a silicone-modified resin to the protective layer forming material. The use etc. are examined (refer patent documents 8-10).
さらに、最近では、環境問題の高まりから、環境対策に積極的に取り組むメーカーが多くなり、環境保全性に優れた材料を用いて製品を構成する動きがある。上記した可逆性感熱記録材料も例外ではなく、特にゴミ問題や森林破壊問題を背景に、今まで使い捨てられていた物を何度でも書き換え可能になることから、可逆性感熱記録材料に代替することで環境問題（エコ）の解決の一助となるとして注目され、盛んに検討され、一部実用化されている。しかしながら、従来の可逆性感熱記録材料の原料は、そのほとんどが石油由来のものであり、本来の趣旨からすると現在の地球規模での環境保全性という面では未だ不十分である。 Furthermore, recently, due to increasing environmental problems, many manufacturers are actively working on environmental measures, and there is a movement to construct products using materials with excellent environmental conservation. The above-mentioned reversible thermosensitive recording material is no exception, and it is possible to rewrite a disposable object as many times as possible, especially against the backdrop of garbage problems and forest destruction problems. Attention has been paid to helping to solve environmental problems (eco), and it has been actively studied and partly put into practical use. However, most of the raw materials for conventional reversible thermosensitive recording materials are derived from petroleum. From the original point of view, the current environmental conservation on a global scale is still insufficient.
非特許文献１、２に見られるように、二酸化炭素を原料とするポリヒドロキシポリウレタン樹脂については以前から知られているが、その応用展開は進んでいないのが実情である。それは、従来から知られている上記の樹脂は、従来の同種系の高分子化合物（石化プラスチック）であるポリウレタン系樹脂に比べて特性面で明らかに劣るからである（特許文献１１、１２）。 As can be seen in Non-Patent Documents 1 and 2, polyhydroxy polyurethane resin using carbon dioxide as a raw material has been known for a long time, but its application development has not progressed. This is because the above-mentioned resins that have been conventionally known are clearly inferior in terms of characteristics as compared to conventional polyurethane-based resins that are the same type of high-molecular compound (fossilized plastic) (Patent Documents 11 and 12).
一方、増加の一途をたどる二酸化炭素の排出に起因すると考えられる地球の温暖化現象は、近年、世界的な問題になっており、二酸化炭素の排出量低減は、全世界的に重要な課題であり、二酸化炭素を製造原料とできる技術の開発が待望されている。さらに枯渇性石化資源（石油）問題の観点からも、バイオマス、メタンなどの再生可能資源への転換が世界的潮流となっている。 On the other hand, the global warming phenomenon, which is thought to result from the ever-increasing carbon dioxide emissions, has become a global problem in recent years, and the reduction of carbon dioxide emissions is an important issue worldwide. There is a long-awaited development of technology that can use carbon dioxide as a raw material for production. Furthermore, from the viewpoint of the depleted petrochemical resources (oil) problem, the shift to renewable resources such as biomass and methane has become a global trend.
上記のような背景下、再び、ポリヒドロキシポリウレタン樹脂が見直されている。すなわち、この樹脂の原料である二酸化炭素は、容易に入手可能で、かつ、持続可能な炭素資源であり、さらに、二酸化炭素を原料とするプラスチックは、温暖化、資源枯渇などの問題を解決する有効な手段であると言えるからである。 Against the background as described above, the polyhydroxy polyurethane resin has been reviewed again. In other words, carbon dioxide, which is the raw material for this resin, is an easily available and sustainable carbon resource, and plastics that use carbon dioxide as a raw material solve problems such as global warming and resource depletion. It is because it can be said that it is an effective means.
このような状況下、感熱記録層を有する可逆性感熱記録材料表面に、良好な耐熱性及び滑性が付与されて、サーマルヘッドなどの発熱体によって画像形成及び消去を何回繰り返しても、また、サーマルヘッドの熱及び圧力が高くても表面のキズ及びヘッド滓付着がなく、さらに、表面に印刷する際の印刷適性が良好であると共に、地球規模での環境保全性を持った環境対応製品の可逆性感熱記録材料の開発が要望されている。 Under such circumstances, the surface of the reversible thermosensitive recording material having the thermosensitive recording layer is imparted with good heat resistance and lubricity, and no matter how many times image formation and erasure are repeated by a heating element such as a thermal head, Even if the thermal head pressure and heat are high, there are no scratches on the surface and no head wrinkles. Furthermore, it has good printability when printing on the surface and is environmentally friendly on a global scale. Development of a reversible thermosensitive recording material is demanded.
したがって、本発明の目的は、耐熱性及び滑性に優れ、サーマルヘッドなどの発熱体によって画像形成及び消去を何回繰り返しても、また、熱及び圧力が高くても表面のキズ及びヘッド滓付着がない滑性保護層を有する可逆性感熱記録材料でありながら、二酸化炭素を原料とし得、地球環境保護の観点からも有用な、環境対応製品を提供し得る技術を開発することにある。 Therefore, the object of the present invention is excellent in heat resistance and slipperiness, and even if image formation and erasing are repeated many times by a heating element such as a thermal head, and even if heat and pressure are high, surface scratches and head wrinkles adhere. The object of the present invention is to develop a technology capable of providing an environmentally-friendly product that can use carbon dioxide as a raw material and is also useful from the viewpoint of protecting the global environment, even though it is a reversible thermosensitive recording material having a slippery protective layer.
上記目的は以下の本発明によって達成される。すなわち、本発明は、基材及び該基材の少なくとも一方の面に設けられた、感熱記録層と、耐熱保護層を含む中間層と、最上層の滑性保護層とをこの順に有する可逆性感熱記録材料において、上記感熱記録層が、高分子樹脂及び該高分子樹脂中に分散された有機低分子物質を主成分としてなる、透明度が温度によって透明な状態から白濁状態までの範囲で可逆的に変化し得、冷却後にはその状態を保持する性質を持つ、前記滑性保護層側からのサーマルヘッド又は熱ロールによる加熱によって繰り返し記録、消去を行うことができるようにするための可逆性感熱記録層であり、かつ、上記滑性保護層が、５員環環状カーボネート化合物とアミン変性ポリシロキサン化合物との反応から誘導されたポリシロキサン変性ポリヒドロキシポリウレタン樹脂を主成分として含む樹脂組成物と、該樹脂の構造中の水酸基と反応する架橋剤とによって形成されている乾燥後の厚さが１．０〜３．０μｍの架橋皮膜であることを特徴とする可逆性感熱記録材料を提供する。 The above object is achieved by the present invention described below. That is, the present invention is a reversible having a base material and a heat-sensitive recording layer, an intermediate layer including a heat-resistant protective layer, and an uppermost slippery protective layer provided in this order on at least one surface of the base material . In the thermosensitive recording material, the thermosensitive recording layer is mainly composed of a polymer resin and an organic low molecular weight substance dispersed in the polymer resin. The transparency is reversible in a range from a transparent state to a cloudy state depending on temperature. Reversible heat-sensitive to allow repeated recording and erasing by heating with a thermal head or heat roll from the slipping protective layer side, which has the property of maintaining the state after cooling. A polysiloxane-modified polyhydroxypolyurea, which is a recording layer and the slip protective layer is derived from a reaction between a 5-membered cyclic carbonate compound and an amine-modified polysiloxane compound. Wherein a resin composition comprising a resin as a main component, the thickness after drying which is formed by a crosslinking agent which reacts with hydroxyl group in the structure of the resin is a crosslinked coating of 1.0~3.0μm A reversible thermosensitive recording material is provided.
本発明の可逆性感熱記録材料の好ましい形態としては、下記のものが挙げられる。前記５員環環状カーボネート化合物が、エポキシ化合物と二酸化炭素を反応させて得られる可逆性感熱記録材料。前記ポリシロキサン変性ポリヒドロキシポリウレタン樹脂が、二酸化炭素を１〜２５質量％含有する可逆性感熱記録材料。前記ポリシロキサン変性ポリヒドロキシポリウレタン樹脂が、その分子中に占めるポリシロキサンセグメントの含有量が１〜７５質量％のものである可逆性感熱記録材料。前記滑性保護層が、前記ポリシロキサン変性ポリヒドロキシポリウレタン樹脂構造中の水酸基と、該水酸基と反応する架橋剤で架橋して形成される可逆性感熱記録材料。前記中間層が、印刷層、着色層、耐熱保護層からなる一層又は多層の組み合わせからなる可逆性感熱記録材料。 Preferred forms of the reversible thermosensitive recording material of the present invention include the following. A reversible thermosensitive recording material obtained by reacting an epoxy compound and carbon dioxide with the 5-membered cyclic carbonate compound. A reversible thermosensitive recording material in which the polysiloxane-modified polyhydroxypolyurethane resin contains 1 to 25% by mass of carbon dioxide. A reversible thermosensitive recording material in which the polysiloxane-modified polyhydroxypolyurethane resin has a polysiloxane segment content in the molecule of 1 to 75% by mass. A reversible thermosensitive recording material in which the slip protective layer is formed by crosslinking with a hydroxyl group in the polysiloxane-modified polyhydroxy polyurethane resin structure and a crosslinking agent that reacts with the hydroxyl group. A reversible thermosensitive recording material in which the intermediate layer comprises a single layer or a combination of multiple layers comprising a printed layer, a colored layer, and a heat-resistant protective layer.
上記本発明によれば、滑性保護層を、ポリシロキサン変性ポリヒドロキシポリウレタン樹脂を用いて形成することで、滑性及び耐熱性に優れ、サーマルヘッド又は熱ロールなどの加熱及び圧力に強く、更にはサーマルヘッドによる表面のキズ及びヘッド滓付着防止、及び印刷適性が良好な可逆性感熱記録材料が提供される。上記樹脂は、このように優れた可逆性感熱記録材料を提供できるものであると同時に、二酸化炭素を原料とし得、樹脂中に二酸化炭素を取り入れることができるので、地球温暖化ガス削減に寄与し得る環境対応製品としての可逆性感熱記録材料の提供が可能となる。 According to the present invention, the slippery protective layer is formed using a polysiloxane-modified polyhydroxypolyurethane resin, so that it is excellent in slipperiness and heat resistance, resistant to heating and pressure such as a thermal head or a heat roll, Provides a reversible thermosensitive recording material that has good thermal aptitude, surface flaws and head wrinkle prevention, and good printability. The above resin can provide such an excellent reversible thermosensitive recording material. At the same time, carbon dioxide can be used as a raw material, and carbon dioxide can be incorporated into the resin, contributing to the reduction of global warming gas. It is possible to provide a reversible thermosensitive recording material as an environmentally friendly product.
次に好ましい実施の形態を挙げて本発明をさらに詳しく説明する。
＜滑性保護層＞
本発明の可逆性感熱記録材料は、基材の少なくとも一方の面に、透明度が温度によって可逆的に変化し得る感熱記録層と、必要に応じてその上に中間層を積層し、さらに最上層に滑性保護層を設けたものであり、かつ、該滑性保護層を下記の構成としたことを特徴とする。すなわち、該滑性保護層を構成する高分子化合物が、５員環環状カーボネート化合物とアミン変性ポリシロキサン化合物との反応から誘導されたポリシロキサン変性ポリヒドロキシポリウレタン樹脂を主成分としたことを特徴とする。
Next, the present invention will be described in more detail with reference to preferred embodiments.
<Sliding protective layer>
The reversible heat-sensitive recording material of the present invention comprises a heat-sensitive recording layer whose transparency can be reversibly changed depending on temperature on at least one surface of a substrate, and an intermediate layer on the heat-sensitive recording layer, if necessary. A slipping protective layer is provided, and the slipping protective layer has the following structure. That is, the polymer compound constituting the slipping protective layer is mainly composed of a polysiloxane-modified polyhydroxypolyurethane resin derived from a reaction between a 5-membered cyclic carbonate compound and an amine-modified polysiloxane compound. To do.
本発明で使用する５員環環状カーボネート化合物は、下記［式−Ａ］で示されるようにエポキシ化合物と二酸化炭素とを反応させて製造することができる。更に詳しくは、エポキシ化合物を有機溶媒の存在下又は不存在下及び触媒の存在下、４０℃〜１５０℃の温度で常圧又は僅かに高められた圧力下、１０〜２０時間、二酸化炭素と反応させることによって得られる。
本発明で使用するエポキシ化合物としては、例えば、次の如き化合物が挙げられる。 Examples of the epoxy compound used in the present invention include the following compounds.
以上に列記したエポキシ化合物は、本発明において使用する好ましい化合物であって、本発明はこれらの例示の化合物に限定されるものではない。従って、上述の例示の化合物のみならず、その他、現在市販されており、市場から容易に入手し得る化合物は、いずれも本発明において使用することができる。 The epoxy compounds listed above are preferable compounds used in the present invention, and the present invention is not limited to these exemplified compounds. Accordingly, not only the compounds exemplified above, but also any other compounds that are currently commercially available and can be easily obtained from the market can be used in the present invention.
本発明で用いる５員環環状カーボネート化合物は、前記したように、エポキシ化合物と二酸化炭素の反応によって得られる。この反応において使用される触媒としては、下記のような塩基触媒及びルイス酸触媒が挙げられる。 As described above, the 5-membered cyclic carbonate compound used in the present invention is obtained by a reaction between an epoxy compound and carbon dioxide. Examples of the catalyst used in this reaction include the following base catalysts and Lewis acid catalysts.
塩基触媒としては、トリエチルアミン、トリブチルアミンなどの第三級アミン類、ジアザビシクロウンデセン、ジアザビシクロオクタン、ピリジンなどの環状アミン類、リチウムクロライド、リチウムブロマイド、フッ化リチウム、塩化ナトリウムなどのアルカリ金属塩類、塩化カルシウムなどのアルカリ土類金属塩類、テトラブチルアンモニウムクロライド、テトラエチルアンモニウムブロマイド、ベンジルトリメチルアンモニウムクロライド、などの四級アンモニウム塩類、炭酸カリウム、炭酸ナトリウムなどの炭酸塩類、酢酸亜鉛、酢酸鉛、酢酸銅、酢酸鉄などの金属酢酸塩類、酸化カルシウム、酸化マグネシウム、酸化亜鉛などの金属酸化物、テトラブチルホスホニウムクロリドなどのホスホニウム塩類が挙げられる。 Base catalysts include tertiary amines such as triethylamine and tributylamine, cyclic amines such as diazabicycloundecene, diazabicyclooctane and pyridine, alkalis such as lithium chloride, lithium bromide, lithium fluoride and sodium chloride. Metal salts, alkaline earth metal salts such as calcium chloride, quaternary ammonium salts such as tetrabutylammonium chloride, tetraethylammonium bromide, benzyltrimethylammonium chloride, carbonates such as potassium carbonate and sodium carbonate, zinc acetate, lead acetate, Examples thereof include metal acetates such as copper acetate and iron acetate, metal oxides such as calcium oxide, magnesium oxide and zinc oxide, and phosphonium salts such as tetrabutylphosphonium chloride.
また、ルイス酸触媒としては、テトラブチル錫、ジブチル錫ジラウレート、ジブチル錫ジアセテート、ジブチル錫オクトエートなどの錫化合物が挙げられる。 Examples of the Lewis acid catalyst include tin compounds such as tetrabutyltin, dibutyltin dilaurate, dibutyltin diacetate, and dibutyltin octoate.
これらの触媒の使用量は、エポキシ化合物５０質量部当たり、０．１〜１００質量部、好ましくは０．３〜２０質量部とすればよい。上記使用量が０．１質量部未満では、触媒としての効果が小さく、多過ぎると最終樹脂の諸性能を低下させるおそれがあるので好ましくない。従って、残留触媒が重大な性能低下を引き起こすような場合は、純水で洗浄して残留触媒を除去してもよい。 The amount of these catalysts used may be 0.1 to 100 parts by weight, preferably 0.3 to 20 parts by weight, per 50 parts by weight of the epoxy compound. If the amount used is less than 0.1 parts by mass, the effect as a catalyst is small, and if it is too much, various performances of the final resin may be deteriorated. Therefore, when the residual catalyst causes a serious performance deterioration, the residual catalyst may be removed by washing with pure water.
エポキシ化合物と二酸化炭素の反応においては使用できる有機溶媒としては、ジメチルホルムアミド、ジメチルスルホオキシド、ジメチルアセトアミド、Ｎ−メチルピロリドン、Ｎ−エチルピロリドン、テトラヒドロフランなどが挙げられる。また、これら有機溶剤と他の貧溶剤、例えば、メチルエチルケトン、キシレン、トルエン、テトラヒドロフラン、ジエチルエーテル、シクロヘキサノンなどの混合系で使用してもよい。 Examples of the organic solvent that can be used in the reaction between the epoxy compound and carbon dioxide include dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, and tetrahydrofuran. These organic solvents and other poor solvents such as methyl ethyl ketone, xylene, toluene, tetrahydrofuran, diethyl ether, and cyclohexanone may be used in a mixed system.
本発明で使用する樹脂は、下記式［式−Ｂ］で示されるように、例えば、上記反応で得た５員環環状カーボネート化合物と、アミン変性ポリシロキサン化合物とを、有機溶媒の存在下、２０℃〜１５０℃の温度下で反応させることで、本発明のポリシロキサン変性ポリヒドロキシポリウレタン樹脂を得ることができる。 As shown by the following formula [Formula-B], the resin used in the present invention is obtained by, for example, combining a 5-membered cyclic carbonate compound obtained by the above reaction and an amine-modified polysiloxane compound in the presence of an organic solvent. By reacting at a temperature of 20 ° C. to 150 ° C., the polysiloxane-modified polyhydroxy polyurethane resin of the present invention can be obtained.
上記反応に使用するアミン変性ポリシロキサン化合物としては、例えば、次の如き化合物が挙げられる。なお、下記式中の低級アルキレン基とは、炭素数１〜６程度のアルキレン基のことである。 Examples of the amine-modified polysiloxane compound used in the above reaction include the following compounds. In addition, the lower alkylene group in a following formula is a C1-C6 alkylene group.
以上に列記したアミン変性ポリシロキサン化合物は、本発明において使用する好ましい化合物であって、本発明はこれらの例示の化合物に限定されるものではない。従って、上述の例示の化合物のみならず、その他現在市販されており、市場から容易に入手し得る化合物は、いずれも本発明において使用することができる。 The amine-modified polysiloxane compounds listed above are preferred compounds used in the present invention, and the present invention is not limited to these exemplified compounds. Accordingly, not only the above-exemplified compounds but also any other compounds that are currently commercially available and can be easily obtained from the market can be used in the present invention.
上記のようにして得られたポリシロキサン変性ポリヒドロキシポリウレタン樹脂は、その分子中に占めるポリシロキサンセグメントの含有量が１〜７５質量％となる量であることが好ましい。すなわち、１質量％未満ではポリシロキサンセグメントに基づく表面エネルギーに伴う機能の発現が不十分となるので好ましくない。また、７５質量％を超えるとポリシロキサン変性ポリヒドロキシウレタン樹脂の機械強度、耐磨耗性などの性能が不十分となるので好ましくはない。より好ましくは２〜６５質量％であり、さらには５〜３０質量％であることがより好ましい。 The polysiloxane-modified polyhydroxypolyurethane resin obtained as described above is preferably an amount such that the content of the polysiloxane segment in the molecule is 1 to 75% by mass. That is, if it is less than 1% by mass, the expression of the function accompanying the surface energy based on the polysiloxane segment becomes insufficient, which is not preferable. On the other hand, if it exceeds 75% by mass, the performance of the polysiloxane-modified polyhydroxyurethane resin such as mechanical strength and abrasion resistance becomes insufficient, such being undesirable. More preferably, it is 2-65 mass%, and it is more preferable that it is 5-30 mass%.
また、本発明のポリシロキサン変性ポリヒドロキシポリウレタン樹脂の数平均分子量（ＧＰＣで測定した標準ポリスチレン換算値）は、２，０００〜１００，０００程度であることが好ましい。さらには、５，０００〜７０，０００程度のものであることがより好ましい。 Moreover, it is preferable that the number average molecular weight (standard polystyrene conversion value measured by GPC) of the polysiloxane modified polyhydroxy polyurethane resin of the present invention is about 2,000 to 100,000. Furthermore, it is more preferable that it is a thing of about 5,000-70,000.
本発明で使用するポリシロキサン変性ポリヒドロキシポリウレタン樹脂は、５員環環状カーボネート化合物と、アミン変性ポリシロキサン化合物との反応から誘導される。このため、該樹脂の構造中の５員環環状カーボネート基がアミン化合物と反応して生成する水酸基が、本発明の可逆性感熱記録材料に対して更なる性能の向上をもたらすことになる。すなわち、水酸基は親水性を有しているため、該樹脂を用いて形成された滑性保護層の接着性を格段に向上させることができる。また、樹脂構造中の水酸基と、該樹脂に添加した架橋剤などとの反応を利用すれば、更なる耐熱性、耐摩耗性、耐擦傷性といった耐久性の向上を図ることができ、より優れた滑性保護層の形成が可能となる。 The polysiloxane-modified polyhydroxypolyurethane resin used in the present invention is derived from a reaction between a 5-membered cyclic carbonate compound and an amine-modified polysiloxane compound. For this reason, the hydroxyl group produced when the 5-membered cyclic carbonate group in the structure of the resin reacts with the amine compound brings about further improvement in the performance of the reversible thermosensitive recording material of the present invention. That is, the hydroxyl group because it has hydrophilic, it is possible to remarkably improve the contact adhesion of lubricous protective layer formed by using the resin. Further, by utilizing the reaction between the hydroxyl group in the resin structure and the crosslinking agent added to the resin, it is possible to further improve durability such as heat resistance, wear resistance, and scratch resistance. A slippery protective layer can be formed.
本発明の可逆性感熱記録材料を構成する滑性保護層は、上記したポリシロキサン変性ポリヒドロキシポリウレタン樹脂からなる被膜として形成できるが、架橋剤を用いて架橋被膜とすることもできる。この際、使用可能な架橋剤としては、水酸基と反応するような架橋剤はすべて使用できる。例えばアルキルチタネート化合物やポリイソシアネート化合物が挙げられる。従来、ポリウレタン樹脂の架橋に使用されている公知のポリイソシアネート化合物であれば特に限定されない。例えば、下記のような構造式のポリイソシアネートと他の化合物との付加体などが挙げられる。 The slippery protective layer constituting the reversible thermosensitive recording material of the present invention can be formed as a film made of the polysiloxane-modified polyhydroxypolyurethane resin, but can also be formed into a crosslinked film using a crosslinking agent. At this time, as a usable crosslinking agent, any crosslinking agent that reacts with a hydroxyl group can be used. Examples include alkyl titanate compounds and polyisocyanate compounds. Any known polyisocyanate compound conventionally used for crosslinking polyurethane resins is not particularly limited. Examples include adducts of polyisocyanates having the following structural formula and other compounds.
また、本発明を特徴づける滑性保護層の形成に際しては、後述する各種中間層に対するコーティング適正や、成膜性の向上及びポリシロキサンセグメントの含有量を調整するなどのために、上記したポリシロキサン変性ポリヒドロキシポリウレタン樹脂に加えて、従来公知の各種バインダー樹脂を混合して使用することができる。この際に使用するバインダー樹脂としては、例えば、上記したポリイソシアネート付加物などの架橋剤と化学的に反応し得るものが好ましいが、反応性を有していないものでも本発明では使用することができる。 Further, when forming the slipping protective layer characterizing the present invention, the above-mentioned polysiloxane is used for the purpose of coating suitability for various intermediate layers, which will be described later, for improving the film-forming property and adjusting the content of the polysiloxane segment. In addition to the modified polyhydroxypolyurethane resin, various conventionally known binder resins can be mixed and used. As the binder resin used in this case, for example, those capable of chemically reacting with a crosslinking agent such as the above-mentioned polyisocyanate adduct are preferable, but those having no reactivity may be used in the present invention. it can.
これらのバインダー樹脂としては、従来から一般に用いられているバインダー樹脂が使用でき、特に限定されない。例えば、アクリル樹脂、ポリウレタン樹脂、ポリエステル樹脂、ポリブタジエン樹脂、シリコーン樹脂、メラミン樹脂、フェノール樹脂、ポリ塩化ビニル樹脂、セルロース樹脂、アルキッド樹脂、変性セルロース樹脂、フッ素樹脂、ポリビニルブチラール樹脂、エポキシ樹脂、ポリアミド樹脂などを使用することができる。また、各種樹脂をシリコーンやフッ素で変性した樹脂なども使用することができる。これらのバインター樹脂を併用する場合、その使用量は本発明のポリシロキサン変性ポリヒドロキシポリウレタン樹脂１００質量部に対して５〜９０質量部、より好ましくは、１０〜６０質量部程度の範囲で用いるとよい。 As these binder resins, conventionally used binder resins can be used and are not particularly limited. For example, acrylic resin, polyurethane resin, polyester resin, polybutadiene resin, silicone resin, melamine resin, phenol resin, polyvinyl chloride resin, cellulose resin, alkyd resin, modified cellulose resin, fluorine resin, polyvinyl butyral resin, epoxy resin, polyamide resin Etc. can be used. Also, resins obtained by modifying various resins with silicone or fluorine can be used. When these binder resins are used in combination, the amount used is 5 to 90 parts by weight, more preferably about 10 to 60 parts by weight, based on 100 parts by weight of the polysiloxane-modified polyhydroxypolyurethane resin of the present invention. Good.
さらに、滑性保護層の耐熱性や滑性を向上させるため、従来公知の有機滑剤、シリカ、炭酸カルシウム、沈降性硫酸バリウム、各種樹脂架橋粒子などの微粒子を含有させることができる。 Furthermore, in order to improve the heat resistance and lubricity of the slippery protective layer, fine particles such as conventionally known organic lubricants, silica, calcium carbonate, precipitated barium sulfate, and various resin cross-linked particles can be contained.
本発明を特徴づける滑性保護層の形成方法は特に限定されない。例えば、上記したポリシロキサン変性ポリヒドロキシポリウレタン樹脂を適当な有機溶剤に溶解又は分散させ、これを、例えば、ワイヤーバー方式、グラビア印刷法、スクリーン印刷法、グラビア版を用いたリバースロールコーティング法などの形成手段により塗工し、乾燥して形成することができる。乾燥温度としては５０〜１４０℃の範囲が好ましい。また、活性保護層を架橋皮膜とする場合は、架橋剤を含有させた樹脂組成物を同様に塗工し、５０〜１００℃の乾燥温度で数時間から数日間処理することによって、十分な架橋皮膜を形成することができる。このようにして形成される滑性保護層の厚さは０．０１〜３．００μｍが好ましく、特に０．１〜２．０μｍが好ましい。 The formation method of the slippery protective layer characterizing the present invention is not particularly limited. For example, the polysiloxane-modified polyhydroxypolyurethane resin described above is dissolved or dispersed in an appropriate organic solvent, and this is, for example, a wire bar method, a gravure printing method, a screen printing method, a reverse roll coating method using a gravure plate, etc. It can be formed by coating with a forming means and drying. The drying temperature is preferably in the range of 50 to 140 ° C. When the active protective layer is a crosslinked film, a resin composition containing a crosslinking agent is applied in the same manner and treated at a drying temperature of 50 to 100 ° C. for several hours to several days. A film can be formed. The thickness of the slippery protective layer thus formed is preferably 0.01 to 3.00 μm, particularly preferably 0.1 to 2.0 μm.
＜基材＞
基材としてはプラスチックフィルム、ガラス板、金属板、紙のようなものが使用でき、様々な厚さのものが可能である。また、それらの表面又は裏面に着色被覆層を設けたもの、着色顔料を混練したプラスチックフィルムなどが使用できる。さらに、プラスチックフィルムに金属蒸着などの反射層を設けたものも使用可能である。
<Base material>
As the substrate, plastic films, glass plates, metal plates, paper, and the like can be used, and various thicknesses are possible. Further, those provided with a colored coating layer on the front or back surface thereof, a plastic film kneaded with a colored pigment, or the like can be used. Further, a plastic film provided with a reflective layer such as metal vapor deposition can be used.
＜感熱記録層＞
本発明の可逆性感熱記録材料を構成する感熱記録層は、高分子樹脂及び該高分子樹脂中に分散された有機低分子物質を主成分とし、透明度が温度によって可逆的に変化し得る可逆性感熱記録層である。本発明の可逆性感熱記録材料は、このような可逆性感熱記録層を有することにより、加熱によって繰り返し記録、消去を行うことができる。以下、可逆性感熱記録層を形成するための各成分について説明する。
<Thermal recording layer>
The thermosensitive recording layer constituting the reversible thermosensitive recording material of the present invention comprises a polymer resin and an organic low molecular weight substance dispersed in the polymer resin as a main component, and the reversible feeling that the transparency can reversibly change with temperature. It is a thermal recording layer. Since the reversible thermosensitive recording material of the present invention has such a reversible thermosensitive recording layer, it can be repeatedly recorded and erased by heating. Hereinafter, each component for forming a reversible thermosensitive recording layer will be described.
（高分子樹脂）
可逆性感熱記録層を構成する高分子樹脂は、後述する有機低分子物質を均一に分散保持した層を形成し得るものであり、透明性が高く、機械的に安定な樹脂が好ましい。このような樹脂としては、例えば、ポリ塩化ビニル、ポリ塩化ビニル−酢酸ビニル共重合体、塩化ビニル−酢酸ビニル−ビニルアルコール共重合体、塩化ビニル−酢酸ビニル−マレイン酸共重合体、塩化ビニル−アクリレート共重合体などの塩化ビニル系共重合体、ポリ塩化ビニリデン、塩化ビニリデン−塩化ビニル共重合体、塩化ビニリデン−アクリロニトリル共重合体などの塩化ビニリデン系共重合体、ポリエステル、ポリアミド、ポリアクリレート又はポリメタクリレート或いはアクリレート−メタクリレート共重合体などが挙げられる。これらは単独で或いは２種以上混合して使用される。
(Polymer resin)
The polymer resin constituting the reversible thermosensitive recording layer is capable of forming a layer in which an organic low molecular weight substance described later is uniformly dispersed and held, and is preferably a highly transparent and mechanically stable resin. Examples of such resins include polyvinyl chloride, polyvinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-vinyl alcohol copolymer, vinyl chloride-vinyl acetate-maleic acid copolymer, vinyl chloride- Vinyl chloride copolymers such as acrylate copolymers, polyvinylidene chloride, vinylidene chloride-vinyl chloride copolymers, vinylidene chloride copolymers such as vinylidene chloride-acrylonitrile copolymers, polyesters, polyamides, polyacrylates or polyacrylates Examples thereof include methacrylates and acrylate-methacrylate copolymers. These may be used alone or in combination of two or more.
（有機低分子物質）
可逆性感熱記録層を構成する有機低分子物質は、上記の高分子樹脂中に粒子状に分散された状態で存在し、その粒径がおよそ０．１〜２μｍの範囲に分布するものが好ましい。一般的には、ワックス、あるいはロウと呼ばれ、室温においては固体状であり、炭素数１０〜６０程度の長鎖アルキル基を含む化合物、長鎖アルキル基からなる脂肪酸、アルコール、エステル、アミド、ケトン、エーテル、チオエーテル、或いはアミンが好ましい。
(Organic low molecular weight substance)
The organic low molecular weight substance constituting the reversible thermosensitive recording layer is preferably present in a state of being dispersed in the above polymer resin in the form of particles and having a particle size distributed in the range of about 0.1 to 2 μm. . Generally, it is called wax or wax and is solid at room temperature, a compound containing a long-chain alkyl group having about 10 to 60 carbon atoms, a fatty acid comprising a long-chain alkyl group, alcohol, ester, amide, Ketones, ethers, thioethers or amines are preferred.
具体的には、以下のものが挙げられる。例えば、ラウリン酸、ドデカン酸、ミリスチン酸、パルミチン酸、ペンタデカン酸、ステアリン酸、アラキン酸、ベヘン酸、ヘンエイコサン酸、トリコサン酸、グリノセリン酸、ペンタコサン酸、セロチン酸、ヘプタコサン酸、モンタン酸、メリシン酸、ノナデカン酸、オレイン酸のような高級脂肪酸化合物；ステアリルアルコール、ベヘニルアルコール、Ｃ３０アルコールのような高級アルコール化合物；ラウリン酸オクタデシル、パルチミン酸テトラデシル、ベヘン酸ドデシル、ステアリン酸メチル、ステアリン酸テトラデシル、ステアリン酸オクタデシル、ステアリン酸ステアリル、ステアリン酸ベヘニル、ベヘニン酸ベヘニル、モンタン酸ベヘニル、ステアリン酸Ｃ３０アルコールエステル、ベヘニン酸Ｃ３０アルコールエステルのような高級脂肪酸エステル化合物；パルチミン酸アミド、ステアリン酸アミド、ベヘン酸アミド、オレイン酸アミド、Ｎ−ステアリルステアリン酸アミド、Ｎ−オレイルパルチミン酸アミド、Ｎ−ステアリルエルカ酸アミド、Ｎ−ステアリルオレイン酸アミドのようなアミド化合物；ジステアリルケトン、ジベヘニルケトンのようなケトン化合物が挙げられる。 Specific examples include the following. For example, lauric acid, dodecanoic acid, myristic acid, palmitic acid, pentadecanoic acid, stearic acid, arachidic acid, behenic acid, heneicosanoic acid, tricosanoic acid, glinoselic acid, pentacosanoic acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, Higher fatty acid compounds such as nonadecanoic acid and oleic acid; higher alcohol compounds such as stearyl alcohol, behenyl alcohol, C30 alcohol; octadecyl laurate, tetradecyl palmitate, dodecyl behenate, methyl stearate, tetradecyl stearate, octadecyl stearate, Of stearyl stearate, behenyl stearate, behenyl behenate, behenyl montanate, stearic acid C30 alcohol ester, behenic acid C30 alcohol ester Higher fatty acid ester compounds such as: palmitic acid amide, stearic acid amide, behenic acid amide, oleic acid amide, N-stearyl stearic acid amide, N-oleyl palmitic acid amide, N-stearyl erucic acid amide, N-stearyl oleic acid amide Examples of such amide compounds include ketone compounds such as distearyl ketone and dibehenyl ketone.
更には、下記のような高級脂肪族エーテル、高級脂肪族チオエーテル、或いは高級脂肪族アミンなどが挙げられるが、これらに限定されることはない。例えば、Ｃ16Ｈ33−Ｏ−Ｃ16Ｈ33、Ｃ16Ｈ33−Ｓ−Ｃ16Ｈ33、Ｃ18Ｈ37−Ｓ−Ｃ18Ｈ37、Ｃ12Ｈ25−Ｓ−Ｃ12Ｈ25、Ｃ19Ｈ39−Ｓ−Ｃ19Ｈ39、Ｃ12Ｈ25−Ｓ−Ｓ−Ｃ12Ｈ25、Ｃ11Ｈ23−ＯＣＯ−ＣＨ2ＣＨ2−Ｏ−ＣＨ2ＣＨ2−ＯＣＯ−Ｃ11Ｈ23、Ｃ17Ｈ35−ＯＣＯ−ＣＨ2ＣＨ2−Ｏ−ＣＨ2ＣＨ2−ＯＣＯ−Ｃ 17Ｈ35、Ｃ12Ｈ25−ＯＣＯ−ＣＨ2ＣＨ2−Ｓ−ＣＨ2ＣＨ2−ＯＣＯ−Ｃ12Ｈ25、Ｃ18Ｈ37−ＯＣＯ−ＣＨ2ＣＨ2−Ｓ−ＣＨ2ＣＨ2−ＯＣＯ−Ｃ18Ｈ37、Ｃ18Ｈ37−ＯＣＯ−ＣＨ2ＣＨ2−ＮＨ−ＣＨ2ＣＨ2−ＯＣＯ−Ｃ18Ｈ37などが挙げられる。これらの長鎖アルキル基含有化合物は、単独で使用してもよいが、２種以上を混合して使用することもできる。 Furthermore, the following higher aliphatic ethers, higher aliphatic thioethers, higher aliphatic amines, and the like are exemplified, but the present invention is not limited thereto. For example, C 16 H 33 —O—C 16 H 33 , C 16 H 33 —S—C 16 H 33 , C 18 H 37 —S—C 18 H 37 , C 12 H 25 —S—C 12 H 25 , C 19 H 39 -S-C 19 H 39, C 12 H 25 -S-S-C 12 H 25, C 11 H 23 -OCO-CH 2 CH 2 -O-CH 2 CH 2 -OCO-C 11 H 23 , C 17 H 35 —OCO—CH 2 CH 2 —O—CH 2 CH 2 —OCO— C 17 H 35 , C 12 H 25 —OCO—CH 2 CH 2 —S—CH 2 CH 2 —OCO—C 12 H 25 , C 18 H 37 —OCO—CH 2 CH 2 —S—CH 2 CH 2 —OCO—C 18 H 37 , C 18 H 37 —OCO—CH 2 CH 2 —NH—CH 2 CH 2 —OCO etc. -C 18 H 37 and the like. These long-chain alkyl group-containing compounds may be used singly or in combination of two or more.
また、可逆的感熱記録層は、前記有機低分子物質（以下、これを低融点有機低分子物質という場合がある）に、それよりも融点の高い有機低分子物質（以下、これを高融点有機低分子物質という場合がある）を添加することで、透明化する温度の幅を広げることもできる。この高融点有機低分子物質としては、融点が８０℃〜１８０℃の物質が好ましく、特に９０℃〜１６０℃の範囲の融点を有する飽和脂肪族ビスアミドや飽和脂肪族ジカルボン酸が好ましい。 In addition, the reversible thermosensitive recording layer is composed of the organic low-molecular substance (hereinafter sometimes referred to as a low-melting-point organic low-molecular substance) and an organic low-molecular substance (hereinafter referred to as a high-melting-point organic substance) having a higher melting point. By adding a low molecular weight substance), it is possible to widen the temperature range for transparency. As the high melting point organic low molecular weight substance, a substance having a melting point of 80 ° C. to 180 ° C. is preferable, and saturated aliphatic bisamide and saturated aliphatic dicarboxylic acid having a melting point in the range of 90 ° C. to 160 ° C. are particularly preferable.
本発明で使用し得る具体的な高融点有機低分子物質としては、以下のものが挙げられる。例えば、飽和脂肪族ビスアミドとしては、エチレンビスステアリン酸アミド、エチレンビスベヘン酸アミド、ヘキサメチレンビスステアリン酸アミド、ヘキサメチレンビスベヘン酸アミド、Ｎ，Ｎ−ジステアリルアジピン酸アミド、Ｎ，Ｎ−ジステアリルエイコサンジ酸アミド、Ｎ，Ｎ−ジステアリルセバシンジ酸アミド、Ｎ，Ｎ−ジラウリルドデカンジ酸アミド、Ｎ，Ｎ−ジステアリルドデカンジ酸アミドなどが挙げられる。 Specific high melting point organic low molecular weight substances that can be used in the present invention include the following. For example, saturated aliphatic bisamides include ethylene bis stearamide, ethylene bis behenamide, hexamethylene bis behenamide, hexamethylene bis behenamide, N, N-distearyl adipate amide, N, N-diamide. Examples include stearyl eicosane diamide, N, N-distearyl sebacic diamide, N, N-dilauryl decanedioic acid amide, N, N-distearyl dodecanedioic acid amide, and the like.
飽和脂肪族ジカルボン酸としては、アジピン酸、ピロリン酸、スベリン酸、アゼライン酸、セバシン酸、ウンデカンジ酸、ドデカンジ酸、トリデカンジ酸、テトラデカンジ酸、ペンタデカンジ酸、ヘキサデカンジ酸、ペプタデカンジ酸、オクタデカンジ酸、ノナデカンジ酸、エイコサンジ酸などが挙げられる。 Saturated aliphatic dicarboxylic acids include adipic acid, pyrophosphoric acid, suberic acid, azelaic acid, sebacic acid, undecanediic acid, dodecanediic acid, tridecanediic acid, tetradecanediic acid, pentadecanediic acid, hexadecanediic acid, peptadecanediic acid, and octadecanediic acid , Nonadecanedioic acid, eicosandioic acid and the like.
しかしながら、これらに限定されるものではなく、前記以外のビスアミド、ジカルボン酸、飽和脂肪酸モノアミド、メチロール酸アミド、不飽和脂肪酸ビスアミド、芳香族系ビスアミドなどの高融点有機低分子物質が使用できる。これら高融点有機低分子物質は、１種又は２種以上を混合して使用することができる。 However, it is not limited to these, and other high-melting-point organic low-molecular substances such as bisamides, dicarboxylic acids, saturated fatty acid monoamides, methylolamides, unsaturated fatty acid bisamides, and aromatic bisamides other than those described above can be used. These high melting point organic low molecular weight substances can be used alone or in combination.
有機低分子物質として、上記低融点有機低分子物質と高融点有機低分子物質とを用いる場合の配合割合は、質量比で９９：１〜４５：５５の範囲であることが好ましい。
この範囲外では透明化温度幅の拡大効果が得られないだけでなく、透明化状態と白濁化状態のコントラスト不足となる場合があるので好ましくない。
When the low melting point organic low molecular weight substance and the high melting point organic low molecular weight substance are used as the organic low molecular weight substance, the blending ratio is preferably in the range of 99: 1 to 45:55 by mass ratio.
Outside this range, not only the effect of expanding the transparent temperature range is not obtained, but also the contrast between the transparent state and the white turbid state may be insufficient, which is not preferable.
さらに、上記した可逆的感熱記録層には、必要に応じて、滑剤、帯電防止剤、可塑剤、分散剤、安定剤、界面活性剤、無機あるいは有機の充填剤などを配合してもよい。 Further, the reversible thermosensitive recording layer may contain a lubricant, an antistatic agent, a plasticizer, a dispersant, a stabilizer, a surfactant, an inorganic or organic filler, if necessary.
上記した可逆的感熱記録層の膜厚は通常１〜４０μｍであり、好ましくは２〜２０μｍである。感熱記録層が厚すぎると層内での熱の分布が発生し好ましくない。一方、感熱記録層がこれより薄いと白濁度が低下してしまい、コントラストが低下してしまうため好ましくない。 The film thickness of the reversible thermosensitive recording layer is usually 1 to 40 μm, preferably 2 to 20 μm. If the heat-sensitive recording layer is too thick, heat distribution in the layer occurs, which is not preferable. On the other hand, if the thermosensitive recording layer is thinner than this, the white turbidity is lowered and the contrast is lowered, which is not preferable.
＜中間層＞
また、本発明の可逆性感熱記録材料には、必要に応じて各種中間層を設けることができる。該中間層は、一層であっても多層の組み合わせからなるものであってもよく、本発明の効果の範囲内であれば、必要に応じて適宜設けることができ、例えば、意匠性を目的とした印刷層や着色層さらには耐熱保護層などを設けることができる。印刷層や着色層は従来公知の材料が使用でき、また耐熱保護層に使用する材料としては、シリコーン樹脂、アクリル樹脂、アルキッド樹脂や、ＵＶ硬化型樹脂、ＥＢ硬化型樹脂が用いられる。
<Intermediate layer>
The reversible thermosensitive recording material of the present invention can be provided with various intermediate layers as required. The intermediate layer may be a single layer or a combination of multiple layers, and can be appropriately provided as necessary within the scope of the effect of the present invention. A printed layer, a colored layer, and a heat-resistant protective layer can be provided. Conventionally known materials can be used for the printing layer and the colored layer, and silicone resin, acrylic resin, alkyd resin, UV curable resin, and EB curable resin are used as the material for the heat-resistant protective layer.
＜その他の層＞
さらに、本発明の効果の範囲内であれば、基材シートと感熱記録層の間に、情報を記録する磁気記録層や、感熱記録層の透明化状態と白濁化状態とのコントラストを向上させるため、基材シート上に金属蒸着などの反射層を設けることもできる。さらには基材シート及び感熱記録層や各種中間層の接着性を高める接着層を設けることもできる。
<Other layers>
Furthermore, if it is within the range of the effect of the present invention, the magnetic recording layer for recording information between the base sheet and the thermal recording layer, and the contrast between the transparent state and the white turbid state of the thermal recording layer are improved. Therefore, a reflective layer such as metal vapor deposition can be provided on the base sheet. Furthermore, an adhesive layer that enhances the adhesion of the base sheet, the heat-sensitive recording layer, and various intermediate layers can also be provided.
本発明の可逆性感熱記録材料は、基材の少なくとも一方の面に設けられた滑性保護層を形成する樹脂組成物に、特有のポリシロキサン変性ポリヒドロキシポリウレタン樹脂を用いているため、該樹脂のポリシロキサンセグメントが保護層表面に配向することとなる。このため、形成された滑性保護層には、該ポリシロキサンセグメントの持つ耐熱性、滑り性、サーマルヘッドへの非粘着性が付与される。また、本発明で使用する樹脂を構成する５員環環状カーボネート化合物は、二酸化炭素を製造原料とすることで、樹脂中に二酸化炭素を取り入れることができる。このため、本発明によって、地球温暖化の原因とされている二酸化炭素の削減の観点からも有用な、従来品では到達できなかった環境対応材料製品としての可逆性感熱記録材料の提供が可能になる。 Since the reversible thermosensitive recording material of the present invention uses a specific polysiloxane-modified polyhydroxypolyurethane resin for the resin composition forming the slippery protective layer provided on at least one surface of the substrate, the resin The polysiloxane segment is oriented on the surface of the protective layer. For this reason, heat resistance, slipperiness, and non-adhesiveness to the thermal head of the polysiloxane segment are imparted to the formed slippery protective layer. The 5-membered cyclic carbonate compound constituting the resin used in the present invention can incorporate carbon dioxide into the resin by using carbon dioxide as a production raw material. For this reason, the present invention makes it possible to provide a reversible thermosensitive recording material that is useful from the viewpoint of reducing carbon dioxide, which is a cause of global warming, as an environmentally friendly material product that could not be achieved with conventional products. Become.
次に、具体的な製造例、重合例、実施例及び比較例をあげて本発明をさらに詳細に説明するが、本発明はこれらの実施例に限定されるものではない。又、以下の各例における「部」及び「％」は特に断りのない限り質量基準である。 Next, the present invention will be described in more detail with reference to specific production examples, polymerization examples, examples and comparative examples, but the present invention is not limited to these examples. In the following examples, “part” and “%” are based on mass unless otherwise specified.
＜製造例１＞（５員環環状カーボネート化合物の製造）
撹拌機、温度計、ガス導入管及び還流冷却器を備えた反応容器中に、下記式Ａで表される２価エポキシ化合物Ａ（ジャパンエポキシレジン（株）製、エピコート８２８；エポキシ当量１８７ｇ／ｍｏｌ）１００部、Ｎ−メチルピロリドン１００部、ヨウ化ナトリウム１．５部を加え均一に溶解させた後、炭酸ガスを０．５リッター／分の速度でバブリングしながら８０℃で３０時間加熱撹拌させた。
<Production Example 1> (Production of 5-membered cyclic carbonate compound)
In a reaction vessel equipped with a stirrer, a thermometer, a gas introduction tube and a reflux condenser, a divalent epoxy compound A represented by the following formula A (Epicoat 828 manufactured by Japan Epoxy Resin Co., Ltd .; epoxy equivalent 187 g / mol) ) After 100 parts, 100 parts of N-methylpyrrolidone and 1.5 parts of sodium iodide were added and dissolved uniformly, the mixture was heated and stirred at 80 ° C. for 30 hours while bubbling carbon dioxide at a rate of 0.5 liters / minute. It was.
反応終了後、得られた溶液を３００部のｎ−ヘキサン中に３００ｒｐｍで高速撹拌しながら徐々に添加した。その後、生成した粉末状生成物をフィルターでろ過し、さらに、ろ過物をメタノールで洗浄し、Ｎ−メチルピロリドン及びヨウ化ナトリウムを除去した。粉末を乾燥機中で乾燥し、白色粉末の５員環環状カーボネート化合物（１−Ａ）１１８部（収率９５％）を得た。 After completion of the reaction, the obtained solution was gradually added to 300 parts of n-hexane with high speed stirring at 300 rpm. Thereafter, the produced powdery product was filtered with a filter, and the filtrate was further washed with methanol to remove N-methylpyrrolidone and sodium iodide. The powder was dried in a drier to obtain 118 parts (yield 95%) of a white powder 5-membered cyclic carbonate compound (1-A).
得られた生成物の赤外吸収スペクトル（堀場製作所 ＦＴ−７２０）は、９１０ｃｍ-1付近のエポキシ基由来のピークが生成物ではほぼ消滅し、１，８００ｃｍ-1付近に原料には存在しない環状カーボネート基のカルボニル基の吸収が確認された。また、生成物の数平均分子量は、４１４（ポリスチレン換算、東ソー；ＧＰＣ−８２２０）であった。得られた５員環環状カーボネート化合物（１−Ａ）中には、１９％の二酸化炭素が固定化されていた。 In the infrared absorption spectrum (Horiba FT-720) of the obtained product, the peak derived from the epoxy group in the vicinity of 910 cm −1 almost disappears in the product, and the cyclic that does not exist in the raw material in the vicinity of 1,800 cm −1. Absorption of the carbonyl group of the carbonate group was confirmed. Moreover, the number average molecular weight of the product was 414 (polystyrene conversion, Tosoh; GPC-8220). In the obtained 5-membered cyclic carbonate compound (1-A), 19% of carbon dioxide was immobilized.
＜製造例２＞（５員環環状カーボネート化合物の製造）
製造例１で用いた式Ａで表される２価エポキシ化合物Ａの代わりに、下記式Ｂで表される２価エポキシ化合物Ｂ（東都化成（株）製、ＹＤＦ−１７０；エポキシ当量１７２ｇ／ｍｏｌ）を用いた以外は、製造例１と同様に反応させて、白色粉末の５員環環状カーボネート化合物（１−Ｂ）１２１部（収率９６％）を得た。得られた生成物について、製造例１の場合と同様に、赤外吸収スペクトル、ＧＰＣ、ＮＭＲで確認した。この結果、得られた５員環環状カーボネート化合物（１−Ｂ）中には、２０．３％の二酸化炭素が固定化されていた。
<Production Example 2> (Production of 5-membered cyclic carbonate compound)
Instead of the divalent epoxy compound A represented by the formula A used in Production Example 1, a divalent epoxy compound B represented by the following formula B (manufactured by Tohto Kasei Co., Ltd., YDF-170; epoxy equivalent 172 g / mol) ) Was used in the same manner as in Production Example 1 to obtain 121 parts (yield 96%) of white powdered 5-membered cyclic carbonate compound (1-B). The obtained product was confirmed by infrared absorption spectrum, GPC and NMR in the same manner as in Production Example 1. As a result, 20.3% of carbon dioxide was immobilized in the obtained 5-membered cyclic carbonate compound (1-B).
＜製造例３＞（５員環環状カーボネート化合物の製造）
製造例１で用いた２価エポキシ化合物Ａの代わりに、下記式Ｃで表される２価エポキシ化合物Ｃ（ナガセケムテックス（株）製、ＥＸ−２１２；エポキシ当量１５１ｇ／ｍｏｌ）を用いた以外は、製造例１と同様に反応させて、無色透明の液状５員環環状カーボネート化合物（１−Ｃ）１１１部（収率８６％）を得た。得られた生成物については、製造例１の場合と同様に、赤外吸収スペクトル、ＧＰＣ、ＮＭＲで確認した。この結果、得られた５員環環状カーボネート化合物（１−Ｃ）中には、２２．５％の二酸化炭素が固定化されていた。
<Production Example 3> (Production of 5-membered cyclic carbonate compound)
Instead of using the divalent epoxy compound A used in Production Example 1, the divalent epoxy compound C represented by the following formula C (manufactured by Nagase ChemteX Corporation, EX-212; epoxy equivalent 151 g / mol) was used. Were reacted in the same manner as in Production Example 1 to obtain 111 parts (yield 86%) of a colorless and transparent liquid 5-membered cyclic carbonate compound (1-C). The obtained product was confirmed by an infrared absorption spectrum, GPC, and NMR as in the case of Production Example 1. As a result, 22.5% of carbon dioxide was immobilized in the obtained 5-membered cyclic carbonate compound (1-C).
＜重合例１〜３＞（ポリシロキサン変性ポリヒドロキシポリウレタン樹脂の製造）
製造例１〜３で得られた５員環環状カーボネート化合物をそれぞれに用いて、下記のような手順で、実施例で用いるポリシロキサン変性ポリヒドロキシポリウレタン樹脂を合成した。先ず、撹拌機、温度計、ガス導入管及び還流冷却器を備えた反応容器を窒素置換し、該容器内に、各５員環環状カーボネート化合物、更に液の固形分が３５％になるようにＮ−メチルピロリドンを加え均一に溶解した。次に、表１に記載した各アミン変性ポリシロキサン化合物を所定当量加え、９０℃の温度で１０時間撹拌し、アミン変性ポリシロキサン化合物が確認できなくなるまで反応させた。得られた３種類のポリシロキサン変性ポリヒドロキシポリウレタン樹脂（固形分３５％溶液）の性状は表１に記載の通りであった。
<Polymerization Examples 1-3> (Production of polysiloxane-modified polyhydroxypolyurethane resin)
Using the 5-membered cyclic carbonate compounds obtained in Production Examples 1 to 3, polysiloxane-modified polyhydroxypolyurethane resins used in the examples were synthesized by the following procedure. First, a reaction vessel equipped with a stirrer, a thermometer, a gas introduction pipe and a reflux condenser is replaced with nitrogen, and each 5-membered cyclic carbonate compound and the solid content of the liquid are 35% in the vessel. N-methylpyrrolidone was added and dissolved uniformly. Next, a predetermined equivalent amount of each amine-modified polysiloxane compound described in Table 1 was added and stirred at a temperature of 90 ° C. for 10 hours, and allowed to react until no amine-modified polysiloxane compound could be confirmed. Properties of the obtained three types of polysiloxane-modified polyhydroxypolyurethane resins (solid content 35% solution) were as shown in Table 1.
＜比較重合例１＞（ポリヒドロキシポリウレタン樹脂の製造）
撹拌機、温度計、ガス導入管及び還流冷却器を備えた反応容器を窒素置換し、該容器内に、製造例１で得られた５員環環状カーボネート化合物、更に液の固形分が３５％になるようにＮ−メチルピロリドンを加え均一に溶解した。次に、ヘキサメチレンジアミンを所定当量加え、９０℃の温度で１０時間撹拌し、アミン化合物が確認できなくなるまで反応させた。得られたポリヒドロキシポリウレタン樹脂の性状は表１に記載の通りであった。
<Comparative polymerization example 1> (Production of polyhydroxypolyurethane resin)
A reaction vessel equipped with a stirrer, a thermometer, a gas introduction pipe and a reflux condenser was replaced with nitrogen, and the 5-membered cyclic carbonate compound obtained in Production Example 1 and the solid content of the liquid were 35% in the vessel. N-methylpyrrolidone was added and dissolved uniformly. Next, a predetermined equivalent of hexamethylenediamine was added, and the mixture was stirred at a temperature of 90 ° C. for 10 hours until the amine compound could not be confirmed. The properties of the obtained polyhydroxy polyurethane resin were as shown in Table 1.
＜比較重合例２＞（ポリウレタン樹脂の製造）
下記のようにして、比較例で用いるポリウレタン樹脂を合成した。撹拌機、温度計、ガス導入管及び還流冷却器を備えた反応容器を窒素置換し、該容器内に、平均分子量約２，０００のポリブチレンアジペート１５０部と、１，４−ブタンジオール１５部とを、２００部のメチルエチルケトンと５０部のジメチルホルムアミドからなる混合有機溶剤中に溶解し、６０℃でよく撹拌しながら６２部の水添加ＭＤＩ（メチレンビス（１，４−シクロヘキサン）−ジイソシアネート）を、１７１部のジメチルホルムアミドに溶解したものを徐々に滴下し、滴下終了後、８０℃で６時間反応させた。
この溶液は固形分３５％で３．２ＭＰａ・ｓ（２５℃）の粘度を有していた。この溶液から得られたフィルムは、破断強度４５ＭＰａで破断伸度４８０％を有し、熱軟化温度は１１０℃であった。
<Comparative polymerization example 2> (Production of polyurethane resin)
The polyurethane resin used in the comparative example was synthesized as follows. A reaction vessel equipped with a stirrer, a thermometer, a gas introduction tube and a reflux condenser was replaced with nitrogen, and 150 parts of polybutylene adipate having an average molecular weight of about 2,000 and 15 parts of 1,4-butanediol were placed in the vessel. Are dissolved in a mixed organic solvent composed of 200 parts of methyl ethyl ketone and 50 parts of dimethylformamide, and 62 parts of water-added MDI (methylene bis (1,4-cyclohexane) -diisocyanate) are added while stirring well at 60 ° C. What was melt | dissolved in 171 parts of dimethylformamide was dripped gradually, and it was made to react at 80 degreeC after completion | finish of dripping for 6 hours.
This solution had a viscosity of 3.2 MPa · s (25 ° C.) at a solid content of 35%. The film obtained from this solution had a breaking strength of 45 MPa, a breaking elongation of 480%, and a thermal softening temperature of 110 ° C.
＜比較重合例３＞（ポリシロキサン変性ポリウレタン樹脂）
＜実施例１〜３及び比較例１〜３＞
上記重合例で得た樹脂をそれぞれに用いて、下記の方法で、基材上に、感熱記録層、耐熱保護層（中間層）、滑性保護層をこの順で形成し、実施例及び比較例の可逆性感熱記録材料を作製した。基材として、１８８μｍのポリエチレンテレフタレートフィルム上に０．１μｍ厚のアルミ層を真空蒸着法により形成した金属反射基材を用いた。
<Examples 1-3 and Comparative Examples 1-3>
Using each of the resins obtained in the above polymerization examples, a heat-sensitive recording layer, a heat-resistant protective layer (intermediate layer), and a slippery protective layer were formed in this order on the substrate by the following method. An example reversible thermosensitive recording material was prepared. As a base material, a metal reflective base material in which an aluminum layer having a thickness of 0.1 μm was formed on a 188 μm polyethylene terephthalate film by a vacuum deposition method was used.
（感熱記録層の形成）
下記配合の溶液を調製し、上記した基材上にワイヤーバーを用いて塗布した後、１４０℃にて４分間加熱乾燥して、厚みが１２μｍの、透明度が温度によって可逆的に変化し得る可逆性感熱記録層を形成した。
（感熱記録層塗料組成；透明化温度範囲 ７５〜１０８℃）
塩化ビニル−酢酸ビニル共重合体（日信化学製） ３０部
ベヘン酸 ７部
セバシン酸 ６部
フタル酸ジ−２エチルヘキシル ３部
ポリイソシアネート（日本ポリウレタン製、コロネートＨＬ） ２部
テトラヒドロフラン １００部
エチレングリコールモノエチルエーテル ７０部
(Formation of thermal recording layer)
After preparing a solution with the following composition and applying it on the above-mentioned base material using a wire bar, it was dried by heating at 140 ° C. for 4 minutes, and the thickness was 12 μm, and the transparency could reversibly change with temperature. A heat-sensitive recording layer was formed.
(Thermosensitive recording layer coating composition; clearing temperature range 75-108 ° C)
Vinyl chloride-vinyl acetate copolymer (manufactured by Nissin Chemical) 30 parts Behenic acid 7 parts Sebacic acid 6 parts Di-2-ethylhexyl phthalate 3 parts Polyisocyanate (Nihon Polyurethane, Coronate HL) 2 parts Tetrahydrofuran 100 parts Ethylene glycol mono 70 parts of ethyl ether
（耐熱保護層の形成）
上記で形成した感熱記録層の上に、下記のようにして中間層である耐熱保護層を形成した。具体的には、アクリル系紫外線硬化樹脂（大日精化工業製）を、感熱記録層の上に乾燥後の厚みが５μｍとなるように塗布した後、紫外線を５００ｍＪ／ｃｍ2照射して、耐熱保護層を形成した。
(Formation of heat-resistant protective layer)
On the heat-sensitive recording layer formed above, a heat-resistant protective layer as an intermediate layer was formed as follows. Specifically, an acrylic ultraviolet curable resin (manufactured by Dainichi Seika Kogyo Co., Ltd.) was applied on the heat-sensitive recording layer so that the thickness after drying was 5 μm, and then irradiated with ultraviolet rays at 500 mJ / cm 2 to provide heat resistance. A protective layer was formed.
（滑性保護層の形成）
先に重合例１〜３及び比較重合例１〜３で調製した樹脂溶液（固形分３５％）をそれぞれ用い、金属反射基材上に形成した感熱記録層及び耐熱保護層の上に、下記のようにして最上層として滑性保護層を形成した。具体的には、まず、上記各樹脂溶液を溶剤（テトラヒドロフラン）で希釈して、これに表２に示したように架橋剤を添加して樹脂組成物をそれぞれ得た。調製した樹脂組成物を、乾燥後の厚みが１．０μｍになるようにワイヤーバーにより塗布し、乾燥機中で乾燥して基材の最上層に滑性保護層を形成し、実施例１〜３及び比較例１〜３の可逆性感熱記録材料を得た。
(Formation of slippery protective layer)
Using the resin solutions (solid content 35%) prepared in Polymerization Examples 1 to 3 and Comparative Polymerization Examples 1 to 3, respectively, on the heat-sensitive recording layer and the heat-resistant protective layer formed on the metal reflective substrate, the following Thus, a slippery protective layer was formed as the uppermost layer. Specifically, first, each resin solution was diluted with a solvent (tetrahydrofuran), and a crosslinking agent was added thereto as shown in Table 2 to obtain resin compositions. The prepared resin composition was applied with a wire bar so that the thickness after drying was 1.0 μm, and dried in a dryer to form a slipping protective layer on the uppermost layer of the substrate. 3 and Comparative Examples 1 to 3 were obtained.
＜評価＞
上記で得た実施例１〜３及び比較例１〜３の各可逆性感熱記録材料について、ライン型サーマルヘッド（８ｄｏｔ／ｍｍ）を用いて画像形成を行い、熱板圧着方式（熱板温度；１００〜１０５℃）にて画像消去する操作を１００回繰り返し、各特性を評価した。
<Evaluation>
For each of the reversible thermosensitive recording materials of Examples 1 to 3 and Comparative Examples 1 to 3 obtained above, image formation was performed using a line type thermal head (8 dots / mm), and a hot plate pressure bonding method (hot plate temperature; The operation of erasing the image at 100 to 105 ° C. was repeated 100 times, and each characteristic was evaluated.
（スティッキング性）
上記の条件にて印字試験を行った際の、サーマルヘッドとの間の押圧操作時における、可逆性感熱記録材料のサーマルヘッドからの離脱性を目視で評価した。なお、最も離脱性の良いものを５とし、最も離脱性の悪いものを１とし、５段階にて評価を行った。
(Sticking)
When the printing test was performed under the above conditions, the releasability of the reversible thermosensitive recording material from the thermal head during a pressing operation with the thermal head was visually evaluated. The evaluation was performed in five steps, with 5 being the best and 1 being the worst.
（ヘッド汚染）
上記条件での実装試験に供したサーマルヘッドの汚れの状態を、光学顕微鏡で観測し、評価した。最も汚れの少ないものを５とし、最も汚れのひどいものを１とし、５段階で相対的に評価を行った。
(Head contamination)
The state of dirt on the thermal head subjected to the mounting test under the above conditions was observed with an optical microscope and evaluated. Evaluation was relatively performed in five stages, with 5 being the least dirty and 1 being the most dirty.
（表面キズ）
上記試験後の各可逆性感熱記録材料表面のキズを目視にて、下記の基準で判定した。
○；キズなし
△；ややキズあり
×；キズあり
(Surface scratches)
The scratches on the surface of each reversible thermosensitive recording material after the above test were visually judged according to the following criteria.
○: No scratch △; Slightly scratch ×: Scratch
（静止摩擦係数）
実施例及び比較例の可逆性感熱記録材料の表面の静止摩擦係数をそれぞれ、表面性試験機（新東科学製）で評価した。
(Static friction coefficient)
The static friction coefficient of the surface of each of the reversible thermosensitive recording materials of Examples and Comparative Examples was evaluated with a surface property tester (manufactured by Shinto Kagaku).
（画像劣化）
初期の白濁濃度と、上記で行った１００回の操作後に画像消去した際における白濁濃度との差を、マクベス反射濃度計（ＲＤ−９１４）で測定し、その差を表３に示した。
(Image degradation)
The difference between the initial cloudiness density and the cloudiness density when the image was erased after 100 operations as described above was measured with a Macbeth reflection densitometer (RD-914). The difference is shown in Table 3.
（環境対応性）
実施例及び比較例の可逆性感熱記録材料の「滑性保護層」の形成材料の各樹脂中における二酸化炭素の固定化の有無で、○×判断した。
(Environmental compatibility)
A determination was made based on whether or not carbon dioxide was immobilized in each resin of the forming material of the “sliding protective layer” of the reversible thermosensitive recording materials of Examples and Comparative Examples.
以上の本発明によれば、基材の一方の面の最上層にポリシロキサン変性ポリヒドロキシポリウレタン樹脂を主成分とする滑性保護層を形成することで、滑性と耐熱性を付与し、サーマルヘッド又は熱ロールなどの加熱及び圧力に強く、更には、サーマルヘッドによる表面のキズ及びヘッド滓付着防止、及び印刷適性が良好な可逆性感熱記録材料が提供されるので、これを利用することで、文字や画像の書き換えが良好な状態で行えるようになる。このため、当該材料を、格納された情報が変更されるＩＣカード類などに適用することで、随時、内容保証のための表示を良好な状態で行うことができるようになるため、活用が期待される。また、本発明で使用するポリシロキサン変性ポリヒドロキシウレタン樹脂は、二酸化炭素を製造原料に利用することができるため、本発明によれば、地球温暖化ガスとされている二酸化炭素削減に寄与し得る地球環境対応製品としての可逆性感熱記録材料の提供が可能になる。 According to the present invention described above, a slippery protective layer mainly composed of a polysiloxane-modified polyhydroxypolyurethane resin is formed on the uppermost layer on one side of the base material, thereby providing slipperiness and heat resistance, and thermal A reversible thermosensitive recording material is provided that is resistant to heating and pressure of a head or a heat roll, and further prevents surface scratches and head wrinkle adhesion due to a thermal head and has good printability. Thus, rewriting of characters and images can be performed in a good state. For this reason, application of this material to IC cards, etc., in which stored information is changed, makes it possible to perform display for content assurance in good condition at any time. Is done. Further, since the polysiloxane-modified polyhydroxyurethane resin used in the present invention can use carbon dioxide as a production raw material, according to the present invention, it can contribute to the reduction of carbon dioxide, which is regarded as a global warming gas. It is possible to provide reversible thermosensitive recording materials as products for the global environment.
Claims (6)
上記感熱記録層が、高分子樹脂及び該高分子樹脂中に分散された有機低分子物質を主成分としてなる、透明度が温度によって透明な状態から白濁状態までの範囲で可逆的に変化し得、冷却後にはその状態を保持する性質を持つ、前記滑性保護層側からのサーマルヘッド又は熱ロールによる加熱によって繰り返し記録、消去を行うことができるようにするための可逆性感熱記録層であり、かつ、
上記滑性保護層が、５員環環状カーボネート化合物とアミン変性ポリシロキサン化合物との反応から誘導されたポリシロキサン変性ポリヒドロキシポリウレタン樹脂を主成分として含む樹脂組成物と、該樹脂の構造中の水酸基と反応する架橋剤とによって形成されている乾燥後の厚さが１．０〜３．０μｍの架橋皮膜であることを特徴とする可逆性感熱記録材料。 In a reversible thermosensitive recording material having a base material and a thermosensitive recording layer provided on at least one surface of the base material , an intermediate layer including a heat-resistant protective layer, and an uppermost slippery protective layer in this order,
The thermosensitive recording layer is mainly composed of a polymer resin and an organic low molecular weight substance dispersed in the polymer resin, and the transparency can reversibly change in a range from a transparent state to a cloudy state depending on the temperature , A reversible thermosensitive recording layer having a property of maintaining its state after cooling, allowing repetitive recording and erasing by heating with a thermal head or a heat roll from the slipping protective layer side , And,
A resin composition comprising, as a main component, a polysiloxane-modified polyhydroxypolyurethane resin derived from a reaction between a 5-membered cyclic carbonate compound and an amine-modified polysiloxane compound ; and a hydroxyl group in the structure of the resin. A reversible thermosensitive recording material comprising a cross-linked film having a thickness of 1.0 to 3.0 μm after drying, which is formed by a cross-linking agent that reacts with the heat-sensitive adhesive.
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