JP2010149303A - Reversible thermosensitive recording material - Google Patents
Reversible thermosensitive recording material Download PDFInfo
- Publication number
- JP2010149303A JP2010149303A JP2008327503A JP2008327503A JP2010149303A JP 2010149303 A JP2010149303 A JP 2010149303A JP 2008327503 A JP2008327503 A JP 2008327503A JP 2008327503 A JP2008327503 A JP 2008327503A JP 2010149303 A JP2010149303 A JP 2010149303A
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- JP
- Japan
- Prior art keywords
- reversible thermosensitive
- thermosensitive recording
- recording material
- layer
- coating solution
- 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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- 239000011574 phosphorus Substances 0.000 description 1
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- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
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Landscapes
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
【課題】本発明の課題は明瞭なコントラストを持つ画像の形成・消去が可能で、帯電を防ぐことにより画像形成装置における搬送不良、印字不良が少ない可逆性感熱記録材料を提供することである。
【解決手段】支持体上に少なくとも可逆性感熱記録層を設けた可逆性感熱性記録材料において、可逆性感熱記録材料を構成する少なくとも一層が親水性スメクタイトを含有する。
【選択図】なしAn object of the present invention is to provide a reversible thermosensitive recording material capable of forming and erasing an image having a clear contrast and preventing charging failure and printing failure in an image forming apparatus by preventing charging.
In a reversible thermosensitive recording material in which at least a reversible thermosensitive recording layer is provided on a support, at least one layer constituting the reversible thermosensitive recording material contains hydrophilic smectite.
[Selection figure] None
Description
本発明は可逆感熱記録材料に関し、より詳しくは帯電を防止することにより画像形成装置における搬送不良、印字不良が少ない可逆性感熱記録材料に関する。 The present invention relates to a reversible heat-sensitive recording material, and more particularly to a reversible heat-sensitive recording material in which there is less conveyance failure and printing failure in an image forming apparatus by preventing charging.
樹脂中に長鎖脂肪族炭化水素基を持つ有機リン酸化合物及び脂肪族カルボン酸の組み合わせにより透明度が変化する材料（例えば、特許文献１参照）もしくは、通常無色ないし淡色の電子供与性染料前駆体及び電子受容性化合物（可逆性顕色剤）の組み合わせにより色調が変化する材料（例えば、特許文献２参照）を用いることで、熱エネルギーを制御することによって可逆的に画像形成及び消去が可能な可逆性感熱記録材料が知られている。 A material whose transparency changes depending on the combination of an organic phosphoric acid compound having a long-chain aliphatic hydrocarbon group and an aliphatic carboxylic acid in the resin (see, for example, Patent Document 1), or an electron-donating dye precursor that is usually colorless to light-colored And a material whose color tone changes depending on the combination of the electron-accepting compound (reversible developer) (for example, see Patent Document 2), it is possible to reversibly form and erase images by controlling thermal energy. Reversible thermosensitive recording materials are known.
このような可逆性感熱記録材料は、磁気記録層を設けたポリエチレンテレフタレートカード等の反対面に設けられ、ポイントカード、プリペイドカード等で繰り返し表示内容を書き換えることができる表示部材として広く使用されている。一方、比較的薄い支持体を用いた可逆性感熱記録材料において、記録層に対して反対面に加熱プレス等の手法により別な基材に貼り合わせて、場合によっては接触式、非接触式のＩＣチップを間に封入するなどして、ポイントカード等として使用する用途も拡大している。 Such a reversible thermosensitive recording material is provided on the opposite surface of a polyethylene terephthalate card or the like provided with a magnetic recording layer, and is widely used as a display member capable of repeatedly rewriting display contents with a point card, prepaid card or the like. . On the other hand, in a reversible thermosensitive recording material using a relatively thin support, the opposite surface of the recording layer is bonded to another substrate by a technique such as a hot press, and in some cases, a contact type or non-contact type Applications for use as point cards or the like by enclosing IC chips in between are also expanding.
さらに近年では上記ポイントカード、プリペイドカード等の範囲を超えた用途として、工程管理カード、ラベル、看板、一般文書記録といったものが拡大しており、より可逆性感熱記録材料の大判化が進んでいる。このことは画像形成装置での搬送、その他一般的取り扱いにおいて、シート摩擦による帯電をより引き起こしやすくなり、シート同士の貼り付きによる装置搬送不良が起こりやすくなる一方、埃や塵等を吸い寄せることによる印字不良を誘発しやすくなる。 Furthermore, in recent years, process management cards, labels, signboards, general document recording, etc. have been expanded as uses beyond the scope of point cards, prepaid cards, etc., and the reversible thermosensitive recording material has become larger. . This is more likely to cause electrification due to sheet friction during conveyance in the image forming apparatus and other general handling, and the conveyance failure of the apparatus due to sticking between sheets tends to occur. It becomes easy to induce printing defects.
この対策として、帯電防止効果を得るための方法が報告されている。例えば、特許文献３では、可逆性感熱記録層もしくはオーバーコート層に高分子カチオン系導電剤を含有させる方法が示されているが、高分子カチオン系導電剤は塗工層中での相溶性が低く、結果的に十分な帯電防止効果を得ることが難しかった。また、特許文献４では、いずれかの層に導電性の金属酸化物半導体粉末を添加する方法、特許文献５では針状導電性フィラーを含む層を設けることが提案されている。しかし、いずれの場合も当該の層は不透明度が上昇し、形成された印字画像の視認性が低下したり、地肌部においては意図しない色調になるという問題があった。また、基材間に無線ＩＣが封入されている場合、金属酸化物半導体粉末もしくは導電性フィラーにより無線信号の遮蔽効果が発生し、読み取り精度が落ちる場合があり、好ましくなかった。また、特許文献６では、いずれかの層にイオン性液体を添加する方法が提案されているが、イオン性液体は層中からブリードアウトする問題があり、安定性の点で十分ではなかった。
本発明の課題は明瞭なコントラストを持つ画像の形成・消去が可能で、帯電を防ぐことにより画像形成装置における搬送不良、印字不良が少ない可逆性感熱記録材料を提供することである。 An object of the present invention is to provide a reversible thermosensitive recording material capable of forming and erasing an image with clear contrast and preventing charging failure and printing failure by preventing charging.
本発明者はこれらの課題を解決すべく検討した結果、下記の発明により上記の課題が解決されることを見いだした。 As a result of studying to solve these problems, the present inventor has found that the above-described problems can be solved by the following invention.
支持体上に少なくとも可逆性感熱記録層を設けた可逆性感熱性記録材料において、可逆性感熱記録材料を構成する少なくとも一層が親水性スメクタイトを含有することを特徴とする可逆性感熱記録材料である。 A reversible thermosensitive recording material comprising at least a reversible thermosensitive recording layer on a support, wherein at least one layer constituting the reversible thermosensitive recording material contains hydrophilic smectite.
親水性スメクタイトは、支持体の可逆性感熱記録層を有する面、もしくは反対側の面の少なくとも一方の面の最表層に含有することが好ましい。 The hydrophilic smectite is preferably contained in the outermost layer of at least one of the surface having the reversible thermosensitive recording layer of the support or the surface on the opposite side.
親水性スメクタイトを含有する層が、架橋性樹脂を含有していることがさらに好ましい。 More preferably, the layer containing hydrophilic smectite contains a crosslinkable resin.
架橋性樹脂が水溶解性または水分散性の紫外線架橋性樹脂であることが特に好ましい。 It is particularly preferable that the crosslinkable resin is a water-soluble or water-dispersible ultraviolet crosslinkable resin.
本発明により、明瞭なコントラストを持つ画像の形成・消去が可能で、画像形成装置における搬送不良、印字不良が少ない可逆性感熱記録材料を得ることができる。 According to the present invention, it is possible to form a reversible thermosensitive recording material capable of forming and erasing an image having a clear contrast and having less conveyance failure and printing failure in the image forming apparatus.
以下に、本発明の可逆性感熱記録材料について詳細に説明する。本発明の可逆性感熱記録材料は少なくとも支持体と可逆性感熱記録層から構成されており、一層以上の親水性スメクタイトを含有する層を持つ。 The reversible thermosensitive recording material of the present invention will be described in detail below. The reversible thermosensitive recording material of the present invention comprises at least a support and a reversible thermosensitive recording layer, and has a layer containing one or more hydrophilic smectites.
本発明において親水性スメクタイトとは、以下の一般式１を有する粘土鉱物である。 In the present invention, hydrophilic smectite is a clay mineral having the following general formula 1.
（化１）
［Ｓｉ8（ＭｇaＬｉb）Ｏ20（ＯＨ）cＦ4-c］-x（Ｎａ+）x 一般式１
（０＜ａ≦６，０＜ｂ≦６，４＜ａ＋ｂ＜８，２ａ＋ｂ≦１２，０≦ｃ≦４，
ｘ＝１２−２ａ−ｂ）
(Chemical formula 1)
[Si 8 (Mg a Li b ) O 20 (OH) c F 4-c] -x (Na +) x Formula 1
(0 <a ≦ 6, 0 <b ≦ 6, 4 <a + b <8, 2a + b ≦ 12, 0 ≦ c ≦ 4
x = 12-2−a−b)
この粘土鉱物は天然にも産するが、合成品としても得られる。スメクタイト系粘土鉱物としては、モンモリロナイト、ソーコナイト、バンデライト、ヘクトライト等があり、いずれのものでも良いが、特にヘクトライトが好ましい。また、天然品、合成品のいずれでも良い。 Although this clay mineral is naturally produced, it can also be obtained as a synthetic product. Examples of the smectite clay mineral include montmorillonite, saconite, bandelite, hectorite, and the like, and any of them may be used, but hectorite is particularly preferable. Moreover, either a natural product or a synthetic product may be used.
このようなスメクタイト系粘土鉱物の層状構造における結晶構造各層は、厚さ約１μｍの２次元小板状を形成しており、この小板ユニットに存在するマグネシウム原子やアルミニウム原子はより低原子価陽イオンの原子と同型置換しており、小板ユニットは負に帯電している。乾燥状態では、この負電荷はプレート面の格子構造外側にある置換可能陽イオン（通常ナトリウムイオン）と釣り合っており、固層ではこれらの粒子はファンデルワールス力により互いに結合し平板の束になっている。 Each layer of crystal structure in the layered structure of such smectite clay minerals forms a two-dimensional platelet with a thickness of about 1 μm, and the magnesium and aluminum atoms present in this platelet unit are lower valence positive. It is isomorphously substituted with ionic atoms, and the platelet unit is negatively charged. In the dry state, this negative charge is balanced with displaceable cations (usually sodium ions) outside the lattice structure of the plate surface. In the solid layer, these particles are bonded together by van der Waals forces into a bundle of flat plates. ing.
これを水中に分散すると、置換可能な陽イオンが水和されて粒子が膨潤を起こして小板が分離し、イオン状態となる。イオン状態では、小板は表面負電荷となり、端部は正電荷となる。このような分散液を合成樹脂フィルム等の絶縁性材料に塗布し、乾燥させることにより、表面に導電性の被膜を形成し、表面の帯電を防止することができることが知られている。 When this is dispersed in water, the replaceable cation is hydrated, causing the particles to swell and the platelets to separate and become an ionic state. In the ionic state, the platelets have a negative surface charge and the edges have a positive charge. It is known that such a dispersion can be applied to an insulating material such as a synthetic resin film and dried to form a conductive film on the surface and prevent surface charging.
また、親水性スメクタイトに４級アンモニウム塩等を作用させて得られる親油性スメクタイトが知られているが、親油性スメクタイトを用いたのでは十分な導電性が得られず、帯電を防止することは困難である。 In addition, lipophilic smectite obtained by allowing quaternary ammonium salt or the like to act on hydrophilic smectite is known. However, if lipophilic smectite is used, sufficient conductivity cannot be obtained and charging can be prevented. Have difficulty.
本発明においては、親水性スメクタイトはどの層に含有させても有効であるが、可逆性感熱記録層に対して同じ側の面、もしくは反対側の面の最表層、もしくはその両方の面の最表層に親水性スメクタイトを含有する層を設けるのがより好ましい。また、親水性スメクタイトは、水中に分散して膨潤を起こし、小板が分離した状態で含有させることが必要である。従って、親水性スメクタイトを含有する層は、分散媒として水を含有する水性塗液を塗布し、これを乾燥させて形成する。また、親水性スメクタイトは、１種または２種以上を混合して使用しても良く、添加量は添加されている層を構成する総固形分に対して３〜８０質量％が好ましく、１０〜５０質量％がより好ましい。 In the present invention, the hydrophilic smectite is effective in any layer, but it is effective for the reversible thermosensitive recording layer on the same surface, the outermost surface on the opposite surface, or both surfaces. It is more preferable to provide a layer containing hydrophilic smectite on the surface layer. Further, the hydrophilic smectite needs to be contained in a state where the platelet is separated by dispersing in water and causing swelling. Therefore, the layer containing hydrophilic smectite is formed by applying an aqueous coating solution containing water as a dispersion medium and drying it. The hydrophilic smectite may be used alone or in combination of two or more, and the addition amount is preferably 3 to 80% by mass with respect to the total solid content constituting the layer to which the hydrophilic smectite is added. 50 mass% is more preferable.
親水性スメクタイトを含有する層の塗布量は、０．１ｇ／ｍ2以上が好ましい。塗布量が０．１ｇ／ｍ2未満であると十分な帯電防止性能が得られない場合がある。親水性スメクタイトを含有する層の塗布量の上限は特に制限されないが、塗布を多くしすぎても帯電防止性能が飽和してしまうので、２０ｇ／ｍ2以下が実用的である。 The coating amount of the layer containing hydrophilic smectite is preferably 0.1 g / m 2 or more. If the coating amount is less than 0.1 g / m 2 , sufficient antistatic performance may not be obtained. The upper limit of the coating amount of the layer containing the hydrophilic smectite is not particularly limited, but the antistatic performance is saturated even if the amount of coating is excessively increased, so 20 g / m 2 or less is practical.
可逆性感熱記録材料においては、繰り返し使用に対する耐久性、耐水性等が要求されるため、可逆性感熱記録材料を構成する各層を堅牢な構成にする必要があり、これらの特性に優れる有機溶剤性の塗料を塗布して各層を形成するのが一般的である。一方、本発明に係わる親水性スメクタイトを含有する層は、水性塗料で形成する必要があり、より高い堅牢性を得るために、架橋性樹脂を含有する水性塗料を使用するのが好ましい。 In reversible thermosensitive recording materials, durability against repeated use, water resistance, etc. are required, so it is necessary to make each layer constituting the reversible thermosensitive recording material robust, and these organic solvents have excellent properties. In general, each layer is formed by applying the above coating. On the other hand, the layer containing the hydrophilic smectite according to the present invention needs to be formed of an aqueous paint, and in order to obtain higher fastness, it is preferable to use an aqueous paint containing a crosslinkable resin.
本発明に係わる親水性スメクタイトの水性塗料に含有させる架橋性樹脂は特に限定されないが、水溶性または水分散性の熱架橋性及び／または活性エネルギー線架橋性樹脂が用いられる。 The crosslinkable resin to be included in the hydrophilic smectite aqueous coating composition according to the present invention is not particularly limited, and water-soluble or water-dispersible thermal crosslinkable and / or active energy ray crosslinkable resins are used.
水溶性または水分散性の熱架橋性樹脂としては、水酸基やカルボキシル基等の架橋剤と反応する基を持つ樹脂、または水酸基やカルボキシル基等を持つモノマーとそれ以外のモノマーを共重合した樹脂等が挙げられる。このような熱架橋性樹脂としては、例えば、フェノキシ樹脂、ポリビニルブチラール樹脂、セルロースアセテートプロピオネート樹脂、セルロースアセテートブチレート樹脂、アクリルポリオール樹脂、ポリエステルポリオール樹脂、ポリウレタンポリオール樹脂等が挙げられる。これらの中でも、アクリルポリオール樹脂、ポリエステルポリオール樹脂、ポリウレタンポリオール樹脂が特に好ましい。 Examples of the water-soluble or water-dispersible thermally crosslinkable resin include a resin having a group that reacts with a crosslinking agent such as a hydroxyl group or a carboxyl group, or a resin obtained by copolymerizing a monomer having a hydroxyl group or a carboxyl group with another monomer. Is mentioned. Examples of such thermally crosslinkable resins include phenoxy resin, polyvinyl butyral resin, cellulose acetate propionate resin, cellulose acetate butyrate resin, acrylic polyol resin, polyester polyol resin, polyurethane polyol resin, and the like. Among these, acrylic polyol resin, polyester polyol resin, and polyurethane polyol resin are particularly preferable.
前記アクリルポリオール樹脂は、（メタ）アクリル酸エステル単量体と、カルボン酸基を有する不飽和単量体、水酸基を有する不飽和単量体、及びその他のエチレン性不飽和単量体とを用い、公知の溶液重合法、懸濁重合法、乳化重合法等に従って合成することができる。 The acrylic polyol resin uses a (meth) acrylic acid ester monomer, an unsaturated monomer having a carboxylic acid group, an unsaturated monomer having a hydroxyl group, and other ethylenically unsaturated monomers. It can be synthesized according to a known solution polymerization method, suspension polymerization method, emulsion polymerization method and the like.
前記水酸基を有する不飽和単量体としては、例えば、ヒドロキシエチルアクリレート（ＨＥＡ）、ヒドロキシプロピルアクリレート（ＨＰＡ）、２−ヒドロキシエチルメタクリレート（ＨＥＭＡ）、２−ヒドロキシプロピルメタクリレート（ＨＰＭＡ）、１−ヒドロキシブチルアクリレート（１−ＨＢＡ）、２−ヒドロキシブチルアクリレート（２−ＨＢＡ）、３−ヒドロキシブチルアクリレート（３−ＨＢＡ）、４−ヒドロキシブチルアクリレート（４−ＨＢＡ）等が用いられるが、第１級水酸基を持つモノマーを使用した方が塗膜のワレ抵抗性や耐久性が良いことから、２−ヒドロキシエチルメタクリレートが好ましく用いられる。 Examples of the unsaturated monomer having a hydroxyl group include hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA), 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl methacrylate (HPMA), and 1-hydroxybutyl. Acrylate (1-HBA), 2-hydroxybutyl acrylate (2-HBA), 3-hydroxybutyl acrylate (3-HBA), 4-hydroxybutyl acrylate (4-HBA), etc. are used. 2-Hydroxyethyl methacrylate is preferably used because the use of the monomer possessed has better crack resistance and durability of the coating film.
前記架橋性樹脂は、架橋剤を用いて架橋させておくことが好ましい。架橋剤としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、イソシアネート類、アミノ樹脂、フェノール樹脂、アミン類、エポキシ化合物等が挙げられる。これらの中でも、イソシアネート類が好ましく、特に好ましくはイソシアネート基を複数持つポリイソシアネート化合物である。 The crosslinkable resin is preferably cross-linked using a cross-linking agent. There is no restriction | limiting in particular as a crosslinking agent, According to the objective, it can select suitably, For example, isocyanates, an amino resin, a phenol resin, amines, an epoxy compound, etc. are mentioned. Among these, isocyanates are preferable, and polyisocyanate compounds having a plurality of isocyanate groups are particularly preferable.
前記イソシアネート類としては、例えば、ヘキサメチレンジイソシアネート（ＨＤＩ）、トリレンジイソシアネート（ＴＤＩ）、キシリレンジイソシアネート（ＸＤＩ）、またはこれらのトリメチロールプロパン等によるアダクトタイプ、ビュレットタイプ、イソシアヌレートタイプ、またはブロック化イソシアネート類等が挙げられる。 Examples of the isocyanates include hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), or adduct type, burette type, isocyanurate type, or blocking with trimethylolpropane. Isocyanates and the like.
水溶性または水分散性の活性エネルギー線架橋性樹脂としては、紫外線架橋性樹脂、電子線架橋性樹脂等が挙げられる。特に紫外線架橋性樹脂は、電子線架橋性樹脂に比べて簡易な装置で、耐久性の高い塗層を形成することができて好ましい。 Examples of the water-soluble or water-dispersible active energy ray crosslinkable resin include ultraviolet ray crosslinkable resins and electron beam crosslinkable resins. In particular, the ultraviolet crosslinkable resin is preferable because it can form a highly durable coating layer with a simpler apparatus than the electron beam crosslinkable resin.
前記活性エネルギー線架橋性樹脂としては、特に制限はなく、公知のものの中から目的に応じて適宜選択することができ、例えば、ウレタンアクリレート系、エポキシアクリレート系、ポリエステルアクリレート系、ポリエーテルアクリレート系、ビニル系、不飽和ポリエステル系のオリゴマーや各種単官能、多官能のアクリレート、メタクリレート、ビニルエステル、エチレン誘導体、アリル化合物等のモノマーが挙げられる。これらの中でも、４官能以上の多官能性のモノマーまたはオリゴマーが特に好ましい。これらのモノマーまたはオリゴマーを２種類以上混合することで樹脂膜の硬さ、収縮度、柔軟性、塗膜強度等を適宜調節することができる。 The active energy ray crosslinkable resin is not particularly limited and can be appropriately selected from known ones according to the purpose. For example, urethane acrylate, epoxy acrylate, polyester acrylate, polyether acrylate, Examples thereof include vinyl and unsaturated polyester oligomers and monomers such as various monofunctional and polyfunctional acrylates, methacrylates, vinyl esters, ethylene derivatives, and allyl compounds. Among these, tetrafunctional or higher polyfunctional monomers or oligomers are particularly preferable. By mixing two or more of these monomers or oligomers, the hardness, shrinkage, flexibility, coating strength, etc. of the resin film can be appropriately adjusted.
前記多官能性モノマーまたはオリゴマーとしては、例えば、トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレート、トリスアクリロイルオキシエチルフォスフェート、ペンタエリスリトールテトラアクリレート、グリセリルプロポキシトリアクリレート、ジペンタエリスリトール・ポリアクリレート、ジペンタエリスリトールのカプロラクトン付加物のポリアクリレート、プロピオン酸・ジペンタエリスリトールトリアクリレート、ヒドロキシピバルアルデヒド変性ジメチロールプロパントリアクリレート、プロピオン酸・ジペンタエリスリトールのテトラアクリレート、ジトリメチロールプロパンテトラアクリレート、プロピオン酸・ジペンタエリスリトールのペンタアクリレート、トリメチロールプロパントリアクリレート付加ウレタンプレポリマー、ジペンタエリスリトールヘキサアクリレート（ＤＰＨＡ）、ＤＰＨＡのε−カプロラクトン付加物等が挙げられる。 Examples of the polyfunctional monomer or oligomer include trimethylolpropane triacrylate, pentaerythritol triacrylate, trisacryloyloxyethyl phosphate, pentaerythritol tetraacrylate, glycerylpropoxytriacrylate, dipentaerythritol polyacrylate, dipentaerythritol. Caprolactone adduct polyacrylate, propionic acid / dipentaerythritol triacrylate, hydroxypivalaldehyde-modified dimethylolpropane triacrylate, propionic acid / dipentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, propionic acid / dipentaerythritol Of pentaacrylate, trimethylolpropane Li acrylate added urethane prepolymer, dipentaerythritol hexaacrylate (DPHA), include ε- caprolactone adducts of DPHA.
また、前記モノマーまたはオリゴマーを紫外線を用いて硬化させるためには、光重合開始剤、光重合促進剤を用いる必要がある。前記光重合開始剤としては、ラジカル反応型とイオン反応型に大別でき、さらにラジカル反応型は光開裂型と水素引抜き型とに分けられる。前記光重合開始剤としては、例えば、イソブチルベンゾインエーテル、イソプロピルベンゾインエーテル、ベンゾインエチルエーテルベンゾインメチルエーテル、１−フェニル−１，２−プロパンジオン−２−（ｏ−エトキシカルボニル）オキシム、２，２−ジメトキシ−２−フェニルアセトフェノンベンジル、ヒドロキシシクロヘキシルフェニルケトン、ジエトキシアセトフェノン、１−［４−（２−ヒドロキシエトキシ）フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オン、ビス（２，４，６−トリメチルベンゾイル）フェニルフォスフィンオキサイド、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、ベンゾフェノン、クロロチオキサントン、２−クロロチオキサントン、イソプロピルチオキサントン、２−メチルチオキサントン、塩素置換ベンゾフェノン等が挙げられ、単独でまたは２種以上混合して使用されるが、これらに限定されるものではない。 Further, in order to cure the monomer or oligomer using ultraviolet rays, it is necessary to use a photopolymerization initiator and a photopolymerization accelerator. The photopolymerization initiator can be roughly classified into a radical reaction type and an ion reaction type, and the radical reaction type is further classified into a photocleavage type and a hydrogen abstraction type. Examples of the photopolymerization initiator include isobutyl benzoin ether, isopropyl benzoin ether, benzoin ethyl ether benzoin methyl ether, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 2,2- Dimethoxy-2-phenylacetophenone benzyl, hydroxycyclohexyl phenyl ketone, diethoxyacetophenone, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, bis (2 , 4,6-trimethylbenzoyl) phenylphosphine oxide, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone, chlorothioxanthone, 2-chlorothioxanthone, isopropylthioxanthate , 2-methyl thioxanthone, include chlorine-substituted benzophenone, are used alone or in admixture, but is not limited thereto.
これら重合開始剤の中で、水溶性あるいは水分散性が良好なものが特に好ましく用いられ、これらの具体例としては、１−［４−（２−ヒドロキシエトキシ）フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オン、ビス（２，４，６−トリメチルベンゾイル）フェニルフォスフィンオキサイド、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン等が挙げられる。 Among these polymerization initiators, those having good water solubility or water dispersibility are particularly preferably used. Specific examples thereof include 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2. -Methyl-1-propan-1-one, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2-hydroxy-2-methyl-1-phenylpropan-1-one and the like.
本発明に用いられる支持体としては、紙、各種不織布、織布、合成樹脂フィルム、合成樹脂ラミネート紙、合成紙、金属箔、ガラス等、あるいはこれらを組み合わせた複合シートを目的に応じて任意に用いることができ、透明、半透明あるいは不透明のいずれであっても良い。また、内部に空洞を持たない構造、あるいは内部に空洞を含有する構造のいずれであっても良い。合成樹脂フィルムとしては、ポリエステルフィルムが耐熱性の点で好ましい。 As the support used in the present invention, paper, various non-woven fabrics, woven fabric, synthetic resin film, synthetic resin laminated paper, synthetic paper, metal foil, glass, etc., or a composite sheet combining these may be arbitrarily selected according to the purpose. Any of transparent, translucent, and opaque can be used. Moreover, any of the structure which does not have a cavity inside, or the structure which contains a cavity inside may be sufficient. As the synthetic resin film, a polyester film is preferable in terms of heat resistance.
本発明に用いられるポリエステルフィルムとしては、ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート、ポリ−１，４−シクロヘキサンジメチレンテレフタレート、ポリキシリレンテレフタレート、ポリエチレンイソフタレート、ポリエチレン−２，６−ナフタレート（ＰＥＮ）等のフィルムが挙げられる。好ましいポリエステルフィルムとしては、強靱性、耐熱性、耐薬品性、寸法安定性、透明性、電気絶縁性に優れるＰＥＴフィルムまたはＰＥＮフィルムが挙げられる。また、これらの樹脂フィルム内に空洞を含有しても良く、表面にコロナ処理等により易接着加工が施されていても良い。 Polyester films used in the present invention include polyethylene terephthalate (PET), polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyxylylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalate (PEN). Etc. are mentioned. Preferred polyester films include PET films or PEN films that are excellent in toughness, heat resistance, chemical resistance, dimensional stability, transparency, and electrical insulation. Further, these resin films may contain cavities, and the surface may be subjected to easy adhesion processing by corona treatment or the like.
本発明に係わる可逆性感熱記録層は、熱により色調または透明度が変化する材料を用いることができる。例えば、樹脂母材中に有機低分子を分散したもので、熱により透明状態と白濁状態を与える可逆性感熱記録層や、通常無色ないし淡色のロイコ染料と加熱によりロイコ染料に可逆的な色調変化を与える可逆性顕色剤を用いて、熱エネルギーを制御することにより画像形成及び消去が可能な可逆性感熱記録層等が挙げられる。視認性などの点で、ロイコ染料を用いた可逆性感熱記録材料が特に優れている。また、可逆性感熱記録層は、色調の異なる可逆性感熱記録層を複数層重ねても良い。 For the reversible thermosensitive recording layer according to the present invention, a material whose color tone or transparency changes with heat can be used. For example, a low molecular weight organic material dispersed in a resin matrix, a reversible thermosensitive recording layer that gives heat a transparent state and a cloudy state, and a reversible color change to a leuco dye by heating with a normally colorless or light leuco dye. And a reversible thermosensitive recording layer capable of forming and erasing an image by controlling heat energy using a reversible developer that gives the color. A reversible thermosensitive recording material using a leuco dye is particularly excellent in terms of visibility. The reversible thermosensitive recording layer may be a stack of a plurality of reversible thermosensitive recording layers having different color tones.
本発明に係わるロイコ染料に可逆的な色調変化を与える可逆性顕色剤は、加熱による画像形成だけでなく、記録画像の消去も考慮された顕色剤であり、可逆性顕色剤を使用した感熱記録層は繰り返し表示内容を書き換えることが可能である。可逆性顕色剤としては下記一般式２、３及び４で示される化合物が好ましいが、特に一般式２で示される化合物が好ましく使用される。なお、本発明はこれに限定されるものではない。本発明に係わる可逆性顕色剤はそれぞれ１種または２種以上を混合して使用しても良い。 The reversible developer that gives a reversible color change to the leuco dye according to the present invention is a developer that takes into consideration not only image formation by heating but also erasure of recorded images, and uses a reversible developer. The heat-sensitive recording layer can repeatedly rewrite the display contents. As the reversible developer, compounds represented by the following general formulas 2, 3, and 4 are preferable, and in particular, a compound represented by the general formula 2 is preferably used. Note that the present invention is not limited to this. The reversible developer according to the present invention may be used alone or in combination of two or more.
一般式２において、Ｘ1及びＸ2はそれぞれ同じであっても、異なっても良い酸素原子、硫黄原子または両末端に炭化水素原子団を含まない−ＣＯＮＨ−結合を最小構成単位とする二価の基を表す。Ｒ1は単結合または炭素数１から１２の二価の炭化水素基を表す。Ｒ2は炭素数１から１８の二価の炭化水素基を表す。好ましくは炭素数１から４の二価の炭化水素基である。Ｒ3は炭素数１から５０の一価の炭化水素基を表し、好ましくは炭素数６から３６の炭化水素基であり、より好ましくは炭素数８から２４の炭化水素基である。Ｒ1及びＲ2は主として、アルキレン基またはアルケニレン基を表し、Ｒ3は主としてアルキル基またはアルケニル基を表す。Ｒ2の場合は、芳香環を含んでいても良い。ｆは０から４の整数を表し、ｆが２以上のとき繰り返されるＲ2及びＸ2は同一であっても異なっていても良い。 In General Formula 2, X 1 and X 2 may be the same or different from each other, and may be different from each other. Represents a group of R 1 represents a single bond or a divalent hydrocarbon group having 1 to 12 carbon atoms. R 2 represents a divalent hydrocarbon group having 1 to 18 carbon atoms. A divalent hydrocarbon group having 1 to 4 carbon atoms is preferred. R 3 represents a monovalent hydrocarbon group having 1 to 50 carbon atoms, preferably a hydrocarbon group having 6 to 36 carbon atoms, and more preferably a hydrocarbon group having 8 to 24 carbon atoms. R 1 and R 2 mainly represent an alkylene group or an alkenylene group, and R 3 mainly represents an alkyl group or an alkenyl group. In the case of R 2 , it may contain an aromatic ring. f represents an integer of 0 to 4, and R 2 and X 2 repeated when f is 2 or more may be the same or different.
一般式２中のＸ1、Ｘ2は両末端に炭化水素原子団を含まない−ＣＯＮＨ−結合を最小構成単位とする二価の基を含むが、その具体例としては、ジアシルアミン（−ＣＯＮＨＣＯ−）、ジアシルヒドラジン（−ＣＯＮＨＮＨＣＯ−）、しゅう酸ジアミド（−ＮＨＣＯＣＯＮＨ−）、アシル尿素（−ＣＯＮＨＣＯＮＨ−、−ＮＨＣＯＮＨＣＯ−）、セミカルバジド（−ＮＨＣＯＮＨＮＨ−、−ＮＨＮＨＣＯＮＨ−）、アシルセミカルバジド（−ＣＯＮＨＮＨＣＯＮＨ−、−ＮＨＣＯＮＨＮＨＣＯ−）、ジアシルアミノメタン（−ＣＯＮＨＣＨ2ＮＨＣＯ−）、１−アシルアミノ−１−ウレイドメタン（−ＣＯＮＨＣＨ2ＮＨＣＯＮＨ−、−ＮＨＣＯＮＨＣＨ2ＮＨＣＯ−）、マロンアミド（−ＮＨＣＯＣＨ2ＣＯＮＨ−）、３−アシルカルバジン酸エステル（−ＣＯＮＨＮＨＣＯＯ−、−ＯＣＯＮＨＮＨＣＯ−）等の基が挙げられるが、好ましくはジアシルヒドラジン、しゅう酸ジアミド、アシルセミカルバジドである。 But X 1, X 2 in the general formula 2 comprises a divalent group of -CONH- bond containing no hydrocarbon atomic group at both ends as minimum unit, and specific examples thereof include Jiashiruamin (-CONHCO -), Diacylhydrazine (-CONHNHCO-), oxalic acid diamide (-NHCONCONH-), acylurea (-CONHCONH-, -NHCONHCO-), semicarbazide (-NHCONHNH-, -NHNHCONH-), acyl semicarbazide (-CONHNHCONH-, -NHCONHNHCO-), diacyl aminomethane (-CONHCH 2 NHCO -), 1- acylamino-1- Ureidometan (-CONHCH 2 NHCONH -, - NHCONHCH 2 NHCO-), malonamide (-NHCOCH 2 CONH -), 3- Ashirukarubaji Ester (-CONHNHCOO -, - OCONHNHCO-) although groups such like, preferably a diacyl hydrazine, oxalic acid diamide, acyl semicarbazide.
本発明に係わる可逆性顕色剤の具体的な例としては以下の構造式（２−１）から構造式（２−１６）に挙げるが、本発明はこれに限定されるものではない。 Specific examples of the reversible developer according to the present invention include the following structural formulas (2-1) to (2-16), but the present invention is not limited thereto.
可逆性顕色剤の具体例の中で、特に好ましい化合物は（２−３）、（２−４）、（２−５）、（２−６）、（２−７）、（２−９）及び（２−１６）である。 Among the specific examples of the reversible developer, particularly preferred compounds are (2-3), (2-4), (2-5), (2-6), (2-7), (2-9). ) And (2-16).
可逆性顕色剤として、下記一般式３及び４で示されるような電子吸引性のフッ素原子を含有するアルコール系化合物も好ましく使用される。 As the reversible developer, an alcohol compound containing an electron-withdrawing fluorine atom as represented by the following general formulas 3 and 4 is also preferably used.
一般式３において、ａは０または１の整数を表す。また、Ｔ1及びＴ2は互いに独立に水素原子、メチル基、フェニル基から選ばれた一員を表し、Ｔ3は水素原子、メチル基、フェニル基、トリフルオロメチル基から選ばれた一員を表す。Ｔ4及びＴ5は互いに独立に単結合または炭素数１〜２０の２価の炭化水素基を表し、Ｔ6は炭素数８〜３０の１価の直鎖脂肪族基を表す。さらに、Ｙ1及びＹ2は互いに独立に単結合または下記（３−１）〜（３−２３）により表される２価の基から選ばれた一員を表すが、Ｙ1及びＹ2が同時に単結合であるものを含まない。また、（３−１）〜（３−２３）により表される２価の基が左右対称形でない場合、これらの基はそのままの向きで一般式３で表される化合物の両隣の基と結合していても良いし、左右反転した形で両隣の基と結合していても良い。 In General Formula 3, a represents an integer of 0 or 1. T 1 and T 2 each independently represent a member selected from a hydrogen atom, a methyl group and a phenyl group, and T 3 represents a member selected from a hydrogen atom, a methyl group, a phenyl group and a trifluoromethyl group. . T 4 and T 5 each independently represent a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and T 6 represents a monovalent linear aliphatic group having 8 to 30 carbon atoms. Y 1 and Y 2 each independently represent a single bond or a member selected from divalent groups represented by the following (3-1) to (3-23), and Y 1 and Y 2 are simultaneously Does not include those that are single bonds. In addition, when the divalent groups represented by (3-1) to (3-23) are not bilaterally symmetric, these groups are bonded to the groups adjacent to the compound represented by Formula 3 in the same direction. It may be bonded to the groups on both sides in a horizontally reversed manner.
一般式４において、ｂは１または２の整数を表し、ｃは１〜３の整数を表す。また、Ｔ7及びＴ8は互いに独立に水素原子、メチル基、フェニル基から選ばれた一員を表し、Ｔ9及びＴ10は互いに独立に単結合または炭素数１〜２０の２価の炭化水素基を表し、Ｔ11は水素原子または炭素数１〜３０の１価の直鎖脂肪族基を表す。さらに、Ｙ3及びＹ4は互いに独立に単結合または下記（３−１）〜（３−２３）により表される２価の基から選ばれた一員を表すが、Ｙ3及びＹ4が同時に単結合であるものを含まない。また、（３−１）〜（３−２３）により表される２価の基が左右対称形でない場合、これらの基はそのままの向きで一般式４で表される化合物の両隣の基と結合していても良いし、左右反転した形で両隣の基と結合していても良い。 In General Formula 4, b represents an integer of 1 or 2, and c represents an integer of 1 to 3. T 7 and T 8 each independently represent a member selected from a hydrogen atom, a methyl group and a phenyl group, and T 9 and T 10 each independently represent a single bond or a divalent hydrocarbon having 1 to 20 carbon atoms. T 11 represents a hydrogen atom or a monovalent linear aliphatic group having 1 to 30 carbon atoms. Y 3 and Y 4 each independently represent a single bond or a member selected from divalent groups represented by the following (3-1) to (3-23), and Y 3 and Y 4 are simultaneously Does not include those that are single bonds. In addition, when the divalent groups represented by (3-1) to (3-23) are not bilaterally symmetric, these groups are bonded to the groups adjacent to the compound represented by Formula 4 in the same direction. It may be bonded to the groups on both sides in a horizontally reversed manner.
前記Ｙ1及びＹ3において、好ましい２価の基としては（３−１８）〜（３−２３）が挙げられ、特に好ましくは（３−１８）、（３−２１）である。 In Y 1 and Y 3 , preferred divalent groups include (3-18) to (3-23), and (3-18) and (3-21) are particularly preferred.
本発明に係わる可逆性顕色剤はそれぞれ１種または２種以上を混合して使用しても良く、通常無色ないし淡色のロイコ染料に対する使用量は、５〜５０００質量％、好ましくは１０〜３０００質量％である。 Each of the reversible developers according to the present invention may be used alone or in combination of two or more. The amount used is usually 5 to 5000% by mass, preferably 10 to 3000, based on a colorless or light leuco dye. % By mass.
本発明に用いられる通常無色ないし淡色のロイコ染料としては、一般に感圧記録紙や感熱記録紙等に用いられるものを用いることができる。具体例としては、例えば下記に挙げるもの等があるが、本発明はこれに限定されるものではない。また、これらロイコ染料は、それぞれ１種または２種以上を混合して使用しても良い。 As the normally colorless or light leuco dye used in the present invention, those generally used for pressure-sensitive recording paper, heat-sensitive recording paper and the like can be used. Specific examples include, for example, those listed below, but the present invention is not limited thereto. These leuco dyes may be used alone or in combination of two or more.
（１）トリアリールメタン系化合物
３，３−ビス（ｐ−ジメチルアミノフェニル）−６−ジメチルアミノフタリド（クリスタルバイオレットラクトン）、３，３−ビス（ｐ−ジメチルアミノフェニル）フタリド、３−（４−ジエチルアミノ−２−エトキシフェニル）−３−（１−エチル−２−メチルインドール−３−イル）フタリド、３−（ｐ−ジメチルアミノフェニル）−３−（２−メチルインドール−３−イル）フタリド、３−（ｐ−ジメチルアミノフェニル）−３−（２−フェニルインドール−３−イル）フタリド、３，３−ビス（１，２−ジメチルインドール−３−イル）−５−ジメチルアミノフタリド、３，３−ビス（１，２−ジメチルインドール−３−イル）−６−ジメチルアミノフタリド、３−（４−ジエチルアミノ−２−ｎ−ヘキシルオキシフェニル）−３−（１−エチル−２−メチルインドール−３−イル）−４−アザフタリド、３−（４−ジエチルアミノ−２−メチルフェニル）−３−（１−エチル−２−メチルインドール−３−イル）−４−アザフタリド、３−（４−ジエチルアミノフェニル）−３−（１−エチル−２−メチルインドール−３−イル）−４−アザフタリド、３−（４−ジメチルアミノ−２−エトキシフェニル）−３−（１−エチル−２−メチルインドール−３−イル）−４−アザフタリド、３−（４−ジエチルアミノ−２−エトキシフェニル）−３−（１−ｎ−オクチル−２−メチルインドール−３−イル）−４−アザフタリド、３−（４−ジエチルアミノ−２−エトキシフェニル）−３−（１−エチル−２−メチルインドール−３−イル）−４−アザフタリド、３，３−ビス（９−エチルカルバゾール−３−イル）−５−ジメチルアミノフタリド、３，３−ビス（２−フェニルインドール−３−イル）−５−ジメチルアミノフタリド、３−ｐ−ジメチルアミノフェニル−３−（１−メチルピロール−２−イル）−６−ジメチルアミノフタリド等が挙げられる。
(1) Triarylmethane compounds 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (crystal violet lactone), 3,3-bis (p-dimethylaminophenyl) phthalide, 3- ( 4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-methylindol-3-yl) Phthalide, 3- (p-dimethylaminophenyl) -3- (2-phenylindol-3-yl) phthalide, 3,3-bis (1,2-dimethylindol-3-yl) -5-dimethylaminophthalide 3,3-bis (1,2-dimethylindol-3-yl) -6-dimethylaminophthalide, 3- (4-diethylamino-2-n) -Hexyloxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3- (4-diethylamino-2-methylphenyl) -3- (1-ethyl-2-methyl) Indol-3-yl) -4-azaphthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3- (4-dimethylamino-2) -Ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-n-octyl-2- Methylindol-3-yl) -4-azaphthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3,3-bis (9-ethylcarbazol-3-yl) -5-dimethylaminophthalide, 3,3-bis (2-phenylindol-3-yl) -5-dimethylaminophthalide , 3-p-dimethylaminophenyl-3- (1-methylpyrrol-2-yl) -6-dimethylaminophthalide and the like.
（２）ジフェニルメタン系化合物
４，４′−ビス（ジメチルアミノフェニル）ベンズヒドリルベンジルエーテル、Ｎ−クロロフェニルロイコオーラミン、Ｎ−２，４，５−トリクロロフェニルロイコオーラミン等が挙げられる。
(2) Diphenylmethane compounds 4,4'-bis (dimethylaminophenyl) benzhydrylbenzyl ether, N-chlorophenyl leucooramine, N-2,4,5-trichlorophenyl leucooramine and the like.
（３）キサンテン系化合物
ローダミンＢアニリノラクタム、ローダミンＢ−ｐ−クロロアニリノラクタム、３−ジエチルアミノ−７−ジベンジルアミノフルオラン、３−ジエチルアミノ−７−オクチルアミノフルオラン、３−ジエチルアミノ−７−フェニルフルオラン、３−ジエチルアミノ−７−クロロフルオラン、３−ジエチルアミノ−６−クロロ−７−メチルフルオラン、３−ジエチルアミノ−７−フェノキシフルオラン、３−ジエチルアミノ−７−（３，４−ジクロロアニリノ）フルオラン、３−ジエチルアミノ−７−（２−クロロアニリノ）フルオラン、３−ジエチルアミノ−６−メチル−７−アニリノフルオラン、３−ジエチルアミノ−６−メチル−７−（３−メチルアニリノ）フルオラン、３−（Ｎ−エチル）トリルアミノ−６−メチル−７−アニリノフルオラン、３−ピペリジノ−６−メチル−７−アニリノフルオラン、３−（Ｎ−エチル）トリルアミノ−６−メチル−７−フェネチルフルオラン、３−ジエチルアミノ−７−（４−ニトロアニリノ）フルオラン、３−ジブチルアミノ−６−メチル−７−アニリノフルオラン、３−（Ｎ−メチル）プロピルアミノ−６−メチル−７−アニリノフルオラン、３−（Ｎ−エチル）イソアミルアミノ−６−メチル−７−アニリノフルオラン、３−（Ｎ−メチル）シクロヘキシルアミノ−６−メチル−７−アニリノフルオラン、３−（Ｎ−エチル）テトラヒドロフリルアミノ−６−メチル−７−アニリノフルオラン等が挙げられる。
(3) Xanthene compounds Rhodamine B anilinolactam, rhodamine Bp-chloroanilinolactam, 3-diethylamino-7-dibenzylaminofluorane, 3-diethylamino-7-octylaminofluorane, 3-diethylamino-7 -Phenylfluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamino-6-chloro-7-methylfluorane, 3-diethylamino-7-phenoxyfluorane, 3-diethylamino-7- (3,4 Dichloroanilino) fluorane, 3-diethylamino-7- (2-chloroanilino) fluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7- (3-methylanilino) fluorane , 3- (N-ethyl) tolylamino-6 -Methyl-7-anilinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3- (N-ethyl) tolylamino-6-methyl-7-phenethylfluorane, 3-diethylamino-7- (4-Nitroanilino) fluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, 3- (N-methyl) propylamino-6-methyl-7-anilinofluorane, 3- (N-ethyl) ) Isoamylamino-6-methyl-7-anilinofluorane, 3- (N-methyl) cyclohexylamino-6-methyl-7-anilinofluorane, 3- (N-ethyl) tetrahydrofurylamino-6-methyl -7-anilinofluorane and the like.
（４）チアジン系化合物
ベンゾイルロイコメチレンブルー、ｐ−ニトロベンゾイルロイコメチレンブルー等が挙
げられる。
(4) Thiazine compounds benzoyl leucomethylene blue, p-nitrobenzoyl leucomethylene blue and the like can be mentioned.
（５）スピロ系化合物
３−メチルスピロジナフトピラン、３−エチルスピロジナフトピラン、３，３′−ジクロロスピロジナフトピラン、３−ベンジルスピロジナフトピラン、３−メチルナフト−（３−メトキシベンゾ）スピロピラン、３−プロピルスピロベンゾピラン等が挙げられる。
(5) Spiro compounds 3-methylspirodinaphthopyran, 3-ethylspirodinaphthopyrans, 3,3'-dichlorospirodinaphthopyrans, 3-benzylspirodinaphthopyrans, 3-methylnaphthyl (3-methoxybenzo) ) Spiropyran, 3-propyl spirobenzopyran and the like.
本発明で用いられる可逆性感熱記録層を得るために使用されるバインダーとしては、例えば、ポリビニルアルコール、変性ポリビニルアルコール、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、メトキシセルロース、カルボキシメチルセルロース、メチルセルロース、酢酸セルロース、ゼラチン、カゼイン、澱粉、ポリアクリル酸ソーダ、ポリビニルピロリドン、ポリアクリルアミド、アクリル酸アミド／アクリル酸エステル共重合体、アクリル酸アミド／アクリル酸エステル／メタクリル酸３元共重合体、スチレン／無水マレイン酸共重合体のアルカリ塩、エチレン／無水マレイン酸共重合体のアルカリ塩等の水溶性高分子、ポリ酢酸ビニル、ポリアクリル酸エステル、ポリメタクリル酸エステル類、ポリスチレン、スチレン／ブタジエン共重合体、アクリロニトリル／ブタジエン共重合体、アクリル酸メチル／ブタジエン共重合体、エチレン／酢酸ビニル共重合体、エチレン／塩化ビニル共重合体、ポリ塩化ビニル、エチレン／塩化ビニリデン共重合体、ポリ塩化ビニリデン等のラテックス類、フェノキシ樹脂、ポリビニルブチラール樹脂、セルロースアセテートプロピオネート樹脂等及びこれらの水酸基、カルボキシル基がイソシアネート類、アミン類、フェノール類、エポキシ類等の架橋剤と反応し、硬化するポリウレタン等の熱架橋性樹脂、電子線架橋性樹脂、紫外線架橋性樹脂が挙げられる。これらの中で、特開平１０−２３０６８０号公報や同１１−５８９６３号公報に記載の、ポリオール樹脂をイソシアネート化合物で架橋して得られる熱架橋性樹脂が好ましい。 Examples of the binder used to obtain the reversible thermosensitive recording layer used in the present invention include polyvinyl alcohol, modified polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, methoxy cellulose, carboxymethyl cellulose, methyl cellulose, cellulose acetate, gelatin, Casein, starch, polyacrylic acid soda, polyvinylpyrrolidone, polyacrylamide, acrylic acid amide / acrylic acid ester copolymer, acrylic acid amide / acrylic acid ester / methacrylic acid terpolymer, styrene / maleic anhydride copolymer Water-soluble polymers such as alkali salts of ethylene, alkali salts of ethylene / maleic anhydride copolymers, polyvinyl acetate, polyacrylic acid esters, polymethacrylic acid esters, polystyrene, / Butadiene copolymer, acrylonitrile / butadiene copolymer, methyl acrylate / butadiene copolymer, ethylene / vinyl acetate copolymer, ethylene / vinyl chloride copolymer, polyvinyl chloride, ethylene / vinylidene chloride copolymer , Latexes such as polyvinylidene chloride, phenoxy resin, polyvinyl butyral resin, cellulose acetate propionate resin and the like, and these hydroxyl groups and carboxyl groups react with crosslinking agents such as isocyanates, amines, phenols, epoxies, Examples thereof include a heat-crosslinkable resin such as polyurethane to be cured, an electron beam crosslinkable resin, and an ultraviolet ray crosslinkable resin. Among these, thermal crosslinkable resins obtained by crosslinking a polyol resin with an isocyanate compound described in JP-A Nos. 10-230680 and 11-58963 are preferable.
可逆性感熱記録層におけるバインダーの使用量としては、該可逆性感熱記録層全質量に対する該バインダー成分の質量百分率が３５％以上６５％以下の範囲内であることが好ましい。この範囲より大きくなると著しく発色濃度が低下し、逆にこの範囲より小さくなると可逆性感熱記録層の耐熱性や機械的強度が低下し、層の変形や発色濃度の低下が起きる。可逆性感熱記録層における該バインダー成分の質量百分率は、４０％以上６０％以下がより好ましく、４５％以上５５％以下がなお一層好ましい。 The amount of binder used in the reversible thermosensitive recording layer is preferably such that the mass percentage of the binder component relative to the total mass of the reversible thermosensitive recording layer is in the range of 35% to 65%. When it is larger than this range, the color density is remarkably lowered. On the other hand, when it is smaller than this range, the heat resistance and mechanical strength of the reversible thermosensitive recording layer are lowered, and the layer is deformed and the color density is lowered. The mass percentage of the binder component in the reversible thermosensitive recording layer is more preferably from 40% to 60%, and even more preferably from 45% to 55%.
また、可逆性感熱記録層の発色感度及び消色温度を調節するための添加剤として、熱可融性物質を可逆性感熱記録層中に含有させることができる。６０〜２００℃の融点を有するものが好ましく、特に８０〜１８０℃の融点を有するものが好ましい。一般の感熱記録紙に用いられている増感剤を使用することもできる。例えば、Ｎ−ヒドロキシメチルステアリン酸アミド、ステアリン酸アミド、パルミチン酸アミド等のワックス類、２−ベンジルオキシナフタレン等のナフトール誘導体、ｐ−ベンジルビフェニル、４−アリルオキシビフェニル等のビフェニル誘導体、１，２−ビス（３−メチルフェノキシ）エタン、２，２′−ビス（４−メトキシフェノキシ）ジエチルエーテル、ビス（４−メトキシフェニル）エーテル等のポリエーテル化合物、炭酸ジフェニル、しゅう酸ジベンジル、しゅう酸ビス（ｐ−メチルベンジル）エステル等の炭酸またはしゅう酸ジエステル誘導体等を併用して添加することができる。 Further, as an additive for adjusting the color development sensitivity and decoloring temperature of the reversible thermosensitive recording layer, a thermofusible substance can be contained in the reversible thermosensitive recording layer. Those having a melting point of 60 to 200 ° C. are preferred, and those having a melting point of 80 to 180 ° C. are particularly preferred. Sensitizers used for general heat-sensitive recording paper can also be used. For example, waxes such as N-hydroxymethyl stearamide, stearamide, and palmitic acid amide, naphthol derivatives such as 2-benzyloxynaphthalene, biphenyl derivatives such as p-benzylbiphenyl and 4-allyloxybiphenyl, 1,2 -Polyether compounds such as bis (3-methylphenoxy) ethane, 2,2'-bis (4-methoxyphenoxy) diethyl ether, bis (4-methoxyphenyl) ether, diphenyl carbonate, dibenzyl oxalate, bis (oxalate) ( Carbonic acid or oxalic acid diester derivatives such as p-methylbenzyl ester can be used in combination.
本発明に係わる可逆性感熱記録層の膜厚は０．１〜２０μｍの範囲が好ましく、３〜１５μｍがより好ましい。 The film thickness of the reversible thermosensitive recording layer according to the present invention is preferably in the range of 0.1 to 20 μm, more preferably 3 to 15 μm.
本発明の可逆性感熱記録材料の層構成は、少なくとも可逆性感熱記録層からなるが、必要に応じて、保護層、各層の間に中間層を設けることや、支持体と可逆性感熱記録層の間に下引き層を設けることもできる。さらに、可逆性感熱記録層が設けられている面及び／または反対側の面に、電気的、磁気的、光学的に情報が記録可能な材料を含んでも良い。また、可逆性感熱記録層が設けられている面と反対側の面にカール防止を目的としてバックコート層を設けることもできる。本発明において、親水性スメクタイトは可逆性感熱記録材料のいずれかの面の最表層に含有させた場合、表面の導電性の向上が大きいためより好ましい。 The layer structure of the reversible thermosensitive recording material of the present invention comprises at least a reversible thermosensitive recording layer. If necessary, a protective layer, an intermediate layer between each layer, a support and a reversible thermosensitive recording layer are provided. An undercoat layer may be provided between the two. Further, the surface on which the reversible thermosensitive recording layer is provided and / or the surface on the opposite side may include a material capable of recording information electrically, magnetically, and optically. In addition, a back coat layer can be provided on the surface opposite to the surface on which the reversible thermosensitive recording layer is provided for the purpose of preventing curling. In the present invention, hydrophilic smectite is more preferable when it is contained in the outermost layer on either side of the reversible thermosensitive recording material because the surface conductivity is greatly improved.
可逆性感熱記録層、保護層、必要に応じて用いる中間層や下引き層のいずれの層において、ブロッキング防止のために、ケイソウ土、クレー、焼成クレー、タルク、カオリン、焼成カオリン、炭酸カルシウム、炭酸マグネシウム、二酸化チタン、酸化亜鉛、酸化珪素、酸化アルミニウム、水酸化アルミニウム、澱粉粒、尿素−ホルマリン樹脂粒子、メラミン樹脂粒子、シリコーン粒子等の顔料や、ステアリン酸亜鉛、ステアリン酸カルシウム等の高級脂肪酸金属塩、パラフィン、酸化パラフィン、ポリエチレン、酸化ポリエチレン、ステアリン酸アミド、カスターワックス等のワックス類を、単独もしくは２種以上含有させることができる。また、レベリング剤、分散剤、界面活性剤、蛍光染料等を１種以上含有させることもできる。 In the reversible thermosensitive recording layer, protective layer, and any intermediate layer or undercoat layer used as necessary, diatomaceous earth, clay, calcined clay, talc, kaolin, calcined kaolin, calcium carbonate, Pigments such as magnesium carbonate, titanium dioxide, zinc oxide, silicon oxide, aluminum oxide, aluminum hydroxide, starch granules, urea-formalin resin particles, melamine resin particles, silicone particles, and higher fatty acid metals such as zinc stearate and calcium stearate Waxes such as salt, paraffin, oxidized paraffin, polyethylene, oxidized polyethylene, stearamide, and castor wax can be contained alone or in combination. One or more leveling agents, dispersants, surfactants, fluorescent dyes and the like can also be contained.
本発明に係わる保護層としては、硬化性樹脂を主成分とし、顔料等を含有していても良い。硬化性樹脂としては、例えば、熱架橋性樹脂、電子線架橋性樹脂、紫外線架橋性樹脂等が挙げられる。熱架橋性樹脂としては、水酸基やカルボキシル基等の架橋剤と反応する基を持つ樹脂、または水酸基やカルボキシル基等を持つモノマーとそれ以外のモノマーを共重合した樹脂等が挙げられる。このような熱架橋性樹脂としては、例えば、フェノキシ樹脂、ポリビニルブチラール樹脂、セルロースアセテートプロピオネート樹脂、セルロースアセテートブチレート樹脂、アクリルポリオール樹脂、ポリエステルポリオール樹脂、ポリウレタンポリオール樹脂等が挙げられる。これらの中でも、アクリルポリオール樹脂、ポリエステルポリオール樹脂、ポリウレタンポリオール樹脂が特に好ましい。この際の架橋剤としては、例えば、イソシアネート類、アミン類、フェノール類、エポキシ類等が挙げられる。 The protective layer according to the present invention may contain a curable resin as a main component and a pigment or the like. Examples of the curable resin include a heat crosslinkable resin, an electron beam crosslinkable resin, and an ultraviolet crosslinkable resin. Examples of the thermally crosslinkable resin include a resin having a group that reacts with a crosslinking agent such as a hydroxyl group or a carboxyl group, or a resin obtained by copolymerizing a monomer having a hydroxyl group, a carboxyl group, or the like with another monomer. Examples of such thermally crosslinkable resins include phenoxy resin, polyvinyl butyral resin, cellulose acetate propionate resin, cellulose acetate butyrate resin, acrylic polyol resin, polyester polyol resin, polyurethane polyol resin, and the like. Among these, acrylic polyol resin, polyester polyol resin, and polyurethane polyol resin are particularly preferable. Examples of the crosslinking agent at this time include isocyanates, amines, phenols, epoxies, and the like.
電子線及び紫外線架橋性樹脂に用いられるモノマーとしては、アクリル系に代表される単官能性モノマー、二官能モノマー、多官能モノマー等が挙げられるが、特に紫外線架橋の際には光重合開始剤、光重合促進剤を用いても良い。 Monomers used for electron beams and ultraviolet crosslinkable resins include monofunctional monomers typified by acrylics, bifunctional monomers, polyfunctional monomers, and the like. A photopolymerization accelerator may be used.
アクリル系モノマーの例としては、ポリエステルアクリレート、エポキシアクリレート、ウレタンアクリレート、シリコーンアクリレート、ポリブタジエンアクリレート等が挙げられる。 Examples of acrylic monomers include polyester acrylate, epoxy acrylate, urethane acrylate, silicone acrylate, polybutadiene acrylate, and the like.
保護層の厚みは０．５〜１０μｍが好ましい。これより薄いと記録画像の形成と消去を多数回にわたって繰り返すことができず、また厚いと記録感度が低下する。保護層は複数の構成であっても良い。 The thickness of the protective layer is preferably 0.5 to 10 μm. If it is thinner than this, formation and erasure of the recorded image cannot be repeated many times, and if it is thicker, the recording sensitivity is lowered. The protective layer may have a plurality of configurations.
また、可逆性感熱記録層、保護層、必要に応じて用いる中間層や下引き層のいずれの層においても紫外線吸収剤や酸化防止剤を含有させることができる。 Further, in any of the reversible thermosensitive recording layer, the protective layer, and the intermediate layer and undercoat layer used as necessary, an ultraviolet absorber and an antioxidant can be contained.
紫外線吸収剤の具体例としては、例えば、フェニルサリシレート、ｐ−ｔｅｒｔ−ブチルフェニルサリシレート、ｐ−オクチルフェニルサリシレート等のサリチル酸フェニルエステル系紫外線吸収剤、２，４−ジヒドロキシベンゾフェノン、２−ヒドロキシ−４−メトキシベンゾフェノン、２−ヒドロキシ−４−ｎ−オクトキシベンゾフェノン、４−ドデシルオキシ−２−ヒドロキシベンゾフェノン、２，２′−ジヒドロキシ−４−メトキシベンゾフェノン等のベンゾフェノン系紫外線吸収剤、２−（２′−ヒドロキシ−５′−メチルフェニル）ベンゾトリアゾール、２−（２′−ヒドロキシ−５′−ｔ−オクチルフェニル）ベンゾトリアゾール、２−（２′−ヒドロキシ−４′−オクトキシフェニル）ベンゾトリアゾール、２−（２′−ヒドロキシ−３′−ｔ−ブチル−５′−メチルフェニル）−５−クロロベンゾトリアゾール等のベンゾトリアゾール系紫外線吸収剤、２−エチルヘキシル−２−シアノ−３，３−ジフェニルアクリレート、エチル−２−シアノ−３，３−ジフェニルアクリレート等のアクリレート系紫外線吸収剤等が挙げられる。これらは単独で用いても良く、または２種類以上を併用しても良い。 Specific examples of the UV absorber include salicylic acid phenyl ester UV absorbers such as phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4- Benzophenone ultraviolet absorbers such as methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2- (2'- Hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- (2'-hi Benzotriazole ultraviolet absorbers such as loxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, ethyl-2-cyano Examples include acrylate ultraviolet absorbers such as −3,3-diphenyl acrylate. These may be used alone or in combination of two or more.
酸化防止剤の具体例としては、例えば、２，６−ジ−ｔ−ブチル−ｐ−クレゾール、２，６−ジ−ｔ−ブチルフェノール、２，４−ジメチル−６−ｔ−ブチルフェノール、ブチルヒドロキシアニソール、２，２′−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）、４，４′−ブチリデンビス（３−メチル−６−ｔ−ブチルフェノール）、４，４′−チオビス（３−メチル−６−ｔ−ブチルフェノール）、テトラキス〔メチレン−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート〕メタン、１，１，３−トリス（２−メチル−４−ヒドロキシ−５−ｔ−ブチルフェニル）ブタン等のフェノール系酸化防止剤、フェニル−β−ナフチルアミン、α−ナフチルアミン、Ｎ，Ｎ′−ジ−ｓｅｃ−ブチル−ｐ−フェニレンジアミン、フェノチアジン、Ｎ，Ｎ′−ジフェニル−ｐ−フェニレンジアミン等のアミン系酸化防止剤、ジラウリルチオジプロピオネート、ジステアリルチオジプロピオネート、ラウリルステアリルチオジプロピオネート、ジミリスチルチオジプロピオネート、ジステアリル−β，β′−チオジブチレート、２−メルカプトベンゾイミダゾール、ジラウリルサルファイド等の硫黄系酸化防止剤、トリフェニルフォスファイト、トリオクタデシルフォスファイト、トリデシルフォスファイト、トリラウリルトリチオフォスファイト、９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナンスレン−１０−オキサイド等のりん系酸化防止剤等が挙げられる。これらは単独で用いても良く、または２種類以上を併用しても良い。 Specific examples of the antioxidant include, for example, 2,6-di-t-butyl-p-cresol, 2,6-di-t-butylphenol, 2,4-dimethyl-6-t-butylphenol, and butylhydroxyanisole. 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl-6- t-butylphenol), tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 1,1,3-tris (2-methyl-4-hydroxy-5-t) Phenolic antioxidants such as -butylphenyl) butane, phenyl-β-naphthylamine, α-naphthylamine, N, N'-di-sec-butyl-p-pheny Amine antioxidants such as range amine, phenothiazine, N, N'-diphenyl-p-phenylenediamine, dilauryl thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, dimyristyl thiodipropio Nitrate, distearyl-β, β'-thiodibutyrate, 2-mercaptobenzimidazole, sulfur antioxidants such as dilauryl sulfide, triphenyl phosphite, trioctadecyl phosphite, tridecyl phosphite, trilauryl trithiophos Examples thereof include phosphorus antioxidants such as phyto and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. These may be used alone or in combination of two or more.
本発明に用いられる可逆性感熱記録材料の発色を行うには、加熱に引き続き急速な冷却が起これば良く、例えばサーマルヘッド、レーザー光等による加熱により可能である。また、加熱後ゆっくり冷却すれば消色し、例えば熱ロール、熱スタンプ、サーマルヘッド、高周波加熱、熱風、電熱ヒーターあるいはハロゲンランプ等の光源からの輻射熱等を用いることにより行える。 In order to perform color development of the reversible thermosensitive recording material used in the present invention, it is sufficient that rapid cooling occurs after heating, and for example, heating by a thermal head, laser light or the like is possible. Moreover, if it cools slowly after a heating, it can erase, for example, using a heat roll, a heat stamp, a thermal head, high frequency heating, a hot air, an radiant heat from a light source such as an electric heater or a halogen lamp.
加熱に使用するレーザーとしては半導体レーザーやＹＡＧレーザーを挙げることができるが、これらに限定されない。これらのレーザー光による加熱を効率良く行うためには、可逆性感熱記録層中に近赤外部に吸収を有する光熱変換材料を含有させるか、あるいは、該光熱変換材料を含有する光熱変換層を可逆性感熱記録層に直接隣接して設けることが好ましい。近赤外部に吸収を有する光熱変換材料としては、例えば白金、チタン、シリコン、クロム、ニッケル、ゲルマニウム、アルミニウム等の金属または半金属の層、日本化薬（株）製のＩＲＧ００２（商品名）やＩＲＧ０２２（商品名）等のインモニウム化合物、金属錯体化合物、シアニン色素、スクワリリウム色素、ナフトキノン色素、フタロシアニン化合物等が挙げられるがこれらに限定されるものではない。好ましい光熱変換材料としては、光熱変換効率、溶剤への溶解性、樹脂への分散性の点でフタロシアニン化合物及び金属錯体化合物が挙げられる。光熱変換材料は単独使用はもとより、２種類以上を混合して用いることができる。その添加量は１ｍｇ／ｍ2から２００ｍｇ／ｍ2が適当であり、５ｍｇ／ｍ2から５０ｍｇ／ｍ2が好ましい。この量より少ないと画像消去に必要なエネルギーを十分に低減できず、印字消去の繰り返し特性が劣化する。またこの量より多いと、光熱変換材料が若干なりとも有している可視部の吸収が大きくなりすぎて画像の視認性が低下する。 Examples of the laser used for heating include, but are not limited to, a semiconductor laser and a YAG laser. In order to efficiently perform the heating with these laser beams, the reversible thermosensitive recording layer contains a photothermal conversion material having absorption in the near infrared part, or the photothermal conversion layer containing the photothermal conversion material is reversible. It is preferably provided directly adjacent to the heat-sensitive recording layer. Examples of photothermal conversion materials having absorption in the near infrared region include layers of metal or semimetal such as platinum, titanium, silicon, chromium, nickel, germanium, and aluminum, IRG002 (trade name) manufactured by Nippon Kayaku Co., Ltd. Examples include, but are not limited to, immonium compounds such as IRG022 (trade name), metal complex compounds, cyanine dyes, squarylium dyes, naphthoquinone dyes, and phthalocyanine compounds. Preferable photothermal conversion materials include phthalocyanine compounds and metal complex compounds in terms of photothermal conversion efficiency, solubility in solvents, and dispersibility in resins. Photothermal conversion materials can be used alone or in combination of two or more. The addition amount is suitably 1 mg / m 2 to 200 mg / m 2 , and preferably 5 mg / m 2 to 50 mg / m 2 . If the amount is less than this amount, the energy required for image erasure cannot be sufficiently reduced, and the repetition characteristics of print erasure deteriorate. On the other hand, when the amount is larger than this amount, the absorption of the visible portion that the photothermal conversion material is slightly increased becomes too large, and the visibility of the image is lowered.
本発明の可逆性感熱記録材料を構成する各層を支持体上に形成する方法は特に制限されるものではなく、従来の方法により形成することができる。例えば、エアーナイフコーター、ブレードコーター、バーコーター、カーテンコーター等の塗抹装置、平板、凸版、凹版、フレキソ、グラビア、スクリーン、ホットメルト等の方式による各種印刷機等を用いることができる。さらに通常の乾燥工程の他、ＵＶ照射・ＥＢ照射により各層を保持させることができる。これらの方法により、１層ずつあるいは多層同時に塗工、印刷することができる。 The method for forming each layer constituting the reversible thermosensitive recording material of the present invention on the support is not particularly limited, and can be formed by a conventional method. For example, smearing devices such as an air knife coater, blade coater, bar coater, curtain coater, etc., various printing machines using a flat plate, letterpress, intaglio, flexo, gravure, screen, hot melt, etc. can be used. Furthermore, each layer can be held by UV irradiation / EB irradiation in addition to a normal drying process. By these methods, it is possible to apply and print one layer at a time or multiple layers simultaneously.
（実施例）
以下、実施例によって本発明をさらに詳しく説明するが、本発明はこの実施例に限定されるものではない。なお、実施例中の部数は質量基準である。
(Example)
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this Example. In addition, the number of parts in an Example is a mass reference | standard.
＜可逆性感熱塗液１の調製＞
ロイコ染料として黒色発色の３−ジ−ｎ−ブチルアミノ−６−メチル−７−アニリノフルオラン２０部、可逆性顕色剤としてＮ−［３−（ｐ−ヒドロキシフェニル）プロピオノ］−Ｎ′−ｎ−ドコサノヒドラジドを１００部、ポリエステルポリオール（大日本インキ化学工業（株）製、商品名：バーノック１１−４０８、有効成分７０質量％）１００部、メチルエチルケトン９５０部の混合物をガラスビーズと共にペイントシェーカーで５時間分散し分散液を得た。この分散液に、イソシアネート化合物（三井化学ポリウレタン工業（株）製、商品名：タケネートＤ−１１０Ｎ、有効成分７５質量％）１３０部とメチルエチルケトン６２部を加え、よく混合し、可逆性感熱塗液１を調製した。
<Preparation of reversible thermosensitive coating liquid 1>
20 parts of black-colored 3-di-n-butylamino-6-methyl-7-anilinofluorane as leuco dye, N- [3- (p-hydroxyphenyl) propiono] -N ′ as reversible developer -Paint a mixture of 100 parts of n-docosanohydrazide, 100 parts of polyester polyol (manufactured by Dainippon Ink and Chemicals, trade name: Burnock 11-408, 70% by mass of active ingredient) and 950 parts of methyl ethyl ketone with glass beads Dispersion was obtained by dispersing for 5 hours with a shaker. To this dispersion is added 130 parts of an isocyanate compound (trade name: Takenate D-110N, active ingredient 75% by mass, manufactured by Mitsui Chemicals Polyurethane Industry Co., Ltd.) and 62 parts of methyl ethyl ketone, mixed well, and reversible thermosensitive coating solution 1 Was prepared.
＜可逆性感熱塗液２の調製＞
ロイコ染料として黒色発色の３−ジ−ｎ−ブチルアミノ−６−メチル−７−アニリノフルオラン２０部、可逆性顕色剤として例示化合物（２−３）を１００部、ポリエステルポリオール（大日本インキ化学工業（株）製、商品名：バーノック１１−４０８、有効成分７０質量％）１００部、メチルエチルケトン９５０部の混合物をガラスビーズと共にペイントシェーカーで５時間分散し分散液を得た。この分散液に、イソシアネート化合物（三井化学ポリウレタン工業（株）製、商品名：タケネートＤ−１１０Ｎ、有効成分７５質量％）１３０部とメチルエチルケトン６２部を加え、よく混合し、可逆性感熱塗液２を調製した。
<Preparation of reversible thermosensitive coating liquid 2>
20 parts of black colored 3-di-n-butylamino-6-methyl-7-anilinofluorane as leuco dye, 100 parts of exemplary compound (2-3) as reversible developer, polyester polyol (Dainippon A mixture of 100 parts of Ink Chemical Industry Co., Ltd., trade name: Barnock 11-408, active mass 70% by mass) and 950 parts of methyl ethyl ketone was dispersed with glass beads for 5 hours with a paint shaker to obtain a dispersion. To this dispersion is added 130 parts of an isocyanate compound (trade name: Takenate D-110N, active ingredient 75% by mass, manufactured by Mitsui Chemicals Polyurethane Industry Co., Ltd.) and 62 parts of methyl ethyl ketone, mixed well, and reversible thermosensitive coating solution 2 Was prepared.
＜可逆性感熱塗液３の調製＞
ロイコ染料として黒色発色の３−ジ−ｎ−ブチルアミノ−６−メチル−７−アニリノフルオラン２０部、可逆性顕色剤として例示化合物（２−７）を１００部、ポリエステルポリオール（大日本インキ化学工業（株）製、商品名：バーノック１１−４０８、有効成分７０質量％）１００部、メチルエチルケトン９５０部の混合物をガラスビーズと共にペイントシェーカーで５時間分散し分散液を得た。この分散液に、イソシアネート化合物（三井化学ポリウレタン工業（株）製、商品名：タケネートＤ−１１０Ｎ、有効成分７５質量％）１３０部とメチルエチルケトン６２部を加え、よく混合し、可逆性感熱塗液３を調製した。
<Preparation of reversible thermosensitive coating liquid 3>
20 parts of black-colored 3-di-n-butylamino-6-methyl-7-anilinofluorane as leuco dye, 100 parts of exemplary compound (2-7) as reversible developer, polyester polyol (Dainippon A mixture of 100 parts of Ink Chemical Industry Co., Ltd., trade name: Barnock 11-408, active mass 70% by mass) and 950 parts of methyl ethyl ketone was dispersed with glass beads for 5 hours with a paint shaker to obtain a dispersion. To this dispersion is added 130 parts of an isocyanate compound (trade name: Takenate D-110N, active ingredient 75% by mass, manufactured by Mitsui Chemicals Polyurethane Industry Co., Ltd.) and 62 parts of methyl ethyl ketone, and they are mixed well. A reversible thermosensitive coating solution 3 Was prepared.
＜親水性スメクタイト塗液１の調製＞
水２８５部に、合成スメクタイト系粘土鉱物（商品名ラポナイトＪＳ：Ｒｏｃｋｗｏｏｄ Ａｄｄｉｔｉｖｅｓ Ｌｉｍｉｔｅｄ製）２０部を添加し、高速ホモジナイザーで１０分間撹拌し、撹拌停止後さらに１時間放置し、合成スメクタイト系粘土鉱物の分散液を調製した。この分散液に水分散ポリエステル樹脂（商品名バイロナールＭＤ−１２００：東洋紡績株式会社製、有効成分３４質量％）２９４部を加え、よく混合し、親水性スメクタイト塗液１を調製した。
<Preparation of hydrophilic smectite coating solution 1>
To 285 parts of water, 20 parts of a synthetic smectite clay mineral (trade name Laponite JS: manufactured by Rockwood Additives Limited) was added, stirred for 10 minutes with a high-speed homogenizer, allowed to stand for another hour after the stirring was stopped, and the synthetic smectite clay mineral A dispersion was prepared. To this dispersion, 294 parts of a water-dispersed polyester resin (trade name: Vylonal MD-1200: manufactured by Toyobo Co., Ltd., active ingredient 34% by mass) was added and mixed well to prepare hydrophilic smectite coating solution 1.
＜親水性スメクタイト塗液２の調製＞
水３９８部に、合成スメクタイト系粘土鉱物（商品名ラポナイトＪＳ：Ｒｏｃｋｗｏｏｄ Ａｄｄｉｔｉｖｅｓ Ｌｉｍｉｔｅｄ製）２０部を添加し、高速ホモジナイザーで１０分間撹拌し、撹拌停止後さらに１時間放置し、合成スメクタイト系粘土鉱物の分散液を調製した。この分散液に水分散性ポリイソシアネート（商品名バーノックＤＮＷ−６０００：大日本インキ化学工業株式会社製、有効成分１００質量％）３６部を加え、高速ホモジナイザーで１０分間撹拌し、水分散性ポリイソシアネートを分散した。さらに、この分散液に水分散アクリルポリオール樹脂（商品名バーノックＷＥ−３０１：大日本インキ化学工業株式会社製、有効成分４５質量％）１４５部を加え、よく混合し、親水性スメクタイト塗液２を調製した。
<Preparation of hydrophilic smectite coating solution 2>
To 398 parts of water, 20 parts of a synthetic smectite clay mineral (trade name Laponite JS: manufactured by Rockwood Additives Limited) was added, stirred for 10 minutes with a high-speed homogenizer, allowed to stand for another hour after the stirring was stopped, and the synthetic smectite clay mineral A dispersion was prepared. 36 parts of water-dispersible polyisocyanate (trade name: Bernock DNW-6000: manufactured by Dainippon Ink & Chemicals, Inc., 100% by mass of active ingredient) was added to this dispersion, and the mixture was stirred with a high-speed homogenizer for 10 minutes. Distributed. Further, 145 parts of a water-dispersed acrylic polyol resin (trade name Barnock WE-301: manufactured by Dainippon Ink & Chemicals, Inc., 45% by mass of active ingredient) was added to this dispersion and mixed well to obtain hydrophilic smectite coating liquid 2 Prepared.
＜親水性スメクタイト塗液３の調製＞
水３５０部に、合成スメクタイト系粘土鉱物（商品名ラポナイトＪＳ：Ｒｏｃｋｗｏｏｄ Ａｄｄｉｔｉｖｅｓ Ｌｉｍｉｔｅｄ製）２０部を添加し、高速ホモジナイザーで１０分間撹拌し、撹拌停止後さらに１時間放置し、合成スメクタイト系粘土鉱物の分散液を調製した。この分散液に水分散ポリウレタンアクリレート系紫外線硬化性樹脂（商品名ビームセットＥＭ−９０：荒川化学工業株式会社製、有効成分４０質量％）２５０部、光重合開始剤（商品名イルガキュア２９５９：チバ・スペシャルティ・ケミカルズ株式会社製、有効成分１００質量％）５部を加え、よく混合し、親水性スメクタイト塗液３を調製した。
<Preparation of hydrophilic smectite coating solution 3>
To 350 parts of water, 20 parts of a synthetic smectite clay mineral (trade name Laponite JS: manufactured by Rockwood Additives Limited) was added, stirred for 10 minutes with a high-speed homogenizer, allowed to stand for another hour after the stirring was stopped, and the synthetic smectite clay mineral A dispersion was prepared. In this dispersion, 250 parts of water-dispersed polyurethane acrylate ultraviolet curable resin (trade name Beam Set EM-90: Arakawa Chemical Industries, Ltd., active ingredient 40% by mass), photopolymerization initiator (trade name Irgacure 2959: Ciba 5 parts of an active ingredient (manufactured by Specialty Chemicals Co., Ltd., 100% by mass) were added and mixed well to prepare a hydrophilic smectite coating solution 3.
＜親水性スメクタイト塗液４の調製＞
水３１０部に、合成スメクタイト系粘土鉱物（商品名ラポナイトＪＳ：Ｒｏｃｋｗｏｏｄ Ａｄｄｉｔｉｖｅｓ Ｌｉｍｉｔｅｄ製）１０部を添加し、高速ホモジナイザーで１０分間撹拌し、撹拌停止後さらに１時間放置し、合成スメクタイト系粘土鉱物の分散液を調製した。この分散液に水分散ポリウレタンアクリレート系紫外線硬化性樹脂（商品名ビームセットＥＭ−９０：荒川化学工業株式会社製、有効成分４０質量％）２５０部、光重合開始剤（商品名イルガキュア２９５９：チバ・スペシャルティ・ケミカルズ株式会社製、有効成分１００質量％）５部を加え、よく混合し、親水性スメクタイト塗液４を調製した。
<Preparation of hydrophilic smectite coating solution 4>
To 310 parts of water, 10 parts of a synthetic smectite clay mineral (trade name Laponite JS: manufactured by Rockwood Additives Limited) is added, stirred for 10 minutes with a high-speed homogenizer, left for another 1 hour after the stirring is stopped, and the synthetic smectite clay mineral A dispersion was prepared. In this dispersion, 250 parts of water-dispersed polyurethane acrylate ultraviolet curable resin (trade name Beam Set EM-90: Arakawa Chemical Industries, Ltd., active ingredient 40% by mass), photopolymerization initiator (trade name Irgacure 2959: Ciba 5 parts of an active ingredient (manufactured by Specialty Chemicals Co., Ltd.) was added and mixed well to prepare a hydrophilic smectite coating solution 4.
＜親水性スメクタイト塗液５の調製＞
水３９０部に、合成スメクタイト系粘土鉱物（商品名ラポナイトＪＳ：Ｒｏｃｋｗｏｏｄ Ａｄｄｉｔｉｖｅｓ Ｌｉｍｉｔｅｄ製）３０部を添加し、高速ホモジナイザーで１０分間撹拌し、撹拌停止後さらに１時間放置し、合成スメクタイト系粘土鉱物の分散液を調製した。この分散液に水分散ポリウレタンアクリレート系紫外線硬化性樹脂（商品名ビームセットＥＭ−９０：荒川化学工業株式会社製、有効成分４０質量％）２５０部、光重合開始剤（商品名イルガキュア２９５９：チバ・スペシャルティ・ケミカルズ株式会社製、有効成分１００質量％）５部を加え、よく混合し、親水性スメクタイト塗液５を調製した。
<Preparation of hydrophilic smectite coating solution 5>
To 390 parts of water, 30 parts of a synthetic smectite clay mineral (trade name Laponite JS: manufactured by Rockwood Additives Limited) was added, stirred for 10 minutes with a high-speed homogenizer, allowed to stand for another 1 hour after stopping the stirring, and the synthetic smectite clay mineral A dispersion was prepared. In this dispersion, 250 parts of water-dispersed polyurethane acrylate ultraviolet curable resin (trade name Beam Set EM-90: Arakawa Chemical Industries, Ltd., active ingredient 40% by mass), photopolymerization initiator (trade name Irgacure 2959: Ciba 5 parts by Specialty Chemicals Co., Ltd., active ingredient 100% by mass) were added and mixed well to prepare hydrophilic smectite coating solution 5.
＜親水性スメクタイト塗液６の調製＞
水４３０部に、合成スメクタイト系粘土鉱物（商品名ラポナイトＪＳ：Ｒｏｃｋｗｏｏｄ Ａｄｄｉｔｉｖｅｓ Ｌｉｍｉｔｅｄ製）４０部を添加し、高速ホモジナイザーで１０分間撹拌し、撹拌停止後さらに１時間放置し、合成スメクタイト系粘土鉱物の分散液を調製した。この分散液に水分散ポリウレタンアクリレート系紫外線硬化性樹脂（商品名ビームセットＥＭ−９０：荒川化学工業株式会社製、有効成分４０質量％）２５０部、光重合開始剤（商品名イルガキュア２９５９：チバ・スペシャルティ・ケミカルズ株式会社製、有効成分１００質量％）５部を加え、よく混合し、親水性スメクタイト塗液６を調製した。
<Preparation of hydrophilic smectite coating liquid 6>
To 430 parts of water, 40 parts of a synthetic smectite clay mineral (trade name: Laponite JS: manufactured by Rockwood Additives Limited) was added, stirred for 10 minutes with a high-speed homogenizer, allowed to stand for another 1 hour after stopping the stirring, and the synthetic smectite clay mineral A dispersion was prepared. In this dispersion, 250 parts of water-dispersed polyurethane acrylate ultraviolet curable resin (trade name Beam Set EM-90: Arakawa Chemical Industries, Ltd., active ingredient 40% by mass), photopolymerization initiator (trade name Irgacure 2959: Ciba 5 parts of Specialty Chemicals Co., Ltd., active ingredient 100% by mass) were added and mixed well to prepare hydrophilic smectite coating solution 6.
＜親水性スメクタイト塗液７の調製＞
水４７０部に、合成スメクタイト系粘土鉱物（商品名ラポナイトＪＳ：Ｒｏｃｋｗｏｏｄ Ａｄｄｉｔｉｖｅｓ Ｌｉｍｉｔｅｄ製）５０部を添加し、高速ホモジナイザーで１０分間撹拌し、撹拌停止後さらに１時間放置し、合成スメクタイト系粘土鉱物の分散液を調製した。この分散液に水分散ポリウレタンアクリレート系紫外線硬化性樹脂（商品名ビームセットＥＭ−９０：荒川化学工業株式会社製、有効成分４０質量％）２５０部、光重合開始剤（商品名イルガキュア２９５９：チバ・スペシャルティ・ケミカルズ株式会社製、有効成分１００質量％）５部を加え、よく混合し、親水性スメクタイト塗液７を調製した。
<Preparation of hydrophilic smectite coating liquid 7>
To 470 parts of water, 50 parts of a synthetic smectite clay mineral (trade name Laponite JS: manufactured by Rockwood Additives Limited) was added, stirred for 10 minutes with a high-speed homogenizer, left for another hour after the stirring was stopped, and the synthetic smectite clay mineral A dispersion was prepared. In this dispersion, 250 parts of water-dispersed polyurethane acrylate ultraviolet curable resin (trade name Beam Set EM-90: Arakawa Chemical Industries, Ltd., active ingredient 40% by mass), photopolymerization initiator (trade name Irgacure 2959: Ciba 5 parts of an active ingredient (manufactured by Specialty Chemicals Co., Ltd., 100% by mass) were added and mixed well to prepare a hydrophilic smectite coating solution 7.
＜親水性スメクタイト塗液８の調製＞
水５５９部に、合成スメクタイト系粘土鉱物（商品名ラポナイトＪＳ：Ｒｏｃｋｗｏｏｄ Ａｄｄｉｔｉｖｅｓ Ｌｉｍｉｔｅｄ製）１１２部を添加し、高速ホモジナイザーで１０分間撹拌し、撹拌停止後さらに１時間放置し、合成スメクタイト系粘土鉱物の分散液を調製した。この分散液に水分散ポリウレタンアクリレート系紫外線硬化性樹脂（商品名ビームセットＥＭ−９０：荒川化学工業株式会社製、有効成分４０質量％）１０２部、光重合開始剤（商品名イルガキュア２９５９：チバ・スペシャルティ・ケミカルズ株式会社製、有効成分１００質量％）２部を加え、よく混合し、親水性スメクタイト塗液８を調製した。
<Preparation of hydrophilic smectite coating liquid 8>
To 559 parts of water, 112 parts of a synthetic smectite clay mineral (trade name: Laponite JS: manufactured by Rockwood Additives Limited) was added, stirred for 10 minutes with a high-speed homogenizer, allowed to stand for another hour after stopping the stirring, and the synthetic smectite clay mineral A dispersion was prepared. In this dispersion, 102 parts of a water-dispersed polyurethane acrylate-based ultraviolet curable resin (trade name Beam Set EM-90: manufactured by Arakawa Chemical Industries, Ltd., 40% by mass of active ingredient), a photopolymerization initiator (trade name: Irgacure 2959: Ciba 2 parts of an active ingredient (manufactured by Specialty Chemicals Co., Ltd., 100% by mass) were added and mixed well to prepare a hydrophilic smectite coating solution 8.
＜親水性スメクタイト塗液９の調製＞
水３５０部に、合成スメクタイト系粘土鉱物（商品名ルーセンタイトＳＷＮ：コープケミカル株式会社製）２０部を添加し、高速ホモジナイザーで１０分間撹拌し、撹拌停止後さらに１時間放置し、合成スメクタイト系粘土鉱物の分散液を調製した。この分散液に水分散ポリウレタンアクリレート系紫外線硬化性樹脂（商品名ビームセットＥＭ−９０：荒川化学工業株式会社製、有効成分４０質量％）２５０部、光重合開始剤（商品名イルガキュア２９５９：チバ・スペシャルティ・ケミカルズ株式会社製、有効成分１００質量％）５部を加え、よく混合し、親水性スメクタイト塗液９を調製した。
<Preparation of hydrophilic smectite coating liquid 9>
To 350 parts of water, 20 parts of a synthetic smectite clay mineral (trade name Lucentite SWN: manufactured by Co-op Chemical Co., Ltd.) is added, stirred for 10 minutes with a high-speed homogenizer, allowed to stand for another hour after stirring is stopped, and then a synthetic smectite clay. A mineral dispersion was prepared. In this dispersion, 250 parts of water-dispersed polyurethane acrylate ultraviolet curable resin (trade name Beam Set EM-90: Arakawa Chemical Industries, Ltd., active ingredient 40% by mass), photopolymerization initiator (trade name Irgacure 2959: Ciba 5 parts of an active ingredient (manufactured by Specialty Chemicals Co., Ltd.) was added and mixed well to prepare a hydrophilic smectite coating solution 9.
＜親水性スメクタイト塗液１０の調製＞
水３５０部に、合成スメクタイト系粘土鉱物（商品名スメクトンＳＡ−１：クニミネ工業株式会社製）２０部を添加し、高速ホモジナイザーで１０分間撹拌し、撹拌停止後さらに１時間放置し、合成スメクタイト系粘土鉱物の分散液を調製した。この分散液に水分散ポリウレタンアクリレート系紫外線硬化性樹脂（商品名ビームセットＥＭ−９０：荒川化学工業株式会社製、有効成分４０質量％）２５０部、光重合開始剤（商品名イルガキュア２９５９：チバ・スペシャルティ・ケミカルズ株式会社製、有効成分１００質量％）５部を加え、よく混合し、親水性スメクタイト塗液１０を調製した。
<Preparation of hydrophilic smectite coating solution 10>
To 350 parts of water, 20 parts of a synthetic smectite clay mineral (trade name: Smecton SA-1: manufactured by Kunimine Kogyo Co., Ltd.) is added, stirred for 10 minutes with a high-speed homogenizer, and allowed to stand for another hour after stopping stirring. A dispersion of clay mineral was prepared. In this dispersion, 250 parts of water-dispersed polyurethane acrylate ultraviolet curable resin (trade name Beam Set EM-90: Arakawa Chemical Industries, Ltd., active ingredient 40% by mass), photopolymerization initiator (trade name Irgacure 2959: Ciba 5 parts of an active ingredient (manufactured by Specialty Chemicals Co., Ltd.) was added and mixed well to prepare a hydrophilic smectite coating solution 10.
＜親油性スメクタイト塗液１の調製＞
メチルエチルケトン４８０部に、合成スメクタイト系粘土鉱物（商品名ルーセンタイトＳＴＮ：コープケミカル株式会社製、構成：親油化処理を行った合成スメクタイト系粘土鉱物）２０部を添加し、高速ホモジナイザーで１０分間撹拌し、合成スメクタイト系粘土鉱物の分散液を調製した。この分散液にウレタンアクリレート系紫外線硬化性樹脂（商品名ユニディックＶ−４２０５：大日本インキ化学工業製、有効成分１００％）１００部を加え、よく混合し、親油性スメクタイト塗液１を調製した。
<Preparation of lipophilic smectite coating solution 1>
To 480 parts of methyl ethyl ketone, 20 parts of synthetic smectite clay mineral (trade name Lucentite STN: manufactured by Co-op Chemical Co., Ltd., composition: synthetic smectite clay mineral subjected to lipophilic treatment) was added and stirred for 10 minutes with a high-speed homogenizer. Then, a dispersion of synthetic smectite clay mineral was prepared. To this dispersion, 100 parts of urethane acrylate ultraviolet curable resin (trade name Unidic V-4205: manufactured by Dainippon Ink & Chemicals, Inc., 100% active ingredient) was added and mixed well to prepare lipophilic smectite coating solution 1. .
＜針状導電性酸化チタン塗液１の調製＞
水３５０部に、針状導電性酸化チタン（商品名ＦＴ−２０００：石原産業株式会社製、構成：アンチモンドープ酸化スズ被覆の酸化チタン）２０部を添加し、高速ホモジナイザーで１０分間撹拌し、針状導電性酸化チタンの分散液を調製した。この分散液に水分散ポリウレタンアクリレート系紫外線硬化性樹脂（商品名ビームセットＥＭ−９０：荒川化学工業株式会社製、有効成分４０質量％）２５０部、光重合開始剤（商品名イルガキュア２９５９：チバ・スペシャルティ・ケミカルズ株式会社製、有効成分１００質量％）５部を加え、よく混合し、針状導電性酸化チタン塗液１を調製した。
＜針状導電性酸化チタン塗液２の調製＞
メチルエチルケトン４８０部に、針状導電性酸化チタン（商品名ＦＴ−２０００：石原産業株式会社製、構成：アンチモンドープ酸化スズ被覆の酸化チタン）２０部を添加し、高速ホモジナイザーで１０分間撹拌し、針状導電性酸化チタンの分散液を調製した。この分散液にウレタンアクリレート系紫外線硬化性樹脂（商品名ユニディックＶ−４２０５：大日本インキ化学工業製、有効成分１００質量％）１００部を加え、よく混合し、針状導電性酸化チタン塗液２を調製した。
<Preparation of needle-like conductive titanium oxide coating solution 1>
To 350 parts of water, 20 parts of acicular conductive titanium oxide (trade name: FT-2000: manufactured by Ishihara Sangyo Co., Ltd., composition: titanium oxide coated with antimony-doped tin oxide) is added and stirred for 10 minutes with a high-speed homogenizer. A dispersion of conductive titanium oxide was prepared. In this dispersion, 250 parts of water-dispersed polyurethane acrylate ultraviolet curable resin (trade name Beam Set EM-90: Arakawa Chemical Industries, Ltd., active ingredient 40% by mass), photopolymerization initiator (trade name Irgacure 2959: Ciba 5 parts of an active ingredient (manufactured by Specialty Chemicals Co., Ltd., 100% by mass) was added and mixed well to prepare an acicular conductive titanium oxide coating solution 1.
<Preparation of needle-like conductive titanium oxide coating solution 2>
To 480 parts of methyl ethyl ketone, 20 parts of acicular conductive titanium oxide (trade name FT-2000: manufactured by Ishihara Sangyo Co., Ltd., constitution: titanium oxide coated with antimony-doped tin oxide) is added and stirred for 10 minutes with a high-speed homogenizer. A dispersion of conductive titanium oxide was prepared. To this dispersion is added 100 parts of urethane acrylate-based ultraviolet curable resin (trade name Unidic V-4205: manufactured by Dainippon Ink and Chemicals, Inc., 100% by mass of active ingredient), mixed well, and acicular conductive titanium oxide coating liquid. 2 was prepared.
＜イオン性液体塗液１の調製＞
メチルエチルケトン４８０部に、イオン性液体（１−ｎ−ブチル−３−メチルイミダゾール・ヘキサフルオロリン酸塩）２０部、ウレタンアクリレート系紫外線硬化性樹脂（商品名ユニディックＶ−４２０５：大日本インキ化学工業製、有効成分１００％）１００部を加え、よく混合し、イオン性液体塗液１を調製した。
<Preparation of ionic liquid coating liquid 1>
480 parts of methyl ethyl ketone, 20 parts of ionic liquid (1-n-butyl-3-methylimidazole / hexafluorophosphate), urethane acrylate ultraviolet curable resin (trade name Unidic V-4205: Dainippon Ink and Chemicals, Inc.) Manufactured, 100% active ingredient) and mixed well to prepare an ionic liquid coating liquid 1.
＜紫外線架橋性樹脂塗液１の調製＞
水２７０部に、水分散ポリウレタンアクリレート系紫外線硬化性樹脂（商品名ビームセットＥＭ−９０：荒川化学工業株式会社製、有効成分４０質量％）２５０部、光重合開始剤（商品名イルガキュア２９５９：チバ・スペシャルティ・ケミカルズ株式会社製、有効成分１００質量％）５部を加え、よく混合し、紫外線架橋性樹脂塗液１を調製した。
<Preparation of UV crosslinkable resin coating solution 1>
270 parts of water, 250 parts of water-dispersed polyurethane acrylate-based ultraviolet curable resin (trade name Beam Set EM-90: Arakawa Chemical Industries, Ltd., active ingredient 40 mass%), photopolymerization initiator (trade name Irgacure 2959: Ciba -5 parts of an active ingredient made by Specialty Chemicals Co., Ltd. was added and mixed well to prepare an ultraviolet crosslinkable resin coating solution 1.
＜紫外線架橋性樹脂塗液２の調製＞
メチルエチルケトン４００部に、ウレタンアクリレート系紫外線硬化性樹脂（商品名ユニディックＶ−４２０５：大日本インキ化学工業製、有効成分１００％）１００部を加え、よく混合し、紫外線架橋性樹脂塗液２を調製した。
<Preparation of UV crosslinkable resin coating solution 2>
To 400 parts of methyl ethyl ketone, add 100 parts of urethane acrylate ultraviolet curable resin (trade name Unidic V-4205: manufactured by Dainippon Ink & Chemicals, Inc., 100% active ingredient) and mix well. Prepared.
親水性スメクタイト塗液１を、厚さ２５０μｍの白色ポリエチレンテレフタレートシート（商品名ルミラー２５０−Ｅ２２：東レ株式会社製）に、固形分塗工量２ｇ／ｍ2となる様に塗布し、１００℃で１分乾燥後、さらに５０℃にて４８時間加温し、下引き層を設けた。その上に、可逆性感熱塗液１を固形分塗工量７．５ｇ／ｍ2となる様に塗布し、１００℃で１分乾燥後、さらに５０℃にて４８時間加温し、可逆性感熱記録層を形成した。その上に、紫外線架橋性樹脂塗液２を固形分塗工量３．０ｇ／ｍ2となるように塗布し、１００℃で１分乾燥後、照射エネルギー８０Ｗ／ｃｍの紫外線ランプ下を９ｍ／分の搬送速度で通して硬化させ、保護層を形成し、可逆性感熱記録材料を作製した。 The hydrophilic smectite coating solution 1 was applied to a white polyethylene terephthalate sheet (trade name Lumirror 250-E22: manufactured by Toray Industries, Inc.) having a thickness of 250 μm so that the solid content coating amount was 2 g / m 2. After drying for 1 minute, the mixture was further heated at 50 ° C. for 48 hours to provide an undercoat layer. On top of this, the reversible thermosensitive coating liquid 1 was applied so that the coating amount of the solid content was 7.5 g / m 2 , dried at 100 ° C. for 1 minute, and further heated at 50 ° C. for 48 hours. A thermal recording layer was formed. On top of this, the UV-crosslinkable resin coating solution 2 was applied so as to have a solid content coating amount of 3.0 g / m 2 , dried at 100 ° C. for 1 minute, and then under a UV lamp with an irradiation energy of 80 W / cm, 9 m / It was cured by passing at a conveying speed of minutes to form a protective layer, and a reversible thermosensitive recording material was produced.
実施例１で、親水性スメクタイト塗液１を用いる代わりに、親水性スメクタイト塗液２を用いる以外は、実施例１と同一条件で、可逆性感熱記録材料を作製した。 A reversible thermosensitive recording material was produced under the same conditions as in Example 1 except that instead of using the hydrophilic smectite coating liquid 1 in Example 1, the hydrophilic smectite coating liquid 2 was used.
親水性スメクタイト塗液３を、厚さ２５０μｍの白色ポリエチレンテレフタレートシート（商品名ルミラー２５０−Ｅ２２：東レ株式会社製）に、固形分塗工量２ｇ／ｍ2となる様に塗布し、１００℃で１分乾燥後、照射エネルギー８０Ｗ／ｃｍの紫外線ランプ下を９ｍ／分の搬送速度で通して硬化させ、下引き層を設けた。その上に、可逆性感熱塗液１を固形分塗工量７．５ｇ／ｍ2となる様に塗布し、１００℃で１分乾燥後、さらに５０℃にて４８時間加温し、可逆性感熱記録層を形成した。その上に、紫外線架橋性樹脂塗液２を固形分塗工量３．０ｇ／ｍ2となるように塗布し、１００℃で１分乾燥後、照射エネルギー８０Ｗ／ｃｍの紫外線ランプ下を９ｍ／分の搬送速度で通して硬化させ、保護層を形成し、可逆性感熱記録材料を作製した。 The hydrophilic smectite coating solution 3 was applied to a white polyethylene terephthalate sheet (trade name Lumirror 250-E22: manufactured by Toray Industries, Inc.) having a thickness of 250 μm so that the solid content coating amount was 2 g / m 2 , at 100 ° C. After drying for 1 minute, the film was cured by passing it under a UV lamp with an irradiation energy of 80 W / cm at a conveying speed of 9 m / min to provide an undercoat layer. On top of this, the reversible thermosensitive coating liquid 1 was applied so that the coating amount of the solid content was 7.5 g / m 2 , dried at 100 ° C. for 1 minute, and further heated at 50 ° C. for 48 hours. A thermal recording layer was formed. On top of this, the UV-crosslinkable resin coating solution 2 was applied so as to have a solid content coating amount of 3.0 g / m 2 , dried at 100 ° C. for 1 minute, and then under a UV lamp with an irradiation energy of 80 W / cm, 9 m / It was cured by passing at a conveying speed of minutes to form a protective layer, and a reversible thermosensitive recording material was produced.
可逆性感熱塗液１を、厚さ２５０μｍの白色ポリエチレンテレフタレートシート（商品名ルミラー２５０−Ｅ２２：東レ株式会社製）に、固形分塗工量７．５ｇ／ｍ2となる様に塗布し、１００℃で１分乾燥後、さらに５０℃にて４８時間加温し、可逆性感熱記録層を形成した。その上に、親水性スメクタイト塗液１を、固形分塗工量２ｇ／ｍ2となる様に塗布し、１００℃で１分乾燥後、さらに５０℃にて４８時間加温し、中間層を設けた。その上に、紫外線架橋性樹脂塗液２を固形分塗工量３．０ｇ／ｍ2となるように塗布し、１００℃で１分乾燥後、照射エネルギー８０Ｗ／ｃｍの紫外線ランプ下を９ｍ／分の搬送速度で通して硬化させ、保護層を形成し、可逆性感熱記録材料を作製した。 The reversible thermosensitive coating liquid 1 is applied to a white polyethylene terephthalate sheet (trade name Lumirror 250-E22: manufactured by Toray Industries, Inc.) having a thickness of 250 μm so that the solid content coating amount is 7.5 g / m 2. After drying at 50 ° C. for 1 minute, the mixture was further heated at 50 ° C. for 48 hours to form a reversible thermosensitive recording layer. On top of this, hydrophilic smectite coating liquid 1 was applied so that the solid content coating amount was 2 g / m 2 , dried at 100 ° C. for 1 minute, and further heated at 50 ° C. for 48 hours to form an intermediate layer. Provided. On top of this, the UV-crosslinkable resin coating solution 2 was applied so as to have a solid content coating amount of 3.0 g / m 2 , dried at 100 ° C. for 1 minute, and then under a UV lamp with an irradiation energy of 80 W / cm, 9 m / It was cured by passing at a conveying speed of minutes to form a protective layer, and a reversible thermosensitive recording material was produced.
実施例４で、親水性スメクタイト塗液１を用いる代わりに、親水性スメクタイト塗液２を用いる以外は、実施例４と同一条件で、可逆性感熱記録材料を作製した。 In Example 4, a reversible thermosensitive recording material was produced under the same conditions as in Example 4 except that the hydrophilic smectite coating liquid 2 was used instead of the hydrophilic smectite coating liquid 1.
可逆性感熱塗液１を、厚さ２５０μｍの白色ポリエチレンテレフタレートシート（商品名ルミラー２５０−Ｅ２２：東レ株式会社製）に、固形分塗工量７．５ｇ／ｍ2となる様に塗布し、１００℃で１分乾燥後、さらに５０℃にて４８時間加温し、可逆性感熱記録層を形成した。その上に、親水性スメクタイト塗液３を、固形分塗工量２ｇ／ｍ2となる様に塗布し、１００℃で１分乾燥後、照射エネルギー８０Ｗ／ｃｍの紫外線ランプ下を９ｍ／分の搬送速度で通して硬化させ、中間層を設けた。その上に、紫外線架橋性樹脂塗液２を固形分塗工量３．０ｇ／ｍ2となるように塗布し、１００℃で１分乾燥後、照射エネルギー８０Ｗ／ｃｍの紫外線ランプ下を９ｍ／分の搬送速度で通して硬化させ、保護層を形成し、可逆性感熱記録材料を作製した。 The reversible thermosensitive coating liquid 1 is applied to a white polyethylene terephthalate sheet (trade name Lumirror 250-E22: manufactured by Toray Industries, Inc.) having a thickness of 250 μm so that the solid content coating amount is 7.5 g / m 2. After drying at 50 ° C. for 1 minute, the mixture was further heated at 50 ° C. for 48 hours to form a reversible thermosensitive recording layer. On top of that, hydrophilic smectite coating solution 3 was applied so that the solid content coating amount was 2 g / m 2 , dried at 100 ° C. for 1 minute, and then under a UV lamp with an irradiation energy of 80 W / cm, 9 m / min. Curing was carried out at a conveying speed to provide an intermediate layer. On top of this, the UV-crosslinkable resin coating solution 2 was applied so as to have a solid content coating amount of 3.0 g / m 2 , dried at 100 ° C. for 1 minute, and then under a UV lamp with an irradiation energy of 80 W / cm, 9 m / It was cured by passing at a conveying speed of minutes to form a protective layer, and a reversible thermosensitive recording material was produced.
可逆性感熱塗液１を、厚さ２５０μｍの白色ポリエチレンテレフタレートシート（商品名ルミラー２５０−Ｅ２２：東レ株式会社製）に、固形分塗工量７．５ｇ／ｍ2となる様に塗布し、１００℃で１分乾燥後、さらに５０℃にて４８時間加温し、可逆性感熱記録層を形成した。その上に、紫外線架橋性樹脂塗液２を固形分塗工量３．０ｇ／ｍ2となるように塗布し、１００℃で１分乾燥後、照射エネルギー８０Ｗ／ｃｍの紫外線ランプ下を９ｍ／分の搬送速度で通して硬化させ、保護層を設けた。次に、白色ポリエチレンテレフタレートシートの可逆性感熱記録層とは反対の面に、親水性スメクタイト塗液１を、固形分塗工量２ｇ／ｍ2となる様に塗布し、１００℃で１分乾燥後、さらに５０℃にて４８時間加温し、バックコート層を形成し、可逆性感熱記録材料を作製した。 The reversible thermosensitive coating liquid 1 is applied to a white polyethylene terephthalate sheet (trade name Lumirror 250-E22: manufactured by Toray Industries, Inc.) having a thickness of 250 μm so that the solid content coating amount is 7.5 g / m 2. After drying at 50 ° C. for 1 minute, the mixture was further heated at 50 ° C. for 48 hours to form a reversible thermosensitive recording layer. On top of this, the UV-crosslinkable resin coating solution 2 was applied so as to have a solid content coating amount of 3.0 g / m 2 , dried at 100 ° C. for 1 minute, and then under a UV lamp with an irradiation energy of 80 W / cm, 9 m / A protective layer was provided by curing at a conveying speed of minutes. Next, the hydrophilic smectite coating solution 1 is applied to the surface of the white polyethylene terephthalate sheet opposite to the reversible thermosensitive recording layer so that the solid content coating amount is 2 g / m 2 and dried at 100 ° C. for 1 minute. Thereafter, the mixture was further heated at 50 ° C. for 48 hours to form a backcoat layer, thereby producing a reversible thermosensitive recording material.
実施例７で、親水性スメクタイト塗液１を用いる代わりに、親水性スメクタイト塗液２を用いる以外は、実施例７と同一条件で、可逆性感熱記録材料を作製した。 In Example 7, a reversible thermosensitive recording material was produced under the same conditions as in Example 7 except that the hydrophilic smectite coating liquid 2 was used instead of the hydrophilic smectite coating liquid 1.
可逆性感熱塗液１を、厚さ２５０μｍの白色ポリエチレンテレフタレートシート（商品名ルミラー２５０−Ｅ２２：東レ株式会社製）に、固形分塗工量７．５ｇ／ｍ2となる様に塗布し、１００℃で１分乾燥後、さらに５０℃にて４８時間加温し、可逆性感熱記録層を形成した。その上に、紫外線架橋性樹脂塗液２を固形分塗工量３．０ｇ／ｍ2となるように塗布し、１００℃で１分乾燥後、照射エネルギー８０Ｗ／ｃｍの紫外線ランプ下を９ｍ／分の搬送速度で通して硬化させ、保護層を設けた。次に、白色ポリエチレンテレフタレートシートの可逆性感熱記録層とは反対の面に、親水性スメクタイト塗液３を、固形分塗工量２ｇ／ｍ2となる様に塗布し、１００℃で１分乾燥後、照射エネルギー８０Ｗ／ｃｍの紫外線ランプ下を９ｍ／分の搬送速度で通して硬化させ、バックコート層を形成し、可逆性感熱記録材料を作製した。 The reversible thermosensitive coating liquid 1 is applied to a white polyethylene terephthalate sheet (trade name Lumirror 250-E22: manufactured by Toray Industries, Inc.) having a thickness of 250 μm so that the solid content coating amount is 7.5 g / m 2. After drying at 50 ° C. for 1 minute, the mixture was further heated at 50 ° C. for 48 hours to form a reversible thermosensitive recording layer. On top of this, the UV-crosslinkable resin coating solution 2 was applied so as to have a solid content coating amount of 3.0 g / m 2 , dried at 100 ° C. for 1 minute, and then under a UV lamp with an irradiation energy of 80 W / cm, 9 m / A protective layer was provided by curing at a conveying speed of minutes. Next, the hydrophilic smectite coating liquid 3 is applied to the surface opposite to the reversible thermosensitive recording layer of the white polyethylene terephthalate sheet so that the solid content coating amount is 2 g / m 2 and dried at 100 ° C. for 1 minute. Thereafter, the film was cured by passing it under an ultraviolet lamp with an irradiation energy of 80 W / cm at a conveyance speed of 9 m / min to form a backcoat layer, thereby producing a reversible thermosensitive recording material.
可逆性感熱塗液１を、厚さ２５０μｍの白色ポリエチレンテレフタレートシート（商品名ルミラー２５０−Ｅ２２：東レ株式会社製）に、固形分塗工量７．５ｇ／ｍ2となる様に塗布し、１００℃で１分乾燥後、さらに５０℃にて４８時間加温し、可逆性感熱記録層を形成した。その上に、親水性スメクタイト塗液１を固形分塗工量３．０ｇ／ｍ2となるように塗布し、１００℃で１分乾燥後、さらに５０℃にて４８時間加温して保護層を形成し、可逆性感熱記録材料を作製した。 The reversible thermosensitive coating liquid 1 is applied to a white polyethylene terephthalate sheet (trade name Lumirror 250-E22: manufactured by Toray Industries, Inc.) having a thickness of 250 μm so that the solid content coating amount is 7.5 g / m 2. After drying at 50 ° C. for 1 minute, the mixture was further heated at 50 ° C. for 48 hours to form a reversible thermosensitive recording layer. On top of that, hydrophilic smectite coating liquid 1 was applied so that the solid content coating amount was 3.0 g / m 2 , dried at 100 ° C. for 1 minute, and further heated at 50 ° C. for 48 hours to protect the layer. To form a reversible thermosensitive recording material.
実施例１０で、親水性スメクタイト塗液１を用いる代わりに、親水性スメクタイト塗液２を用いる以外は、実施例１０と同一条件で、可逆性感熱記録材料を作製した。 A reversible thermosensitive recording material was produced under the same conditions as in Example 10 except that instead of using the hydrophilic smectite coating liquid 1 in Example 10, the hydrophilic smectite coating liquid 2 was used.
可逆性感熱塗液１を、厚さ２５０μｍの白色ポリエチレンテレフタレートシート（商品名ルミラー２５０−Ｅ２２：東レ株式会社製）に、固形分塗工量７．５ｇ／ｍ2となる様に塗布し、１００℃で１分乾燥後、さらに５０℃にて４８時間加温し、可逆性感熱記録層を形成した。その上に、親水性スメクタイト塗液３を固形分塗工量３．０ｇ／ｍ2となるように塗布し、１００℃で１分乾燥後、照射エネルギー８０Ｗ／ｃｍの紫外線ランプ下を９ｍ／分の搬送速度で通して硬化させ、保護層を形成し、可逆性感熱記録材料を作製した。 The reversible thermosensitive coating liquid 1 is applied to a white polyethylene terephthalate sheet (trade name Lumirror 250-E22: manufactured by Toray Industries, Inc.) having a thickness of 250 μm so that the solid content coating amount is 7.5 g / m 2. After drying at 50 ° C. for 1 minute, the mixture was further heated at 50 ° C. for 48 hours to form a reversible thermosensitive recording layer. On top of this, hydrophilic smectite coating liquid 3 was applied so that the solid content coating amount was 3.0 g / m 2 , dried at 100 ° C. for 1 minute, and then 9 m / minute under an ultraviolet lamp with an irradiation energy of 80 W / cm. Then, the film was cured by passing it at a conveying speed to form a protective layer, and a reversible thermosensitive recording material was produced.
実施例１２で、親水性スメクタイト塗液３を用いる代わりに、親水性スメクタイト塗液４を用いる以外は、実施例１２と同一条件で、可逆性感熱記録材料を作製した。 A reversible thermosensitive recording material was produced under the same conditions as in Example 12 except that instead of using the hydrophilic smectite coating solution 3 in Example 12, the hydrophilic smectite coating solution 4 was used.
実施例１２で、親水性スメクタイト塗液３を用いる代わりに、親水性スメクタイト塗液５を用いる以外は、実施例１２と同一条件で、可逆性感熱記録材料を作製した。 A reversible thermosensitive recording material was produced under the same conditions as in Example 12 except that instead of using the hydrophilic smectite coating solution 3 in Example 12, the hydrophilic smectite coating solution 5 was used.
実施例１２で、親水性スメクタイト塗液３を用いる代わりに、親水性スメクタイト塗液６を用いる以外は、実施例１２と同一条件で、可逆性感熱記録材料を作製した。 In Example 12, a reversible thermosensitive recording material was produced under the same conditions as in Example 12 except that the hydrophilic smectite coating liquid 3 was used instead of the hydrophilic smectite coating liquid 3.
実施例１２で、親水性スメクタイト塗液３を用いる代わりに、親水性スメクタイト塗液７を用いる以外は、実施例１２と同一条件で、可逆性感熱記録材料を作製した。 A reversible thermosensitive recording material was produced under the same conditions as in Example 12 except that instead of using the hydrophilic smectite coating solution 3 in Example 12, the hydrophilic smectite coating solution 7 was used.
実施例１２で、親水性スメクタイト塗液３を用いる代わりに、親水性スメクタイト塗液８を用いる以外は、実施例１２と同一条件で、可逆性感熱記録材料を作製した。 In Example 12, a reversible thermosensitive recording material was produced under the same conditions as in Example 12 except that the hydrophilic smectite coating liquid 3 was used instead of the hydrophilic smectite coating liquid 3.
実施例１２で、親水性スメクタイト塗液３を用いる代わりに、親水性スメクタイト塗液９を用いる以外は、実施例１２と同一条件で、可逆性感熱記録材料を作製した。 A reversible thermosensitive recording material was produced under the same conditions as in Example 12 except that instead of using the hydrophilic smectite coating solution 3 in Example 12, the hydrophilic smectite coating solution 9 was used.
実施例１２で、親水性スメクタイト塗液３を用いる代わりに、親水性スメクタイト塗液１０を用いる以外は、実施例１２と同一条件で、可逆性感熱記録材料を作製した。 In Example 12, a reversible thermosensitive recording material was prepared under the same conditions as in Example 12 except that the hydrophilic smectite coating solution 3 was used instead of the hydrophilic smectite coating solution 3.
実施例１で、可逆性感熱塗液１を用いる代わりに、可逆性感熱塗液２を用いる以外は、実施例１と同一条件で、可逆性感熱記録材料を作製した。 A reversible thermosensitive recording material was produced under the same conditions as in Example 1 except that the reversible thermosensitive coating liquid 2 was used instead of the reversible thermosensitive coating liquid 1 in Example 1.
実施例１で、可逆性感熱塗液１を用いる代わりに、可逆性感熱塗液３を用いる以外は、実施例１と同一条件で、可逆性感熱記録材料を作製した。 A reversible thermosensitive recording material was produced under the same conditions as in Example 1 except that the reversible thermosensitive coating liquid 3 was used instead of the reversible thermosensitive coating liquid 1 in Example 1.
実施例４で、親水性スメクタイト塗液１を用いる代わりに、親水性スメクタイト塗液２を用い、可逆性感熱塗液１を用いる代わりに、可逆性感熱塗液２を用いる以外は、実施例４と同一条件で、可逆性感熱記録材料を作製した。 In Example 4, instead of using the hydrophilic smectite coating liquid 1, the hydrophilic smectite coating liquid 2 is used, and instead of using the reversible thermosensitive coating liquid 1, the reversible thermosensitive coating liquid 2 is used. A reversible thermosensitive recording material was produced under the same conditions as those described above.
実施例４で、親水性スメクタイト塗液１を用いる代わりに、親水性スメクタイト塗液２を用い、可逆性感熱塗液１を用いる代わりに、可逆性感熱塗液３を用いる以外は、実施例４と同一条件で、可逆性感熱記録材料を作製した。 In Example 4, instead of using the hydrophilic smectite coating liquid 1, the hydrophilic smectite coating liquid 2 is used, and instead of using the reversible thermosensitive coating liquid 1, the reversible thermosensitive coating liquid 3 is used. A reversible thermosensitive recording material was produced under the same conditions as in Example 1.
実施例９で、可逆性感熱塗液１を用いる代わりに、可逆性感熱塗液２を用いる以外は、実施例９と同一条件で、可逆性感熱記録材料を作製した。 In Example 9, a reversible thermosensitive recording material was produced under the same conditions as Example 9 except that the reversible thermosensitive coating liquid 2 was used instead of the reversible thermosensitive coating liquid 1.
実施例９で、可逆性感熱塗液１を用いる代わりに、可逆性感熱塗液３を用いる以外は、実施例９と同一条件で、可逆性感熱記録材料を作製した。 A reversible thermosensitive recording material was produced under the same conditions as in Example 9 except that the reversible thermosensitive coating liquid 3 was used instead of the reversible thermosensitive coating liquid 1 in Example 9.
実施例１２で、可逆性感熱塗液１を用いる代わりに、可逆性感熱塗液２を用いる以外は、実施例１２と同一条件で、可逆性感熱記録材料を作製した。 In Example 12, a reversible thermosensitive recording material was produced under the same conditions as Example 12 except that the reversible thermosensitive coating liquid 2 was used instead of using the reversible thermosensitive coating liquid 1.
実施例１２で、可逆性感熱塗液１を用いる代わりに、可逆性感熱塗液３を用いる以外は、実施例１２と同一条件で、可逆性感熱記録材料を作製した。 In Example 12, a reversible thermosensitive recording material was produced under the same conditions as Example 12 except that the reversible thermosensitive coating liquid 3 was used instead of using the reversible thermosensitive coating liquid 1.
（比較例１）
実施例３で、親水性スメクタイト塗液３を用いる代わりに、針状導電性酸化チタン塗液１を用いる以外は、実施例３と同一条件で、可逆性感熱記録材料を作製した。
(Comparative Example 1)
In Example 3, a reversible thermosensitive recording material was produced under the same conditions as in Example 3 except that the needle-like conductive titanium oxide coating solution 1 was used instead of using the hydrophilic smectite coating solution 3.
（比較例２）
実施例３で、親水性スメクタイト塗液３を用いる代わりに、針状導電性酸化チタン塗液２を用いる以外は、実施例３と同一条件で、可逆性感熱記録材料を作製した。
(Comparative Example 2)
In Example 3, a reversible thermosensitive recording material was prepared under the same conditions as in Example 3 except that the needle-like conductive titanium oxide coating solution 2 was used instead of using the hydrophilic smectite coating solution 3.
（比較例３）
実施例３で、親水性スメクタイト塗液３を用いる代わりに、イオン性液体塗液１を用いる以外は、実施例３と同一条件で、可逆性感熱記録材料を作製した。
(Comparative Example 3)
In Example 3, a reversible thermosensitive recording material was produced under the same conditions as Example 3 except that the ionic liquid coating liquid 1 was used instead of the hydrophilic smectite coating liquid 3.
（比較例４）
実施例３で、親水性スメクタイト塗液３を用いる代わりに、紫外線架橋性樹脂塗液１を用いる以外は、実施例３と同一条件で、可逆性感熱記録材料を作製した。
(Comparative Example 4)
In Example 3, a reversible thermosensitive recording material was produced under the same conditions as in Example 3 except that the UV-crosslinkable resin coating solution 1 was used instead of the hydrophilic smectite coating solution 3.
（比較例５）
実施例３で、親水性スメクタイト塗液３を用いる代わりに、紫外線架橋性樹脂塗液２を用いる以外は、実施例３と同一条件で、可逆性感熱記録材料を作製した。
(Comparative Example 5)
In Example 3, a reversible thermosensitive recording material was produced under the same conditions as in Example 3 except that the UV-crosslinkable resin coating solution 2 was used instead of the hydrophilic smectite coating solution 3.
（比較例６）
実施例６で、親水性スメクタイト塗液３を用いる代わりに、針状導電性酸化チタン塗液１を用いる以外は、実施例６と同一条件で、可逆性感熱記録材料を作製した。
(Comparative Example 6)
A reversible thermosensitive recording material was produced under the same conditions as in Example 6 except that instead of using the hydrophilic smectite coating solution 3 in Example 6, the needle-like conductive titanium oxide coating solution 1 was used.
（比較例７）
実施例６で、親水性スメクタイト塗液３を用いる代わりに、針状導電性酸化チタン塗液２を用いる以外は、実施例６と同一条件で、可逆性感熱記録材料を作製した。
(Comparative Example 7)
A reversible thermosensitive recording material was produced under the same conditions as in Example 6 except that instead of using the hydrophilic smectite coating solution 3 in Example 6, the needle-like conductive titanium oxide coating solution 2 was used.
（比較例８）
実施例６で、親水性スメクタイト塗液３を用いる代わりに、イオン性液体塗液１を用いる以外は、実施例６と同一条件で、可逆性感熱記録材料を作製した。
(Comparative Example 8)
In Example 6, a reversible thermosensitive recording material was produced under the same conditions as in Example 6 except that the ionic liquid coating liquid 1 was used instead of the hydrophilic smectite coating liquid 3.
（比較例９）
実施例１２で、親水性スメクタイト塗液３を用いる代わりに、紫外線架橋性樹脂塗液１を用いる以外は、実施例１２と同一条件で、可逆性感熱記録材料を作製した。
（比較例１０）
実施例１２で、親水性スメクタイト塗液３を用いる代わりに、紫外線架橋性樹脂塗液２を用いる以外は、実施例１２と同一条件で、可逆性感熱記録材料を作製した。
(Comparative Example 9)
In Example 12, a reversible thermosensitive recording material was produced under the same conditions as in Example 12 except that the UV-crosslinkable resin coating solution 1 was used instead of the hydrophilic smectite coating solution 3.
(Comparative Example 10)
In Example 12, a reversible thermosensitive recording material was produced under the same conditions as in Example 12 except that the ultraviolet crosslinkable resin coating solution 2 was used instead of using the hydrophilic smectite coating solution 3.
（比較例１１）
実施例１２で、親水性スメクタイト塗液３を用いる代わりに、針状導電性酸化チタン塗液１を用いる以外は、実施例１２と同一条件で、可逆性感熱記録材料を作製した。
(Comparative Example 11)
In Example 12, a reversible thermosensitive recording material was produced under the same conditions as in Example 12 except that the needle-like conductive titanium oxide coating solution 1 was used instead of using the hydrophilic smectite coating solution 3.
（比較例１２）
実施例１２で、親水性スメクタイト塗液３を用いる代わりに、針状導電性酸化チタン塗液２を用いる以外は、実施例１２と同一条件で、可逆性感熱記録材料を作製した。
(Comparative Example 12)
A reversible thermosensitive recording material was produced under the same conditions as in Example 12 except that instead of using the hydrophilic smectite coating solution 3 in Example 12, the needle-like conductive titanium oxide coating solution 2 was used.
（比較例１３）
実施例１２で、親水性スメクタイト塗液３を用いる代わりに、イオン性液体塗液１を用いる以外は、実施例１２と同一条件で、可逆性感熱記録材料を作製した。
(Comparative Example 13)
In Example 12, a reversible thermosensitive recording material was produced under the same conditions as Example 12 except that the ionic liquid coating liquid 1 was used instead of the hydrophilic smectite coating liquid 3.
（比較例１４）
実施例９で、親水性スメクタイト塗液３を用いる代わりに、針状導電性酸化チタン塗液１を用いる以外は、実施例９と同一条件で、可逆性感熱記録材料を作製した。
(Comparative Example 14)
In Example 9, a reversible thermosensitive recording material was produced under the same conditions as in Example 9 except that the needle-like conductive titanium oxide coating solution 1 was used instead of using the hydrophilic smectite coating solution 3.
（比較例１５）
実施例９で、親水性スメクタイト塗液３を用いる代わりに、針状導電性酸化チタン塗液２を用いる以外は、実施例９と同一条件で、可逆性感熱記録材料を作製した。
(Comparative Example 15)
A reversible thermosensitive recording material was produced under the same conditions as in Example 9, except that instead of using the hydrophilic smectite coating solution 3 in Example 9, the needle-like conductive titanium oxide coating solution 2 was used.
（比較例１６）
実施例９で、親水性スメクタイト塗液１を用いる代わりに、イオン性液体塗液１を用いる以外は、実施例９と同一条件で、可逆性感熱記録材料を作製した。
(Comparative Example 16)
A reversible thermosensitive recording material was produced under the same conditions as in Example 9 except that the ionic liquid coating liquid 1 was used instead of the hydrophilic smectite coating liquid 1 in Example 9.
（比較例１７）
実施例３で、親水性スメクタイト塗液３を用いる代わりに、親油性スメクタイト塗液１を用いる以外は、実施例３と同一条件で、可逆性感熱記録材料を作製した。
(Comparative Example 17)
A reversible thermosensitive recording material was produced under the same conditions as in Example 3 except that the lipophilic smectite coating solution 1 was used instead of the hydrophilic smectite coating solution 3 in Example 3.
（比較例１８）
実施例６で、親水性スメクタイト塗液３を用いる代わりに、親油性スメクタイト塗液１を用いる以外は、実施例６と同一条件で、可逆性感熱記録材料を作製した。
(Comparative Example 18)
A reversible thermosensitive recording material was produced under the same conditions as in Example 6 except that the lipophilic smectite coating solution 1 was used instead of the hydrophilic smectite coating solution 3 in Example 6.
（比較例１９）
実施例１２で、親水性スメクタイト塗液３を用いる代わりに、親油性スメクタイト塗液１を用いる以外は、実施例１２と同一条件で、可逆性感熱記録材料を作製した。
(Comparative Example 19)
A reversible thermosensitive recording material was produced under the same conditions as in Example 12 except that the lipophilic smectite coating solution 1 was used instead of the hydrophilic smectite coating solution 3 in Example 12.
（比較例２０）
実施例９で、親水性スメクタイト塗液３を用いる代わりに、親油性スメクタイト塗液１を用いる以外は、実施例９と同一条件で、可逆性感熱記録材料を作製した。
(Comparative Example 20)
A reversible thermosensitive recording material was produced under the same conditions as in Example 9 except that the lipophilic smectite coating solution 1 was used instead of the hydrophilic smectite coating solution 3 in Example 9.
以上のように作製した可逆性感熱記録材料について評価試験を行った。結果は表１に示すとおりとなった。各評価項目は、下記の様に実施した。 An evaluation test was performed on the reversible thermosensitive recording material produced as described above. The results are as shown in Table 1. Each evaluation item was implemented as follows.
［帯電電位］
自転可能な外径７０ｍｍのポリテトラフルオロエチレン製のローラーに、上記で作製した可逆性感熱記録材料を、可逆性感熱記録層が外側になるように該ローラーの全幅、全周にわたり貼り付けた。さらに、該ローラーに貼り付けられた可逆性感熱記録材料の表面の円周上の一カ所をローラーの全幅にわたり擦る様に、アクリル繊維製不織布片を設置した。温度２３℃・相対湿度５０％の環境下で、該ローラーを毎分３００回転で回転させながら、アクリル繊維製不織布が接触している場所より、回転方向に回転軸を中心に９０度下流側の帯電電位を、帯電電位測定装置（商品名ＦＭＸ−００２：シムコジャパン株式会社製）で測定した。次に、回転させたままアクリル繊維製不織布を取り除き、１０秒後の帯電電位を同様にして測定した。帯電電位は、アクリル繊維製不織布が接触させた状態と、アクリル繊維製不織布を取り除き１０秒後で測定することによって、可逆性感熱記録材料の帯電とその減衰を測定しており、いずれも値の低い方が帯電し難いことを表しており、発明の効果が大きい。結果は、アクリル繊維製不織布を接触させているときの帯電電位を表１の接触中の欄に、アクリル繊維製不織布を取り除き１０秒後の帯電電位を表１の１０秒後の欄に示した。
[Charging potential]
The reversible thermosensitive recording material produced above was attached to a roller made of polytetrafluoroethylene having an outer diameter of 70 mm capable of rotation, over the entire width and circumference of the roller so that the reversible thermosensitive recording layer was on the outside. Furthermore, an acrylic fiber non-woven fabric piece was placed so that one place on the circumference of the surface of the reversible thermosensitive recording material affixed to the roller was rubbed over the entire width of the roller. While rotating the roller at 300 revolutions per minute in an environment of a temperature of 23 ° C. and a relative humidity of 50%, it is 90 degrees downstream from the place where the non-woven fabric made of acrylic fiber is in contact with the rotation axis about the rotation axis. The charging potential was measured with a charging potential measuring device (trade name FMX-002: manufactured by Simco Japan Co., Ltd.). Next, the non-woven fabric made of acrylic fiber was removed while rotating, and the charging potential after 10 seconds was measured in the same manner. The charging potential is measured by measuring the charging of the reversible thermosensitive recording material and its attenuation by measuring 10 seconds after the acrylic fiber nonwoven fabric is in contact with the acrylic fiber nonwoven fabric. The lower one indicates that it is less likely to be charged, and the effect of the invention is great. As a result, the charging potential when the non-woven fabric made of acrylic fiber is in contact is shown in the column in contact in Table 1, and the non-woven fabric made of acrylic fiber is removed and the charging potential after 10 seconds is shown in the column after 10 seconds in Table 1. .
［シートの貼り付き難さ］
同一の可逆性感熱記録材料シート１０枚を表面と裏面が互いに密着するように重ね合わせ、１００時間静置後、シートを１枚ずつに引き離し、引き離し時の引き離し易さを評価した。結果を表１の貼り付き難さの欄に示した。表１中、○は容易に引き離すことができる、△は引き離す際にやや抵抗感がある、×は引き離し時の抵抗が大きいことを示す。
[Difficulty of sticking sheets]
Ten sheets of the same reversible thermosensitive recording material were overlapped so that the front surface and the back surface were in close contact with each other, and allowed to stand for 100 hours, then the sheets were separated one by one, and the ease of separation at the time of separation was evaluated. The results are shown in the column of difficulty of sticking in Table 1. In Table 1, ◯ indicates that it can be easily separated, Δ indicates that there is a slight resistance when being separated, and x indicates that the resistance during separation is large.
［繰り返し印字・消去］
表１に繰り返し印字・消去の試験結果を示す。繰り返し印字・消去の方法については、上記実施例及び比較例にて作製した得られた可逆性感熱記録材料をクレジットカード状に打ち抜き、カードプリンター（商品名ＫＵ−Ｒ３０２１：パナソニックコミュニケーションズ株式会社製）にて消去印字モードで印字を行った。消去印字とは、カードを挿してから再びカードが出てくるまでに画像が書き換えられるもので、消去はセラミックヒーター（イレーズバー）、引き続き印字はサーマルヘッドで行う。条件としては、印字エネルギーは約０．４５ｍＪ／ｄｏｔとし、セラミックヒーターの消去エネルギーはエネルギー不足による消え残りがなく、かつオーバーエネルギーによるカブリがない領域の中心値に設定した。この条件で、消去印字を２分間隔で３０回繰り返した。
[Repeat Print / Erase]
Table 1 shows the repeated printing / erasing test results. For the method of repeated printing and erasing, the reversible thermosensitive recording material produced in the above examples and comparative examples was punched out into a credit card, and a card printer (trade name KU-R3021: manufactured by Panasonic Communications Co., Ltd.) was used. Printing was performed in the erase print mode. Erase printing is a method in which an image is rewritten from when a card is inserted to when the card comes out again. Erase is performed with a ceramic heater (erase bar), and printing is subsequently performed with a thermal head. As the conditions, the printing energy was set to about 0.45 mJ / dot, and the erasing energy of the ceramic heater was set to the center value of a region where there was no disappearance due to insufficient energy and no fogging due to over energy. Under these conditions, erasure printing was repeated 30 times at 2-minute intervals.
３０回目の印字濃度を印字部の濃度をマクベス濃度計ＲＤ９１８の黒濃度にて測定した。結果を表１の印字濃度の欄に示した。さらに、印字面を観察して、埃等の異物付着による印字欠けの有無を評価した。結果を表１の印字欠けの欄に示した。 The printing density at the 30th time was measured by the black density of the Macbeth densitometer RD918. The results are shown in the printing density column of Table 1. Further, the printed surface was observed to evaluate the presence or absence of printing defects due to adhesion of foreign matters such as dust. The results are shown in the missing print column in Table 1.
表１から明らかなように、実施例１〜２７の可逆性感熱記録材料は、アクリル繊維製不織布を接触させているときの帯電電位が低いと共に、アクリル繊維製不織布を取り除いてから１０秒後の帯電電位も低く、帯電が起こり難かった。また、シートの貼り付きが少なく、少ない力で引き剥がすことができた。さらに、親水性スメクタイトを含有させる場所に依存せずに、常に高い印字濃度を得ることができ、印字欠けの発生もなかった。 As is clear from Table 1, the reversible thermosensitive recording materials of Examples 1 to 27 had a low charging potential when contacting the acrylic fiber nonwoven fabric and 10 seconds after the acrylic fiber nonwoven fabric was removed. The charging potential was low and charging was difficult to occur. Moreover, there was little sticking of a sheet | seat and it was able to peel off with little force. Furthermore, it was possible to always obtain a high printing density without depending on the location where the hydrophilic smectite was contained, and there was no occurrence of printing defects.
一方、針状導電性酸化チタンを含有する比較例１、２、６、７、１１、１２、１４、１５は、親水性スメクタイトを含有させた場合より帯電しやすく、シートの貼り付きも多めで、印字欠けの発生も見られた。また、針状導電性酸化チタンを含有する層の透明度が低いため、可逆性感熱記録層よりも表面に近い層に針状導電性酸化チタンを含有させた、比較例６、７、１１、１２では、印字濃度が非常に低かった。 On the other hand, Comparative Examples 1, 2, 6, 7, 11, 12, 14, and 15 containing acicular conductive titanium oxide are easier to be charged than when hydrophilic smectite is contained, and the sheet is more sticky. Also, the occurrence of missing prints was observed. Further, since the transparency of the layer containing acicular conductive titanium oxide is low, Comparative Examples 6, 7, 11, 12 in which acicular conductive titanium oxide is contained in a layer closer to the surface than the reversible thermosensitive recording layer. Then, the print density was very low.
イオン性液体を含有する比較例３、８、１３、１６は、親水性スメクタイトを含有させた場合よりシートの貼り付きが大きかった。比較例１３、１６は、イオン性液体が表面にマイグレートしたため、表面がベタついており、シートの貼り付きが特に大きかった。また、イオン性液体をリライト層が設けられいる面に含有させた比較例３，８，１３では、印字濃度がやや低めであった。これは、イオン性液体が可逆感熱記録層内に浸透して発色を阻害したものと考えられる。 In Comparative Examples 3, 8, 13, and 16 containing the ionic liquid, the sticking of the sheet was larger than when the hydrophilic smectite was contained. In Comparative Examples 13 and 16, since the ionic liquid migrated to the surface, the surface was sticky, and the sticking of the sheet was particularly large. In Comparative Examples 3, 8, and 13 in which the ionic liquid was contained on the surface on which the rewritable layer was provided, the print density was slightly low. This is considered that the ionic liquid penetrated into the reversible thermosensitive recording layer and inhibited color development.
また、親油性スメクタイトを含有する比較例１７〜２０は、親水性スメクタイトを含有させた場合より帯電しやすく、シートの貼り付きが多く、印字欠けの発生も見られた。 In addition, Comparative Examples 17 to 20 containing lipophilic smectite were more easily charged than those containing hydrophilic smectite, the sheet was often stuck, and printing defects were also observed.
本発明の可逆性感熱記録材料は、明瞭なコントラストを持つ画像の形成・消去が可能で、帯電を防ぐことにより画像形成装置における搬送不良、印字不良が少ない可逆性感熱記録材料として利用することができる。 The reversible thermosensitive recording material of the present invention can be used as a reversible thermosensitive recording material capable of forming and erasing an image with clear contrast and preventing charging failure and printing failure by preventing charging. it can.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012029546A1 (en) * | 2010-08-31 | 2012-03-08 | Ricoh Company, Ltd. | Reversible thermosensitive recording medium and reversible thermosensitive recording member |
| JP2015036237A (en) * | 2013-08-15 | 2015-02-23 | 王子ホールディングス株式会社 | Thermal recording material |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012029546A1 (en) * | 2010-08-31 | 2012-03-08 | Ricoh Company, Ltd. | Reversible thermosensitive recording medium and reversible thermosensitive recording member |
| JP2012051185A (en) * | 2010-08-31 | 2012-03-15 | Ricoh Co Ltd | Reversible thermosensitive recording medium and reversible thermosensitive recording member |
| CN103079831A (en) * | 2010-08-31 | 2013-05-01 | 株式会社理光 | Reversible thermosensitive recording medium and reversible thermosensitive recording member |
| RU2531904C1 (en) * | 2010-08-31 | 2014-10-27 | Рикох Компани, Лтд. | Reversible thermosensitive medium for printing and reversible thermosensitive element for printing |
| US8877680B2 (en) | 2010-08-31 | 2014-11-04 | Ricoh Company, Ltd. | Reversible thermosensitive recording medium and reversible thermosensitive recording member |
| KR101496598B1 (en) | 2010-08-31 | 2015-02-26 | 가부시키가이샤 리코 | Reversible thermosensitive recording medium and reversible thermosensitive recording member |
| CN103079831B (en) * | 2010-08-31 | 2015-04-22 | 株式会社理光 | Reversible thermosensitive recording medium and reversible thermosensitive recording member |
| JP2015036237A (en) * | 2013-08-15 | 2015-02-23 | 王子ホールディングス株式会社 | Thermal recording material |
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