JP5949304B2 - Thermosensitive recording material and method for producing the same - Google Patents
Thermosensitive recording material and method for producing the same Download PDFInfo
- Publication number
- JP5949304B2 JP5949304B2 JP2012177305A JP2012177305A JP5949304B2 JP 5949304 B2 JP5949304 B2 JP 5949304B2 JP 2012177305 A JP2012177305 A JP 2012177305A JP 2012177305 A JP2012177305 A JP 2012177305A JP 5949304 B2 JP5949304 B2 JP 5949304B2
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- recording material
- antistatic layer
- parts
- heat
- starch
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- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Heat Sensitive Colour Forming Recording (AREA)
Description
本発明は感熱記録体に関し、特に湿度条件等の外部環境や、記録速度等の記録条件に影響されることなく、常に安定した記録を行うことができる感熱記録体及びその製造方法に関するものである。 The present invention relates to a heat-sensitive recording material, and more particularly to a heat-sensitive recording material that can always perform stable recording without being affected by external conditions such as humidity conditions and recording conditions such as recording speed, and a method for manufacturing the same. .
無色または淡色の塩基性染料と有機または無機の呈色剤との呈色反応を利用し、熱により両発色物質を接触させて記録像を得るようにした感熱記録体はよく知られている。かかる感熱記録体は比較的安価であり、また記録機器がコンパクトで且つその保守も比較的容易であるため、ファクシミリやプリンター、更には各種計算機等の記録媒体として幅広い分野で使用されている。しかしながら、例えば、低湿度環境下で記録すると、記録機器と記録紙との摩擦帯電等によって記録紙の通紙適性が低下し、紙詰まりや記録機器への貼り付きが起きたり、サーマルヘッドや他の回路の破損、異常、誤動作等が発生したりする問題がある。このため、金属酸化物、金属ハロゲン化物、高分子電解質、界面活性剤、吸湿性物質等の各種導電性物質により記録体を処理することが提案されている（特許文献１〜４参照）。 A heat-sensitive recording material is known which utilizes a color reaction between a colorless or light-colored basic dye and an organic or inorganic colorant to bring a recording image into contact with both coloring materials by heat. Such a heat-sensitive recording material is relatively inexpensive and has a compact recording device and is relatively easy to maintain, so that it is used in a wide range of fields as a recording medium for facsimiles, printers, and various computers. However, for example, when recording is performed in a low humidity environment, the suitability of passing the recording paper decreases due to frictional charging between the recording device and the recording paper, paper jamming or sticking to the recording device occurs, a thermal head or other There is a problem that circuit breakage, abnormality, malfunction, etc. occur. For this reason, it has been proposed to treat the recording material with various conductive materials such as metal oxides, metal halides, polymer electrolytes, surfactants, hygroscopic materials (see Patent Documents 1 to 4).
一方、医療用途等の解像度に優れた感熱記録体、多色化、或いはオーバーヘッドプロジェクター（ＯＨＰ）に使用する目的等で支持体としてプラスチックフィルムや合成紙を使用した感熱記録体が提案されている。支持体にプラスチックフィルムを用いた場合、静電気による問題が顕著であり、特に低湿度条件下での摩擦帯電が著しく、上記の如き導電性物質では、十分な帯電防止効果は得られていない。帯電防止性能を高めるために導電性物質を多量に使用すると、導電度はある程度高められるものの、感熱記録体に不用な地肌発色（所謂地肌カブリ）現象が発生する問題がある。また、導電性物質が高分子電解質の場合では、感熱記録体の製造中に凝集等の問題が発生し、歩留まりの低下や連続操業性に問題が発生している。導電性を向上させるため、金属系の導電剤の使用が提案されている。しかしながら、金属体は高価であるため経済的に好ましくなく、また金属体は感熱記録体を着色する等の問題があり、満足の行く品質が得られていないのが実情である。このような問題を解決するために、帯電防止層に粘土鉱物であるスメクタイト粘土やヘクトライト粘土を含有する帯電防止層を設けることが提案されている（特許文献５〜７参照）。 On the other hand, a heat-sensitive recording material excellent in resolution for medical use, a heat-sensitive recording material using a plastic film or a synthetic paper as a support has been proposed for the purpose of using multiple colors or an overhead projector (OHP). When a plastic film is used for the support, the problem due to static electricity is remarkable, and frictional charging is particularly remarkable under low humidity conditions, and the conductive material as described above does not provide a sufficient antistatic effect. When a large amount of a conductive material is used to improve the antistatic performance, the conductivity is increased to some extent, but there is a problem that a background coloring (so-called background fogging) phenomenon that is unnecessary for the heat-sensitive recording material occurs. In the case where the conductive material is a polymer electrolyte, problems such as aggregation occur during the production of the thermosensitive recording material, resulting in a decrease in yield and continuous operability. In order to improve conductivity, use of a metal-based conductive agent has been proposed. However, since the metal body is expensive, it is economically unfavorable, and the metal body has problems such as coloring the heat-sensitive recording medium, and the actual situation is that satisfactory quality is not obtained. In order to solve such problems, it has been proposed to provide an antistatic layer containing smectite clay or hectorite clay, which are clay minerals, in the antistatic layer (see Patent Documents 5 to 7).
スメクタイト粘土及びヘクトライト粘土は、水に濃度１０％程度までは均質なゾルまたはゲル状の塗液として調製でき、支持体に塗布、乾燥すると優れた導電性を有する帯電防止層を形成することが可能である。しかしながら、スメクタイト粘土もしくはヘクトライト粘土を水分散体塗液として調製し、連続操業にて支持体に塗布する場合、連続操業に起因する塗液濃度の変動等により粘度が部分的に極端に増加し、粘土成分に起因する凝集物が発生し、例えばバーコーティング等の塗布工程ではバー筋や塗布ムラが発生する問題がある。このような問題が発生した場合には、塗液の作り直しや、塗布速度を下げる等の製造効率の悪い操業が行われているのが実情である。 Smectite clay and hectorite clay can be prepared as a uniform sol or gel-like coating solution up to a concentration of about 10% in water, and can form an antistatic layer having excellent conductivity when applied to a support and dried. Is possible. However, when smectite clay or hectorite clay is prepared as an aqueous dispersion coating solution and applied to a support by continuous operation, the viscosity partially increases due to fluctuations in the concentration of the coating solution resulting from continuous operation. Aggregates resulting from clay components are generated, and there is a problem that, for example, bar stripes and coating unevenness occur in a coating process such as bar coating. When such a problem occurs, the actual situation is that operations with poor production efficiency such as remaking the coating liquid and lowering the coating speed are being carried out.
本発明は、低湿度環境から高湿度環境まで外部環境の湿度変化に影響されず、高速記録においても地肌カブリ現象やブロッキング現象を伴うことなく安定した記録が可能であり、且つ製造時の安定性に優れる感熱記録体及びその製造方法を提供することを主な目的とする。 The present invention is not affected by humidity changes in the external environment from a low humidity environment to a high humidity environment, enables stable recording without any background fogging or blocking phenomenon even at high speed recording, and stability during manufacturing. The main object of the present invention is to provide a heat-sensitive recording material excellent in heat resistance and a method for producing the same.
本発明者等は、上記従来技術に鑑み、鋭意検討を重ねた結果、支持体の一方の面に感熱記録層を備え、他方の面（以下、支持体の裏面ともいう）に特定の帯電防止層を備えることにより、上記問題点を解決するに至った。即ち、本発明は、下記の感熱記録体及びその製造方法に係る。 As a result of intensive studies in view of the above prior art, the present inventors have provided a thermosensitive recording layer on one side of the support, and a specific antistatic property on the other side (hereinafter also referred to as the back side of the support). By providing the layer, the above-mentioned problems have been solved. That is, the present invention relates to the following thermal recording material and a method for producing the same.
項１：支持体の一方の面に、無色または淡色の塩基性染料と、前記塩基性染料と反応する呈色剤を含有する感熱記録層を備え、他方の面に帯電防止層を備えた感熱記録体において、前記帯電防止層がスメクタイト粘土及びヘクトライト粘土から選ばれる少なくとも１種、リン酸塩、並びに澱粉及びその誘導体から選ばれる少なくとも１種を含有することを特徴とする感熱記録体。 Item 1: A thermosensitive recording layer comprising a colorless or light-colored basic dye and a colorant that reacts with the basic dye on one side of the support, and an antistatic layer on the other side In the recording material, the antistatic layer contains at least one selected from smectite clay and hectorite clay, phosphate, and at least one selected from starch and derivatives thereof.
項２：前記支持体の透気度が５０秒以下である、項１に記載の感熱記録体。 Item 2: The thermal recording material according to Item 1, wherein the support has an air permeability of 50 seconds or less.
項３：前記リン酸塩と、澱粉及びその誘導体から選ばれる少なくとも１種との質量比率が、１：９９〜５５：４５である、項１または２に記載の感熱記録体。 Item 3: The thermal recording material according to Item 1 or 2, wherein a mass ratio of the phosphate to at least one selected from starch and derivatives thereof is 1:99 to 55:45.
項４：前記帯電防止層がスメクタイト粘土及びヘクトライト粘土から選ばれる少なくとも１種、リン酸塩、並びに澱粉及びその誘導体から選ばれる少なくとも１種を含有する帯電防止層用塗液をロールコーターにより塗布及び乾燥して形成されたものである、項１〜３のいずれか１項に記載の感熱記録体。 Item 4: An antistatic layer coating solution containing at least one selected from smectite clay and hectorite clay, at least one selected from phosphate, and starch and derivatives thereof is applied by a roll coater. Item 4. The heat-sensitive recording material according to any one of Items 1 to 3, which is formed by drying.
項５：前記ロールコーターが表面に幅１〜１０μｍのクラックを有するアプリケーターロールを備えている、項１〜４のいずれか１項に記載の感熱記録体。 Item 5: The heat-sensitive recording material according to any one of Items 1 to 4, wherein the roll coater includes an applicator roll having a crack having a width of 1 to 10 μm on the surface.
項６：支持体の一方の面に、無色または淡色の塩基性染料と、前記塩基性染料と反応する呈色剤を含有する感熱記録層を設け、他方の面に帯電防止層を設ける感熱記録体の製造方法において、スメクタイト粘土及びヘクトライト粘土から選ばれる少なくとも１種、リン酸塩、並びに澱粉及びその誘導体から選ばれる少なくとも１種を含有する帯電防止層用塗液を塗布及び乾燥して帯電防止層を形成することを特徴とする感熱記録体の製造方法。 Item 6: Thermal recording in which a thermal recording layer containing a colorless or light-colored basic dye and a colorant that reacts with the basic dye is provided on one side of the support, and an antistatic layer is provided on the other side In the method for producing a body, an antistatic layer coating liquid containing at least one selected from smectite clay and hectorite clay, phosphate, and at least one selected from starch and derivatives thereof is applied and dried to be charged. A method for producing a thermal recording material, comprising forming a prevention layer.
項７：前記帯電防止層用塗液をロールコーターにより塗布及び乾燥する、項６に記載の感熱記録体の製造方法。 Item 7: The method for producing a heat-sensitive recording material according to Item 6, wherein the antistatic layer coating solution is applied and dried by a roll coater.
本発明の感熱記録体は、極めて均一な帯電防止層が得られ、且つ低湿度環境から高湿度環境まで外部環境の変化に影響されず、高速記録においても地肌カブリ現象やブロッキング現象を伴うことなく安定した記録が可能であり、且つ製造時の安定性に優れる。 The heat-sensitive recording material of the present invention provides a very uniform antistatic layer and is not affected by changes in the external environment from a low-humidity environment to a high-humidity environment, and is free from background fogging and blocking even in high-speed recording. Stable recording is possible, and the stability during production is excellent.
本発明における帯電防止層は、スメクタイト粘土及びヘクトライト粘土から選ばれる少なくとも１種、リン酸塩、並びに澱粉及びその誘導体から選ばれる少なくとも１種を含有している。 The antistatic layer in the present invention contains at least one selected from smectite clay and hectorite clay, phosphate, and at least one selected from starch and derivatives thereof.
本発明の帯電防止層に用いられるスメクタイト粘土及びヘクトライト粘土とは、結晶質のクレー鉱物で、３層構造を有する無制限膨張グループに属し、それぞれ天然品及び合成品があり、いずれも本発明に好ましく適用できる。 The smectite clay and hectorite clay used in the antistatic layer of the present invention are crystalline clay minerals, belonging to an unlimited expansion group having a three-layer structure, and there are natural products and synthetic products, both of which are in the present invention. It can be preferably applied.
スメクタイト粘土は、例えば次式、〔（Ｓｉ８−ａＡｌａ）（Ｍｇ６−ｂＡｌｂ）・Ｏ２０（ＯＨ）４〕−・Ｍ＋ ａ−ｂ（備考；Ｍ＋は殆どすべてＮａ＋であり、ａ−ｂ＞０である。）で表示される。 Smectite clays, for example, the following equation, [(Si 8-a Al a) (Mg 6-b Al b) · O 20 (OH) 4 ] - · M + a-b (Remark; M + is almost all Na + And ab> 0).
ヘクトライト粘土は、例えば次式、〔（Ｓｉ８（Ｍｇ５．３４Ｌｉ０．６６）Ｏ２０（ＯＨ，Ｆ）４）〕Ｍ＋ ０．６６（備考；Ｍ＋は殆どすべてＮａ＋である。）で表示されるものがあり、市販のものでは、ロックウッド社製のラポナイトＢ、ラポナイトＳが知られている。 Hectorite clay is, for example, the following formula: [(Si 8 (Mg 5.34 Li 0.66 ) O 20 (OH, F) 4 )] M + 0.66 (Remarks; M + is almost all Na + . )), And commercially available products such as Laponite B and Laponite S manufactured by Rockwood are known.
また、中央層が全て水酸基となった次式、〔（Ｓｉ８（Ｍｇ５．３４Ｌｉ０．６６）Ｏ２０（ＯＨ）４）〕Ｍ＋ ０．６６（備考；Ｍ＋は常にＮａ＋である。）で表示されるヘクトライト粘土の例としては、ロックウッド社製のラポナイトＲＤ、ラポナイトＲＤＳ、ラポナイトＸＬＧ、ラポナイトＸＬＳ等がある。 In addition, the following formula in which the central layer is all hydroxyl groups, [(Si 8 (Mg 5.34 Li 0.66 ) O 20 (OH) 4 )] M + 0.66 (Remarks; M + is always Na + Examples of the hectorite clay displayed in the above are Laponite RD, Laponite RDS, Laponite XLG, Laponite XLS, etc. manufactured by Rockwood.
上記の如きラポナイトは白色粉末で、水に加えるとラポナイトＢ、ＲＤ、ＸＬＧはゲルを、またラポナイトＳ、ＲＤＳ、ＸＬＳはゾルを、それぞれ容易に形成する。例えばラポナイトは、結晶構造の各層の厚さは約１ｎｍで２次元に延長して小板を形成する。この小板ユニットに存在するマグネシウム原子が、より低原子価陽イオンのリチウム原子と同形置換しており、小板ユニットは負に帯電しているが、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（普通はナトリウムイオン）と釣り合っている。このラポナイトを脱イオン水中に１．５〜２．０質量％の濃度で分散させると、格子構造外側にある置換可能陽イオンがイオン化して、小板面から拡散し、小板面は負の電荷を得て相互に反発して小板ユニットか、バラバラに分散したコロイド状分散液、即ちゾルを形成する。分散された小板には全体に固有の負電荷が存在し、小板の端部には周囲媒体からのイオン吸着により、わずかな局部電荷を帯びる。これは溶液中のイオンの種類と濃度及び媒体のｐＨに依存するが、通常は陽イオンのみが吸着され、端部は正電荷を帯びることになる。結果として、端−面結合が生じて代表的な「カードハウス」構造が形成され、ゲルが形成される。このゲルの強度はラポナイトの濃度に依存し、低濃度の場合、比較的緩やかな粒子連鎖の網目が形成されゲル強度は低いが、濃度が増加すれば粒子連鎖の網目が充填されるため、強度が急速に増す。 Laponite as described above is a white powder, and when added to water, Laponite B, RD, and XLG easily form a gel, and Laponite S, RDS, and XLS easily form a sol. For example, in the case of laponite, the thickness of each layer of the crystal structure is about 1 nm and extends in two dimensions to form a platelet. The magnesium atom present in this platelet unit is isomorphously substituted with the lithium atom of the lower valence cation, and the platelet unit is negatively charged, but in the dry state, this negative charge is the lattice of the plate surface. It is balanced with a replaceable cation (usually a sodium ion) outside the structure. When this laponite is dispersed in deionized water at a concentration of 1.5 to 2.0 mass%, the replaceable cation outside the lattice structure is ionized and diffuses from the platelet surface, and the platelet surface is negative. The charge is repelled and repels each other to form a platelet unit or a dispersed colloidal dispersion, ie, a sol. The dispersed platelet has a negative charge inherent to the whole, and the edge of the platelet has a small local charge due to ion adsorption from the surrounding medium. This depends on the type and concentration of ions in the solution and the pH of the medium, but usually only cations are adsorbed and the edges are positively charged. As a result, end-to-face bonds occur to form a typical “card house” structure and form a gel. The strength of this gel depends on the concentration of laponite. When the concentration is low, a relatively loose particle chain network is formed and the gel strength is low, but as the concentration increases, the particle chain network is filled. Increase rapidly.
このような性質を有するラポナイトを帯電防止層の塗液に用いた場合、塗布工程において低濃度でも適度な粘性を有し、支持体上で、表面の乱れが少なく、塗布面のコントロールが容易であり、且つ接着性も比較的良好である。また置換可能イオンを有するため、常湿度環境下では勿論、低湿度環境下においても優れた導電性を有するものと考えられる。 When laponite having such properties is used for the coating solution of the antistatic layer, it has an appropriate viscosity even at a low concentration in the coating process, has little surface disturbance on the support, and can easily control the coating surface. And adhesion is relatively good. Moreover, since it has a replaceable ion, it is considered that it has excellent conductivity not only in a normal humidity environment but also in a low humidity environment.
上記スメクタイト粘土及びヘクトライト粘土は、水に濃度１０％程度までは均質なゾルまたはゲル状の塗液として調製でき、支持体に塗布、乾燥すると優れた導電性を示す。しかしながら、支持体に、スメクタイト粘土若しくはヘクトライト粘土を単に水分散体塗液として調製し、塗布した場合、水中での分散安定性が低く、凝集による析出物が発生し易いため、例えばバーコーティング等の塗布工程でバー筋や塗りムラ等の塗布欠陥を生じる問題がある。 The smectite clay and hectorite clay can be prepared as a uniform sol or gel coating solution up to a concentration of about 10% in water, and exhibit excellent conductivity when applied to a support and dried. However, when smectite clay or hectorite clay is simply prepared as an aqueous dispersion coating solution on the support and applied, the dispersion stability in water is low, and precipitates due to aggregation tend to occur. There is a problem of causing application defects such as bar streaks and uneven coating in the application process.
本発明では、上記スメクタイト粘土やヘクトライト粘土の水分散物中に分散剤としてリン酸塩を含有させることにより、スメクタイト粘土やヘクトライト粘土の水中での分散状態を安定化し、凝集による析出物の発生を抑制し、安定した分散液を調製することができる。 In the present invention, by adding a phosphate as a dispersant in the aqueous dispersion of the smectite clay or hectorite clay, the dispersion state of the smectite clay or hectorite clay in water is stabilized, and the precipitates due to aggregation are dispersed. Generation | occurrence | production can be suppressed and the stable dispersion liquid can be prepared.
本発明に用いられるリン酸塩としては、第一リン酸ナトリウム、第二リン酸ナトリウム、第三リン酸ナトリウム、ピロリン酸ナトリウム、酸性ピロリン酸ナトリウム、トリポリリン酸ナトリウム、テトラポリリン酸ナトリウム、ヘキサメタリン酸ナトリウム、酸性ヘキサメタリン酸ナトリウム、またはこれらのカリウム塩、カルシウム塩、マグネシウム塩等が例示できる。特に、ナトリウム塩が、安価で製造が容易であることから、本発明におけるリン酸塩として好ましく用いることができる。 Examples of the phosphate used in the present invention include monobasic sodium phosphate, dibasic sodium phosphate, tribasic sodium phosphate, sodium pyrophosphate, acidic sodium pyrophosphate, sodium tripolyphosphate, sodium tetrapolyphosphate, sodium hexametaphosphate , Acidic sodium hexametaphosphate, or potassium, calcium and magnesium salts thereof. In particular, a sodium salt can be preferably used as a phosphate in the present invention because it is inexpensive and easy to produce.
本発明において、これらのリン酸塩の添加量は特に限定するものではないが、スメクタイト粘土及びヘクトライト粘土から選ばれる少なくとも１種の合計１００質量部に対して好ましくは０．１〜２０質量部、より好ましくは１〜１５質量部、更に好ましくは５〜１５質量部程度が用いられる。 In the present invention, the addition amount of these phosphates is not particularly limited, but is preferably 0.1 to 20 parts by mass with respect to at least one total of 100 parts by mass selected from smectite clay and hectorite clay. More preferably, 1 to 15 parts by mass, and still more preferably about 5 to 15 parts by mass are used.
また、本発明の効果を阻害しない範囲において、他の分散剤を併用することもできる。 In addition, other dispersants can be used in combination as long as the effects of the present invention are not impaired.
本発明では、帯電防止層に水溶性樹脂として澱粉及びその誘導体から選ばれる少なくとも１種を用いることにより、塗液に適度な保水性を発現させ、塗布時における均一な塗布面を形成することができ、塗りムラの少ない均一性の高い帯電防止層を得ることができる。 In the present invention, by using at least one selected from starch and derivatives thereof as a water-soluble resin in the antistatic layer, it is possible to develop an appropriate water retention in the coating liquid and form a uniform coated surface at the time of coating. And a highly uniform antistatic layer with little coating unevenness can be obtained.
澱粉の誘導体としては、例えば、アセチル化アジピン酸架橋澱粉、アセチル化リン酸化架橋澱粉、アセチル化酸化澱粉、オクテニルコハク酸澱粉ナトリウム、酢酸澱粉、酸化澱粉、ヒドロキシプロピル澱粉、ヒドロキシプロピル化リン酸架橋澱粉、リン酸モノエステル化リン酸架橋澱粉、リン酸化澱粉、リン酸架橋澱粉、カルボキシメチル澱粉、カチオン澱粉等が挙げられる。 Examples of starch derivatives include acetylated adipic acid crosslinked starch, acetylated phosphorylated crosslinked starch, acetylated oxidized starch, sodium octenyl succinate starch, acetate starch, oxidized starch, hydroxypropyl starch, hydroxypropylated phosphate crosslinked starch, Examples include phosphoric acid monoesterified phosphoric acid crosslinked starch, phosphorylated starch, phosphoric acid crosslinked starch, carboxymethyl starch, and cationic starch.
澱粉及びその誘導体は適度な保水性を有することから、後述するアプリケートロール表面に微細なクラックを無数有するロールコーターにより、薄膜塗布を連続的に行なう操業時において、アプリケートロールの微細クラックの目詰まり発生による問題がなく、また乾燥後の接着力も充分であることから、本発明の水溶性樹脂として好ましく用いられる。 Since starch and its derivatives have moderate water retention, clogging of fine cracks in the applicator roll occurs during operations in which thin film coating is continuously performed by a roll coater having countless fine cracks on the surface of the application roll described later. Therefore, it is preferably used as the water-soluble resin of the present invention.
また、本発明における帯電防止層には、本発明の効果を阻害しない範囲において、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、及びエチルセルロース等のセルロース誘導体、ポリアクリル酸ソーダ、ポリビニルアルコール、ポリビニルピロリドン、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アルカリ塩、ポリアクリルアミド、アルギン酸ソーダ、ゼラチン、及びカゼイン等の水溶性高分子材料、ポリ酢酸ビニル、ポリウレタン、スチレン−ブタジエン共重合体、ポリアクリル酸、ポリアクリル酸エステル、塩化ビニル−酢酸ビニル共重合体、ポリブチルメタクリレート、エチレン−酢酸ビニル共重合体、及びスチレン−ブタジエン−アクリル系共重合体等の疎水性重合体のラテックス等を併用してもよい。 In addition, the antistatic layer in the present invention includes cellulose derivatives such as methoxycellulose, carboxymethylcellulose, methylcellulose, and ethylcellulose, polyacrylic acid soda, polyvinyl alcohol, polyvinylpyrrolidone, and acrylic acid amide as long as the effects of the present invention are not impaired. -Highly water-soluble such as acrylic acid ester copolymer, acrylic acid amide-acrylic acid ester-methacrylic acid ternary copolymer, styrene-maleic anhydride copolymer alkali salt, polyacrylamide, sodium alginate, gelatin, and casein Molecular materials, polyvinyl acetate, polyurethane, styrene-butadiene copolymer, polyacrylic acid, polyacrylate ester, vinyl chloride-vinyl acetate copolymer, polybutyl methacrylate, ethylene-vinyl acetate copolymer Body, and styrene - butadiene - may be used in combination with latexes such hydrophobic polymer such as an acrylic copolymer.
本発明における帯電防止層は、例えば、水を分散媒体として、上記のスメクタイト粘土及びヘクトライト粘土から選ばれる少なくとも１種、リン酸塩、並びに澱粉及びその誘導体から選ばれる少なくとも１種と、必要により各種助剤を混合することにより調製された帯電防止層用塗液を、支持体の裏面に乾燥後の重量で好ましくは０．１〜１０ｇ／ｍ２程度、より好ましくは０．１〜５ｇ／ｍ２程度、更に好ましくは０．２〜５ｇ／ｍ２程度となるように塗布及び乾燥して形成される。助剤としては、顔料、消泡剤、濡れ剤、防腐剤、増粘剤等の公知のものを用いることができる。 The antistatic layer in the present invention, for example, using water as a dispersion medium, at least one selected from the above smectite clay and hectorite clay, at least one selected from phosphate, starch, and derivatives thereof, if necessary. The coating solution for an antistatic layer prepared by mixing various auxiliaries is preferably about 0.1 to 10 g / m 2 , more preferably 0.1 to 5 g / m 2 by weight after drying on the back surface of the support. m 2 approximately, is further preferably applied and dried such that 0.2-5 g / m 2 approximately formed. As the auxiliary agent, known substances such as pigments, antifoaming agents, wetting agents, preservatives, thickeners and the like can be used.
本発明における帯電防止層は、リン酸塩と、澱粉及びその誘導体から選ばれる少なくとも１種との質量比率が１：９９〜５５：４５であることが好ましく、１０：９０〜５０：５０であることがより好ましい。これにより、スメクタイト粘土及びヘクトライト粘土から選ばれる少なくとも１種を帯電防止層の全固形量中、好ましくは４０〜９０質量％、より好ましくは５０〜９０質量％、更に好ましくは６５〜８５質量％程度と高配合にすることができ、低塗布量で十分な導電性を発揮できる。また、高配合によっても分散液の安定性を損なわず、異物や筋状の塗布欠陥のない塗布面を効果的に得ることができる。この理由については明らかでないが、リン酸塩と、澱粉及びその誘導体から選ばれる少なくとも１種との相互作用により、保水性を効果的に向上できるためと考えられる。 In the antistatic layer of the present invention, the mass ratio of phosphate and at least one selected from starch and derivatives thereof is preferably 1:99 to 55:45, and is 10:90 to 50:50. It is more preferable. Accordingly, at least one selected from smectite clay and hectorite clay is preferably 40 to 90% by mass, more preferably 50 to 90% by mass, and still more preferably 65 to 85% by mass in the total solid content of the antistatic layer. It can be blended with a high degree, and sufficient conductivity can be exhibited with a low coating amount. Moreover, even if it is highly blended, the stability of the dispersion liquid is not impaired, and a coated surface free from foreign matter and streak-like coating defects can be obtained effectively. Although it is not clear about this reason, it is considered that water retention can be effectively improved by the interaction between phosphate and at least one selected from starch and derivatives thereof.
本発明では、帯電防止層用塗液は、例えばスロットダイ、スライドビード、カーテン、エアナイフ、ブレード、グラビア、バー、ロッド、ロールコーター等の塗布方式により塗布される。これらの中でも、回転するロールに塗液を塗り付け、該ロールに塗り付けた塗液を支持体に塗布するロールコーターが、塗液ロスや塗布時の欠陥発生量が少なく、好ましく用いられる。特に、リバースロールコーターは、高速塗布において薄膜を均一に塗布する観点から好ましい。更に、表面に幅１〜１０μｍのクラックを無数に有するアプリケートロールを備えたロールコーターは、薄膜をより均一に塗布する観点から、本発明の塗布方式として好ましい。なお、クラック幅は、表面を１０００倍で撮影した１０枚の写真からクラック幅の平均値を測定したものである。 In the present invention, the antistatic layer coating solution is applied by a coating method such as a slot die, a slide bead, a curtain, an air knife, a blade, a gravure, a bar, a rod, or a roll coater. Among these, a roll coater in which a coating liquid is applied to a rotating roll and the coating liquid applied to the roll is applied to a support is preferably used because the coating liquid loss and the amount of defects generated during application are small. In particular, a reverse roll coater is preferable from the viewpoint of uniformly applying a thin film in high-speed coating. Furthermore, a roll coater provided with an applicator roll having innumerable cracks having a width of 1 to 10 μm on the surface is preferable as a coating method of the present invention from the viewpoint of more uniformly coating a thin film. The crack width is a value obtained by measuring the average value of the crack width from ten photographs taken at a magnification of 1000 times on the surface.
本発明では、支持体の一方の面に感熱記録層を含む各層を形成する任意の過程において、他方の面に帯電防止層を形成することができる。感熱記録体を巻き取りの状態で製造する方法においては、支持体側の剥離帯電を抑えて、記録面に付着する塵ホコリ等によるコスレ汚れや印字の白抜けを防ぐ観点から、帯電防止層を形成した後に感熱記録層を形成することが好ましい。 In the present invention, an antistatic layer can be formed on the other surface in an arbitrary process of forming each layer including the thermosensitive recording layer on one surface of the support. In the method of manufacturing a heat-sensitive recording material in a wound state, an antistatic layer is formed from the viewpoint of suppressing peeling electrification on the support side and preventing scumming stains due to dust and the like adhering to the recording surface and white spots of printing. After that, it is preferable to form a heat-sensitive recording layer.
本発明における支持体は、例えば、上質紙（酸性紙、中性紙）、中質紙、コート紙、アート紙、グラシン紙等の紙支持体、並びに樹脂ラミネート紙等、ポリオレフィン系合成紙、合成繊維紙、不織布、合成樹脂フィルム等の支持体を用いることができる。これらの中でも、本発明では、帯電防止層に含有される澱粉及びその誘導体との接着力に優れるという観点から、紙支持体を用いることが好ましい。 The support in the present invention is, for example, a paper support such as high-quality paper (acidic paper, neutral paper), medium-quality paper, coated paper, art paper, glassine paper, and resin-laminated paper, polyolefin-based synthetic paper, synthetic paper, etc. Supports such as fiber paper, nonwoven fabric, and synthetic resin film can be used. Among these, in the present invention, it is preferable to use a paper support from the viewpoint of excellent adhesion to starch and derivatives thereof contained in the antistatic layer.
また、支持体としては、透気度が５０秒以下であることが好ましい。本発明では、透気度が低いほど（数値が小さいほど）、塗液の吸収性を高めて、塗液を支持体の内部にまで十分に浸透させることができるため、塗液のハジキや泳ぎムラといった塗布欠陥を減らして、より一層均一な帯電防止層を得ることができる。また、このため、スメクタイト粘土やヘクトライト粘土を含んだ塗液を高速で塗布することも可能となり、高速での塗布においても十分な塗布量を得ることができ、更なる塗布速度の高速化することができる。しかも、上述の通り、帯電防止層用塗液の保水性に優れるため、塗液中の水が紙へ浸透する速度を抑えて、ウェット張力切れによる紙切れ発生を効果的に抑えることができる。一般に支持体として紙支持体を用いる場合、透気度は、例えば、原紙を構成するパルプのフリーネス、填料等の灰分の添加率等を変更することにより調節することができる。透気度を５０秒以下に調節するには、パルプのＣ．Ｓ．Ｆフリーネスを４００ｍｌ以上とすることが好ましい。ここで、透気度は、ＪＩＳ Ｐ ８１１７：２００９に準じて測定される王研式透気度である。 The support preferably has an air permeability of 50 seconds or less. In the present invention, the lower the air permeability (the smaller the numerical value), the higher the absorbability of the coating liquid and the sufficient penetration of the coating liquid into the support. By reducing coating defects such as unevenness, a more uniform antistatic layer can be obtained. For this reason, it is also possible to apply a coating liquid containing smectite clay or hectorite clay at high speed, and a sufficient application amount can be obtained even at high speed application, further increasing the application speed. be able to. In addition, as described above, the antistatic layer coating liquid is excellent in water retention, and therefore, the speed at which water in the coating liquid permeates into the paper can be suppressed, and the occurrence of paper breakage due to wet tension breakage can be effectively suppressed. In general, when a paper support is used as the support, the air permeability can be adjusted, for example, by changing the freeness of pulp constituting the base paper, the addition rate of ash such as filler, and the like. To adjust the air permeability to 50 seconds or less, the pulp C.I. S. The F freeness is preferably 400 ml or more. Here, the air permeability is the Oken air permeability measured according to JIS P 8117: 2009.
本発明の感熱記録層は、塩基性染料、呈色剤、バインダー等を含有する。塩基性染料としては、各種公知の無色または淡色の塩基性染料が挙げられる。例えば、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、３，３−ビス（ｐ−ジメチルアミノフェニル）フタリド、３−（ｐ−ジメチルアミノフェニル）−３−（１，２−ジメチルインドール−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、３，３−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、３，３−ビス（９−エチルカルバゾール−３−イル）−６−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）−６−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−３−イル）−６−ジメチルアミノフタリド等のトリアリルメタン系染料、４，４’−ビス−ジメチルアミノベンズヒドリルベンジルエーテル、Ｎ−ハロフェニル−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のジフェニルメタン系染料、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のチアジン系染料、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−フェニル−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−（６’−メトキシベンゾ）スピロピラン、３−プロピル−スピロ−ジベンゾピラン等のスピロ系染料、ローダミン−Ｂアニリノラクタム、ローダミン（ｐ−ニトロアニリノ）ラクタム、ローダミン（ｏ−クロロアニリノ）ラクタム等のラクタム系染料、３−ジメチルアミノ−７−メトキシフルオラン、３−ジエチルアミノ−６−メトキシフルオラン、３−ジエチルアミノ−７−メトキシフルオラン、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−メチル−７−クロロフルオラン、３−ジエチルアミノ−６，７−ジメチルフルオラン、３−（Ｎ−エチル−ｐ−トルイジノ）−７−メチルフルオラン、３−ジエチルアミノ−７−Ｎ−アセチル−Ｎ−メチルアミノフルオラン、３−ジエチルアミノ−７−Ｎ−メチルアミノフルオラン、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−Ｎ−メチル−Ｎ−ベンジルアミノフルオラン、３−ジエチルアミノ−７−Ｎ−クロロエチル−Ｎ−メチルアミノフルオラン、３−ジエチルアミノ−７−Ｎ−ジエチルアミノフルオラン、３−（Ｎ−エチル−ｐ−トルイジノ）−６−メチル−７−アニリノフルオラン、３−（Ｎ−エチル−ｐ−トルイジノ）−６−メチル−７−（ｐ−トルイジノ）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−７−（２−カルボメトキシ−アニリノ）フルオラン、３−（Ｎ−シクロヘキシル−Ｎ−メチルアミノ）−６−メチル−７−アニリノフルオラン、３−ピロリジノ−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−ジエチルアミノ−６−メチル−７−キシリジノフルオラン、３−ジエチルアミノ−７−（ｏ−クロロアニリノ）フルオラン、３−ジブチルアミノ−７−（ｏ−クロロアニリノ）フルオラン、３−ピロリジノ−６−メチル−７−ｐ−ブチルアニリノフルオラン、３−ジエチルアミノ−７−（ｏ−フルオロアニリノ）フルオラン、３−ジブチルアミノ−７−（ｏ−フルオロアニリノ）フルオラン、３−（Ｎ−メチル−Ｎ−ｎ−アミル）アミノ−６−メチル−７−アニリノフルオラン、３−（Ｎ−エチル−Ｎ−ｎ−アミル）アミノ−６−メチル−７−アニリノフルオラン、３−（Ｎ−エチル−Ｎ−ｉｓｏ−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−Ｎ−ｎ−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−Ｎ−ｎ−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−Ｎ−β−エチルヘキシル）アミノ−６−メチル−７−アニリノフルオラン等のフルオラン系染料等が挙げられる。なお、これらの塩基性染料は必要に応じて２種以上を併用することができる。 The heat-sensitive recording layer of the present invention contains a basic dye, a colorant, a binder and the like. Examples of the basic dye include various known colorless or light-colored basic dyes. For example, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3,3-bis (p-dimethylaminophenyl) phthalide, 3- (p-dimethylaminophenyl) -3- (1 , 2-Dimethylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-methylindol-3-yl) phthalide, 3,3-bis (1,2-dimethylindole-3) -Yl) -5-dimethylaminophthalide, 3,3-bis (1,2-dimethylindol-3-yl) -6-dimethylaminophthalide, 3,3-bis (9-ethylcarbazol-3-yl) ) -6-dimethylaminophthalide, 3,3-bis (2-phenylindol-3-yl) -6-dimethylaminophthalide, 3-p-dimethylaminophenyl-3- (1) Triarylmethane dyes such as methylpyrrol-3-yl) -6-dimethylaminophthalide, 4,4′-bis-dimethylaminobenzhydrylbenzyl ether, N-halophenyl-leucooramine, N-2,4 Diphenylmethane dyes such as 1,5-trichlorophenyl leucooramine, thiazine dyes such as benzoyl leucomethylene blue and p-nitrobenzoyl leucomethylene blue, 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3-phenyl- Spiro dyes such as spiro-dinaphthopyran, 3-benzyl-spiro-dinaphthopyran, 3-methyl-naphtho- (6′-methoxybenzo) spiropyran, 3-propyl-spiro-dibenzopyran, rhodamine-B anilinolactam, rhodamine ( p-nitro Nilino) lactam, lactam dyes such as rhodamine (o-chloroanilino) lactam, 3-dimethylamino-7-methoxyfluorane, 3-diethylamino-6-methoxyfluorane, 3-diethylamino-7-methoxyfluorane, 3- Diethylamino-7-chlorofluorane, 3-diethylamino-6-methyl-7-chlorofluorane, 3-diethylamino-6,7-dimethylfluorane, 3- (N-ethyl-p-toluidino) -7-methylfluor Oran, 3-diethylamino-7-N-acetyl-N-methylaminofluorane, 3-diethylamino-7-N-methylaminofluorane, 3-diethylamino-7-dibenzylaminofluorane, 3-diethylamino-7- N-methyl-N-benzylaminofluorane, 3-diethylamino -7-N-chloroethyl-N-methylaminofluorane, 3-diethylamino-7-N-diethylaminofluorane, 3- (N-ethyl-p-toluidino) -6-methyl-7-anilinofluorane, 3 -(N-ethyl-p-toluidino) -6-methyl-7- (p-toluidino) fluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-7- (2-carbomethoxy) -Anilino) fluorane, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3-piperidino-6 Methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-xylidinofluorane, 3-diethylamino-7- (o-chloroa Lino) fluorane, 3-dibutylamino-7- (o-chloroanilino) fluorane, 3-pyrrolidino-6-methyl-7-p-butylanilinofluorane, 3-diethylamino-7- (o-fluoroanilino) fluorane 3-dibutylamino-7- (o-fluoroanilino) fluorane, 3- (N-methyl-Nn-amyl) amino-6-methyl-7-anilinofluorane, 3- (N-ethyl- N-n-amyl) amino-6-methyl-7-anilinofluorane, 3- (N-ethyl-N-iso-amyl) amino-6-methyl-7-anilinofluorane, 3- (N- Methyl-Nn-hexyl) amino-6-methyl-7-anilinofluorane, 3- (N-ethyl-Nn-hexyl) amino-6-methyl-7-anilinofluorane, 3- ( N Ethyl -N-beta-ethylhexyl) fluoran dyes such as amino-6-methyl-7-anilinofluoran and the like. In addition, these basic dyes can use 2 or more types together as needed.
また、呈色剤としては、上記塩基性染料と熱時接触して呈色する無機または有機の酸性物質が挙げられる。例えば、４−ｔｅｒｔ−ブチルフェノール、α−ナフトール、β−ナフトール、４−アセチルフェノール、４−フェニルフェノール、ハイドロキノン、４，４’−イソプロピリデンジフェノール（ビスフェノールＡ）、２，２’−メチレンビス（４−クロルフェノール）、４，４’−シクロヘキシリデンジフェノール、１，３−ジ〔２−（４−ヒドロキシフェニル）−２−プロピル〕ベンゼン、４，４’−ジヒドロキシジフェニルサルファイド、ビス（３−アリル−４−ヒドロキシフェニル）スルホン、４−ヒドロキシ−４’−イソプロポキシジフェニルスルホン、４，４’−ジヒドロキシジフェニルスルホン、２，４’−ジヒドロキシジフェニルスルホン、ヒドロキシノンモノベンジルエーテル、４−ヒドロキシベンゾフェノン、２，４−ジヒドロキシベンゾフェノン、２，４，４’−トリヒドロキシベンゾフェノン、２，２’，４，４’−テトラヒドロキシベンゾフェノン、Ｎ−ｐ−トルエンスルホニル−Ｎ’−３−（ｐ−トルエンスルホニルオキシ）フェニルウレア、４，４’−ビス［（４−メチル−３−フェノキシカルボニルアミノフェニル）ウレイド］ジフェニルスルホン、４，４’−ビス（ｐ−トルエンスルホニルアミノカルボニルアミノ）ジフェニルメタン、４−ヒドロキシフタル酸ジメチル、４−ヒドロキシ安息香酸メチル、４−ヒドロキシ安息香酸エチル、４−ヒドロキシ安息香酸プロピル、４−ヒドロキシ安息香酸−ｓｅｃ−ブチル、４−ヒドロキシ安息香酸ペンチル、４−ヒドロキシ安息香酸フェニル、４−ヒドロキシ安息香酸ベンジル、４−ヒドロキシ安息香酸トリル、４−ヒドロキシ安息香酸クロロフェニル、４−ヒドロキシ安息香酸フェニルプロピル、４−ヒドロキシ安息香酸フェネチル、４− ヒドロキシ安息香酸−ｐ−クロロベンジル、４−ヒドロキシ安息香酸−ｐ−メトキシベンジル、ノボラック型フェノール樹脂、フェノール重合体等のフェノール性化合物、安息香酸、ｐ−ｔｅｒｔ−ブチル安息香酸、トリクロル安息香酸、テレフタル酸、３−ｓｅｃ−ブチル−４−ヒドロキシ安息香酸、３−シクロヘキシル−４−ヒドロキシ安息香酸、３，５−ジメチル−４−ヒドロキシ安息香酸、サリチル酸、３−イソプロピルサリチル酸、３−ｔｅｒｔ−ブチルサリチル酸、３−ベンジルサリチル酸、３−（α−メチルベンジル）サリチル酸、３−クロル−５−（α−メチルベンジル）サリチル酸、３，５−ジ−ｔｅｒｔ−ブチルサリチル酸、３−フェニル−５−（α，α−ジメチルベンジル）サリチル酸、３，５−ジ−α−メチルベンジルサリチル酸等の芳香族カルボン酸、及びこれらフェノール性化合物、芳香族カルボン酸と例えば亜鉛、マグネシウム、アルミニウム、カルシウム、チタン、マンガン、スズ、ニッケル等の多価金属との塩等の有機酸性物質等が例示される。これらの呈色剤も勿論必要に応じて２種以上を併用することができる。 Examples of the colorant include inorganic or organic acidic substances that are colored by contact with the basic dye when heated. For example, 4-tert-butylphenol, α-naphthol, β-naphthol, 4-acetylphenol, 4-phenylphenol, hydroquinone, 4,4′-isopropylidenediphenol (bisphenol A), 2,2′-methylenebis (4 -Chlorophenol), 4,4'-cyclohexylidene diphenol, 1,3-di [2- (4-hydroxyphenyl) -2-propyl] benzene, 4,4'-dihydroxydiphenyl sulfide, bis (3-allyl) -4-hydroxyphenyl) sulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfone, 2,4'-dihydroxydiphenylsulfone, hydroxynon monobenzyl ether, 4-hydroxybenzophenone, 2 , 4-Di Hydroxybenzophenone, 2,4,4′-trihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, Np-toluenesulfonyl-N′-3- (p-toluenesulfonyloxy) phenylurea, 4,4′-bis [(4-methyl-3-phenoxycarbonylaminophenyl) ureido] diphenylsulfone, 4,4′-bis (p-toluenesulfonylaminocarbonylamino) diphenylmethane, dimethyl 4-hydroxyphthalate, 4- Methyl hydroxybenzoate, ethyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate, 4-hydroxybenzoate-sec-butyl, pentyl 4-hydroxybenzoate, phenyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 4-hydroxy-benzo Acid tolyl, chlorophenyl 4-hydroxybenzoate, phenylpropyl 4-hydroxybenzoate, phenethyl 4-hydroxybenzoate, 4-hydroxybenzoic acid-p-chlorobenzyl, 4-hydroxybenzoic acid-p-methoxybenzyl, novolak type phenol Resins, phenolic compounds such as phenol polymers, benzoic acid, p-tert-butylbenzoic acid, trichlorobenzoic acid, terephthalic acid, 3-sec-butyl-4-hydroxybenzoic acid, 3-cyclohexyl-4-hydroxybenzoic acid 3,5-dimethyl-4-hydroxybenzoic acid, salicylic acid, 3-isopropylsalicylic acid, 3-tert-butylsalicylic acid, 3-benzylsalicylic acid, 3- (α-methylbenzyl) salicylic acid, 3-chloro-5- (α -Methylbenzyl) salicyl Aromatic carboxylic acids such as 3,5-di-tert-butylsalicylic acid, 3-phenyl-5- (α, α-dimethylbenzyl) salicylic acid, 3,5-di-α-methylbenzylsalicylic acid, and their phenolic properties Examples thereof include organic acidic substances such as salts of compounds, aromatic carboxylic acids and polyvalent metals such as zinc, magnesium, aluminum, calcium, titanium, manganese, tin and nickel. Of course, these colorants can also be used in combination of two or more as required.
塩基性染料と呈色剤の使用比率は、用いられる塩基性染料や呈色剤の種類に応じて適宜選択されるもので、特に限定するものではないが、一般に塩基性染料１質量部に対して１〜２０質量部、好ましくは２〜１０質量部程度の呈色剤が使用される。 The use ratio of the basic dye and the colorant is appropriately selected according to the type of the basic dye and the colorant used, and is not particularly limited, but is generally 1 part by mass of the basic dye. 1 to 20 parts by weight, preferably about 2 to 10 parts by weight of the colorant is used.
塩基性染料と呈色剤を含む感熱記録層用塗液は、一般に水を分散媒体とし、ボールミル、アトライター、サンドミル等の攪拌、粉砕機により塩基性染料と呈色剤とを一緒に、または別々に分散する等して得られた分散液を用いて調製される。 The heat-sensitive recording layer coating solution containing a basic dye and a colorant generally uses water as a dispersion medium, agitation such as a ball mill, an attritor or a sand mill, and a basic dye and a colorant together with a pulverizer, or It is prepared using a dispersion obtained by dispersing separately.
感熱記録層用塗液中には、通常バインダーとして澱粉類、ヒドロキシエチルセルロース、メチルセルロース、カルボキシメチルセルロース、ゼラチン、カゼイン、アラビアゴム、ポリビニルアルコール、アセトアセチル変性ポリビニルアルコール、ジアセトン変性ポリビニルアルコール、カルボキシ変性ポリビニルアルコール、珪素変性ポリビニルアルコール、ジイソブチレン−無水マレイン酸共重合体塩、スチレン−無水マレイン酸共重合体塩、エチレン−アクリル酸共重合体塩、スチレン−アクリル酸共重合体塩、スチレン−ブタジエン共重合体エマルジョン、尿素樹脂、メラミン樹脂、アミド樹脂等が、感熱記録層の全固形量中２〜４０質量％程度、好ましくは５〜２５質量％程度用いられる。 In the heat-sensitive recording layer coating liquid, starch, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, gum arabic, polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, Silicon-modified polyvinyl alcohol, diisobutylene-maleic anhydride copolymer salt, styrene-maleic anhydride copolymer salt, ethylene-acrylic acid copolymer salt, styrene-acrylic acid copolymer salt, styrene-butadiene copolymer Emulsions, urea resins, melamine resins, amide resins and the like are used in an amount of about 2 to 40% by mass, preferably about 5 to 25% by mass, based on the total solid content of the thermosensitive recording layer.
更に、感熱記録層用塗液中には必要に応じて各種の助剤を添加することができ、例えばジオクチルスルホコハク酸ナトリウム、ドデシルベンゼンスルホン酸ナリウム、ラウリルアルコール硫酸エステル−ナトリウム塩、脂肪酸金属塩等の分散剤、ベンゾフェノン系等の紫外線吸収剤、その他消泡剤、蛍光染料、着色染料等が適宜添加される。 Furthermore, various auxiliary agents can be added to the coating solution for the heat-sensitive recording layer as necessary. For example, sodium dioctylsulfosuccinate, sodium dodecylbenzenesulfonate, lauryl alcohol sulfate-sodium salt, fatty acid metal salt, etc. A dispersing agent, a benzophenone-based ultraviolet absorber, other antifoaming agents, fluorescent dyes, colored dyes and the like are appropriately added.
また、必要に応じてステアリン酸亜鉛、ステアリン酸カルシウム、ポリエチレンワックス、カルナバロウ、パラフィンワックス、エステルワックス等のワックス類、ステアリン酸アミド、ステアリン酸メチレンビスアミド、パルミチン酸アミド、ヤシ脂肪酸アミド等の脂肪酸アミド類、２，２’−メチレンビス（４−メチル−６−ｔｅｒｔ−ブチルフェノール）、１，１，３−トリス（２−メチル−４−ヒドロキシ−５−ｔｅｒｔ−ブチルフェニル）ブタン等のヒンダードフェノール類、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−ヒドロキシ−４−ベンジルオキシベンゾフェノン等の紫外線吸収剤、１，２−ジ（３−メチルフェノキシ）エタン、１，２−ジフェノキシエタン、１−フェノキシ−２−（４−メチルフェノキシ）エタン、テレフタル酸ジメチルエステル、テレフタル酸ジブチルエステル、テレフタル酸ジベンジルエステル、ｐ−ベンジルビフェニル、１，４−ジメトキシナフタレン、１，４−ジエトキシナフタレン、１−ヒドロキシナフトエ酸フェニルエステル等のエステル類、更には各種公知の熱可融性物質やカオリン、クレー、タルク、炭酸カルシウム、焼成クレー、酸化チタン、珪藻土、微粒子状無水シリカ、活性白土等の無機顔料を添加することもできる。また、本発明の所望の効果を損なわない範囲で通常の導電性物質を添加することもできる。 In addition, if necessary, waxes such as zinc stearate, calcium stearate, polyethylene wax, carnauba wax, paraffin wax, ester wax, stearic acid amide, stearic acid methylenebisamide, palmitic acid amide, coconut fatty acid amide and other fatty acid amides, Hindered phenols such as 2,2′-methylenebis (4-methyl-6-tert-butylphenol) and 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane; UV absorbers such as-(2'-hydroxy-5'-methylphenyl) benzotriazole and 2-hydroxy-4-benzyloxybenzophenone, 1,2-di (3-methylphenoxy) ethane, 1,2-diphenoxy Ethane, 1-phenoxy-2- (4- Tilphenoxy) ethane, terephthalic acid dimethyl ester, terephthalic acid dibutyl ester, terephthalic acid dibenzyl ester, p-benzylbiphenyl, 1,4-dimethoxynaphthalene, 1,4-diethoxynaphthalene, 1-hydroxynaphthoic acid phenyl ester, etc. Esters may be added to various known heat-fusible substances and inorganic pigments such as kaolin, clay, talc, calcium carbonate, calcined clay, titanium oxide, diatomaceous earth, fine particulate anhydrous silica, activated clay and the like. Moreover, a normal electroconductive substance can also be added in the range which does not impair the desired effect of this invention.
本発明の感熱記録体において、感熱記録層の形成方法については特に限定されるものではなく、例えばバーコーティング、エアナイフコーティング、ブレードコーティング等により、感熱記録層用塗液を支持体の一方の面に塗布及び乾燥する方法等によって形成される。また、塗布量についても特に限定されるものではなく、通常乾燥重量で１〜２０ｇ／ｍ２程度、より好ましくは２〜１０ｇ／ｍ２程度の範囲で調節される。 In the thermosensitive recording material of the present invention, the method for forming the thermosensitive recording layer is not particularly limited. For example, the coating solution for the thermosensitive recording layer is applied to one surface of the support by bar coating, air knife coating, blade coating or the like. It is formed by a method of applying and drying. The coating amount is not particularly limited, and is usually adjusted in the range of about 1 to 20 g / m 2 , more preferably about 2 to 10 g / m 2 in terms of dry weight.
本発明では、感熱記録層上に保護層を設けてもよい。これにより、記録走行性、耐摩擦カブリ性、耐薬品性等を向上させることができる。 In the present invention, a protective layer may be provided on the thermosensitive recording layer. As a result, it is possible to improve the recording running property, the anti-friction fog property, the chemical resistance and the like.
保護層は、例えば、水を媒体とし、バインダー、必要により顔料、架橋剤、ワックス、滑剤等を混合することにより調製された保護層用塗液を、乾燥後の塗布量が好ましくは０．５〜１０ｇ／ｍ２程度、より好ましくは１〜５ｇ／ｍ２となるように感熱記録層上に塗布及び乾燥して形成される。バインダーとしては、感熱記録層用塗液に使用できるものの中から適宜選択することができる。 The protective layer is, for example, a coating amount for the protective layer prepared by mixing water, a binder, and optionally a pigment, a crosslinking agent, a wax, a lubricant, etc. to 10 g / m 2, more preferably about formed by applying and drying a heat-sensitive recording layer so that 1 to 5 g / m 2. The binder can be appropriately selected from those that can be used for the thermal recording layer coating liquid.
本発明では、必要に応じて、支持体と感熱記録層との間に、下塗層を設けることもできる。これにより、記録感度をより高めることができる。下塗層は、吸油量が７０ｍｌ／１００ｇ以上、特に８０〜１５０ｍｌ／１００ｇ程度の吸油性顔料、及び／または有機中空粒子、及び／または熱膨張性粒子、並びにバインダーを含有する下塗層用塗液を支持体上に塗布及び乾燥して形成される。ここで、吸油量はＪＩＳ Ｋ ５１０１に記載の方法に従い、求められる値である。下塗層用塗液の塗布量は、乾燥重量で３〜２０ｇ／ｍ２程度が好ましく、４〜１２ｇ／ｍ２程度がより好ましい。 In the present invention, an undercoat layer can be provided between the support and the heat-sensitive recording layer as necessary. Thereby, the recording sensitivity can be further increased. The undercoat layer comprises an oil-absorbing pigment having an oil absorption of 70 ml / 100 g or more, particularly about 80 to 150 ml / 100 g, and / or organic hollow particles and / or thermally expandable particles, and a binder. It is formed by applying and drying a liquid on a support. Here, the oil absorption is a value determined according to the method described in JIS K 5101. The coating amount of the undercoat layer coating solution is preferably about 3 to 20 g / m 2 by dry weight, and more preferably about 4 to 12 g / m 2 .
下塗層中のバインダーとしては、感熱記録層に使用できるものの中から適宜選択することができる。これらのバインダーの中でも、澱粉−酢酸ビニルグラフト共重合体、ポリビニルアルコール、スチレン−ブタジエン系ラテックス等が好ましい。 The binder in the undercoat layer can be appropriately selected from those usable in the heat-sensitive recording layer. Among these binders, starch-vinyl acetate graft copolymer, polyvinyl alcohol, styrene-butadiene latex and the like are preferable.
更に、本発明では、各層を形成した後、または全ての層を形成し終えた後の任意の過程でスーパーカレンダーによる平滑化処理を施すこともできる。本発明の感熱記録体には、感熱記録体の裏面に粘着剤処理を施して粘着ラベルに加工したり、インクジェット記録適性を付与したりする等、感熱記録体の製造分野における各種の公知技術が必要に応じて付加し得るものである。 Furthermore, in the present invention, a smoothing process using a super calendar can be performed in an arbitrary process after forming each layer or after all layers have been formed. The heat-sensitive recording material of the present invention has various known techniques in the field of manufacturing a heat-sensitive recording material, such as applying a pressure-sensitive adhesive treatment to the back surface of the heat-sensitive recording material to process it into a pressure-sensitive adhesive label or imparting ink jet recording suitability. It can be added as necessary.
本発明を実施例により更に詳しく説明するが、本発明はこれらにより限定されるものではない。なお、特に断わらない限り、「部」及び「％」は、それぞれ「質量部」及び「質量％」を示す。 The present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, “part” and “%” indicate “part by mass” and “% by mass”, respectively.
実施例及び比較例で使用した分散液の平均粒子径は、レーザー回折式粒度分布測定装置ＳＡＬＤ２２００（島津製作所社製）を用いて体積平均粒子径を測定した。 The average particle size of the dispersions used in Examples and Comparative Examples was measured using a laser diffraction particle size distribution analyzer SALD2200 (manufactured by Shimadzu Corporation).
実施例１
・紙支持体の作製
ＮＢＫＰ（Ｃ．Ｓ．Ｆ．５５０ｍｌ）２５部、ＬＢＫＰ（Ｃ．Ｓ．Ｆ．５６０ｍｌ）７５部を配合したパルプスラリーに、填料としてカオリンを紙灰分が５．０％になるように添加し、更に、サイズ剤としてロジンサイズを絶乾パルプに対して１．５％、硫酸アルミニウム２．０％を添加して紙料とした。この紙料を長網多筒式シリンダードライヤー抄紙機で抄紙し、４段スーパーカレンダーで処理して５８ｇ／ｍ２の紙支持体を得た。この紙支持体の王研式透気度は、１０秒であった。
Example 1
・ Preparation of paper support In a pulp slurry containing 25 parts of NBKP (C.S.F. 550 ml) and 75 parts of LBKP (C.S.F. 560 ml), kaolin as a filler is reduced to 5.0%. Furthermore, the rosin size as a sizing agent was added to 1.5% and 2.0% of aluminum sulfate with respect to the absolutely dry pulp to obtain a paper stock. This stock was made with a long mesh multi-cylinder cylinder dryer and processed with a 4-stage super calender to obtain a paper support of 58 g / m 2 . This paper support had a Oken air permeability of 10 seconds.
・下塗層用塗液の調製
焼成カオリン（商品名：アンシレックス９３、ＢＡＳＦ社製）６０部を水８０部に分散して得られた分散物に、微小中空粒子（商品名：ローペイクＳＮ−１０５５、ローム＆ハース社製、固形分濃度２６．５％）７５部、スチレン・ブタジエン系ラテックス（商品名：Ｌ−１５７１、旭化成ケミカルズ社製、固形分濃度４８％）３１部と、カルボキシメチルセルロース（商品名：セロゲン７Ａ、第一工業製薬社製）２．５部、同じくカルボキシメチルセルロース（商品名：セロゲンＡＧガム、第一工業製薬社製）１部、及び水１５．５部からなる組成物を混合攪拌して、下塗層用塗液を得た。
-Preparation of coating solution for undercoat layer Fine hollow particles (trade name: Ropaque SN-) were prepared by dispersing 60 parts of calcined kaolin (trade name: Ansilex 93, manufactured by BASF) in 80 parts of water. 1055, 75 parts by Rohm & Haas, solid content 26.5%), 31 parts styrene-butadiene latex (trade name: L-1571, manufactured by Asahi Kasei Chemicals, solid content 48%), carboxymethylcellulose ( Product name: Serogen 7A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2.5 parts, a composition comprising 1 part of carboxymethyl cellulose (trade name: Serogen AG gum, Daiichi Kogyo Seiyaku Co., Ltd.) and 15.5 parts of water. Mixing and stirring were performed to obtain an undercoat layer coating solution.
・Ａ液（ロイコ染料分散液）調製
３−（Ｎ−エチル−Ｎ−イソアミル）アミノ−６−メチル−７−アニリノフルオラン１０部、メチルセルロースの５％水溶液５部、及び水４０部からなる組成物を、サンドミルで平均粒子径が１μｍになるまで粉砕してＡ液を得た。
Preparation of liquid A (leuco dye dispersion) 3- (N-ethyl-N-isoamyl) amino-6-methyl-7-anilinofluorane 10 parts, 5 parts of 5% aqueous solution of methylcellulose, and 40 parts of water The composition was pulverized with a sand mill until the average particle size became 1 μm to obtain Liquid A.
・Ｂ液（呈色剤分散液）調製
４−ヒドロキシ−４’−イソプロポキシジフェニルスルホン３０部、メチルセルロースの５％水溶液５部、及び水８０部からなる組成物を、サンドミルで平均粒子径が１μｍになるまで粉砕してＢ液を得た。
-Preparation of liquid B (coloring agent dispersion) A composition consisting of 30 parts of 4-hydroxy-4'-isopropoxydiphenylsulfone, 5 parts of a 5% aqueous solution of methylcellulose, and 80 parts of water was mixed with an average particle diameter of 1 [mu] m using a sand mill. The liquid B was obtained by pulverizing.
・Ｃ液（増感剤分散液）調製
１，２−ジ（３−メチルフェノキシ）エタン２０部、メチルセルロースの５％水溶液５部、及び水５５部からなる組成物を、サンドミルで平均粒子径が１．５μｍになるまで粉砕し、Ｃ液を得た。
-Preparation of liquid C (sensitizer dispersion) A composition comprising 20 parts of 1,2-di (3-methylphenoxy) ethane, 5 parts of a 5% aqueous solution of methylcellulose, and 55 parts of water was averaged in a sand mill. The mixture was pulverized to 1.5 μm to obtain liquid C.
・感熱記録層用塗液の調製
Ａ液５５部、Ｂ液１１５部、Ｃ液８０部、ポリビニルアルコールの１０％水溶液８０部、及び炭酸カルシウム３５部からなる組成物を混合攪拌して感熱記録層用塗液を得た。
-Preparation of coating solution for heat-sensitive recording layer A composition comprising 55 parts of liquid A, 115 parts of liquid B, 80 parts of liquid C, 80 parts of a 10% aqueous solution of polyvinyl alcohol, and 35 parts of calcium carbonate was mixed and stirred to produce a heat-sensitive recording layer. A coating solution was obtained.
・保護層用塗液の調製
アセトアセチル変性ポリビニルアルコールの１０％水溶液２００部、カオリン（商品名：ＵＷ−９０、ＢＡＳＦ社製）１００部、ステアリン酸亜鉛の３０％水分散液３０部、及び水１００部からなる組成物を混合攪拌して保護層用塗液を得た。
-Preparation of coating liquid for protective layer 200 parts of 10% aqueous solution of acetoacetyl-modified polyvinyl alcohol, 100 parts of kaolin (trade name: UW-90, manufactured by BASF), 30 parts of 30% aqueous dispersion of zinc stearate, and water A composition comprising 100 parts was mixed and stirred to obtain a protective layer coating solution.
・帯電防止層用塗液Ｉの調製
酸化澱粉の８％水溶液（商品名：エースＣ、王子コーンスターチ社製）９０部、ピロリン酸ナトリウム（商品名：ナンカリンＳ１、燐化学工業社製）６部、合成ヘクトライト粘土（商品名：ラポナイトＢ、ロックウッド社製）４５部、及び水６５０部からなる組成物を混合攪拌して、帯電防止層用塗液を得た。
Preparation of coating solution I for antistatic layer 90 parts of 8% aqueous solution of oxidized starch (trade name: Ace C, manufactured by Oji Cornstarch Co., Ltd.), 6 parts of sodium pyrophosphate (trade name: Nankaline S1, manufactured by Phosphor Chemical Industries Co., Ltd.) A composition comprising 45 parts of synthetic hectorite clay (trade name: Laponite B, manufactured by Rockwood) and 650 parts of water was mixed and stirred to obtain a coating solution for an antistatic layer.
・感熱記録体の作製
巻取り状の紙支持体を用いて、紙支持体の裏面に、帯電防止層用塗液Ｉを乾燥後の塗布量が０．５ｇ／ｍ２となるように、アプリケーターロール表面に幅３μｍのクラックが無数に存在するリバースロールコーターにより、塗工速度５００ｍ／分で塗布及び乾燥して帯電防止層を形成した後、一旦ワインダーに巻き取った。更に、この帯電防止層が形成された巻取り状の紙支持体を用いて、紙支持体の反対側の面に、支持体に近い側から下塗層用塗液、感熱記録層用塗液、及び保護層用塗液の順に乾燥後の塗布量が、それぞれ６．０ｇ／ｍ２、４．５ｇ／ｍ２、及び２．０ｇ／ｍ２となるように塗布及び乾燥して、下塗層、感熱記録層、及び保護層を形成し、保護層表面をスーパーカレンダーで平滑化処理して巻取り状の感熱記録体を得た。
- by the manufacturing winding shape of the paper support of the thermosensitive recording medium, on the back surface of the paper support, the coating solution I antistatic layer as the coating amount after drying of 0.5 g / m 2, the applicator An antistatic layer was formed by coating and drying at a coating speed of 500 m / min with a reverse roll coater having innumerable cracks having a width of 3 μm on the roll surface, and then wound around a winder. Further, by using the roll-shaped paper support on which the antistatic layer is formed, an undercoat layer coating liquid and a thermal recording layer coating liquid are formed on the opposite surface of the paper support from the side close to the support. , and the coating amount after drying in the order of protective layer coating solution, respectively 6.0 g / m 2, was applied and dried so that 4.5 g / m 2, and 2.0 g / m 2, subbing A layer, a heat-sensitive recording layer, and a protective layer were formed, and the surface of the protective layer was smoothed with a super calender to obtain a wound heat-sensitive recording material.
実施例２
実施例１の帯電防止層用塗液の調製において、合成ヘクトライト粘土４５部に代えて、合成スメクタイト粘土（商品名：スメクトンＳＡ−１、クニミネ工業社製）４５部を用いた以外は、実施例１と同様にして感熱記録体を得た。
Example 2
In the preparation of the coating solution for the antistatic layer of Example 1, it was carried out except that 45 parts of synthetic smectite clay (trade name: Smecton SA-1, manufactured by Kunimine Kogyo Co., Ltd.) was used instead of 45 parts of synthetic hectorite clay. A heat-sensitive recording material was obtained in the same manner as in Example 1.
実施例３
・帯電防止層用塗液ＩＩの調製
酸化澱粉の８％水溶液（商品名：エースＣ、王子コーンスターチ社製）１５０部、ピロリン酸ナトリウム（商品名：ナンカリンＳ１、燐化学工業社製）３部、合成ヘクトライト粘土（商品名：ラポナイトＢ、ロックウッド社製）６０部、及び水８００部からなる組成物を混合攪拌して、帯電防止層用塗液を得た。
Example 3
-Preparation of coating solution II for antistatic layer 8 parts aqueous solution of oxidized starch (trade name: Ace C, manufactured by Oji Cornstarch Co., Ltd.), 150 parts of sodium pyrophosphate (trade name: Nankaline S1, manufactured by Phosphor Chemical Industries Co., Ltd.) A composition comprising 60 parts of synthetic hectorite clay (trade name: Laponite B, manufactured by Rockwood) and 800 parts of water was mixed and stirred to obtain a coating solution for an antistatic layer.
・感熱記録体の作製
実施例１の感熱記録体の作製において、帯電防止層用塗液Ｉに代えて、上記の帯電防止層用塗液ＩＩを用いた以外は、実施例１と同様にして感熱記録体を得た。
-Preparation of thermosensitive recording material In the preparation of the thermosensitive recording material of Example 1, in place of the antistatic layer coating solution I, the above antistatic layer coating solution II was used in the same manner as in Example 1, except that A heat-sensitive recording material was obtained.
実施例４
・帯電防止層用塗液ＩＩＩの調製
酸化澱粉の８％水溶液（商品名：エースＣ、王子コーンスターチ社製）１１０部、ピロリン酸ナトリウム（商品名：ナンカリンＳ１、燐化学工業社製）５部、合成ヘクトライト粘土（商品名：ラポナイトＢ、ロックウッド社製）３５部、及び水５００部からなる組成物を混合攪拌して、帯電防止層用塗液ＩＩＩを得た。
Example 4
-Preparation of coating solution III for antistatic layer 110 parts of 8% aqueous solution of oxidized starch (trade name: Ace C, manufactured by Oji Cornstarch Co., Ltd.), 5 parts of sodium pyrophosphate (trade name: Nankaline S1, manufactured by Phosphor Chemical Industries Co., Ltd.) A composition comprising 35 parts of synthetic hectorite clay (trade name: Laponite B, manufactured by Rockwood) and 500 parts of water was mixed and stirred to obtain a coating solution III for an antistatic layer.
・感熱記録体の作製
実施例１の感熱記録体の作製において、帯電防止層用塗液Ｉに代えて、上記の帯電防止層用塗液ＩＩＩを用いた以外は、実施例１と同様にして感熱記録体を得た。
-Preparation of thermosensitive recording material In the preparation of the thermosensitive recording material of Example 1, it was the same as Example 1 except that the above-described antistatic layer coating liquid III was used instead of antistatic layer coating liquid I. A heat-sensitive recording material was obtained.
実施例５
実施例１の紙支持体の作製において、パルプのフリーネスを変更し、ＬＢＫＰ（Ｃ．Ｓ．Ｆ．５６０ｍｌ）７５部に代えて、ＬＢＫＰ（Ｃ．Ｓ．Ｆ．４１０ｍｌ）７５部とした以外は、実施例１と同様にして感熱記録体を得た。この紙支持体の王研式透気度は、５０秒であった。
Example 5
In the production of the paper support of Example 1, the pulp freeness was changed, except that 75 parts of LBKP (C.S.F. 410 ml) was used instead of 75 parts of LBKP (C.S.F. 560 ml). In the same manner as in Example 1, a heat-sensitive recording material was obtained. The paper support was Oken type air permeability of 50 seconds.
比較例１
実施例１の感熱記録体の作製において、帯電防止層を設けなかった以外は、実施例１と同様にして感熱記録体を得た。
Comparative Example 1
A thermosensitive recording material was obtained in the same manner as in Example 1 except that no antistatic layer was provided in the production of the thermosensitive recording material of Example 1.
比較例２
実施例１の帯電防止層用塗液の調製において、酸化澱粉の８％水溶液（商品名：エースＣ、王子コーンスターチ社製）１００部に代えて、ポリビニルアルコールの８％水溶液（商品名：ＰＶＡ１１７、クラレ社製）１００部を用いた以外は、実施例１と同様にして感熱記録体を得た。
Comparative Example 2
In the preparation of the coating solution for the antistatic layer of Example 1, instead of 100 parts of an 8% aqueous solution of oxidized starch (trade name: Ace C, manufactured by Oji Cornstarch), an 8% aqueous solution of polyvinyl alcohol (trade name: PVA117, A thermal recording material was obtained in the same manner as in Example 1 except that 100 parts of Kuraray Co., Ltd. were used.
比較例３
実施例１の帯電防止層用塗液の調製において、ピロリン酸ナトリウム５部に代えて、分散剤としてポリオキシエチレンジステアレート５部を用いた以外は、実施例１と同様にして感熱記録体を得た。
Comparative Example 3
In the preparation of the coating solution for the antistatic layer of Example 1, in the same manner as in Example 1, except that 5 parts of polyoxyethylene distearate was used as a dispersant instead of 5 parts of sodium pyrophosphate, a thermal recording material. Got.
かくして得られた感熱記録体について、以下の評価を行った。その結果を表１に示す。 The thermosensitive recording material thus obtained was evaluated as follows. The results are shown in Table 1.
（裏面の塗布欠陥）
幅５００ｍｍの感熱記録体の裏面に、帯電防止用塗液を５００ｍ／分のスピードにて、長さ１００００ｍの塗布及び乾燥を行った後、裏面に発生した異物や筋状欠陥を目視にて観察し、下記の基準で評価した。
○：異物や筋状欠陥の発生がなく、問題ない。
△：異物や筋状欠陥が散見される。
×：異物や筋状の欠陥の発生が著しく、問題である。
(Reverse coating defect)
After applying a coating solution for antistatic at a speed of 500 m / min to a back surface of a 500 mm wide thermal recording material at a speed of 500 m / min and drying, visually observe foreign matter and streak defects generated on the back surface. And evaluated according to the following criteria.
○: No foreign matter or streak defects are generated and there is no problem.
(Triangle | delta): A foreign material and a streak defect are scattered.
X: The occurrence of foreign matter and streak defects is significant and is a problem.
（アプリケーターロールの目詰まり）
幅５００ｍｍの感熱記録体の裏面に、帯電防止用塗液を５００ｍ／分のスピードにて長さ１００００ｍの塗布を行った後、リバースロールコーターのアプリケーターロール表面の目詰まりに起因するアプリケーターロールへの帯電防止用塗液の濡れ状況を目視にて観察し、下記の基準で評価した。
○：アプリケーターロールの濡れ性は、非常に良好な状態であり、問題なし。
△：アプリケーターロールの濡れ性が若干低下しているが、問題のないレベル。
×：アプリケーターロールの濡れ性が低下著しく、全面に目詰まりが発生しており、使用不可の状態。
(Clogged applicator roll)
After applying the antistatic coating liquid to the back surface of the thermal recording material having a width of 500 mm for a length of 10000 m at a speed of 500 m / min, the applicator roll is coated on the applicator roll due to clogging on the applicator roll surface of the reverse roll coater. The state of wetting of the antistatic coating solution was visually observed and evaluated according to the following criteria.
○: The wettability of the applicator roll is in a very good state and there is no problem.
(Triangle | delta): The level which does not have a problem although the wettability of an applicator roll has fallen a little.
X: The wettability of the applicator roll is remarkably lowered, the entire surface is clogged, and it cannot be used.
（裏面電気抵抗）
シート状に断裁した感熱記録体の裏面の電気抵抗値を以下の条件にて測定し、下記の基準で評価した。
測定機器：ＨＰ製 ＨＰ４３３９Ｂ ＨＩＧＨＲＥＳＩＳＴＡＮＣＥ ＭＥＴＥＲ
測定方法：１００Ｖ、３０ｓｅｃ、５ｋｇ荷重
測定環境：１０℃−１０％ＲＨ
○：裏面の電気抵抗値が１０１４Ω未満であり、問題なし。
×：裏面の電気抵抗値が１０１４Ω以上であり、問題あり。
(Reverse electrical resistance)
The electrical resistance value of the back surface of the thermal recording material cut into a sheet was measured under the following conditions, and evaluated according to the following criteria.
Measuring equipment: HP4339B HIGHRESISTANCE METER made by HP
Measurement method: 100 V, 30 sec, 5 kg load Measurement environment: 10 ° C.-10% RH
○: The electrical resistance value on the back surface is less than 10 14 Ω, and there is no problem.
X: The electrical resistance value on the back surface is 10 14 Ω or more, which is problematic.
本発明の感熱記録体は、支持体の裏面に極めて均一な帯電防止層を備え、且つ低湿度環境から高湿度環境まで外部環境の変化に影響されず、高速記録においても地肌カブリ現象やブロッキング現象を伴うことなく安定した記録が可能であり、且つ製造時の安定性に優れる。このため、本発明の感熱記録体は、ファクシミリやプリンター、更には各種計算機等の記録媒体として幅広い分野で使用できるものである。 The heat-sensitive recording material of the present invention has a very uniform antistatic layer on the back surface of the support, and is not affected by changes in the external environment from a low-humidity environment to a high-humidity environment. Stable recording can be performed without causing any troubles, and the stability during production is excellent. For this reason, the thermosensitive recording material of the present invention can be used in a wide range of fields as a recording medium for facsimiles, printers, and various computers.
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| JP2610682B2 (en) * | 1988-08-22 | 1997-05-14 | 王子製紙株式会社 | Thermal recording medium |
| JP2673260B2 (en) * | 1988-12-23 | 1997-11-05 | 王子製紙株式会社 | Thermal recording medium |
| JP2815954B2 (en) * | 1990-01-10 | 1998-10-27 | 王子製紙株式会社 | Thermal recording medium |
| JPH05177935A (en) * | 1991-12-27 | 1993-07-20 | Kanzaki Paper Mfg Co Ltd | Thermal recording material and its manufacturing method |
| JPH05331798A (en) * | 1992-05-26 | 1993-12-14 | New Oji Paper Co Ltd | Applicator roll for coating |
| JPH0781234A (en) * | 1993-09-13 | 1995-03-28 | New Oji Paper Co Ltd | Heat-sensitive recording paper |
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