JP2012196925A - Heat-sensitive recording medium - Google Patents
Heat-sensitive recording medium Download PDFInfo
- Publication number
- JP2012196925A JP2012196925A JP2011063966A JP2011063966A JP2012196925A JP 2012196925 A JP2012196925 A JP 2012196925A JP 2011063966 A JP2011063966 A JP 2011063966A JP 2011063966 A JP2011063966 A JP 2011063966A JP 2012196925 A JP2012196925 A JP 2012196925A
- Authority
- JP
- Japan
- Prior art keywords
- heat
- tosylureido
- sensitive recording
- mass
- parts
- 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.)
- Granted
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Landscapes
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
Description
本発明は、高記録濃度で、記録部の耐可塑剤性、耐油性に優れ、しかも高温高湿環境下でも地肌カブリが少ない感熱記録体に関する。 The present invention relates to a heat-sensitive recording material having a high recording density, excellent plasticizer resistance and oil resistance of a recording area, and little background fogging even in a high temperature and high humidity environment.
無色乃至は淡色のロイコ染料と該ロイコ染料の電子受容体として作用できる呈色剤とを、熱により反応させて発色させることにより記録像を得るようにした感熱記録体がよく知られている。 A heat-sensitive recording material is known in which a recording image is obtained by reacting a colorless or light-colored leuco dye and a color former capable of acting as an electron acceptor of the leuco dye with heat to cause color development.
このような感熱記録体に用いられる呈色剤としては、記録濃度が高い記録部が得られる一方、記録部以外の地肌部では、所謂地肌カブリの少ない（地肌部の白色度が高い）ものが求められる。
更に、記録部については、種々の環境における長期間の保存性が求められることから、特に耐油性、耐可塑剤性に優れることが求められる。
このような要件を充足すべく、呈色剤、呈色助剤について、種々の提案がなされている。
As the colorant used in such a heat-sensitive recording material, a recording portion having a high recording density can be obtained, while a background portion other than the recording portion has a so-called background fogging (a whiteness of the background portion is high). Desired.
Further, the recording part is required to have excellent oil resistance and plasticizer resistance since long-term storage stability in various environments is required.
In order to satisfy such requirements, various proposals have been made for colorants and color assistants.
例えば、記録部の耐油性、耐可塑剤性に優れた新たな電子受容体として、４，４’−（３−トシルウレイド）ジフェニルメタン、４，４’−（３−トシルウレイド）ジフェニルエーテル、或いは特定のＮ−アリールスルホニル（チオ）尿素類が提案されている（特許文献１及び２参照）。４，４’−（３−トシルウレイド）ジフェニルメタン、４，４’−（３−トシルウレイド）ジフェニルエーテル、或いは前記特定のＮ−アリールスルホニル（チオ）尿素類は、感熱記録層中の含有量を上げるほど、感熱記録体の発色濃度、記録部の耐可塑剤性、耐油性が高くなるが、高温高湿保存下における白紙部の発色（地肌カブリ）が目立ち、高温高湿保存後の画像視認性が低下するという問題があった。 For example, 4,4 ′-(3-tosylureido) diphenylmethane, 4,4 ′-(3-tosylureido) diphenyl ether, or specific N as a new electron acceptor excellent in oil resistance and plasticizer resistance of the recording portion -Arylsulfonyl (thio) ureas have been proposed (see Patent Documents 1 and 2). 4,4 ′-(3-tosylureido) diphenylmethane, 4,4 ′-(3-tosylureido) diphenyl ether, or the specific N-arylsulfonyl (thio) ureas increase the content in the thermosensitive recording layer. The color density of the heat-sensitive recording medium, the plasticizer resistance and oil resistance of the recording area are increased, but the color development (background fogging) of the white paper area under high temperature and high humidity storage is conspicuous, and the image visibility after storage at high temperature and high humidity is reduced. There was a problem to do.
また、呈色剤または呈色剤の一部として、４−アリルオキシ−４’−ヒドロキシジフェニルスルホンの使用（特許文献３参照）が記載されており、更に前記呈色剤と併用して使用する呈色剤として、オリゴマー型呈色剤（特許文献４参照）、４，４’−ジヒドロキシジフェニルスルホン（特許文献５参照）、または２，４’−ジヒドロキシジフェニルスルホン（特許文献６参照）の記載がある。その他に、４−アリルオキシ−４’−ヒドロキシジフェニルスルホンに加えて、ウレアウレタン化合物（特許文献７参照）、特定の増感剤としてｐ−アセチルビフェニル（特許文献８参照）、特定の保存性改良剤としてメチル化メチロールメラミン縮合物（特許文献９参照）を使用した感熱記録体が記載されている。更に、４−アリルオキシ−４’−ヒドロキシジフェニルスルホンに加えて、ロイコ染料，呈色剤及び各種保存安定剤を併用する感熱記録体（特許文献１０参照）が記載されているが、いずれの感熱記録体においても、記録感度及び記録像の保存性について満足のいく特性のものが得られていないのが現状である。 In addition, the use of 4-allyloxy-4′-hydroxydiphenylsulfone (see Patent Document 3) is described as a colorant or a part of the colorant, and further used in combination with the colorant. As the colorant, there is a description of an oligomer type colorant (see Patent Document 4), 4,4′-dihydroxydiphenylsulfone (see Patent Document 5), or 2,4′-dihydroxydiphenylsulfone (see Patent Document 6). . In addition to 4-allyloxy-4′-hydroxydiphenylsulfone, a urea urethane compound (see Patent Document 7), p-acetylbiphenyl (see Patent Document 8) as a specific sensitizer, and a specific preservative improver Describes a heat-sensitive recording material using a methylated methylol melamine condensate (see Patent Document 9). Furthermore, in addition to 4-allyloxy-4′-hydroxydiphenylsulfone, there is described a thermal recording material (see Patent Document 10) in which a leuco dye, a colorant, and various storage stabilizers are used in combination. Even in the case of a human body, no satisfactory characteristics have been obtained with respect to recording sensitivity and storability of recorded images.
本発明は、以上のような事情に鑑みてなされたものであり、その目的とするところは、発色感度が高く、記録部の耐油性、耐可塑剤性が極めて良好であり、しかも高温高湿保存下でも地肌カブリが問題とならない、長期保存性に優れた感熱記録体を提供することにある。 The present invention has been made in view of the circumstances as described above. The object of the present invention is high color development sensitivity, extremely good oil resistance and plasticizer resistance of the recording area, and high temperature and high humidity. An object of the present invention is to provide a thermal recording material excellent in long-term storage, in which background fogging does not become a problem even under storage.
本発明者は、上記課題を解決すべく、鋭意研究を行った結果、下記の技術的事項を基礎として構成される本発明に至ったのである。
（１）支持体上に、ロイコ染料及び呈色剤を含有する感熱記録層を有する感熱記録体において、前記呈色剤として、４，４’−（３−トシルウレイド）ジフェニルメタン、４，４’−（３−（トシルウレイド）ジフェニルエーテル、Ｎ−（ｐ−トシル）−Ｎ'−フェニルウレア及び、ブチル ４−（３−トシルウレイド）ベンゾエートから選ばれる少なくとも１種を含有し、更に４−ヒドロキシ−４’−ｎ−プロポキシジフェニルスルホンを含有することを特徴とする感熱記録体。
（２）前記感熱記録層は、前記感熱記録層全固形分に対して、４，４’−（３−トシルウレイド）ジフェニルメタン、４，４’−（３−（トシルウレイド）ジフェニルエーテル、Ｎ−（ｐ−トシル）−Ｎ'−フェニルウレア及び、ブチル ４−（３−トシルウレイド）ベンゾエートから選ばれる少なくとも１種を５〜２０質量％、及び４−ヒドロキシ−４’−ｎ−プロポキシジフェニルスルホンを１〜１５質量％含有する、（１）に記載の感熱記録体。
As a result of intensive studies to solve the above problems, the present inventor has arrived at the present invention configured on the basis of the following technical matters.
(1) In a heat-sensitive recording material having a heat-sensitive recording layer containing a leuco dye and a colorant on a support, 4,4 ′-(3-tosylureido) diphenylmethane, 4,4′- (3- (tosylureido) diphenyl ether, N- (p-tosyl) -N′-phenylurea) and at least one selected from butyl 4- (3-tosylureido) benzoate, and further 4-hydroxy-4′- A heat-sensitive recording material comprising n-propoxydiphenyl sulfone.
(2) The thermosensitive recording layer is composed of 4,4 ′-(3-tosylureido) diphenylmethane, 4,4 ′-(3- (tosylureido) diphenyl ether, N- (p- Tosyl) -N′-phenylurea and at least one selected from butyl 4- (3-tosylureido) benzoate is 5 to 20% by mass, and 4-hydroxy-4′-n-propoxydiphenylsulfone is 1 to 15% by mass. The heat-sensitive recording material according to (1), comprising:
本発明の感熱記録体は、呈色剤として、４，４’−（３−トシルウレイド）ジフェニルメタン、４，４’−（３−（トシルウレイド）ジフェニルエーテル、Ｎ−（ｐ−トシル）−Ｎ'−フェニルウレア及び、ブチル ４−（３−トシルウレイド）ベンゾエートから選ばれる少なくとも１種を含有し、更に４−ヒドロキシ−４’−ｎ−プロポキシジフェニルスルホンを含有することにより、記録部の耐油性、耐可塑剤性を有すると共に、記録濃度、地肌部の耐熱湿性にも優れている。 In the heat-sensitive recording material of the present invention, 4,4 ′-(3-tosylureido) diphenylmethane, 4,4 ′-(3- (tosylureido) diphenyl ether, N- (p-tosyl) -N′-phenyl is used as a colorant. It contains at least one selected from urea and butyl 4- (3-tosylureido) benzoate, and further contains 4-hydroxy-4′-n-propoxydiphenylsulfone, so that it has oil resistance and plasticizer in the recording area. And has excellent recording density and heat and moisture resistance of the background portion.
本発明の感熱記録体は、支持体上に、ロイコ染料及び呈色剤を含有する感熱記録層を有する感熱記録体において、前記呈色剤として、４，４’−（３−トシルウレイド）ジフェニルメタン、４，４’−（３−（トシルウレイド）ジフェニルエーテル、Ｎ−（ｐ−トシル）−Ｎ'−フェニルウレア及び、ブチル ４−（３−トシルウレイド）ベンゾエートから選ばれる少なくとも１種を含有し、更に４−ヒドロキシ−４’−ｎ−プロポキシジフェニルスルホンを含有するものである。 The heat-sensitive recording material of the present invention is a heat-sensitive recording material having a heat-sensitive recording layer containing a leuco dye and a colorant on a support, and as the colorant, 4,4 ′-(3-tosylureido) diphenylmethane, Containing at least one selected from 4,4 ′-(3- (tosylureido) diphenyl ether, N- (p-tosyl) -N′-phenylurea, and butyl 4- (3-tosylureido) benzoate; It contains hydroxy-4′-n-propoxydiphenylsulfone.
〔支持体〕
本発明の感熱記録体に用いられる支持体としては、特に限定しないが、例えば、中性または酸性の上質紙、合成紙、透明または半透明のプラスチックフィルム、白色のプラスチックフィルム等が挙げられる。支持体の厚みは特に限定しないが、通常、２０〜２００μｍ程度である。
[Support]
The support used in the heat-sensitive recording material of the present invention is not particularly limited, and examples thereof include neutral or acidic high-quality paper, synthetic paper, transparent or translucent plastic film, and white plastic film. Although the thickness of a support body is not specifically limited, Usually, it is about 20-200 micrometers.
〔感熱記録層〕
感熱記録層中には、ロイコ染料と、呈色剤として、４，４’−（３−トシルウレイド）ジフェニルメタン、４，４’−（３−（トシルウレイド）ジフェニルエーテル、Ｎ−（ｐ−トシル）−Ｎ'−フェニルウレア及び、ブチル ４−（３−トシルウレイド）ベンゾエートから選ばれる少なくとも１種が含有されており、更に４−ヒドロキシ−４’−ｎ−プロポキシジフェニルスルホンが含有されている。
以下、各順に説明する。
(Thermosensitive recording layer)
In the heat-sensitive recording layer, leuco dye and, as a colorant, 4,4 ′-(3-tosylureido) diphenylmethane, 4,4 ′-(3- (tosylureido) diphenyl ether, N- (p-tosyl) -N It contains at least one selected from '-phenylurea and butyl 4- (3-tosylureido) benzoate, and further contains 4-hydroxy-4'-n-propoxydiphenylsulfone.
Hereinafter, each will be described in order.
＜ロイコ染料＞
感熱記録層に使用される無色乃至は淡色のロイコ染料としては、各種公知のものが使用でき、具体的には、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−（４−ジエチルアミノ−２−メチルフェニル）−３−（４−ジメチルアミノフェニル）−６−ジメチルアミノフタリド、フルオラン等の青発色性染料、３−（Ｎ−エチル−Ｎ−ｐ−トリル）アミノ−７−Ｎ−メチルアニリノフルオラン、３−ジエチルアミノ−７−アニリノフルオラン、３−ジエチルアミノ−７−ジベンジルアミノフルオラン等の緑発色性染料、３，６−ビス（ジエチルアミノ）フルオラン−γ−アニリノラクタム、３−シクロヘキシルアミノ−６−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−７−クロロフルオラン等の赤発色性染料、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、３−（Ｎ−メチル−Ｎ−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−ジエチルアミノ−６−メチル−７−アニリノフルオラン、３−ジ（ｎ−ブチル）アミノ−６−メチル−７−アニリノフルオラン、３−ジ（ｎ−ペンチル）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−（ｏ−クロロフェニルアミノ）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−（Ｎ−エチル−Ｎ−テトラヒドロフルフリルアミノ）−６−メチル−７−アニリノフルオラン、３−ジエチルアミノ−６−クロロ−７−アニリノフルオラン、３−ジメチルアミノ−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、２，２−ビス｛４−〔６’−（Ｎ−シクロヘキシル−Ｎ−メチルアミノ）−３’−メチルスピロ〔フタリド−３，９’−キサンテン−２’−イルアミノ〕フェニル｝プロパン、３−ジエチルアミノ−７−（３’−トリフルオロメチルフェニル）アミノフルオラン等の黒発色性染料、３，３−ビス〔１−（４−メトキシフェニル）−１−（４−ジメチルアミノフェニル）エチレン−２−イル〕−４，５，６，７−テトラクロロフタリド、３，３−ビス〔１−（４−メトキシフェニル）−１−（４−ピロリジノフェニル）エチレン−２−イル〕−４，５，６，７−テトラクロロフタリド、３−ｐ−（ｐ−ジメチルアミノアニリノ）アニリノ−６−メチル−７−クロロフルオラン、３−ｐ−（ｐ−クロロアニリノ）アニリノ−６−メチル−７−クロロフルオラン、３，６−ビス（ジメチルアミノ）フルオレン−９−スピロ−３’−（６’−ジメチルアミノ）フタリド等の近赤外領域に吸収波長を有する染料等。勿論、これらに限定されるものではなく、また必要に応じて２種以上を併用することもできる。
<Leuco dye>
As the colorless or light-colored leuco dye used in the heat-sensitive recording layer, various known ones can be used. Specifically, for example, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide Blue coloring dyes such as 3- (4-diethylamino-2-methylphenyl) -3- (4-dimethylaminophenyl) -6-dimethylaminophthalide and fluorane, 3- (N-ethyl-Np- Tolyl) amino-7-N-methylanilinofluorane, 3-diethylamino-7-anilinofluorane, 3-diethylamino-7-dibenzylaminofluorane, etc., green coloring dye, 3,6-bis (diethylamino) ) Fluorane-γ-anilinolactam, 3-cyclohexylamino-6-chlorofluorane, 3-diethylamino-6-methyl-7-chlorofluorane Red coloring dyes such as 3-diethylamino-7-chlorofluorane, 3- (N-ethyl-N-isoamyl) amino-6-methyl-7-anilinofluorane, 3- (N-methyl-N-cyclohexyl) ) Amino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-di (n-butyl) amino-6-methyl-7-anilinofluorane, 3-di (n-pentyl) amino-6-methyl-7-anilinofluorane, 3-diethylamino-7- (o-chlorophenylamino) fluorane, 3- (N-ethyl-p-toluidino) -6-methyl -7-anilinofluorane, 3- (N-ethyl-p-toluidino) -6-methyl-7- (p-toluidino) fluorane, 3- (N-ethyl-N-tetrahydrofurfuryl) Amino) -6-methyl-7-anilinofluorane, 3-diethylamino-6-chloro-7-anilinofluorane, 3-dimethylamino-6-methyl-7-anilinofluorane, 3-pyrrolidino-6 -Methyl-7-anilinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 2,2-bis {4- [6 '-(N-cyclohexyl-N-methylamino) -3' Black coloring dyes such as methyl spiro [phthalide-3,9′-xanthen-2′-ylamino] phenyl} propane, 3-diethylamino-7- (3′-trifluoromethylphenyl) aminofluorane, 3,3- Bis [1- (4-methoxyphenyl) -1- (4-dimethylaminophenyl) ethylene-2-yl] -4,5,6,7-tetrachlorophthalide, 3,3-bis [1- ( -Methoxyphenyl) -1- (4-pyrrolidinophenyl) ethylene-2-yl] -4,5,6,7-tetrachlorophthalide, 3-p- (p-dimethylaminoanilino) anilino-6 Methyl-7-chlorofluorane, 3-p- (p-chloroanilino) anilino-6-methyl-7-chlorofluorane, 3,6-bis (dimethylamino) fluorene-9-spiro-3 '-(6' A dye having an absorption wavelength in the near infrared region such as dimethylamino) phthalide; Of course, it is not limited to these, Moreover, 2 or more types can also be used together as needed.
＜呈色剤＞
４，４’−（３−トシルウレイド）ジフェニルメタン、４，４’−（３−（トシルウレイド）ジフェニルエーテル、Ｎ−（ｐ−トシル）−Ｎ'−フェニルウレア及び、ブチル ４−（３−トシルウレイド）ベンゾエートから選ばれる少なくとも１種を感熱記録層中に呈色剤として使用すると、記録部の耐油性、耐可塑剤性に優れた感熱記録体を得ることができ、更に、４−ヒドロキシ−４’−ｎ−プロポキシジフェニルスルホンを呈色剤として併用すると、記録部の耐油性、耐可塑剤性を維持したまま、発色感度を上げるとともに、感熱記録体が高温高湿環境に置かれた時の地肌カブリを防止することができるため、高温高湿環境保存後でも画像の視認性の良好な感熱記録体を得ることができる。
<Coloring agent>
From 4,4 ′-(3-tosylureido) diphenylmethane, 4,4 ′-(3- (tosylureido) diphenyl ether, N- (p-tosyl) -N′-phenylurea and butyl 4- (3-tosylureido) benzoate When at least one selected from the above is used as a colorant in the heat-sensitive recording layer, a heat-sensitive recording material excellent in oil resistance and plasticizer resistance of the recording portion can be obtained, and 4-hydroxy-4′-n. -When propoxydiphenyl sulfone is used as a colorant, the color development sensitivity is improved while maintaining the oil resistance and plasticizer resistance of the recording area, and the background fogging when the thermal recording material is placed in a high-temperature and high-humidity environment. Therefore, it is possible to obtain a heat-sensitive recording material having good image visibility even after storage in a high temperature and high humidity environment.
４，４’−（３−トシルウレイド）ジフェニルメタン、４，４’−（３−（トシルウレイド）ジフェニルエーテル、Ｎ−（ｐ−トシル）−Ｎ'−フェニルウレア及び、ブチル ４−（３−トシルウレイド）ベンゾエートから選ばれる少なくとも１種は、感熱記録層中に、感熱記録層固形分に対して、５〜２０質量％含有することが好ましく、より好ましくは６〜２０質量％、最も好ましくは７〜１８質量％含有される。 From 4,4 ′-(3-tosylureido) diphenylmethane, 4,4 ′-(3- (tosylureido) diphenyl ether, N- (p-tosyl) -N′-phenylurea and butyl 4- (3-tosylureido) benzoate The at least one selected is preferably contained in the heat-sensitive recording layer in an amount of 5 to 20% by weight, more preferably 6 to 20% by weight, and most preferably 7 to 18% by weight, based on the solid content of the heat-sensitive recording layer. Contained.
４，４’−（３−トシルウレイド）ジフェニルメタン、４，４’−（３−（トシルウレイド）ジフェニルエーテル、Ｎ−（ｐ−トシル）−Ｎ'−フェニルウレア及び、ブチル ４−（３−トシルウレイド）ベンゾエートから選ばれる少なくとも１種の感熱記録層中の含有量を５質量％以上とすることで、記録部の耐油性、耐可塑剤性が、より優れた感熱記録体を得ることができ、２０質量％以下とすることで、高温高湿環境に置かれた時の地肌カブリのより少ない感熱記録体を得ることができる。 From 4,4 ′-(3-tosylureido) diphenylmethane, 4,4 ′-(3- (tosylureido) diphenyl ether, N- (p-tosyl) -N′-phenylurea and butyl 4- (3-tosylureido) benzoate By setting the content in at least one selected heat-sensitive recording layer to 5% by mass or more, a heat-sensitive recording material with more excellent oil resistance and plasticizer resistance of the recording part can be obtained, and 20% by mass. By making the following, it is possible to obtain a heat-sensitive recording material with less background fog when placed in a high-temperature and high-humidity environment.
４−ヒドロキシ−４’−ｎ−プロポキシジフェニルスルホンは、感熱記録層中、１〜１５質量％含有することが好ましく、より好ましくは２〜１０質量％、最も好ましくは２〜９質量％である。 4-hydroxy-4'-n-propoxydiphenyl sulfone is preferably contained in the heat-sensitive recording layer in an amount of 1 to 15% by mass, more preferably 2 to 10% by mass, and most preferably 2 to 9% by mass.
４−ヒドロキシ−４’−ｎ−プロポキシジフェニルスルホンの感熱記録層中の含有量を１質量％以上とすることで、発色感度の高い感熱記録体を得ることができ、１５質量％以下とすることで、記録部の耐油性、耐可塑剤性が、より優れた感熱記録体を得ることができる。 When the content of 4-hydroxy-4′-n-propoxydiphenylsulfone in the heat-sensitive recording layer is 1% by mass or more, a heat-sensitive recording material having high color development sensitivity can be obtained, and the content is 15% by mass or less. Thus, it is possible to obtain a heat-sensitive recording material having more excellent oil resistance and plasticizer resistance of the recording portion.
また、前記４，４’−（３−トシルウレイド）ジフェニルメタン、４，４’−（３−（トシルウレイド）ジフェニルエーテル、Ｎ−（ｐ−トシル）−Ｎ'−フェニルウレア及び、ブチル ４−（３−トシルウレイド）ベンゾエートから選ばれる少なくとも１種と４−ヒドロキシ−４’−ｎ−プロポキシジフェニルスルホンの合計含有量が、前記感熱記録層全固形分に対して、９〜２７質量％であることが好ましく、１０〜２５質量％であることがより好ましい。前記呈色剤の合計含有量を感熱記録層全固形分の９質量％以上とすることで実用十分な発色感度を得ることができ、２７質量％以下とすることで、ヘッドカスの発生が少ないプリンタ適性の優れた感熱記録体を得ることができる。 In addition, 4,4 ′-(3-tosylureido) diphenylmethane, 4,4 ′-(3- (tosylureido) diphenyl ether, N- (p-tosyl) -N′-phenylurea, and butyl 4- (3-tosylureido) ) The total content of at least one selected from benzoate and 4-hydroxy-4′-n-propoxydiphenyl sulfone is preferably 9 to 27% by mass with respect to the total solid content of the heat-sensitive recording layer. It is more preferable that the total colorant content is 9% by mass or more based on the total solid content of the heat-sensitive recording layer. By doing so, it is possible to obtain a thermal recording material excellent in printer suitability with less generation of head debris.
前記呈色剤は、各種公知の粉砕処理により平均粒子径０．１〜３．０μｍの粒状にして感熱記録層に含有されることが好ましく、０．３〜１．５μｍの粒状にして感熱記録層に含有されることがより好ましい。 The colorant is preferably contained in the heat-sensitive recording layer in the form of granules having an average particle size of 0.1 to 3.0 μm by various known pulverization treatments, and is made to be 0.3 to 1.5 μm in the form of heat-sensitive recording. More preferably, it is contained in the layer.
また、感熱記録層における４，４’−（３−トシルウレイド）ジフェニルメタン、４，４’−（３−（トシルウレイド）ジフェニルエーテル、Ｎ−（ｐ−トシル）−Ｎ'−フェニルウレア及び、ブチル ４−（３−トシルウレイド）ベンゾエートから選ばれる少なくとも１種に対する４−ヒドロキシ−４’−ｎ−プロポキシジフェニルスルホンの含有比率は、４，４’−（３−トシルウレイド）ジフェニルメタン及び４，４’−（３−トシルウレイド）ジフェニルエーテルから選ばれる少なくとも１種の合計量１００質量％に対し、５〜９０質量％であることが好ましく、より好ましくは１０〜８０質量％であり、最も好ましくは２０〜７０質量％である。 Further, 4,4 ′-(3-tosylureido) diphenylmethane, 4,4 ′-(3- (tosylureido) diphenyl ether, N- (p-tosyl) -N′-phenylurea, and butyl 4- ( The content ratio of 4-hydroxy-4′-n-propoxydiphenyl sulfone to at least one selected from 3-tosylureido) benzoate is 4,4 ′-(3-tosylureido) diphenylmethane and 4,4 ′-(3-tosylureido) ) It is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and most preferably 20 to 70% by mass with respect to 100% by mass of the total amount of at least one selected from diphenyl ether.
４，４’−（３−トシルウレイド）ジフェニルメタン、４，４’−（３−（トシルウレイド）ジフェニルエーテル、Ｎ−（ｐ−トシル）−Ｎ'−フェニルウレア及び、ブチル ４−（３−トシルウレイド）ベンゾエートから選ばれる少なくとも１種の合計量１００質量％に対し、５質量％以上とすることにより、高温高湿保存下の地肌カブリを少なくすることができ、一方、９０質量％以下とすることにより、記録部における耐油性、耐可塑剤性を高めることができる。 From 4,4 ′-(3-tosylureido) diphenylmethane, 4,4 ′-(3- (tosylureido) diphenyl ether, N- (p-tosyl) -N′-phenylurea and butyl 4- (3-tosylureido) benzoate By setting the amount to 5% by mass or more with respect to 100% by mass of the total amount of at least one selected, the background fogging under high temperature and high humidity storage can be reduced, while by setting the amount to 90% by mass or less, recording is performed. Oil resistance and plasticizer resistance in the part can be improved.
本発明で使用する呈色剤は、４，４’−（３−トシルウレイド）ジフェニルメタン、４，４’−（３−（トシルウレイド）ジフェニルエーテル、Ｎ−（ｐ−トシル）−Ｎ'−フェニルウレア及び、ブチル ４−（３−トシルウレイド）ベンゾエートから選ばれる少なくとも１種と、更に４−ヒドロキシ−４’−ｎ−プロポキシジフェニルスルホンを併用するものであるが、必要に応じて、支障のない範囲で各種公知の材料、例えば活性白土、アタパルジャイト、コロイダルシリカ、珪酸アルミニウム等の無機酸性物質、４，４’−イソプロピリデンジフェノール、１，１−ビス（４−ヒドロキシフェニル）−１−フェニルエタン、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン、２，２−ビス（４−ヒドロキシフェニル）−４−メチルペンタン、２，４’−ジヒドロキシジフェニルスルホン、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、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’−ジヒドロキシジフェニルスルフィド、ヒドロキノンモノベンジルエーテル、４−ヒドロキシ安息香酸ベンジル、４，４’−ジヒドロキシジフェニルスルホン、４−ヒドロキシ−４’−イソプロポキシジフェニルスルホン、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’−メチルジフェニルスルホン、４−ヒドロキシフェニル−４’−ベンジルオキシフェニルスルホン、３，４−ジヒドロキシフェニル−４’−メチルフェニルスルホン等のフェノール性化合物、Ｎ，Ｎ’−ジ−ｍ−クロロフェニルチオウレア等のチオ尿素化合物、Ｎ−（ｐ−トルエンスルホニル）カルバモイル酸ｐ−クミルフェニルエステル、Ｎ−（ｐ−トルエンスルホニル）カルバモイル酸ｐ−ベンジルオキシフェニルエステル、Ｎ−（ｏ−トルオイル）−ｐ−トルエンスルホアミド、Ｎ−（ｐ−トルエンスルホニル）−Ｎ’−（ｐ−トリル）尿素等の分子内に−ＳＯ２ＮＨ−結合を有する有機化合物、ｐ−クロロ安息香酸、４−〔２−（ｐ−メトキシフェノキシ）エチルオキシ〕サリチル酸、４−〔３−（ｐ−トリルスルホニル）プロピルオキシ〕サリチル酸、５−〔ｐ−（２−ｐ−メトキシフェノキシエトキシ）クミル〕サリチル酸等の芳香族カルボン酸、及びこれら芳香族カルボン酸の亜鉛、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、更にはチオシアン酸亜鉛のアンチピリン錯体、テレフタルアルデヒド酸と他の芳香族カルボン酸との複合亜鉛塩等の有機酸性物質等を併用することができる。 Coloring agents used in the present invention are 4,4 ′-(3-tosylureido) diphenylmethane, 4,4 ′-(3- (tosylureido) diphenyl ether, N- (p-tosyl) -N′-phenylurea, and Butyl 4- (3-tosylureido) benzoate and 4-hydroxy-4′-n-propoxydiphenyl sulfone are used in combination, but various known types are available as long as there is no problem. Materials such as activated clay, attapulgite, colloidal silica, aluminum silicate and other inorganic acidic substances, 4,4′-isopropylidenediphenol, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1 -Bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) -4-methylpen 2,4′-dihydroxydiphenylsulfone, 4,4′-bis [(4-methyl-3-phenoxycarbonylaminophenyl) ureido] diphenylsulfone, Np-toluenesulfonyl-N′-3- (p- Toluenesulfonyloxy) phenyl urea, 4,4′-dihydroxydiphenyl sulfide, hydroquinone monobenzyl ether, benzyl 4-hydroxybenzoate, 4,4′-dihydroxydiphenyl sulfone, 4-hydroxy-4′-isopropoxydiphenyl sulfone, bis (3-allyl-4-hydroxyphenyl) sulfone, 4-hydroxy-4′-methyldiphenylsulfone, 4-hydroxyphenyl-4′-benzyloxyphenylsulfone, 3,4-dihydroxyphenyl-4′-methylphenylsulfone, etc. Phenolic compound , Thiourea compounds such as N, N′-di-m-chlorophenylthiourea, N- (p-toluenesulfonyl) carbamoyl acid p-cumylphenyl ester, N- (p-toluenesulfonyl) carbamoyl acid p-benzyloxy Organic compounds having —SO 2 NH— bond in the molecule such as phenyl ester, N- (o-toluoyl) -p-toluenesulfoamide, N- (p-toluenesulfonyl) -N ′-(p-tolyl) urea , P-chlorobenzoic acid, 4- [2- (p-methoxyphenoxy) ethyloxy] salicylic acid, 4- [3- (p-tolylsulfonyl) propyloxy] salicylic acid, 5- [p- (2-p-methoxyphenoxy) Ethoxy) cumyl] aromatic carboxylic acids such as salicylic acid, and zinc, magnesium, aluminum of these aromatic carboxylic acids, Combined use of salts with polyvalent metals such as calcium, titanium, manganese, tin, nickel, and organic acid substances such as zinc thiocyanate antipyrine complex, complex zinc salts of terephthalaldehyde acid and other aromatic carboxylic acids, etc. can do.
＜バインダー＞
感熱記録層用塗液中には通常バインダーとして、各種の樹脂が使用される。かかるバインダーとしては、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、アラビアガム、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、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、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、ポリウレタン樹脂等の少なくとも１種が、感熱記録層の全固形分に対して５〜５０質量％程度、特に１０〜４０質量％程度の範囲で配合される。
<Binder>
Various resins are usually used as binders in the thermal recording layer coating solution. Examples of such binders include starches, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, gum arabic, polyvinyl alcohol, carboxy modified polyvinyl alcohol, acetoacetyl modified polyvinyl alcohol, diacetone 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 emulsion, urea resin, melamine resin, At least one of an amide resin and a polyurethane resin is blended in the range of about 5 to 50% by mass, particularly about 10 to 40% by mass with respect to the total solid content of the heat-sensitive recording layer.
＜その他の成分＞
本発明の感熱記録体において、感熱記録層は、前記呈色剤、ロイコ染料及びバインダーに加えて、更に、増感剤、保存性改良剤、その他の各種助剤を含有していてもよい。
<Other ingredients>
In the heat-sensitive recording material of the present invention, the heat-sensitive recording layer may further contain a sensitizer, a storability improving agent and other various auxiliary agents in addition to the color former, leuco dye and binder.
（増感剤）
本発明の感熱記録層中には増感剤を添加してもよく、例えばステアリン酸アミド、メトキシカルボニル−Ｎ−ステアリン酸ベンズアミルド、Ｎ−ベンゾイルステアリン酸アミド、Ｎ−エイコサン酸アミド、エチレンビスステアリン酸アミド、ベヘン酸アミド、メチレンビスステアリン酸アミド、Ｎ−メチロールステアリン酸アミド、テレフタル酸ジベンジル、テレフタル酸ジメチル、テレフタル酸ジオクチル、ｐ−ベンジルオキシ安息香酸ベンジル、１−ヒドロキシ−２−ナフトエ酸フェニル、２−ナフチルベンジルエーテル、ｍ−ターフェニル、ｐ−ベンジルビフェニル、シュウ酸ジ−ｐ−クロロベンジルエステル、シュウ酸ジ−ｐ−メチルベンジルエステル、ｐ−トリルビフェニルエーテル、ジ（ｐ−メトキシフェノキシエチル）エーテル、１，２−ジ（３−メチルフェノキシ）エタン、１，２−ジ（４−メチルフェノキシ）エタン、１，２−ジ（４−メトキシフェノキシ）エタン、１，２−ジ（４−クロロフェノキシ）エタン、１，２−ジフェノキシエタン、１−（４−メトキシフェノキシ）−２−（３−メチルフェノキシ）エタン、ｐ−メチルチオフェニルベンジルエーテル、１，４−ジ（フェニルチオ）ブタン、ｐ−アセトトルイジド、ｐ−アセトフェネチジド、Ｎ−アセトアセチル−ｐ−トルイジン、ジ（β−ビフェニルエトキシ）ベンゼン、ｐ−ジ（ビニルオキシエトキシ）ベンゼン、１−イソプロピルフェニル−２−フェニルエタン等が例示され、支障のない範囲で併用できる。
増感剤を使用する場合、その使用量は、増感のために有効な量とすればよいが、通常は、感熱記録層全固形分に対して２〜４０質量％が好ましく、特に５〜２５質量％程度の範囲で配合されるのがより好ましい。
(Sensitizer)
A sensitizer may be added to the heat-sensitive recording layer of the present invention, such as stearamide, methoxycarbonyl-N-stearic acid benzamyl, N-benzoyl stearamide, N-eicosanoic acid amide, ethylenebisstearic acid. Amides, behenic acid amides, methylenebis stearic acid amides, N-methylol stearic acid amides, dibenzyl terephthalate, dimethyl terephthalate, dioctyl terephthalate, benzyl p-benzyloxybenzoate, phenyl 1-hydroxy-2-naphthoate, 2 -Naphtylbenzyl ether, m-terphenyl, p-benzylbiphenyl, oxalic acid di-p-chlorobenzyl ester, oxalic acid di-p-methylbenzyl ester, p-tolylbiphenyl ether, di (p-methoxyphenoxyethyl) ether 1,2-di (3-methylphenoxy) ethane, 1,2-di (4-methylphenoxy) ethane, 1,2-di (4-methoxyphenoxy) ethane, 1,2-di (4-chlorophenoxy) ) Ethane, 1,2-diphenoxyethane, 1- (4-methoxyphenoxy) -2- (3-methylphenoxy) ethane, p-methylthiophenylbenzyl ether, 1,4-di (phenylthio) butane, p-acetoluidide P-acetophenetide, N-acetoacetyl-p-toluidine, di (β-biphenylethoxy) benzene, p-di (vinyloxyethoxy) benzene, 1-isopropylphenyl-2-phenylethane and the like, Can be used as long as there is no hindrance.
When a sensitizer is used, the amount used may be an effective amount for sensitization, but usually 2 to 40% by mass is preferable with respect to the total solid content of the heat-sensitive recording layer. It is more preferable to blend in the range of about 25% by mass.
（保存性改良剤）
本発明の感熱記録層中には保存性改良剤を添加してもよく、例えば２，２’−メチレンビス（４−メチル−６−ｔｅｒｔ−ブチルフェノール）、２，２’−メチレンビス（４−エチル−６−ｔｅｒｔ−ブチルフェノール）、２，２’−エチリデンビス（４，６−ジ−ｔｅｒｔ−ブチルフェノール）、４，４’−チオビス（２−メチル−６−ｔｅｒｔ−ブチルフェノール）、４，４’−ブチリデンビス（６−ｔｅｒｔ−ブチル−ｍ−クレゾール）、１−〔α−メチル−α−（４’−ヒドロキシフェニル）エチル〕−４−〔α’，α’−ビス（４’−ヒドロキシフェニル）エチル〕ベンゼン、１，１，３−トリス（２−メチル−４−ヒドロキシ−５−シクロヘキシルフェニル）ブタン、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、４，４’−チオビス（３−メチルフェノール）、４，４’−ジヒドロキシ−３，３’，５，５’−テトラブロモジフェニルスルホン、４，４’−ジヒドロキシ−３，３’，５，５’−テトラメチルジフェニルスルホン、２，２−ビス（４−ヒドロキシ−３，５−ジブロモフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３，５−ジクロロフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３，５−ジメチルフェニル）プロパン等のヒンダードフェノール化合物、１，４−ジグリシジルオキシベンゼン、４，４’−ジグリシジルオキシジフェニルスルホン、４−ベンジルオキシ−４’−（２−メチルグリシジルオキシ）ジフェニルスルホン、テレフタル酸ジグリシジル、クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂等のエポキシ化合物、Ｎ，Ｎ’−ジ−２−ナフチル−ｐ−フェニレンジアミン、２，２’−メチレンビス（４，６−ジ−ｔｅｒｔ−ブチルフェニル）ホスフェイトのナトリウムまたは多価金属塩、ビス（４−エチレンイミノカルボニルアミノフェニル）メタン等が挙げられる。
保存性改良剤を使用する場合、その使用量は、保存性改良のために有効な量とすればよいが、通常は、感熱記録層全固形分に対して１〜３０質量％程度、特に５〜２０質量％程度の範囲で配合されるのが好ましい。
(Preservation improver)
In the heat-sensitive recording layer of the present invention, a storability improving agent may be added, for example, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-). 6-tert-butylphenol), 2,2′-ethylidenebis (4,6-di-tert-butylphenol), 4,4′-thiobis (2-methyl-6-tert-butylphenol), 4,4′-butylidenebis (6-tert-butyl-m-cresol), 1- [α-methyl-α- (4′-hydroxyphenyl) ethyl] -4- [α ′, α′-bis (4′-hydroxyphenyl) ethyl] Benzene, 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butyl) Enyl) butane, 4,4′-thiobis (3-methylphenol), 4,4′-dihydroxy-3,3 ′, 5,5′-tetrabromodiphenylsulfone, 4,4′-dihydroxy-3,3 ′ , 5,5'-tetramethyldiphenylsulfone, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2, Hindered phenol compounds such as 2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,4-diglycidyloxybenzene, 4,4′-diglycidyloxydiphenylsulfone, 4-benzyloxy-4 ′ -(2-methylglycidyloxy) diphenylsulfone, diglycidyl terephthalate, cresol novolac epoxy resin, phenol novola Type epoxy resin, epoxy compound such as bisphenol A type epoxy resin, N, N′-di-2-naphthyl-p-phenylenediamine, 2,2′-methylenebis (4,6-di-tert-butylphenyl) Examples include sodium or polyvalent metal salts of phosphate, bis (4-ethyleneiminocarbonylaminophenyl) methane, and the like.
When a preservability improver is used, the amount used may be an effective amount for improving the preservability, but is usually about 1 to 30% by mass, particularly 5 based on the total solid content of the heat-sensitive recording layer. It is preferable to mix in the range of about ˜20% by mass.
また、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トリウム、ラウリルアルコール硫酸エステルナトリウム、脂肪酸金属塩等の分散剤、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、消泡剤、着色染料、及び顔料等が適宜添加される。顔料としては、例えばカオリン、クレー、炭酸カルシウム、焼成クレー、焼成カオリン、酸化チタン、水酸化アルミニウム、珪藻土、微粒子状無水シリカ、活性白土等の無機顔料や、スチレンマイクロボール、ナイロンパウダー、ポリエチレンパウダー、尿素・ホルマリン樹脂フィラー、生澱粉粒子等の有機顔料等が挙げられる。 In addition, various auxiliary agents can be added to the heat-sensitive recording layer coating liquid as necessary. For example, sodium dioctylsulfosuccinate, sodium dodecylbenzenesulfonate, sodium lauryl alcohol sulfate, fatty acid metal salt, etc. Agents, zinc stearate, calcium stearate, polyethylene wax, carnauba wax, paraffin wax, ester wax and other waxes, antifoaming agents, colored dyes, pigments and the like are added as appropriate. Examples of pigments include inorganic pigments such as kaolin, clay, calcium carbonate, calcined clay, calcined kaolin, titanium oxide, aluminum hydroxide, diatomaceous earth, particulate anhydrous silica, activated clay, styrene microballs, nylon powder, polyethylene powder, Examples include urea / formalin resin filler, organic pigments such as raw starch particles.
〔感熱記録層用塗液〕
以上のような成分、即ち、ロイコ染料、４，４’−（３−トシルウレイド）ジフェニルメタン、４，４’−（３−（トシルウレイド）ジフェニルエーテル、Ｎ−（ｐ−トシル）−Ｎ'−フェニルウレア及び、ブチル ４−（３−トシルウレイド）ベンゾエートから選ばれる少なくとも１種、４−ヒドロキシ−４’−ｎ−プロポキシジフェニルスルホン、増感剤、接着成分、更に必要に応じて添加される添加物を、水媒体に分散させてなる塗工液（感熱記録層用塗液）を調製する。なお、一般には水を分散媒体とし、ボールミル、アトライター、サンドミル等の攪拌・粉砕機によりロイコ染料、呈色剤、増感剤等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配合して調製される。
[Coating liquid for thermal recording layer]
Ingredients such as leuco dye, 4,4 '-(3-tosylureido) diphenylmethane, 4,4'-(3- (tosylureido) diphenyl ether, N- (p-tosyl) -N'-phenylurea and , At least one selected from butyl 4- (3-tosylureido) benzoate, 4-hydroxy-4′-n-propoxydiphenylsulfone, a sensitizer, an adhesive component, and, if necessary, an additive added to water Prepare a coating solution (heat-sensitive recording layer coating solution) dispersed in a medium, and generally use water as a dispersion medium, and a leuco dye or colorant using a ball mill, attritor, sand mill, or other agitation / pulverizer. It is prepared by blending a dispersion obtained by dispersing sensitizers or the like together or separately.
〔下塗り層〕
本発明では、必要であれば、支持体と感熱記録層との間に、記録感度をより高めるために、下塗り層を設けることが好ましい。下塗り層は、吸油量が７０ｍｌ／１００ｇ以上、特に８０〜１５０ｍｌ／１００ｇ程度の吸油性顔料、及び／または中空粒子、及び／または熱膨張性粒子、並びに接着剤を主成分とする下塗り層用塗液を支持体上に塗布乾燥して形成される。ここで、前記吸油量はＪＩＳ Ｋ ５１０１に記載の方法に従い求められる値である。
(Undercoat layer)
In the present invention, if necessary, an undercoat layer is preferably provided between the support and the thermosensitive recording layer in order to further increase the recording sensitivity. The undercoat layer has an oil absorption amount of 70 ml / 100 g or more, in particular, about 80 to 150 ml / 100 g of an oil-absorbing pigment, and / or hollow particles, and / or thermally expandable particles, and an undercoat layer coating mainly composed of an adhesive. 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.
前記吸油性顔料としては、各種公知のものが使用できるが、具体例としては、焼成カオリン、無定形シリカ、軽質炭酸カルシウム、タルク等の無機顔料が挙げられる。これら吸油性顔料の一次粒子の平均粒子径は０．０１〜５μｍ程度、特に０．０２〜３μｍ程度であるのが好ましい。吸油性顔料の使用量は、広い範囲から選択できるが、一般に下塗り層全固形分に対して２〜９５質量％程度、特に５〜９０質量％程度であるのが好ましい。 Various known pigments can be used as the oil-absorbing pigment. Specific examples include inorganic pigments such as calcined kaolin, amorphous silica, light calcium carbonate, and talc. The average particle diameter of the primary particles of these oil-absorbing pigments is preferably about 0.01 to 5 μm, particularly about 0.02 to 3 μm. The amount of the oil-absorbing pigment can be selected from a wide range, but generally it is preferably about 2 to 95% by mass, particularly preferably about 5 to 90% by mass with respect to the total solid content of the undercoat layer.
前記中空粒子としては、従来公知のもの、例えば、膜材がアクリル系樹脂、スチレン系樹脂、塩化ビニリデン系樹脂等からなる中空率が５０〜９９％程度の粒子が例示できる。ここで中空率は（ｄ／Ｄ）×１００で求められる値である。該式中、ｄは有機中空粒子の内径を示し、Ｄは有機中空粒子の外径を示す。有機中空粒子の平均粒子径は０．５〜１０μｍ程度、特に１〜３μｍ程度であるのが好ましい。前記有機中空粒子の使用量は、広い範囲から選択できるが、一般に下塗り層全固形分に対して２〜９０質量％程度、特に５〜７０質量％程度であるのが好ましい。 Examples of the hollow particles include conventionally known particles, for example, particles having a hollow ratio of about 50 to 99% in which the film material is made of an acrylic resin, a styrene resin, a vinylidene chloride resin, or the like. Here, the hollowness is a value obtained by (d / D) × 100. In the formula, d represents the inner diameter of the organic hollow particles, and D represents the outer diameter of the organic hollow particles. The average particle diameter of the organic hollow particles is preferably about 0.5 to 10 μm, particularly preferably about 1 to 3 μm. The amount of the organic hollow particles used can be selected from a wide range, but generally it is preferably about 2 to 90% by mass, particularly preferably about 5 to 70% by mass, based on the total solid content of the undercoat layer.
なお、前記吸油性無機顔料を有機中空粒子と併用する場合、吸油性無機顔料と有機中空粒子とは前記使用量範囲で使用し、且つ吸油性無機顔料と有機中空粒子の合計量が下塗り層全固形分に対して、５〜９０質量％程度、特に１０〜８０質量％程度であるのが好ましい。 When the oil-absorbing inorganic pigment is used in combination with the organic hollow particles, the oil-absorbing inorganic pigment and the organic hollow particles are used within the above-mentioned usage amount range, and the total amount of the oil-absorbing inorganic pigment and the organic hollow particles is the entire undercoat layer. The solid content is preferably about 5 to 90% by mass, and more preferably about 10 to 80% by mass.
また、前記接着剤としては、前記感熱記録層に使用される接着剤、特に澱粉−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。
前記接着剤の使用割合は広い範囲で選択できるが、一般には下塗り層全固形分に対して５〜３０質量％程度、特に１０〜２０質量％程度の量で使用するのが好ましい。
The adhesive is preferably an adhesive used for the heat-sensitive recording layer, particularly starch-vinyl acetate graft copolymer, polyvinyl alcohol, styrene-butadiene latex and the like.
The use ratio of the adhesive can be selected within a wide range, but generally it is preferably used in an amount of about 5 to 30% by mass, particularly about 10 to 20% by mass, based on the total solid content of the undercoat layer.
〔保護層〕
本発明の感熱記録体は、感熱記録層上に、可塑剤や油等の薬品に対する記録像の保存性、或いは記録適性を改良する目的で保護層を設けることも出来る。
[Protective layer]
In the heat-sensitive recording material of the present invention, a protective layer can be provided on the heat-sensitive recording layer for the purpose of improving the preservability of the recorded image with respect to chemicals such as a plasticizer and oil, or the recording suitability.
保護層形成用塗液の調製方法については特に限定するものではなく、一般に水を分散媒体とし、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、アラビアガム、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、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、珪素変性ポリビニルアルコール等のバインダー、及び必要に応じてカオリン、水酸化アルミニウム、軽質炭酸カルシウム、微粒子シリカ等の顔料を混合、攪拌して調製される。 The method for preparing the coating liquid for forming the protective layer is not particularly limited. Generally, water is used as a dispersion medium, and starches, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, gum arabic, polyvinyl alcohol, carboxy-modified polyvinyl alcohol. It is prepared by mixing and stirring a binder such as acetoacetyl-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol, silicon-modified polyvinyl alcohol, and pigments such as kaolin, aluminum hydroxide, light calcium carbonate, and fine particle silica as necessary.
保護層は、顔料を使用することなく、前記バインダー及び必要に応じて後述の各種助剤の１種以上を使用して形成することもできる。
また、保護層は、前記バインダーと前記顔料とを併用して形成することもできる。この場合、前記バインダーの使用量は、特に限定されず広い範囲から適宜選択できるが、一般には、保護層全固形分に対して１〜９５質量％程度、特に２〜８０質量％程度とするのが好ましい。また、顔料の使用量も、特に限定されず広い範囲から適宜選択できるが、一般には、保護層全固形分に対して１〜９５質量％程度、特に２〜９０質量％程度とするのが好ましい。
A protective layer can also be formed using the said binder and the 1 or more types of the various adjuvant mentioned later as needed, without using a pigment.
The protective layer can also be formed by using the binder and the pigment in combination. In this case, the amount of the binder used is not particularly limited and can be appropriately selected from a wide range, but is generally about 1 to 95% by mass, particularly about 2 to 80% by mass with respect to the total solid content of the protective layer. Is preferred. Further, the amount of the pigment used is not particularly limited and can be appropriately selected from a wide range, but generally it is preferably about 1 to 95% by mass, particularly preferably about 2 to 90% by mass with respect to the total solid content of the protective layer. .
更に、保護層用塗液中には、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滑剤、ジオクチルスルホコハク酸ナトリウム等の界面活性剤（分散剤、湿潤剤）、消泡剤、カリミョウバンや酢酸アルミニウム等の水溶性多価金属塩等の各種助剤を適宜添加することもできる。また耐水性を一層向上させるためにグリオキザ−ル、硼酸、ジアルデヒド澱粉、ヒドラジド系化合物、エポキシ系化合物等の硬化剤を併用することもできる。 Furthermore, in the protective layer coating solution, a surfactant such as zinc stearate, calcium stearate, polyethylene wax, carnauba wax, paraffin wax, ester wax, or a surfactant such as sodium dioctylsulfosuccinate (dispersant, wetting) Agent), an antifoaming agent, and various auxiliary agents such as water-soluble polyvalent metal salts such as potassium alum and aluminum acetate can be appropriately added. In order to further improve the water resistance, a curing agent such as glyoxal, boric acid, dialdehyde starch, hydrazide compound, epoxy compound and the like can be used in combination.
特に、保護層中に、２−（２’−ヒドロキシ−３’−ドデシル−５’−メチルフェニル）ベンゾトリアゾール等の常温で液体の紫外線吸収剤を内包したマイクロカプセルを、保護層全固形分に対して紫外線吸収剤が１０〜４０質量％程度、特に１５〜３８質量％程度となるように添加すると光暴露に対して地肌部の黄変や記録像の退色が著しく改良される。 In particular, microcapsules encapsulating a UV absorber that is liquid at room temperature, such as 2- (2′-hydroxy-3′-dodecyl-5′-methylphenyl) benzotriazole, in the protective layer are added to the total solid content of the protective layer. On the other hand, when the ultraviolet absorber is added so as to be about 10 to 40% by mass, particularly about 15 to 38% by mass, the yellowing of the background and the fading of the recorded image are remarkably improved with respect to light exposure.
前記下塗り層、感熱記録層及び保護層の形成方法については特に限定されず、例えばエアナイフコーティング、バリバーブレードコーティング、ピュアブレードコーティング、ロッドブレードコーティング、ショートドウェルコーティング、カーテンコーティング、ダイコーティング等の適当な塗布方法により下塗り層用塗液を支持体上に塗布・乾燥した後、感熱記録層用塗液、更に保護層用塗液を前記下塗り層上に塗布・乾燥する等の方法で形成される。 The method for forming the undercoat layer, the heat-sensitive recording layer, and the protective layer is not particularly limited. For example, suitable methods such as air knife coating, varibar blade coating, pure blade coating, rod blade coating, short dwell coating, curtain coating, and die coating can be used. The undercoat layer coating solution is applied and dried on the support by a coating method, and then the thermal recording layer coating solution and further the protective layer coating solution are applied and dried on the undercoat layer.
下塗り層を設ける場合、下塗り層用塗液の塗布量は乾燥重量で３〜２０ｇ／ｍ２程度、好ましくは５〜１２ｇ／ｍ２程度である。感熱記録層用塗液の塗布量は乾燥重量で２〜１２ｇ／ｍ２程度、好ましくは３〜１０ｇ／ｍ２程度である。保護層を設ける場合、保護層用塗液の塗布量は乾燥重量で０．５〜１５ｇ／ｍ２程度、好ましくは１．０〜８ｇ／ｍ２程度の範囲で調節される。 If an undercoat layer, the coating amount of the undercoat layer coating solution 3 to 20 g / m 2 approximately by dry weight, preferably 5~12g / m 2 approximately. The coating amount of the heat-sensitive recording layer coating composition is 2~12g / m 2 approximately by dry weight, preferably 3 to 10 g / m 2 approximately. When the protective layer is provided, the coating amount of the protective layer coating solution is adjusted in the range of about 0.5 to 15 g / m 2 , preferably about 1.0 to 8 g / m 2 in terms of dry weight.
なお、必要に応じて感熱記録体の裏面側にも塗工層を設け、保存性やプリンタ適性を高めたり、強光沢を持たせることも可能である。各層塗抹後にスーパーカレンダー掛け等の平滑化処理を施したり、或い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、磁気記録層や印刷用塗被層、更には熱転写記録層、インクジェット記録層を設ける等、感熱記録体製造分野における各種の公知技術が必要に応じて付加することができる。 If necessary, a coating layer can also be provided on the back side of the heat-sensitive recording medium to improve storage stability and printer suitability, or to give a strong gloss. Applying a smoothing process such as supercalendering after coating each layer, or applying an adhesive treatment to the back side of the thermal recording material to process it into an adhesive label, magnetic recording layer, printing coating layer, and thermal transfer recording layer Various known techniques in the heat-sensitive recording material manufacturing field, such as providing an ink jet recording layer, can be added as necessary.
以下、本発明を実施例により、更に具体的に説明するが、勿論、本発明の範囲はこれらに限定されるものではない。また、特に断らない限り、例中の「部」及び「％」は、それぞれ「質量部」及び「質量％」を示す。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but of course, the scope of the present invention is not limited thereto. Unless otherwise specified, “part” and “%” in the examples represent “part by mass” and “% by mass”, respectively.
実施例１
・下塗り層用塗液の調製
球状樹脂粒子分散液（商品名：グロスデール１３０Ｓ、組成：スチレン、平均粒子径：０．８μｍ、三井化学社製、固形分濃度５３質量％）９０部、焼成カオリン（商品名：アンシレックス、エンゲルハード社製）の５０％水分散液（平均粒子径：０．６μｍ）１２０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質量％）１０部、酸化澱粉の１０％水溶液５０部、及び水２０部からなる組成物を、混合・攪拌して下塗り層用塗液を得た。
Example 1
-Preparation of coating solution for undercoat layer Spherical resin particle dispersion (trade name: Grosdale 130S, composition: styrene, average particle size: 0.8 μm, manufactured by Mitsui Chemicals, solid content concentration 53 mass%) 90 parts, calcined kaolin 120 parts of 50% aqueous dispersion (trade name: Ansilex, Engelhard) (average particle size: 0.6 μm), styrene-butadiene latex (trade name: L-1571, manufactured by Asahi Kasei Chemicals, solid content A composition comprising 10 parts (concentration 48% by mass), 50 parts of a 10% aqueous solution of oxidized starch, and 20 parts of water was mixed and stirred to obtain an undercoat layer coating solution.
・Ａ液調製
３−ジ（ｎ−ブチル）アミノ−６−メチル−７−アニリノフルオラン１００部、鹸化度６０モル％、重合度２００のポリビニルアルコールの２０％水溶液５０部、天然油脂系消泡剤の５％エマルジョン２０部、及び水８０部からなる組成物（懸濁液）を、サンドミルによりレーザー回折式粒径測定器ＳＡＬＤ２２００（島津製作所社製）によるメジアン径が０．５μｍとなるように粉砕処理してＡ液を得た。
Preparation of solution A 3-di (n-butyl) amino-6-methyl-7-anilinofluorane 100 parts, saponification degree 60 mol%, polymerization degree 200 polyvinyl alcohol 20% aqueous solution 50 parts, natural fat-based A composition (suspension) consisting of 20 parts of a 5% emulsion of foam and 80 parts of water was subjected to a sand mill so that the median diameter by a laser diffraction particle size analyzer SALD2200 (manufactured by Shimadzu Corporation) would be 0.5 μm. A liquid A was obtained by grinding.
・Ｂ液調製
４，４’−（３−トシルウレイド）ジフェニルメタン１００部、スルホン変性ポリビニルアルコール（商品名：ゴーセランＬ−３２６６、日本合成化学社製）の２０％水溶液５０部、天然油脂系消泡剤の５％エマルジョン１０部、及び水９０部からなる組成物（懸濁液）を、サンドミルによりレーザー回折式粒径測定器ＳＡＬＤ２２００（島津製作所社製）によるメジアン径が１．０μｍとなるように粉砕処理してＢ液を得た。
Preparation of liquid B 100 parts of 4,4 ′-(3-tosylureido) diphenylmethane, 50 parts of a 20% aqueous solution of sulfone-modified polyvinyl alcohol (trade name: Gocelan L-3266, manufactured by Nippon Synthetic Chemical Co., Ltd.), natural fat-based antifoaming agent A composition (suspension) consisting of 10 parts of a 5% emulsion and 90 parts of water was pulverized with a sand mill so that the median diameter was 1.0 μm using a laser diffraction particle size analyzer SALD2200 (manufactured by Shimadzu Corporation). It processed and obtained B liquid.
・Ｃ液調製
４−ヒドロキシ−４’−ｎ−プロポキシジフェニルスルホン（商品名：トミラックＫＮ、ＡＰＩ社製）１００部、スルホン変性ポリビニルアルコ−ル（商品名：ゴ−セランＬ−３２６６、日本合成化学社製）の２０％水溶液５０部、天然油脂系消泡剤の５％エマルジョン１０部、及び水９０部からなる組成物（懸濁液）をサンドミルによりレーザー回折式粒径測定器ＳＡＬＤ２２００（島津製作所社製）によるメジアン径が１．０μｍとなるように粉砕処理してＣ液を得た。
-Solution C preparation 4-hydroxy-4'-n-propoxydiphenylsulfone (trade name: Tomirac KN, manufactured by API) 100 parts, sulfone-modified polyvinyl alcohol (trade name: Go-Selan L-3266, Nippon Synthetic Chemical Co., Ltd.) A composition (suspension) consisting of 50 parts of a 20% aqueous solution, 10 parts of a 5% emulsion of a natural fat and oil-based antifoaming agent, and 90 parts of water was subjected to a laser diffraction particle size analyzer SALD2200 (Shimadzu Corporation) using a sand mill. The liquid C was obtained by grinding so that the median diameter was 1.0 μm.
・Ｄ液調製
シュウ酸ジ−ｐ−メチルベンジルエステル１００部、スルホン変性ポリビニルアルコール（商品名：ゴーセランＬ−３２６６、前出）の２０％水溶液５０部、天然油脂系消泡剤の５％エマルジョン２部、及び水９８部からなる組成物を、サンドミルによりレーザー回折式粒径測定器ＳＡＬＤ２２００（島津製作所社製）によるメジアン径が１．０μｍとなるように粉砕処理してＤ液を得た。
-Preparation of solution D 100 parts of di-p-methylbenzyl oxalate, 50 parts of a 20% aqueous solution of sulfone-modified polyvinyl alcohol (trade name: Gocelan L-3266, supra), 5% emulsion 2 of natural fat and oil antifoaming agent 2 Part D and 98 parts of water were pulverized with a sand mill so that the median diameter was 1.0 μm using a laser diffraction particle size analyzer SALD2200 (manufactured by Shimadzu Corp.) to obtain a liquid D.
・感熱記録層用塗液の調製
Ａ液２５．０部、Ｂ液３７．５部、Ｃ液１２．５部、Ｄ液３７．５部、微粒子無定形シリカ（商品名：ミズカシールＰ−５２７、水澤化学工業社製）１０部、水酸化アルミニウム（商品名：ハイジライトＨ−４２、昭和軽金属工業社製）２０部、鹸化度９８モル％、重合度１０００のポリビニルアルコールの１２％水溶液１２５部、ステアリン酸亜鉛分散液（商品名：ハイドリンＺ−８−３６、固形分濃度３６％、中京油脂社製）１３．９部、及び水１８．６部を混合・攪拌して感熱記録層用塗液を調製した。
-Preparation of coating solution for heat-sensitive recording layer A solution 25.0 parts, solution B 37.5 parts, solution C 12.5 parts, solution D 37.5 parts, particulate amorphous silica (trade name: Mizukaseal P-527, 10 parts by Mizusawa Chemical Industry Co., Ltd., 20 parts by aluminum hydroxide (trade name: Hygielite H-42, Showa Light Metal Industry Co., Ltd.), 125 parts by weight of a 12% aqueous solution of polyvinyl alcohol having a saponification degree of 98 mol% and a polymerization degree of 1000 Zinc stearate dispersion (trade name: Hydrin Z-8-36, solid content concentration 36%, manufactured by Chukyo Yushi Co., Ltd.) 13.9 parts and 18.6 parts of water were mixed and stirred to obtain a thermal recording layer coating solution. Was prepared.
・感熱記録体の作製
６４ｇ／ｍ２の上質紙（酸性紙）の一方の面に、下塗り層用塗液を乾燥後の塗布量が８ｇ／ｍ２となるように塗布・乾燥して下塗り層を形成し、感熱記録層用塗液を乾燥後の塗布量が３．５ｇ／ｍ２となるように塗布・乾燥して感熱記録層を形成した後、スーパーキャレンダー処理を施し、感熱記録体を得た。
・ Preparation of thermosensitive recording material On one surface of 64 g / m 2 high-quality paper (acidic paper), the undercoat layer coating solution was applied and dried so that the coating amount after drying was 8 g / m 2. After forming the heat-sensitive recording layer by applying and drying the heat-sensitive recording layer coating solution so that the coating amount after drying is 3.5 g / m 2 , super calender treatment is performed, Got.
実施例２
実施例１の感熱記録層用塗液の調製において、Ｃ液の量を１２．５部から２．５部に変更した以外は、実施例１と同様にして感熱記録体を得た。
Example 2
A heat-sensitive recording material was obtained in the same manner as in Example 1 except that the amount of liquid C was changed from 12.5 parts to 2.5 parts in the preparation of the heat-sensitive recording layer coating liquid of Example 1.
実施例３
実施例１の感熱記録層用塗液の調製において、Ｂ液の量を３７．５部から２０部に変更した以外は、実施例１と同様にして感熱記録体を得た。
Example 3
A heat-sensitive recording material was obtained in the same manner as in Example 1 except that the amount of liquid B was changed from 37.5 parts to 20 parts in the preparation of the heat-sensitive recording layer coating liquid of Example 1.
実施例４
実施例１の感熱記録層用塗液の調製において、Ｂ液の量を３７．５部から８７．５部に変更した以外は、実施例１と同様にして感熱記録体を得た。
Example 4
A thermosensitive recording material was obtained in the same manner as in Example 1 except that the amount of the liquid B was changed from 37.5 parts to 87.5 parts in the preparation of the thermosensitive recording layer coating liquid of Example 1.
実施例５
実施例１のＢ液調製において、４，４’−（３−トシルウレイド）ジフェニルメタンの代わりに、４，４’−（３−トシルウレイド）ジフェニルエーテルを用いた以外は、実施例１と同様にして感熱記録体を得た。
Example 5
Thermosensitive recording was performed in the same manner as in Example 1, except that 4,4 ′-(3-tosylureido) diphenylmethane was used instead of 4,4 ′-(3-tosylureido) diphenylmethane in the preparation of Liquid B of Example 1. Got the body.
実施例６
実施例１の感熱記録層用塗液の調製において、Ｂ液の量を３７．５部から２０部に、Ｃ液の量を１２．５部から２０部に変更した以外は、実施例１と同様にして感熱記録体を得た。
Example 6
In the preparation of the heat-sensitive recording layer coating solution of Example 1, Example 1 is the same as Example 1 except that the amount of solution B is changed from 37.5 parts to 20 parts and the amount of solution C is changed from 12.5 parts to 20 parts. A heat-sensitive recording material was obtained in the same manner.
実施例７
実施例１の感熱記録層用塗液の調製において、Ｂ液の量を３７．５部から４５部に、Ｃ液の量を１２．５部から２部に変更した以外は、実施例１と同様にして感熱記録体を得た。
Example 7
In the preparation of the heat-sensitive recording layer coating liquid of Example 1, the amount of liquid B was changed from 37.5 parts to 45 parts, and the amount of liquid C was changed from 12.5 parts to 2 parts. A heat-sensitive recording material was obtained in the same manner.
実施例８
実施例１のＢ液調製において、４，４’−（３−トシルウレイド）ジフェニルメタンの代わりに、Ｎ−（ｐ−トシル）−Ｎ'−フェニルウレアを用いた以外は、実施例１と同様にして感熱記録体を得た。
Example 8
In the preparation of the liquid B of Example 1, the same procedure as in Example 1 was performed except that N- (p-tosyl) -N′-phenylurea was used instead of 4,4 ′-(3-tosylureido) diphenylmethane. A heat-sensitive recording material was obtained.
実施例９
実施例１のＢ液調製において、４，４’−（３−トシルウレイド）ジフェニルメタンの代わりに、ブチル ４−（３−トシルウレイド）ベンゾエートを用いた以外は、実施例１と同様にして感熱記録体を得た。
Example 9
A thermosensitive recording material was prepared in the same manner as in Example 1 except that butyl 4- (3-tosylureido) benzoate was used in place of 4,4 ′-(3-tosylureido) diphenylmethane in the preparation of solution B of Example 1. Obtained.
比較例１
実施例１の感熱記録層用塗料の調製において、Ｃ液を使用しなかった以外は、実施例１と同様にして感熱記録体を得た。
Comparative Example 1
A heat-sensitive recording material was obtained in the same manner as in Example 1 except that the liquid C was not used in the preparation of the heat-sensitive recording layer coating material of Example 1.
比較例２
実施例１の感熱記録層用塗料の調製において、Ｂ液の量を３７．５部から１００部に変更し、Ｃ液を使用しなかった以外は、実施例１と同様にして感熱記録体を得た。
Comparative Example 2
In the preparation of the thermal recording layer paint of Example 1, the thermal recording medium was prepared in the same manner as in Example 1 except that the amount of B liquid was changed from 37.5 parts to 100 parts and no C liquid was used. Obtained.
比較例３
実施例１のＢ液調製において、４，４’−（３−トシルウレイド）ジフェニルメタンの代わりに、２，２’−〔４−（４−ヒドロキシフェニルスルホニル）フェノキシ〕ジエチルエーテル（商品名：Ｄ−９０、日本曹達社製）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 liquid B of Example 1, 2,2 ′-[4- (4-hydroxyphenylsulfonyl) phenoxy] diethyl ether (trade name: D-90) was used instead of 4,4 ′-(3-tosylureido) diphenylmethane. Except for using Nippon Soda Co., Ltd.), a thermal recording material was obtained in the same manner as in Example 1.
比較例４
実施例１のＣ液調製において、４−ヒドロキシ−４’−ｎ−プロポキシジフェニルスルホンの代わりに、４−ヒドロキシ−４’−イソプロポキシジフェニルスルホン（商品名：Ｄ−８、日本曹達社製）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 4
In the preparation of solution C of Example 1, 4-hydroxy-4'-isopropoxydiphenylsulfone (trade name: D-8, manufactured by Nippon Soda Co., Ltd.) was used instead of 4-hydroxy-4'-n-propoxydiphenylsulfone. A thermosensitive recording material was obtained in the same manner as in Example 1 except that it was used.
比較例５
実施例１の感熱記録層用塗液の調製において、Ｂ液を使用せず、Ｃ液の量を１２．５部から５０部に変更した以外は、実施例１と同様にして感熱記録体を得た。
Comparative Example 5
In the preparation of the thermal recording layer coating liquid of Example 1, the thermal recording medium was prepared in the same manner as in Example 1 except that the liquid B was not used and the amount of the liquid C was changed from 12.5 parts to 50 parts. Obtained.
かくして得られた感熱記録体について以下の評価試験を行い、その結果を表１に記載した。 The following evaluation test was performed on the heat-sensitive recording material thus obtained, and the results are shown in Table 1.
(１）記録濃度
感熱記録評価機（商品名：ＴＨ−ＰＭＤ、大倉電機社製）を用いて、印加エネルギー０．３４ｍＪ／ドットにて各感熱記録体を印字し、記録部及び未記録部（地肌部）の濃度をマクベス濃度計（商品名：ＲＤ−９１４型、マクベス社製）のビジュアルモードで測定した。
数値が大きい程、印字の濃度が濃いことを示しており、記録部については、実用上、１．２０以上であることが必要とされる一方、地肌部については数値が小さいほど好ましく、０．２を超えると、地肌カブリが問題となる。
(1) Recording density Using a thermal recording evaluation machine (trade name: TH-PMD, manufactured by Okura Electric Co., Ltd.), each thermal recording medium was printed at an applied energy of 0.34 mJ / dot, and a recorded portion and an unrecorded portion ( The density of the background portion was measured in a visual mode of a Macbeth densitometer (trade name: RD-914, manufactured by Macbeth).
The larger the numerical value, the higher the density of printing, and the recording portion is required to be 1.20 or more practically. If it exceeds 2, background fog becomes a problem.
（２）耐熱性
記録前の各感熱記録体を６０°Ｃ、３０％ＲＨ雰囲気下で２４時間放置した後の地肌部の濃度をマクベス濃度計（商品名：ＲＤ−９１４型、マクベス社製）のビジュアルモードで測定した。
数値が小さいほど好ましく、０．２を超えると、地肌カブリが問題となる。
(2) Heat resistance Macbeth densitometer (trade name: RD-914, manufactured by Macbeth Co., Ltd.) after the thermal recording medium before recording was left for 24 hours in an atmosphere of 60 ° C. and 30% RH. Measured in visual mode.
The smaller the value, the better. When it exceeds 0.2, background fog becomes a problem.
（３）耐湿熱性
記録前の各感熱記録体を４０°Ｃ、８０％ＲＨ雰囲気下で２４時間放置した後の地肌部の濃度をマクベス濃度計（商品名：ＲＤ−９１４型、マクベス社製）のビジュアルモードで測定した。
数値が小さいほど好ましく、０．２を超えると、地肌カブリが問題となる。
(3) Moisture and heat resistance Macbeth densitometer (trade name: RD-914 type, manufactured by Macbeth Co., Ltd.) after leaving each thermosensitive recording medium before recording in an atmosphere of 40 ° C. and 80% RH for 24 hours. Measured in visual mode.
The smaller the value, the better. When it exceeds 0.2, background fog becomes a problem.
（４）耐油性
記録濃度測定用で発色させた各感熱記録体の記録部にサラダ油を表面塗布し、２４時間放置後に表面をガーゼで拭いた後の記録部の濃度をマクベス濃度計（商品名：ＲＤ−９１４型、マクベス社製）のビジュアルモードで測定した。また、下記式により、記録部の保存率を求めた。サラダ油塗布処理後の記録濃度０．６以上で、保存率５０％以上であれば問題ない。
保存率（％）＝測定値（記録濃度）÷処理前の記録濃度×１００
(4) Oil resistance Salad oil was coated on the surface of each heat-sensitive recording medium that had been colored for recording density measurement, and the density of the recording area after wiping the surface with gauze after standing for 24 hours was measured with a Macbeth densitometer (trade name) : RD-914 type, manufactured by Macbeth). Further, the storage ratio of the recording part was obtained by the following formula. There is no problem if the recording density after the salad oil coating treatment is 0.6 or more and the storage rate is 50% or more.
Storage rate (%) = measured value (recording density) ÷ recording density before processing × 100
（５）耐可塑剤性
ポリカーボネイトパイプ（４０ｍｍφ）上にラップフィルム（商品名：ハイラップＫＭＡ−Ｗ、三井化学社製）を３重に巻付け、その上に記録濃度測定用で発色させた各感熱記録体を載せ、更にその上にラップフィルムを３重に巻き付けて４０°Ｃで２４時間放置した後の記録部の濃度をマクベス濃度計（商品名：ＲＤ−９１４型、マクベス社製）のビジュアルモードで測定した。また、記録部の保存率を、耐油性の場合と同様に、上記式に基づいて、算出した。
処理後の記録濃度０．６以上で、保存率５０％以上であれば問題ない。
(5) Plasticizer resistance Each heat sensitive material in which a wrap film (trade name: High Wrap KMA-W, manufactured by Mitsui Chemicals Co., Ltd.) is wrapped in three layers on a polycarbonate pipe (40 mmφ), and then colored for recording density measurement. Visual density of Macbeth densitometer (trade name: RD-914 type, manufactured by Macbeth Co., Ltd.) after the recording medium is placed and the wrapping film is wrapped in three layers on it and left at 40 ° C. for 24 hours. Measured in mode. Further, the storage rate of the recording part was calculated based on the above formula, as in the case of oil resistance.
There is no problem if the recording density after processing is 0.6 or more and the storage rate is 50% or more.
表１からわかるように、４，４’−（３−トシルウレイド）ジフェニルメタンを単独で使用した場合、感熱記録層中、１６質量％では記録濃度が低く（比較例１）、３０質量％以上含有させることによって記録濃度を確保することができても、地肌部の耐熱性、耐湿熱性が問題となるレベルにまで低下した（比較例２）。 As can be seen from Table 1, when 4,4 ′-(3-tosylureido) diphenylmethane is used alone, the recording density is low at 16% by mass in the thermosensitive recording layer (Comparative Example 1), and 30% by mass or more is contained. Thus, even if the recording density could be ensured, the heat resistance and heat-and-moisture resistance of the background portion were lowered to a problem level (Comparative Example 2).
一方、４，４’−（３−トシルウレイド）ジフェニルメタンまたは４，４’−（３−トシルウレイド）ジフェニルエーテルと４−ヒドロキシ−４’−ｎ−プロポキシジフェニルスルホンを組み合わせて用いることにより、地肌部の耐熱性、耐湿熱性を低下させることなく、記録濃度、記録部の耐油性、耐可塑剤性を改善できることがわかる（実施例１〜７）。 On the other hand, by using 4,4 ′-(3-tosylureido) diphenylmethane or 4,4 ′-(3-tosylureido) diphenyl ether in combination with 4-hydroxy-4′-n-propoxydiphenylsulfone, the heat resistance of the background portion is obtained. It can be seen that the recording density, the oil resistance of the recording area, and the plasticizer resistance can be improved without lowering the heat and moisture resistance (Examples 1 to 7).
また、４，４’−（３−トシルウレイド）ジフェニルメタンと４−ヒドロキシ−４’−ｎ−プロポキシジフェニルスルホンを組み合わせて用いる場合であっても、４，４’−（３−トシルウレイド）ジフェニルメタンの含有量が２９質量％と多い場合には、地肌部の耐熱性、耐湿熱性が低下する傾向にあった（実施例４）。 Even when 4,4 ′-(3-tosylureido) diphenylmethane and 4-hydroxy-4′-n-propoxydiphenylsulfone are used in combination, the content of 4,4 ′-(3-tosylureido) diphenylmethane When there is much 29 mass%, there existed a tendency for the heat resistance of a ground part, and heat-and-moisture resistance to fall (Example 4).
但し、４−ヒドロキシ−４’−ｎ−プロポキシジフェニルスルホン／４，４’−（３−トシルウレイド）ジフェニルメタンの比率が０．９を超えると、記録部耐油性、耐可塑剤性の改良効果が低下し（実施例６）、反対に上記比率が０．０５未満では、記録濃度が低下する傾向にある（実施例７）。 However, if the ratio of 4-hydroxy-4′-n-propoxydiphenylsulfone / 4,4 ′-(3-tosylureido) diphenylmethane exceeds 0.9, the effect of improving the oil resistance and plasticizer resistance of the recording area is reduced. On the contrary, when the ratio is less than 0.05, the recording density tends to decrease (Example 7).
以上から、４，４’−（３−トシルウレイド）ジフェニルメタン及び４，４’−（３−トシルウレイド）ジフェニルエーテルから選ばれる少なくとも１種と、４−ヒドロキシ−４’−ｎ−プロポキシジフェニルスルホンを所定範囲内（好ましくは前者の化合物５〜２０質量％、後者の化合物１〜１５質量％、より好ましくは前者の化合物６〜２０質量％、後者の化合物２〜１０質量％、最も好ましくは前者の化合物７〜１８質量％、後者の化合物２〜９質量％）で配合すると共に、両化合物の配合量比率（４−ヒドロキシ−４’−ｎ−プロポキシジフェニルスルホン／４，４’−（３−トシルウレイド）ジフェニルメタン及び４，４’−（３−トシルウレイド）ジフェニルエーテルから選ばれる少なくとも１種）を０．０５〜０．９の範囲内とすることが好ましいことがわかる。 From the above, at least one selected from 4,4 ′-(3-tosylureido) diphenylmethane and 4,4 ′-(3-tosylureido) diphenyl ether and 4-hydroxy-4′-n-propoxydiphenylsulfone are within a predetermined range. (Preferably 5-20% by mass of the former compound, 1-15% by mass of the latter compound, more preferably 6-20% by mass of the former compound, 2-10% by mass of the latter compound, most preferably 7-7% by mass of the former compound. 18% by mass, the latter compound 2-9% by mass), and the compounding ratio of both compounds (4-hydroxy-4′-n-propoxydiphenylsulfone / 4,4 ′-(3-tosylureido) diphenylmethane and 4,4 ′-(3-tosylureido) diphenyl ether) within the range of 0.05 to 0.9 It can be seen that it is preferable to.
実施例及び比較例で示した通り、本発明の感熱記録体は、発色感度が高く、記録部の耐油性、耐可塑剤性が極めて良好であり、しかも高温高湿保存下でも地肌カブリがもんだいとならない少ない、長期保存性に優れた感熱記録体である。 As shown in the examples and comparative examples, the heat-sensitive recording material of the present invention has high color development sensitivity, extremely good oil resistance and plasticizer resistance in the recording area, and background fogging even under high temperature and high humidity storage. It is a heat-sensitive recording material that has a long and long shelf life.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011063966A JP5741109B2 (en) | 2011-03-23 | 2011-03-23 | Thermal recording material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014218062A (en) * | 2013-05-10 | 2014-11-20 | 王子ホールディングス株式会社 | Thermosensitive recording material |
| JP2022071576A (en) * | 2020-10-28 | 2022-05-16 | 王子ホールディングス株式会社 | Heat-sensitive recording medium |
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| JPH0532061A (en) * | 1991-08-02 | 1993-02-09 | Oji Paper Co Ltd | Thermal recording material |
| JPH05147357A (en) * | 1991-10-04 | 1993-06-15 | Oji Paper Co Ltd | Thermal recording material |
| JPH11254837A (en) * | 1998-03-09 | 1999-09-21 | Nippon Paper Industries Co Ltd | Thermal recording body |
| JPH11286173A (en) * | 1998-04-02 | 1999-10-19 | Nippon Paper Industries Co Ltd | Thermal recording medium |
| JP2002113948A (en) * | 2000-10-11 | 2002-04-16 | Nippon Paper Industries Co Ltd | Thermal recording body |
| JP2003182233A (en) * | 2001-12-20 | 2003-07-03 | Fuji Photo Film Co Ltd | Thermal recording material |
| JP2004299288A (en) * | 2003-03-31 | 2004-10-28 | Nippon Paper Industries Co Ltd | Thermosensitive recording body |
| JP2010194924A (en) * | 2009-02-26 | 2010-09-09 | Oji Paper Co Ltd | Heat-sensitive recording medium |
| JP2011031504A (en) * | 2009-08-03 | 2011-02-17 | Oji Paper Co Ltd | Thermal recording material |
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| JPH0532061A (en) * | 1991-08-02 | 1993-02-09 | Oji Paper Co Ltd | Thermal recording material |
| JPH05147357A (en) * | 1991-10-04 | 1993-06-15 | Oji Paper Co Ltd | Thermal recording material |
| JPH11254837A (en) * | 1998-03-09 | 1999-09-21 | Nippon Paper Industries Co Ltd | Thermal recording body |
| JPH11286173A (en) * | 1998-04-02 | 1999-10-19 | Nippon Paper Industries Co Ltd | Thermal recording medium |
| JP2002113948A (en) * | 2000-10-11 | 2002-04-16 | Nippon Paper Industries Co Ltd | Thermal recording body |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2014218062A (en) * | 2013-05-10 | 2014-11-20 | 王子ホールディングス株式会社 | Thermosensitive recording material |
| JP2022071576A (en) * | 2020-10-28 | 2022-05-16 | 王子ホールディングス株式会社 | Heat-sensitive recording medium |
| JP7327351B2 (en) | 2020-10-28 | 2023-08-16 | 王子ホールディングス株式会社 | Thermal recording medium |
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| JP5741109B2 (en) | 2015-07-01 |
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