JP5741116B2 - Thermal recording material - Google Patents
Thermal recording material Download PDFInfo
- Publication number
- JP5741116B2 JP5741116B2 JP2011067466A JP2011067466A JP5741116B2 JP 5741116 B2 JP5741116 B2 JP 5741116B2 JP 2011067466 A JP2011067466 A JP 2011067466A JP 2011067466 A JP2011067466 A JP 2011067466A JP 5741116 B2 JP5741116 B2 JP 5741116B2
- Authority
- JP
- Japan
- Prior art keywords
- heat
- tosylureido
- sensitive recording
- recording layer
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
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- BPLKDVGMXNZCQO-UHFFFAOYSA-N benzyl 4-phenylmethoxybenzoate Chemical compound C=1C=C(OCC=2C=CC=CC=2)C=CC=1C(=O)OCC1=CC=CC=C1 BPLKDVGMXNZCQO-UHFFFAOYSA-N 0.000 description 1
- NEPKLUNSRVEBIX-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,4-dicarboxylate Chemical compound C=1C=C(C(=O)OCC2OC2)C=CC=1C(=O)OCC1CO1 NEPKLUNSRVEBIX-UHFFFAOYSA-N 0.000 description 1
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- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- OJLOUXPPKZRTHK-UHFFFAOYSA-N dodecan-1-ol;sodium Chemical compound [Na].CCCCCCCCCCCCO OJLOUXPPKZRTHK-UHFFFAOYSA-N 0.000 description 1
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- ZJOLCKGSXLIVAA-UHFFFAOYSA-N ethene;octadecanamide Chemical compound C=C.CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O ZJOLCKGSXLIVAA-UHFFFAOYSA-N 0.000 description 1
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- 239000008269 hand cream Substances 0.000 description 1
- FEEPBTVZSYQUDP-UHFFFAOYSA-N heptatriacontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O FEEPBTVZSYQUDP-UHFFFAOYSA-N 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- VYQNWZOUAUKGHI-UHFFFAOYSA-N monobenzone Chemical compound C1=CC(O)=CC=C1OCC1=CC=CC=C1 VYQNWZOUAUKGHI-UHFFFAOYSA-N 0.000 description 1
- 229960000990 monobenzone Drugs 0.000 description 1
- RQAQWBFHPMSXKR-UHFFFAOYSA-N n-(4-chlorophenyl)-3-(phosphonooxy)naphthalene-2-carboxamide Chemical compound OP(O)(=O)OC1=CC2=CC=CC=C2C=C1C(=O)NC1=CC=C(Cl)C=C1 RQAQWBFHPMSXKR-UHFFFAOYSA-N 0.000 description 1
- MJGLMEMIYDUEHA-UHFFFAOYSA-N n-(4-methylphenyl)-3-oxobutanamide Chemical compound CC(=O)CC(=O)NC1=CC=C(C)C=C1 MJGLMEMIYDUEHA-UHFFFAOYSA-N 0.000 description 1
- JHOKTNSTUVKGJC-UHFFFAOYSA-N n-(hydroxymethyl)octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCO JHOKTNSTUVKGJC-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- DVVFBRPYROBXHJ-UHFFFAOYSA-N n-octadecanoylbenzamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NC(=O)C1=CC=CC=C1 DVVFBRPYROBXHJ-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
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- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000005441 o-toluyl group Chemical group [H]C1=C([H])C(C(*)=O)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
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- 235000014593 oils and fats Nutrition 0.000 description 1
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- QHDYIMWKSCJTIM-UHFFFAOYSA-N phenyl 1-hydroxynaphthalene-2-carboxylate Chemical compound C1=CC2=CC=CC=C2C(O)=C1C(=O)OC1=CC=CC=C1 QHDYIMWKSCJTIM-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 229940050271 potassium alum Drugs 0.000 description 1
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Landscapes
- Heat Sensitive Colour Forming Recording (AREA)
Description
本発明は、無色乃至は淡色のロイコ染料と呈色剤との発色反応を利用した感熱記録体に関し、記録感度と記録像の保存性に優れた感熱記録体に関するものである。 The present invention relates to a heat-sensitive recording material using a coloring reaction between a colorless or light-colored leuco dye and a color former, and relates to a heat-sensitive recording material excellent in recording sensitivity and storage stability of a recorded image.
無色乃至は淡色のロイコ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、且つその保守も容易な為、ファクシミリや各種計算機等の記録媒体としてのみならず巾広い分野において使用されている。 A heat-sensitive recording material is known which utilizes a color reaction between a colorless or light-colored leuco dye and an organic or inorganic colorant to obtain a recorded image by bringing both coloring materials into contact with each other by heat. Such heat-sensitive recording materials are relatively inexpensive, and the recording equipment is compact and easy to maintain, so that they are used not only as recording media for facsimiles and various computers but also in a wide range of fields.
その利用分野として、例えばＰＯＳ（ｐｏｉｎｔ ｏｆ ｓａｌｅｓ）システム用のレジ用紙及びチケット用紙が挙げられるが、同システムの拡大と共にその使用環境、使用方法も多様化しており、厳しい条件下での使用が増加してきている。またプリンタの印字速度も年々増加し、更に低い印字エネルギーでも印字できる事が望まれている。更に領収書としても使用されるため、記録部の油や可塑剤、事務用品、ハンドクリーム等、種々の薬品に対する保存性や捺印性が良好なことも必要である。 The fields of use include, for example, cash register paper and ticket paper for POS (point of sales) systems, but with the expansion of the system, the use environment and use methods are diversified, and use under severe conditions increases. Have been doing. In addition, the printing speed of printers is increasing year by year, and it is desired that printing can be performed with lower printing energy. Further, since it is also used as a receipt, it is necessary that the storage and the sealability with respect to various chemicals such as oil, plasticizer, office supplies, and hand cream in the recording section are good.
支持体上にロイコ染料と呈色剤を主成分とする感熱記録層を設けた感熱記録体にあっては、発色反応が可逆的であるため、発色画像が経時的に消色する事が知られている。この消色は曝光、高温、高湿雰囲気下で加速され、更に可塑剤、油等の接触によって速やかに進行し、記録画像が読取り不可能なまでに消色してしまうことがある。また、パーキングチケット用紙として感熱記録体を使用した場合、車中に放置され、特に夏場は高温の過酷な雰囲気下におかれるため、感熱記録体の非印字部が発色してしまい、印字部（記録像）とのコントラストがなくなり、極端な場合には読取りが不可能となることもある。 In a heat-sensitive recording material provided with a heat-sensitive recording layer mainly composed of a leuco dye and a colorant on a support, it is known that the color-development reaction is reversible, so that the color-development image disappears with time. It has been. This decolorization is accelerated under exposure, high temperature and high humidity atmosphere, and further proceeds rapidly by contact with a plasticizer, oil, etc., and the recorded image may be decolored until it cannot be read. In addition, when a thermal recording medium is used as a parking ticket sheet, it is left in the vehicle, and particularly in the summer, it is placed in a harsh and high temperature atmosphere. The contrast with the recorded image) is lost, and in extreme cases, reading may be impossible.
このような問題に対し、記録像の保存性を向上させるため、感熱記録層上に保護層を設ける方法や、感熱記録層中にエポキシ化合物を添加する方法等が提案されているが、いずれも油や可塑剤に対して十分な印字保存性改善の効果が得られていない。また保護層を設けた場合、記録感度の低下という欠点を有していた。また、近年高い印字保存性を有する呈色剤の開発が進み、前記曝光、高温、高湿雰囲気下での消色や高温下でのコントラスト低下の問題も解決されつつあるが、記録感度が低いという欠点がある。 In order to improve the storability of the recorded image against such problems, a method of providing a protective layer on the heat-sensitive recording layer, a method of adding an epoxy compound to the heat-sensitive recording layer, and the like have been proposed. A sufficient effect of improving print storage stability with respect to oil and plasticizer is not obtained. Further, when the protective layer is provided, there is a disadvantage that the recording sensitivity is lowered. In recent years, development of colorants having high print storage stability has progressed, and the problems of exposure, high-temperature, decolorization under high-humidity atmospheres and low-contrast problems at high temperatures are being solved, but the recording sensitivity is low. There is a drawback.
このような要件を充足すべく、呈色剤について、種々の提案がなされている。 In order to satisfy such requirements, various proposals have been made for colorants.
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）。
しかし、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、記録部の耐可塑剤性、耐油性は改善されるものの、高い記録濃度が得られ難く、高い記録濃度を得るためには増配する必要があるが、そうした場合は高温高湿保存下における白紙部（地肌部）の発色が見られる等、地肌部の耐熱湿性が劣っている。
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).
However, 4,4 ′-(3-tosylureido) diphenylmethane, 4,4 ′-(3-tosylureido) diphenyl ether, or the specific N-arylsulfonyl (thio) ureas described above are resistant to plasticizer and oil in the recording area. Although the performance is improved, it is difficult to obtain a high recording density, and in order to obtain a high recording density, it is necessary to increase the number of copies. In such a case, the color of the white paper portion (background portion) under high temperature and high humidity storage is observed. Etc. The heat and humidity resistance of the background is inferior.
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。 The use of 4-allyloxy-4′-hydroxydiphenylsulfone (see Patent Document 3) is described as a colorant or a part of the colorant, and the colorant used in combination with the colorant. As 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.
本発明の課題は、記録感度と記録像の保存性に優れ、地肌カブリが少なく、しかも耐スティッキング性に優れた感熱記録体を提供することにある。 An object of the present invention is to provide a heat-sensitive recording material that is excellent in recording sensitivity and storage stability of a recorded image, has little background fogging, and is excellent in sticking resistance.
（１）支持体上に、ロイコ染料、呈色剤及び増感剤を含有する感熱記録層を有する感熱記録体において、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−（３−トシル）−Ｎ’−フェニルウレア、及びブチル ４−（ｐ−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、増感剤として２−ナフチルベンジルエーテルを、感熱記録層に含まれる全呈色剤の合計質量に対して５０〜２００質量％含有することを特徴とする感熱記録体。 (1) In a heat-sensitive recording material having a heat-sensitive recording layer containing a leuco dye, a colorant and a sensitizer on the support, 4,4 ′-(3-tosylureido) diphenylmethane, 4, It contains at least one selected from 4 ′-(3- (tosylureido) diphenyl ether, N- (3-tosyl) -N′-phenylurea, and butyl 4- (p-tosylureido) benzoate, and 2 as a sensitizer. -A thermal recording material comprising naphthyl benzyl ether in an amount of 50 to 200% by mass based on the total mass of all colorants contained in the thermal recording layer.
（２）感熱記録層に、呈色剤として更に４−アリルオキシ−４’−ヒドロキシジフェニルスルホンを含有する（１）に記載の感熱記録体。 (2) The heat-sensitive recording material according to (1), wherein the heat-sensitive recording layer further contains 4-allyloxy-4'-hydroxydiphenylsulfone as a colorant.
（３）前記４−アリルオキシ−４’−ヒドロキシジフェニルスルホンの感熱記録層中の含有量が、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種の感熱記録層中の合計質量に対して５〜９０質量％である（１）または（２）に記載の感熱記録体。 (3) The content of the 4-allyloxy-4′-hydroxydiphenylsulfone in the heat-sensitive recording layer is such that the 4,4 ′-(3-tosylureido) diphenylmethane, 4,4 ′-(3- (tosylureido) diphenylether, 5 to 90% by mass based on the total mass in at least one thermosensitive recording layer selected from N- (p-tosyl) -N′-phenylurea and butyl 4- (3-tosylureido) benzoate (1 ) Or (2).
本発明の感熱記録体は、記録感度と記録像の保存性に優れた効果を有し、地肌カブリが少なく、しかも耐スティッキング性に優れた感熱記録体を提供することが可能となった。 The heat-sensitive recording material of the present invention has an effect excellent in recording sensitivity and storage stability of a recorded image, and it is possible to provide a heat-sensitive recording material having little background fogging and excellent in sticking resistance.
〔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種を含有し、増感剤として２−ナフチルベンジルエーテルを、感熱記録層に含まれる全呈色剤の合計質量に対して５０〜２００質量％含有するものである。
(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 ′ -Containing at least one selected from phenylurea and butyl 4- (3-tosylureido) benzoate, with 2-naphthylbenzyl ether as a sensitizer, based on the total mass of all colorants contained in the heat-sensitive recording layer 50 to 200% by mass.
以下、各順に説明する。
（呈色剤）
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種であり、更に４−アリルオキシ−４’−ヒドロキシジフェニルスルホンを併用することが好ましい。
Hereinafter, each will be described in order.
(Coloring agent)
The colorants 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 is at least one selected from 4-benzoyloxy-4′-hydroxydiphenyl sulfone.
４−アリルオキシ−４’−ヒドロキシジフェニルスルホンを併用する場合、その感熱記録層中の含有量は、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種の感熱記録層中の合計質量に対して５〜９０質量％であることが好ましい。５質量％以上とすることにより、所望の記録感度が得られ易く、９０質量％以下とすることにより、記録部の保存性（耐油性、耐可塑剤性）が低下することを防ぐことができる。 When 4-allyloxy-4′-hydroxydiphenylsulfone is used in combination, the content in the thermosensitive recording layer is 4,4 ′-(3-tosylureido) diphenylmethane, 4,4 ′-(3- (tosylureido) diphenylether. , N- (p-tosyl) -N′-phenylurea, and butyl 4- (3-tosylureido) benzoate, 5 to 90% by mass with respect to the total mass in the heat-sensitive recording layer. When the content is 5% by mass or more, desired recording sensitivity is easily obtained, and when the content is 90% by mass or less, the storage stability (oil resistance and plasticizer resistance) of the recording portion is prevented from being lowered. be able to.
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、及び４−アリルオキシ−４’−ヒドロキシジフェニルスルホン以外に、必要に応じて、支障のない範囲で各種公知の呈色剤、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。 From 4,4 ′-(3-tosylureido) diphenylmethane, 4,4 ′-(3- (tosylureido) diphenyl ether, N- (p-tosyl) -N′-phenylurea, and butyl 4- (3-tosylureido) benzoate In addition to at least one selected and 4-allyloxy-4′-hydroxydiphenylsulfone, various known colorants such as activated clay, attapulgite, colloidal silica, aluminum silicate and the like can be used as long as necessary. Inorganic acidic substance, 4,4′-isopropylidenediphenol, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis ( 4-hydroxyphenyl) -4-methylpentane, 2,4′-dihydroxydiphenylsulfone 4,4′-bis [(4-methyl-3-phenoxycarbonylaminophenyl) ureido] diphenylsulfone, Np-toluenesulfonyl-N′-3- (p-toluenesulfonyloxy) phenylurea, 4,4 '-Dihydroxydiphenyl sulfide, hydroquinone monobenzyl ether, benzyl 4-hydroxybenzoate, 4,4'-dihydroxydiphenyl sulfone, 4-hydroxy-4'-isopropoxydiphenyl sulfone, bis (3-allyl-4-hydroxyphenyl) Phenolic compounds such as sulfone, 4-hydroxy-4'-methyldiphenylsulfone, 4-hydroxyphenyl-4'-benzyloxyphenylsulfone, 3,4-dihydroxyphenyl-4'-methylphenylsulfone, N, N'- Di-m-chlorophenylthiouree Thiourea compounds such as N- (p-toluenesulfonyl) carbamoyl acid p-cumylphenyl ester, N- (p-toluenesulfonyl) carbamoyl acid p-benzyloxyphenyl ester, N- (o-toluoyl) -p- Organic compounds having a —SO 2 NH— bond in the molecule such as 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-methoxyphenoxyethoxy) cumyl] salicylic acid and the like, and These aromatic carboxylic acids zinc, magnesium, aluminum, calcium, titanium, manganese, tin, nickel In addition, a salt with a polyvalent metal such as an organic acid substance such as an antipyrine complex of zinc thiocyanate, a complex zinc salt of terephthalaldehyde acid and another aromatic carboxylic acid, or the like can be used in combination.
（増感剤）
本発明では感熱記録層に増感剤として、２−ナフチルベンジルエーテルを感熱記録層中に使用される呈色剤の合計固形分質量に対して、５０〜２００質量％含有するものであり、より好ましくは７０〜１５０質量％含有するものである。
２−ナフチルベンジルエーテルの含有量が５０質量％未満では、充分な記録濃度が得られ難い、また、２００質量％を超えると、高温または高湿環境で保存した場合の白紙カブリが発生する、或いは、印画時のスティッキングによる画像不良が発生し易くなる。
(Sensitizer)
In the present invention, the heat-sensitive recording layer contains 2-naphthylbenzyl ether as a sensitizer in an amount of 50 to 200% by mass based on the total solid content of the colorant used in the heat-sensitive recording layer. Preferably it contains 70-150 mass%.
If the content of 2-naphthylbenzyl ether is less than 50% by mass, it is difficult to obtain a sufficient recording density, and if it exceeds 200% by mass, blank fog occurs when stored in a high temperature or high humidity environment, or Image defects due to sticking during printing are likely to occur.
また本発明の所望の効果に支障のない範囲で、他の増感剤も併用できる。具体的には、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、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る。 Further, other sensitizers can be used in combination as long as the desired effects of the present invention are not hindered. Specifically, stearic acid amide, methoxycarbonyl-N-stearic acid benzamylide, N-benzoyl stearic acid amide, N-eicosanoic acid amide, ethylene bis stearic acid amide, behenic acid amide, methylene bis stearic acid amide, N-methylol Stearic acid amide, dibenzyl terephthalate, dimethyl terephthalate, dioctyl terephthalate, benzyl p-benzyloxybenzoate, phenyl 1-hydroxy-2-naphthoate, m-terphenyl, p-benzylbiphenyl, di-p-oxalate 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 -Methylfe Xyl) 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.
（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.
（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、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. Such binders include starches, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, gum arabic, polyvinyl alcohol, carboxy modified polyvinyl alcohol, acetoacetyl modified polyvinyl alcohol, silicon modified polyvinyl alcohol, diisobutylene / maleic anhydride copolymer. Compound salt, styrene / maleic anhydride copolymer salt, ethylene / acrylic acid copolymer salt, styrene / acrylic acid copolymer salt, styrene / butadiene copolymer emulsion, urea resin, melamine resin, amide resin, polyurethane resin Are blended in a range of about 5 to 50% by mass, particularly about 10 to 40% by mass, based on the total solid content of the thermosensitive recording layer.
（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、感熱記録層の全固形分に対して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 it is usually about 1 to 30% by mass with respect to the total solid content of the thermosensitive recording layer. It is preferable to mix | blend in the range of about 5-20 mass%.
（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、増感剤、バインダー及び保存性改良剤に加えて、更に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 various other auxiliaries in addition to the color former, leuco dye, sensitizer, binder and preservability improver.
（感熱記録層用塗液）
前記各種成分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材料を配合して調製される。
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。
(Coating liquid for thermal recording layer)
The thermosensitive recording layer coating liquid containing the above-mentioned various components generally uses water as a dispersion medium, and a leuco dye, a colorant, a sensitizer, etc. together or separately by a stirring / pulverizing machine such as a ball mill, an attritor, or a sand mill. It is prepared by blending materials obtained by dispersing or the like.
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.
〔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／または有機中空粒子、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とが好ましい。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 is for an undercoat layer mainly composed of an oil-absorbing pigment and / or organic hollow particles and / or thermally expandable particles having an oil absorption amount of 70 ml / 100 g or more, particularly about 80 to 150 ml / 100 g, and an adhesive. It is preferably formed by applying and drying a coating 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 types of oil-absorbing pigments can be used, and specific examples thereof 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.
また、有機中空粒子としては、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。 Moreover, as an organic hollow particle, a conventionally well-known thing, for example, the particle | grains whose hollow rate consists of an acrylic resin, a styrene resin, a vinylidene chloride resin etc. about 50-99% can be illustrated. 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 storage stability 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、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、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 and silicon-modified polyvinyl alcohol and, if necessary, a pigment such as kaolin, light calcium carbonate, and fine particle silica.
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ができる。
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、保護層の全固形量に対して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、保護層の全固形量に対して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 be formed using the said binder and 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. In general, it is about 1 to 95% by mass, particularly about 2 to 90% by mass with respect to the total solid content of the protective layer. preferable.
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、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. Further, in order to further improve the water resistance, a curing agent such as glyoxal, boric acid, dialdehyde starch, and epoxy compound 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、保護層の全固形量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, in the protective layer, microcapsules encapsulating an ultraviolet absorber that is liquid at room temperature, such as 2- (2′-hydroxy-3′-dodecyl-5′-methylphenyl) benzotriazole, 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.
本発明の感熱記録体において、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。 In the thermal recording material of the present invention, the method for forming the undercoat layer, the thermal recording layer and the protective layer is not particularly limited. For example, air knife coating, varibar blade coating, pure blade coating, rod blade coating, short dwell coating, curtain coating After coating and drying the undercoat layer coating liquid on the support by an appropriate coating method such as die coating, the thermal recording layer coating liquid and further the protective layer coating liquid are coated and dried on the undercoat layer, etc. It is formed by the method.
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保護層を設け、一層保存性を高めたり、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や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し得るものである。 If necessary, a protective layer can also be provided on the back side of the heat-sensitive recording material to further improve the storage stability or give it a high 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。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to these examples. Unless otherwise specified, “part” and “%” in the examples represent “part by mass” and “% by mass”, respectively.
（実施例１（参考例））
・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 (reference example) )
Preparation of coating solution for undercoat layer 90 parts of spherical resin particle dispersion (trade name: Grosdale 130S, composition: styrene, average particle size: 0.8 μm, Mitsui Chemicals, solid content concentration 53 mass%), 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 of a 48% by weight concentration, 50 parts of a 10% aqueous solution of oxidized starch, and 20 parts of water was mixed and stirred to obtain a coating solution for an undercoat layer.
・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、サンドミルにより平均粒子径が０．５μｍとなる様に処理してＡ液を得た。
Solution A preparation 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 and oil A composition (suspension) consisting of 20 parts of a 5% emulsion of foaming agent and 80 parts of water was treated with a sand mill so that the average particle size was 0.5 μm to obtain liquid A.
・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、サンドミルにより平均粒子径が１．０μｍとなる様に処理してＢ液を得た。
-B liquid preparation 4,4 '-(3-tosylureido) diphenylmethane 100 parts, sulfone modified polyvinyl alcohol (trade name: Gocelan L-3266, manufactured by Nippon Synthetic Chemical Co., Ltd.) 50% 20% aqueous solution, natural fat-based antifoaming agent A composition (suspension) comprising 10 parts of a 5% emulsion and 90 parts of water was treated with a sand mill so that the average particle size was 1.0 μm to obtain a liquid B.
・Ｃ液調製
４−アリルオキシ−４’−ヒドロキシジフェニルスルホン（商品名：ＢＰＳ−ＭＡＥ、日華化学社製）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平均粒子径が１．０μｍとなる様に処理してＣ液を得た。
-Solution C preparation 4-allyloxy-4'-hydroxydiphenyl sulfone (trade name: BPS-MAE, manufactured by Nikka Chemical Co., Ltd.), sulfone-modified polyvinyl alcohol (trade name: Go-Selan L-3266, Nihon Gosei) A composition (suspension) consisting of 50 parts of a 20% aqueous solution (made by Kagaku Co., Ltd.), 10 parts of a 5% emulsion of a natural fat and oil-based antifoaming agent, and 90 parts of water is adjusted to a mean particle size of 1.0 μm by a sand mill. To obtain a liquid C.
・Ｄ液調製
２−ナフチルベンジルエーテル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、サンドミルにより平均粒子径が１．０μｍとなる様に処理してＤ液を得た。
Solution D Preparation 2-Naphthyl benzyl ether 100 parts, sulfone-modified polyvinyl alcohol (trade name: Gocelan L-3266, supra) 50% 20% aqueous solution, natural oils and fats antifoaming agent 5% emulsion 2 parts, and water The composition consisting of 98 parts was treated with a sand mill so that the average particle size was 1.0 μm 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、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 25.0 parts of liquid A, 37.5 parts of liquid B, 37.5 parts of liquid D, fine particle amorphous silica (trade name: Mizukaseal P-527, manufactured by Mizusawa Chemical Co., Ltd.) 10 Parts, 20 parts of aluminum hydroxide (trade name: Heidilite H-42, Showa Light Metal Industry Co., Ltd.), 125 parts of 12% aqueous solution of polyvinyl alcohol having a saponification degree of 98 mol% and a polymerization degree of 1000, zinc stearate dispersion (product) (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 prepare a thermal recording layer coating solution.
・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重量が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重量が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を施し、感熱記録体を得た。
- on one surface of woodfree paper having produced 64 g / m 2 (acid paper) of the heat-sensitive recording material, forming an undercoat layer, an undercoat layer coating solution weight after drying by coating and drying so that 8 g / m 2 The heat-sensitive recording layer coating solution was applied and dried so that the weight after drying was 3.5 g / m 2 to form a heat-sensitive recording layer, and then a super calender was applied to obtain a heat-sensitive recording material.
（実施例２（参考例））
実施例１（参考例）の感熱記録層用塗液の調製において、Ｄ液の量を３７．５部から２２．５部に減量した以外は、実施例１（参考例）と同様にして感熱記録体を得た。
(Example 2 (reference example) )
Heat sensitivity was the same as in Example 1 (Reference Example) , except that in the preparation of the thermal recording layer coating liquid of Example 1 (Reference Example) , the amount of Liquid D was reduced from 37.5 parts to 22.5 parts. A record was obtained.
（実施例３（参考例））
実施例１（参考例）の感熱記録層用塗液の調製において、Ｄ液の量を３７．５部から６０部に増量した以外は、実施例１（参考例）と同様にして感熱記録体を得た。
(Example 3 (reference example) )
In the preparation of the thermal recording layer coating liquid of Example 1 (Reference Example), the thermal recording material was the same as Example 1 (Reference Example) except that the amount of D liquid was increased from 37.5 parts to 60 parts. Got.
（実施例４）
実施例１（参考例）の感熱記録層用塗液の調製において、Ｃ液を１２．５部追加した以外は、実施例１（参考例）と同様にして感熱記録体を得た。
Example 4
In the preparation of the heat-sensitive recording layer coating solution of Example 1 (Reference Example), except for adding the Solution C 12.5 parts to obtain a heat-sensitive recording layer in Example 1 (Reference Example).
（実施例５（参考例））
実施例１（参考例）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（参考例）と同様にして感熱記録体を得た。
(Example 5 (reference example) )
Example 1 (Reference) In the preparation of solution B in Reference Example 1, except that 4,4 ′-(3-tosylureido) diphenylmethane was used instead of 4,4 ′-(3-tosylureido) diphenylmethane. A thermal recording material was obtained in the same manner as in Example .
（実施例６）
実施例１（参考例）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、実施例１（参考例）の感熱記録層用塗液の調製において、Ｃ液を１２．５部追加した以外は、実施例１（参考例）と同様にして感熱記録体を得た。
(Example 6)
In the preparation of the liquid B of Example 1 (Reference Example) , 4,4 ′-(3-tosylureido) diphenyl ether was used instead of 4,4 ′-(3-tosylureido) diphenylmethane, and Example 1 (Reference Example) was used. A heat-sensitive recording material was obtained in the same manner as in Example 1 (Reference Example) except that 12.5 parts of liquid C was added in the preparation of the heat-sensitive recording layer coating solution.
（実施例７（参考例））
実施例１（参考例）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（参考例）と同様にして感熱記録体を得た。
(Example 7 (reference example) )
Example 1 Example 1 except that N- (p-tosyl) -N′-phenylurea was used in place of 4,4 ′-(3-tosylureido) diphenylmethane in the preparation of solution B in Reference Example. A thermosensitive recording material was obtained in the same manner as in (Reference Example) .
（実施例８）
実施例１（参考例）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、実施例１（参考例）の感熱記録層用塗液の調製において、Ｃ液を１２．５部追加した以外は、実施例１（参考例）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 (Reference Example) , N- (p-tosyl) -N′-phenylurea was used instead of 4,4 ′-(3-tosylureido) diphenylmethane, and Example 1 (Reference Example) in the preparation of the heat-sensitive recording layer coating solution), except for adding the solution C 12.5 parts to obtain a heat-sensitive recording layer in example 1 (reference example).
（実施例９（参考例））
実施例１（参考例）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（参考例）と同様にして感熱記録体を得た。
(Example 9 (reference example) )
Example 1 (Reference Example) Except that butyl 4- (3-tosylureido) benzoate was used instead of 4,4 ′-(3-tosylureido) diphenylmethane in the preparation of solution B in Example 1 (Reference Example) In the same manner, a heat-sensitive recording material was obtained.
（実施例１０）
実施例１（参考例）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用い、実施例１（参考例）の感熱記録層用塗液の調製において、Ｃ液を１２．５部追加した以外は、実施例１（参考例）と同様にして感熱記録体を得た。
(Example 10)
In the preparation of the liquid B of Example 1 (Reference Example) , butyl 4- (3-tosylureido) benzoate was used in place of 4,4 ′-(3-tosylureido) diphenylmethane, and the heat sensitivity of Example 1 (Reference Example) was used. A thermosensitive recording material was obtained in the same manner as in Example 1 (Reference Example) except that 12.5 parts of C solution was added in the preparation of the recording layer coating solution.
（比較例１）
実施例１（参考例）の感熱記録層用塗料の調製において、Ｄ液の量を３７．５部から７．５部に減量以外は、実施例１（参考例）と同様にして感熱記録体を得た。
(Comparative Example 1)
In the preparation of the thermal recording layer coating material of Example 1 (Reference Example), the thermal recording medium was prepared in the same manner as in Example 1 (Reference Example) except that the amount of D liquid was reduced from 37.5 parts to 7.5 parts. Got.
（比較例２）
実施例１（参考例）の感熱記録層用塗料の調製において、Ｄ液の量を３７．５部から９０部に増量した以外は、実施例１（参考例）と同様にして感熱記録体を得た。
(Comparative Example 2)
In the preparation of the heat-sensitive recording layer coating material of Example 1 (Reference Example), except that increasing the amount of Solution D to 90 parts 37.5 parts, the heat-sensitive recording layer in Example 1 (Reference Example) Obtained.
（比較例３）
実施例１（参考例）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（参考例）と同様にして感熱記録体を得た。
(Comparative Example 3)
In the preparation of solution B in Example 1 (Reference Example) , 2,2 ′-[4- (4-hydroxyphenylsulfonyl) phenoxy] diethyl ether (trade name) was used instead of 4,4 ′-(3-tosylureido) diphenylmethane. : D-90 manufactured by Nippon Soda Co., Ltd.) was used in the same manner as in Example 1 (Reference Example) to obtain a heat-sensitive recording material.
（比較例４）
実施例１（参考例）のＤ液調製において、２−ナフチルベンジルエーテルの代わりに、１，２−ジ（３−メチルフェノキシ）エタン（商品名：ＫＳ−２３２、三光社製）を用いた以外は、実施例１（参考例）と同様にして感熱記録体を得た。
(Comparative Example 4)
Example 1 (Reference Example) In preparation of solution D, 1,2-di (3-methylphenoxy) ethane (trade name: KS-232, manufactured by Sanko Co., Ltd.) was used instead of 2-naphthylbenzyl ether. Were the same as in Example 1 (Reference Example) to obtain a heat-sensitive recording material.
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）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 is 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, 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）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) The density of the background after leaving each thermosensitive recording medium before heat-resistant recording in an atmosphere of 60 ° C. and 30% RH for 24 hours was measured with a Macbeth densitometer (trade name: RD-914 type, Macbeth). 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、９０％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）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) The density of the background after leaving each heat-sensitive recording material before moisture and heat resistance recording in an atmosphere of 40 ° C. and 90% RH for 24 hours was measured with a Macbeth densitometer (trade name: RD-914, Macbeth). 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）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) Salad oil was applied to the surface of the recording part of each thermal recording material developed for measuring the oil-resistant recording density, and the density of the recording part after wiping the surface with gauze after standing for 24 hours was measured with a Macbeth densitometer (trade name) : RD-914 type, Macbeth Co.) visual mode. 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）を三重に巻付け、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三重に巻き付けて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）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) Each thermal recording in which a wrap film (trade name: High Wrap KMA-W, manufactured by Mitsui Chemicals Co., Ltd.) is wrapped three times on a plasticizer-resistant polycarbonate pipe (40 mmφ) and colored for recording density measurement. Put the body on it, wrap the wrap film in triplicate and let it stand at 40 ° C for 24 hours, then measure the density of the recording part in the Macbeth densitometer (trade name: RD-914, Macbeth) visual mode did. 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.
（６）耐スティッキング性
感熱記録評価機（商品名：ＴＨ−ＰＭＤ、大倉電機社製）を用いて、市松パターン（印字部の印加エネルギーは０．３４ｍＪ／ドット）で印字した際の、耐スティッキング性を下記の基準で評価した。感熱記録体の最表層がプリンターのヘッドに粘着して、部分的に印字できないことを「白飛び」といい、感熱記録体の最表層がプリンターのヘッドに粘着することにより引き起こされるプリンターの騒音を「騒音」という。
○：白飛びの発生がなく、騒音も殆どない。
△：僅かに白飛びが見られるが、実用上問題ない程度で、騒音は殆どない。
×：白飛びが頻発し、騒音も大きい。
(6) Sticking resistance when printing with a checkered pattern (the applied energy of the printing part is 0.34 mJ / dot) using a sticking-resistant thermal recording evaluation machine (trade name: TH-PMD, manufactured by Okura Electric Co., Ltd.) Sex was evaluated according to the following criteria. The fact that the outermost layer of the thermal recording medium sticks to the printer head and cannot be partially printed is called “whiteout”. The noise of the printer caused by the outermost layer of the thermal recording medium sticking to the printer head It is called “noise”.
○: No whiteout occurs and there is almost no noise.
Δ: Slight whitening is observed, but there is almost no noise in practical use.
X: White spots occur frequently and noise is high.
実施例及び比較例で示した通り、本発明の感熱記録体は、記録感度と記録像の保存性に優れた効果を有し、地肌カブリが少なく、しかも耐スティッキング性に優れた感熱記録体である。 As shown in the examples and comparative examples, the thermosensitive recording material of the present invention has an excellent effect on recording sensitivity and storage stability of the recorded image, has little background fogging, and is excellent in sticking resistance. is there.
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