JP7373214B2 - Heat-sensitive recording material, phenylenediamine urea derivative, and heat-sensitive recording layer - Google Patents
Heat-sensitive recording material, phenylenediamine urea derivative, and heat-sensitive recording layer Download PDFInfo
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- JP7373214B2 JP7373214B2 JP2021131277A JP2021131277A JP7373214B2 JP 7373214 B2 JP7373214 B2 JP 7373214B2 JP 2021131277 A JP2021131277 A JP 2021131277A JP 2021131277 A JP2021131277 A JP 2021131277A JP 7373214 B2 JP7373214 B2 JP 7373214B2
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- heat
- sensitive recording
- urea
- bis
- phenyl
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- -1 N,N'-bis(3-[{4-methylphenyl}sulfonylamino]phenyl)urea Chemical compound 0.000 claims description 102
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Images
Landscapes
- Heat Sensitive Colour Forming Recording (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、フェニレンジアミン尿素誘導体を顕色剤として用いた感熱記録材料に関する。また、本発明は、フェニレンジアミン尿素誘導体、及び、感熱記録層に関する。 The present invention relates to a heat-sensitive recording material using a phenylenediamine urea derivative as a color developer. The present invention also relates to a phenylenediamine urea derivative and a heat-sensitive recording layer.
一般に、感熱記録材料は、支持体と、その支持体上に塗工液を塗工して形成した感熱記録層とを備える。塗工液としては、常温で無色ないし淡色の塩基性染料と有機顕色剤とをそれぞれ微細な粒子に粉砕分散した後、混合してなる混合物に、増感剤、バインダー、滑剤、その他の各種添加剤等を添加したものが用いられる。支持体としては、紙、プラスティックフィルム、加工紙等が用いられる。このような感熱記録材料は、感熱記録層に感熱ヘッド、熱ペン等で熱エネルギーを加えることにより、発色記録が得られる。このような感熱記録材料は、既に広く実用化されている。また、感熱記録材料としては、感熱記録層がレーザー光を吸収して熱に変換する光変換物質を含有するものも普及している。 Generally, a heat-sensitive recording material includes a support and a heat-sensitive recording layer formed by applying a coating liquid onto the support. The coating liquid is prepared by grinding and dispersing a colorless or light-colored basic dye and an organic developer into fine particles at room temperature, and then adding a sensitizer, binder, lubricant, and other various ingredients to the mixture. Those to which additives and the like are added are used. Paper, plastic film, processed paper, etc. are used as the support. In such a heat-sensitive recording material, color recording can be obtained by applying thermal energy to the heat-sensitive recording layer using a heat-sensitive head, a thermal pen, or the like. Such heat-sensitive recording materials have already been widely put into practical use. Further, as heat-sensitive recording materials, those whose heat-sensitive recording layer contains a light conversion substance that absorbs laser light and converts it into heat are also popular.
このような感熱記録材料は、比較的簡単な装置で記録画像が得られ、保守が容易なこと、騒音が発生しないこと等の利点がある。そのため、感熱記録材料は、計測記録計、ファクシミリ、各種プリンター、ラベル印字機、乗車券、チケットの発券機等の広範囲な分野で利用されている。 Such heat-sensitive recording materials have advantages such as being able to obtain recorded images with a relatively simple device, being easy to maintain, and not generating noise. Therefore, heat-sensitive recording materials are used in a wide range of fields such as measurement recorders, facsimiles, various printers, label printing machines, train tickets, and ticket issuing machines.
上記のように、感熱記録材料の用途は拡大している。感熱記録材料は、ガス、水道、電気料金等の領収書を始めとして、金融機関の現金自動預け払い機（ＡＴＭ）の利用明細書、財務関係の記録用紙、観劇等のチケット用紙、ナンバーズ、競馬や競艇等のゲーミングチケット用紙等の投票券、鉄道、バス等の切符や領収書、航空タグ用紙、物流関係のラベル用紙、総菜やおにぎり等の食品用ラベル用紙、コンビエンスストアーやスーパーマーケット等の販売時点情報管理（ＰＯＳ）レジ用紙、医療用ラベル、心電図用紙、医療診断用のフィルム感熱、交通系定期券等で使用されている。また、感熱記録材料は、用途により様々な特性が要求されている。 As mentioned above, the uses of heat-sensitive recording materials are expanding. Thermal recording materials include receipts for gas, water, and electricity bills, usage statements for automated teller machines (ATMs) at financial institutions, financial records, ticket forms for theaters, numbers, and horse racing. Sales of voting tickets such as gaming tickets for and boat races, tickets and receipts for trains, buses, etc., aviation tag paper, label paper for logistics, label paper for food such as delicatessen dishes and rice balls, convenience stores and supermarkets, etc. It is used in point-of-sale (POS) register paper, medical labels, electrocardiogram paper, thermal film for medical diagnosis, transportation commuter passes, etc. Further, heat-sensitive recording materials are required to have various properties depending on their use.
感熱記録材料に求められる性能としては、未印字部の白色度と種々の環境条件における未印字部の白色度、印字部の発色濃度とその印字部の保存性等が挙げられる。特に印字部の保存性としては、例えば、耐熱性、耐湿熱性、耐水性、耐光性、耐油性、耐可塑剤性等の種々の試験に対する耐性が求められる。 The performance required of a heat-sensitive recording material includes the whiteness of the unprinted area, the whiteness of the unprinted area under various environmental conditions, the color density of the printed area, and the storage stability of the printed area. In particular, the storage stability of the printed portion requires resistance to various tests such as heat resistance, heat and humidity resistance, water resistance, light resistance, oil resistance, and plasticizer resistance.
このように感熱記録材料の用途が拡大するに伴って、これまでに感熱記録材料の顕色剤として数多くのものが提案されてきた。感熱記録材料の顕色剤としては、例えば、４，４’－イソプロピリデンジフェノール（例えば、特許文献１参照）、４，４’－ジヒドロキシジフェニルスルホン（例えば、特許文献２参照）、４－アリルオキシ－４’－ヒドロキシ－ジフェニルスルホン（例えば、特許文献３参照）、４－ヒドロキシ－４’－イソプロピルオキシ－ジフェニルスルホン（例えば、特許文献４参照）、Ｎ－３－〔（ｐ－トルエンスルホニル）オキシ〕フェニル－Ｎ’－（ｐ－トルエンスルホニル）－尿素（例えば、特許文献５参照）、Ｎ－［２－（３－フェニルウレイド）フェニル］－ベンゼンスルホンアミド（例えば、特許文献６、７参照）等が知られている。
As the uses of heat-sensitive recording materials have expanded in this way, many color developers have been proposed for heat-sensitive recording materials. Examples of color developers for heat-sensitive recording materials include 4,4'-isopropylidene diphenol (see, for example, Patent Document 1), 4,4'-dihydroxydiphenylsulfone (for example, see Patent Document 2), and 4-allyloxy. -4'-hydroxy-diphenylsulfone (for example, see Patent Document 3), 4-hydroxy-4'-isopropyloxy-diphenylsulfone (for example, see Patent Document 4), N-3-[(p-toluenesulfonyl)oxy ] Phenyl-N'-(p-toluenesulfonyl)-urea (see, for example, Patent Document 5), N-[2-(3-phenylureido)phenyl]-benzenesulfonamide (see, for example,
しかし、４，４’－イソプロピリデンジフェノール、４，４’－ジヒドロキシジフェニルスルホン、４－アリルオキシ－４’－ヒドロキシ－ジフェニルスルホン、４－ヒドロキシ－４’－イソプロピルオキシ－ジフェニルスルホン、Ｎ－［２－（３－フェニルウレイド）フェニル］－ベンゼンスルホンアミドを含む感熱記録材料は、印字部の各種保存安定性が十分でなかった。 However, 4,4'-isopropylidene diphenol, 4,4'-dihydroxydiphenylsulfone, 4-allyloxy-4'-hydroxy-diphenylsulfone, 4-hydroxy-4'-isopropyloxy-diphenylsulfone, N-[2 The heat-sensitive recording material containing -(3-phenylureido)phenyl]-benzenesulfonamide did not have sufficient storage stability in various types of printed areas.
Ｎ－３－〔（ｐ－トルエンスルホニル）オキシ〕フェニル－Ｎ’－（ｐ－トルエンスルホニル）－尿素は、発色感度や保存性が改善されている。Ｎ－３－〔（ｐ－トルエンスルホニル）オキシ〕フェニル－Ｎ’－（ｐ－トルエンスルホニル）－尿素は、トルエンスルホニルイソシナネートから誘導されるトルエンスルホニル尿素基およびトルエンスルホニルクロライドから誘導される芳香族スルホン酸アリールエステル基の２つの官能基を有し、芳香族スルホン酸アリールエステル基は水に対して安定である（例えば、非特許文献１参照）。一方、Ｎ－３－〔（ｐ－トルエンスルホニル）オキシ〕フェニル－Ｎ’－（ｐ－トルエンスルホニル）－尿素のトルエンスルホニル尿素基は、元来アミノ基等の保護基として活用されてきたものであるが、水によって容易に加水分解される。 N-3-[(p-toluenesulfonyl)oxy]phenyl-N'-(p-toluenesulfonyl)-urea has improved color development sensitivity and storage stability. N-3-[(p-toluenesulfonyl)oxy]phenyl-N'-(p-toluenesulfonyl)-urea is a toluenesulfonylurea group derived from toluenesulfonyl isocyanate and an aromatic derivative derived from toluenesulfonyl chloride. It has two functional groups of the aromatic sulfonic acid aryl ester group, and the aromatic sulfonic acid aryl ester group is stable to water (for example, see Non-Patent Document 1). On the other hand, the toluenesulfonylurea group of N-3-[(p-toluenesulfonyl)oxy]phenyl-N'-(p-toluenesulfonyl)-urea has originally been used as a protecting group for amino groups, etc. However, it is easily hydrolyzed by water.
特許文献７には、ベンゼンスルホンアミド誘導体として、ＲＳＯ２－ＮＨ基の置換基を有するジフェニル尿素誘導体が記載されている。しかしながら、特許文献７には、ジフェニル尿素誘導体の具体的な化合物や、その化合物の合成例、特性および実施例ついては記載されていなかった。 Patent Document 7 describes a diphenyl urea derivative having an RSO 2 --NH group substituent as a benzenesulfonamide derivative. However, Patent Document 7 does not describe specific compounds of diphenyl urea derivatives, synthesis examples, characteristics, and examples of the compounds.
近年、４，４’－イソプロピリデンジフェノールや４，４’－ビスフェノールスルホン等は、内分泌攪乱等の環境衛生上の問題が指摘され、使用を制限する地域もある。また、他のフェノール系顕色剤も水性毒性等の課題を有している。そのため、これらの問題のない非フェノール系顕色剤が求められている。 In recent years, 4,4'-isopropylidenediphenol, 4,4'-bisphenol sulfone, and the like have been pointed out to have environmental health problems such as endocrine disruption, and their use is restricted in some regions. Other phenolic color developers also have problems such as aqueous toxicity. Therefore, there is a need for non-phenolic color developers that do not have these problems.
本発明は、上記事情に鑑みてなされたものであって、発色濃度、白色度、および印字部の耐熱性、耐水性、耐油性、保存性等の感熱記録材料としての要求性能を満たす感熱記録材料を提供することを目的とする。 The present invention has been made in view of the above circumstances, and is a heat-sensitive recording material that satisfies the required performance as a heat-sensitive recording material such as color density, whiteness, and heat resistance, water resistance, oil resistance, and preservability of the printed area. The purpose is to provide materials.
本発明者等は、鋭意検討した結果、本発明の新規なフェニレンジアミン尿素誘導体が感熱記録材料の顕色剤として利用できることを見出し、本発明を完成するに至った。 As a result of extensive studies, the present inventors have found that the novel phenylenediamine urea derivative of the present invention can be used as a color developer for heat-sensitive recording materials, and have completed the present invention.
すなわち、本発明は以下の態様を含む。
［１］ 支持体と、前記支持体上に設けられた感熱記録層と、を備える感熱記録材料であって、前記感熱記録層は、常温で無色ないし淡色の塩基性染料と、加熱により前記塩基性染料と反応して呈色し得る顕色剤と、を含有し、前記顕色剤は、下記式（１）～（４）で表される化合物からなる群から選ばれる少なくとも１種のフェニレンジアミン尿素誘導体である、感熱記録材料。
That is, the present invention includes the following aspects.
[1] A heat-sensitive recording material comprising a support and a heat-sensitive recording layer provided on the support, wherein the heat-sensitive recording layer contains a basic dye that is colorless or light-colored at room temperature, and a base dye that is colored by heating. a color developer capable of forming a color by reacting with a color dye, and the color developer is at least one type of phenylene selected from the group consisting of compounds represented by the following formulas (1) to (4). A heat-sensitive recording material that is a diamine urea derivative.
［２］ 前記顕色剤は、下記式（５）で表されるフェニレンジアミン尿素誘導体である、［１］に記載の感熱記録材料。 [2] The heat-sensitive recording material according to [1], wherein the color developer is a phenylenediamine urea derivative represented by the following formula (5).
［３］ 下記式（１）～（４）で表される化合物からなる群から選ばれる少なくとも１種のフェニレンジアミン尿素誘導体。 [3] At least one phenylenediamine urea derivative selected from the group consisting of compounds represented by the following formulas (1) to (4).
［４］ Ｎ，Ｎ’－ビス（３－［｛４－メチルフェニル｝スルホニルアミノ］フェニル）尿素、Ｎ，Ｎ’－ビス（４－［｛４－メチルフェニル｝スルホニルアミノ］フェニル）尿素、Ｎ，Ｎ’－ビス（３－［｛フェニルスルホニル｝アミノ］フェニル）尿素、Ｎ，Ｎ’－ビス（３－［｛２，４，６－トリメチルフェニル｝スルホニルアミノ］フェニル）尿素、Ｎ，Ｎ’－ビス（３－［｛ベンジルスルホニル｝アミノ］フェニル）尿素、又は、Ｎ，Ｎ’－ビス（３－［｛２－ナフチルスルホニル｝アミノ］フェニル）尿素である、［３］に記載のフェニレンジアミン尿素誘導体。 [4] N,N'-bis(3-[{4-methylphenyl}sulfonylamino]phenyl)urea, N,N'-bis(4-[{4-methylphenyl}sulfonylamino]phenyl)urea, N , N'-bis(3-[{phenylsulfonyl}amino]phenyl)urea, N,N'-bis(3-[{2,4,6-trimethylphenyl}sulfonylamino]phenyl)urea, N,N' - The phenylenediamine according to [3], which is bis(3-[{benzylsulfonyl}amino]phenyl)urea or N,N'-bis(3-[{2-naphthylsulfonyl}amino]phenyl)urea Urea derivative.
［５］ 常温で無色ないし淡色の塩基性染料と、加熱により前記塩基性染料と反応して呈色し得る顕色剤と、を含有する感熱記録層であって、
前記顕色剤が、［３］又は［４］に記載のフェニレンジアミン尿素誘導体を含有する、感熱記録層。
[5] A heat-sensitive recording layer containing a basic dye that is colorless or light-colored at room temperature and a color developer that can react with the basic dye and develop a color when heated,
A heat-sensitive recording layer, wherein the color developer contains the phenylenediamine urea derivative according to [3] or [4].
［６］ ［５］に記載の感熱記録層を含む、支持体。
［７］ ［５］に記載の感熱記録層を含む、紙、プラスティックフィルム、又は、加工紙。
［８］ 支持体と、前記支持体上に設けられた［５］に記載の感熱記録層と、を備える感熱記録材料。
［９］ 前記支持体が、紙、プラスティックフィルム、又は、加工紙であって、
前記感熱記録材料が、感熱記録紙、感熱記録プラスティックフィルム、又は、感熱記録加工紙である、［８］に記載の感熱記録材料。
［１０］ 前記支持体が、紙、再生紙、合成紙、プラスティックフィルム、不織布、又は、金属箔である、［１］又は［２］に記載の感熱記録材料。
[6] A support comprising the heat-sensitive recording layer according to [5].
[7] Paper, plastic film, or processed paper comprising the heat-sensitive recording layer according to [5].
[8] A heat-sensitive recording material comprising a support and the heat-sensitive recording layer according to [5] provided on the support.
[9] The support is paper, plastic film, or processed paper,
The heat-sensitive recording material according to [8], wherein the heat-sensitive recording material is a heat-sensitive recording paper, a heat-sensitive recording plastic film, or a heat-sensitive recording processed paper.
[10] The heat-sensitive recording material according to [1] or [2], wherein the support is paper, recycled paper, synthetic paper, plastic film, nonwoven fabric, or metal foil.
本発明によれば、発色濃度、白色度、および印字部の耐熱性、耐水性、耐油性、保存性等の感熱記録材料としての要求性能を満たす感熱記録材料を提供することができる。 According to the present invention, it is possible to provide a heat-sensitive recording material that satisfies the required performance as a heat-sensitive recording material, such as color density, whiteness, and heat resistance, water resistance, oil resistance, and storage stability of the printed portion.
本発明の感熱記録材料の実施の形態について説明する。
なお、本実施の形態は、発明の趣旨をより良く理解させるために具体的に説明するものであり、特に指定のない限り、本発明を限定するものではない。
Embodiments of the heat-sensitive recording material of the present invention will be described.
It should be noted that the present embodiment is specifically explained in order to better understand the gist of the invention, and is not intended to limit the invention unless otherwise specified.
［感熱記録材料］
本実施形態の感熱記録材料は、支持体と、その支持体上に設けられた感熱記録層と、を備える。前記感熱記録層は、常温で無色ないし淡色の塩基性染料と、加熱により前記塩基性染料と反応して呈色し得る顕色剤と、を含有する。前記顕色剤は、下記式（１）～（４）で表される化合物からなる群から選ばれる少なくとも１種のフェニレンジアミン尿素誘導体である。
[Heat-sensitive recording material]
The heat-sensitive recording material of this embodiment includes a support and a heat-sensitive recording layer provided on the support. The heat-sensitive recording layer contains a basic dye that is colorless or light-colored at room temperature, and a color developer that can react with the basic dye and develop a color when heated. The color developer is at least one phenylenediamine urea derivative selected from the group consisting of compounds represented by the following formulas (1) to (4).
以下、本実施形態の感熱記録材料に用いられるフェニレンジアミン尿素誘導体の具体例を示す。なお、フェニレンジアミン尿素誘導体は、以下に示すものに限定されず、上記式（１）～（４）で表される化合物に該当するものであれば用いることができる。また、以下に示すフェニレンジアミン尿素誘導体は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。さらに、本実施形態におけるフェニレンジアミン尿素誘導体は、従来公知の顕色剤と併用することもでき、例えば、下記の顕色剤と併用することもできる。 Specific examples of the phenylenediamine urea derivative used in the heat-sensitive recording material of this embodiment are shown below. Note that the phenylenediamine urea derivative is not limited to those shown below, and any compound that corresponds to the compounds represented by the above formulas (1) to (4) can be used. Further, the phenylenediamine urea derivatives shown below may be used alone or in combination of two or more. Furthermore, the phenylenediamine urea derivative in this embodiment can also be used in combination with a conventionally known color developer, for example, the following color developer.
本実施形態におけるフェニレンジアミン尿素誘導体と併用可能な顕色剤の具体例としては、Ｎ－３－〔（ｐ－トルエンスルホニル）オキシ〕フェニル－Ｎ’－（ｐ－トルエンスルホニル）－尿素（商品名：ＰＦ－２０１、Ｓｏｌｅｎｉｓ社製）、Ｎ－［２－（３－フェニルウレイド）フェニル］－ベンゼンスルホンアミド（商品名：ＮＫＫ－１３０４、日本曹達社製）、３－〔（３―フェニルウレイド）フェニル〕＝４－メチルベンゼンスルホナート、Ｎ－（ｍ－トリルアミノカルボニル）－メチオニン、Ｎ－（ｍ－トリルアミノカルボニル）－フェニルアラニン、Ｎ－（フェニルアミノカルボニル）－フェニルアラニン、Ｎ，Ｎ’－ビス［３－（ｐ－トルエンスルホニルオキシ）フェニル］尿素、Ｎ，Ｎ’－ビス［３－（ベンゼンスルホニルオキシ）フェニル］尿素、Ｎ，Ｎ’－ビス［３－（メシチレンスルホニルオキシ）フェニル］尿素等のＮ，Ｎ’－ビスアリール尿素誘導体等の公知の非フェノール顕色剤、４，４’－イソプロピリデンジフェノール（ＢＰＡ）、４，４’－ジヒドロキシジフェニルスルホン（ＢＰＳ）、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）、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：ＴＧＳＡ、日本化薬社製）、４－ヒドロキシ－４’－イソプロポキシスルホン（商品名：Ｄ－８、日本曹達社製）等の公知の顕色剤が挙げられる。
これら顕色剤と本実施形態におけるフェニレンジアミン尿素誘導体とを併用することにより、これら公知の顕色剤の課題である保存性を更に向上させることが可能となる。
A specific example of a color developer that can be used in combination with the phenylenediamine urea derivative in this embodiment is N-3-[(p-toluenesulfonyl)oxy]phenyl-N'-(p-toluenesulfonyl)-urea (trade name : PF-201, manufactured by Solenis), N-[2-(3-phenylureido)phenyl]-benzenesulfonamide (trade name: NKK-1304, manufactured by Nippon Soda), 3-[(3-phenylureido) Phenyl]=4-methylbenzenesulfonate, N-(m-tolylaminocarbonyl)-methionine, N-(m-tolylaminocarbonyl)-phenylalanine, N-(phenylaminocarbonyl)-phenylalanine, N,N'-bis [3-(p-toluenesulfonyloxy)phenyl]urea, N,N'-bis[3-(benzenesulfonyloxy)phenyl]urea, N,N'-bis[3-(mesitylenesulfonyloxy)phenyl]urea, etc. Known non-phenolic color developers such as N,N'-bisarylurea derivatives of -Hydroxydiphenylsulfone (trade name: BPS-MAE, manufactured by NICCA Chemical Co., Ltd.), 4-allyloxy-4'-hydroxy-diphenylsulfone (trade name: TGSA, manufactured by Nippon Kayaku Co., Ltd.), 4-hydroxy-4'- Known color developers such as isopropoxysulfone (trade name: D-8, manufactured by Nippon Soda Co., Ltd.) may be used.
By using these color developers together with the phenylenediamine urea derivative in this embodiment, it becomes possible to further improve the storage stability, which is a problem of these known color developers.
上記式（１）で表されるフェニレンジアミン尿素誘導体としては、例えば、Ｎ，Ｎ’－ビス（３－［｛ベンジルスルホニル｝アミノ］フェニル）尿素、Ｎ，Ｎ’－ビス（３－［｛フェニルスルホニル｝アミノ］フェニル）尿素、Ｎ，Ｎ’－ビス（３－［｛４－メチルフェニル｝スルホニルアミノ］フェニル）尿素、Ｎ，Ｎ’－ビス（３－［｛３－メチルフェニル｝スルホニルアミノ］フェニル）尿素、Ｎ，Ｎ’－ビス（３－［｛２－メチルフェニル｝スルホニルアミノ］フェニル）尿素、Ｎ，Ｎ’－ビス（３－［｛２、５－ジメチルフェニル｝スルホニルアミノ］フェニル）尿素、Ｎ，Ｎ’－ビス（３－［｛２，４，６－トリメチルフェニル｝スルホニルアミノ］フェニル）尿素、Ｎ，Ｎ’－ビス（４－［｛ベンジルスルホニル｝アミノ］フェニル）尿素、Ｎ，Ｎ’－ビス（４－［｛フェニルスルホニル｝アミノ］フェニル）尿素、Ｎ，Ｎ’－ビス（４－［｛４－メチルフェニル｝スルホニルアミノ］フェニル）尿素、Ｎ，Ｎ’－ビス（４－［｛３－メチルフェニル｝スルホニルアミノ］フェニル）尿素、Ｎ，Ｎ’－ビス（４－［｛２－メチルフェニル｝スルホニルアミノ］フェニル）尿素、Ｎ，Ｎ’－ビス（４－［｛２，５－ジメチルフェニル｝スルホニルアミノ］フェニル）尿素、Ｎ，Ｎ’－ビス（４－［｛２，４，６－トリメチルフェニル｝スルホニルアミノ］フェニル）尿素、Ｎ，Ｎ’－ビス（２－［｛ベンジルスルホニル｝アミノ］フェニル）尿素、Ｎ，Ｎ’－ビス（２－［｛フェニルスルホニル｝アミノ］フェニル）尿素、Ｎ，Ｎ’－ビス（２－［｛４－メチルフェニル｝スルホニルアミノ］フェニル）尿素、Ｎ，Ｎ’－ビス（２－［｛３－メチルフェニル｝スルホニルアミノ］フェニル）尿素、Ｎ，Ｎ’－ビス（２－［｛２－メチルフェニル｝スルホニルアミノ］フェニル）尿素、Ｎ，Ｎ’－ビス（２－［｛２，５－ジメチルフェニル｝スルホニルアミノ］フェニル）尿素、Ｎ，Ｎ’－ビス（２－［｛２，４，６－トリメチルフェニル｝スルホニルアミノ］フェニル）尿素、等が挙げられる。 Examples of the phenylenediamine urea derivative represented by the above formula (1) include N,N'-bis(3-[{benzylsulfonyl}amino]phenyl)urea, N,N'-bis(3-[{phenyl sulfonyl}amino]phenyl)urea, N,N'-bis(3-[{4-methylphenyl}sulfonylamino]phenyl)urea, N,N'-bis(3-[{3-methylphenyl}sulfonylamino] phenyl)urea, N,N'-bis(3-[{2-methylphenyl}sulfonylamino]phenyl)urea, N,N'-bis(3-[{2,5-dimethylphenyl}sulfonylamino]phenyl) Urea, N,N'-bis(3-[{2,4,6-trimethylphenyl}sulfonylamino]phenyl)urea, N,N'-bis(4-[{benzylsulfonyl}amino]phenyl)urea, N , N'-bis(4-[{phenylsulfonyl}amino]phenyl)urea, N,N'-bis(4-[{4-methylphenyl}sulfonylamino]phenyl)urea, N,N'-bis(4 -[{3-methylphenyl}sulfonylamino]phenyl)urea, N,N'-bis(4-[{2-methylphenyl}sulfonylamino]phenyl)urea, N,N'-bis(4-[{2 ,5-dimethylphenyl}sulfonylamino]phenyl)urea, N,N'-bis(4-[{2,4,6-trimethylphenyl}sulfonylamino]phenyl)urea, N,N'-bis(2-[ {benzylsulfonyl}amino]phenyl)urea, N,N'-bis(2-[{phenylsulfonyl}amino]phenyl)urea, N,N'-bis(2-[{4-methylphenyl}sulfonylamino]phenyl ) urea, N,N'-bis(2-[{3-methylphenyl}sulfonylamino]phenyl)urea, N,N'-bis(2-[{2-methylphenyl}sulfonylamino]phenyl)urea, N , N'-bis(2-[{2,5-dimethylphenyl}sulfonylamino]phenyl)urea, N,N'-bis(2-[{2,4,6-trimethylphenyl}sulfonylamino]phenyl)urea , etc.
上記式（２）で表されるフェニレンジアミン尿素誘導体としては、例えば、Ｎ，Ｎ’－ビス（３－［｛４－メチルベンジルスルホニル｝アミノ］フェニル）尿素、Ｎ，Ｎ’－ビス（４－［｛４－メチルベンジルスルホニル｝アミノ］フェニル）尿素、Ｎ，Ｎ’－ビス（２－［｛４－メチルベンジルスルホニル｝アミノ］フェニル）尿素等が挙げられる。 Examples of the phenylenediamine urea derivative represented by the above formula (2) include N,N'-bis(3-[{4-methylbenzylsulfonyl}amino]phenyl)urea, N,N'-bis(4- Examples include [{4-methylbenzylsulfonyl}amino]phenyl)urea, N,N'-bis(2-[{4-methylbenzylsulfonyl}amino]phenyl)urea, and the like.
上記式（３）で表されるフェニレンジアミン尿素誘導体としては、例えば、Ｎ，Ｎ’－ビス（３－［｛１－ナフチルスルホニル｝アミノ］フェニル）尿素、Ｎ，Ｎ’－ビス（４－［｛１－ナフチルスルホニル｝アミノ］フェニル）尿素、Ｎ，Ｎ’－ビス（２－［｛１－ナフチルスルホニル｝アミノ］フェニル）尿素等が挙げられる。 Examples of the phenylenediamine urea derivative represented by the above formula (3) include N,N'-bis(3-[{1-naphthylsulfonyl}amino]phenyl)urea, N,N'-bis(4-[ Examples include {1-naphthylsulfonyl}amino]phenyl)urea, N,N'-bis(2-[{1-naphthylsulfonyl}amino]phenyl)urea, and the like.
上記式（４）で表されるフェニレンジアミン尿素誘導体としては、例えば、Ｎ，Ｎ’－ビス（３－［｛２－ナフチルスルホニル｝アミノ］フェニル）尿素、Ｎ，Ｎ’－ビス（４－［｛２－ナフチルスルホニル｝アミノ］フェニル）尿素、Ｎ，Ｎ’－ビス（２－［｛２－ナフチルスルホニル｝アミノ］フェニル）尿素等が挙げられる。 Examples of the phenylenediamine urea derivative represented by the above formula (4) include N,N'-bis(3-[{2-naphthylsulfonyl}amino]phenyl)urea, N,N'-bis(4-[ Examples include {2-naphthylsulfonyl}amino]phenyl)urea, N,N'-bis(2-[{2-naphthylsulfonyl}amino]phenyl)urea, and the like.
上記のフェニレンジアミン尿素誘導体のなかでも、特に、下記式（５）で表されるＮ，Ｎ’－ビス（３－［｛２，４，６－トリメチルフェニル｝スルホニルアミノ］フェニル）尿素は、耐水性および耐油性に優れ、耐水性試験および耐油性試験では、感熱記録層における記録部（印字部）の変色や濃度低下が少なく好適である。 Among the above-mentioned phenylenediamine urea derivatives, N,N'-bis(3-[{2,4,6-trimethylphenyl}sulfonylamino]phenyl)urea represented by the following formula (5) is particularly suitable for water resistance. It is suitable because it has excellent properties in water resistance and oil resistance, and there is little discoloration or decrease in density of the recorded portion (printed portion) in the heat-sensitive recording layer in water resistance tests and oil resistance tests.
本実施形態の感熱記録材料に用いられるフェニレンジアミン尿素誘導体は、対応するフェニレンジアミンを塩基存在下でモノスルホン化した後、各種の尿素化方法により尿素化する方法で合成される。
モノスルホン化の工程は、塩基存在下、活性水素を有しない有機溶媒中あるいは水－非水溶性有機溶媒の２相溶媒中、０℃～９０℃の反応温度で、フェニレンジアミンを反応させることにより実施される。
反応終了後、反応液を分液操作あるいは再結晶操作することによって、反応液からフェニレンジアミンモノスルホン化物が精製分離される。
The phenylenediamine urea derivative used in the heat-sensitive recording material of this embodiment is synthesized by monosulfonating the corresponding phenylenediamine in the presence of a base, and then converting it into urea using various urea conversion methods.
The monosulfonation step is carried out by reacting phenylenediamine in the presence of a base in an organic solvent without active hydrogen or in a two-phase solvent of water and a water-insoluble organic solvent at a reaction temperature of 0°C to 90°C. Implemented.
After the reaction is completed, the phenylenediamine monosulfonated product is purified and separated from the reaction solution by separating or recrystallizing the reaction solution.
尿素化の工程は、カルボニルジイミダゾールや尿素等のカルボニル基導入試剤を用いて、フェニレンジアミンモノスルホン化物を尿素化することにより実施される。尿素化の反応は、活性水素を有しない有機溶媒中あるいは水－非水溶性有機溶媒の２相溶媒中、０℃～２００℃の反応温度で実施される。
反応終了後、反応液を分液操作あるいは再結晶操作することによって、反応液からフェニレンジアミン尿素誘導体が精製単離される。
The urea formation step is carried out by urea formation of the phenylenediamine monosulfonated product using a carbonyl group-introducing reagent such as carbonyldiimidazole or urea. The ureation reaction is carried out at a reaction temperature of 0° C. to 200° C. in an organic solvent without active hydrogen or in a two-phase solvent of water and a water-insoluble organic solvent.
After the reaction is completed, the phenylenediamine urea derivative is purified and isolated from the reaction solution by separating or recrystallizing the reaction solution.
上記の反応の反応式の一例を下記に示す。 An example of the reaction formula for the above reaction is shown below.
（フェニレンジアミンのモノスルホン化工程）
フェニレンジアミンのモノスルホン化工程の反応式の一例を下記式（６）に示す。
(Monosulfonation process of phenylenediamine)
An example of the reaction formula of the monosulfonation step of phenylenediamine is shown in the following formula (6).
（フェニレンジアミンモノトシル化物の尿素化工程）
フェニレンジアミンモノトシル化物の尿素化工程の反応式の一例を下記式（７）に示す。
(Urea conversion process of phenylenediamine monotosylated product)
An example of the reaction formula of the urea conversion step of phenylenediamine monotosylated product is shown in the following formula (7).
本実施形態の感熱記録材料において、常温で無色ないし淡色の塩基性染料としては、従来公知のロイコ染料から選ぶことができ、例えば、トリフェニルメタン系化合物、フルオラン系化合物、ジフェニルメタン系化合物、スピロ系化合物、フルオレン系化合物、チアジン系化合物等が挙げられる。 In the heat-sensitive recording material of this embodiment, the basic dye that is colorless or light-colored at room temperature can be selected from conventionally known leuco dyes, such as triphenylmethane compounds, fluoran compounds, diphenylmethane compounds, and spiro-based dyes. compounds, fluorene compounds, thiazine compounds, and the like.
トリフェニルメタン系化合物としては、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、３，３－ビス（ｐ－ジメチルアミノフェニル）フタリド、３，３－ビス（ｐ－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－エトキシフェニル）－３－（１－エチル－２－メチルインドール－３－イル）－４－アザフタリド、３－（１－エチル－２－メチルインドール－３－イル）－３－（４－ジエチルアミノ－２－ｎ－ヘキシルオキシフェニル）－４－アザフタリド、３－（１－エチル－２－メチルインドール－３－イル）－３－（４－ジエチルアミノ）－２－メチルフェニル－４－アザフタリド、３－（４－ジエチルアミノフェニル）－３－（１－エチル－２－メチルインドール－３－イル）フタリド、３－（２－メチル－１－ｎ－オクチルインドール－３－イル）－３－（４－ジエチルアミノ－２－エトキシフェニル）－４－アザフタリド、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、３，３’－ビス（１－ｎ－アミル－２－メチルインドール－３－イル）フタリド、３，３’－ビス（１－ｎ－ブチル－２－メチルインドール－３－イル）フタリド、３，３’－ビス（１－エチル－２－メチルインドール－３－イル）フタリド、３，３’－ビス（ｐ－ジメチルアミノフェニル）フタリド等が挙げられる。 Examples of triphenylmethane compounds include 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3,3-bis(p-dimethylaminophenyl)phthalide, and 3,3-bis( p-Methylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3- (1-ethyl-2-methylindol-3-yl)-3-(4-diethylamino-2-n-hexyloxyphenyl)-4-azaphthalide, 3-(1-ethyl-2-methylindol-3-yl) )-3-(4-diethylamino)-2-methylphenyl-4-azaphthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3-(2 -Methyl-1-n-octylindol-3-yl)-3-(4-diethylamino-2-ethoxyphenyl)-4-azaphthalide, 2,2-bis{4-[6'-(N-cyclohexyl-N -methylamino)-3'-methylspiro[phthalido-3,9'-xanthene]-2'-ylamino]phenyl}propane, 3,3'-bis(1-n-amyl-2-methylindol-3-yl ) phthalide, 3,3'-bis(1-n-butyl-2-methylindol-3-yl) phthalide, 3,3'-bis(1-ethyl-2-methylindol-3-yl) phthalide, 3 , 3'-bis(p-dimethylaminophenyl)phthalide, and the like.
フルオラン系化合物としては、例えば、３－ジエチルアミノ－７－ジベンジルアミノベンゾ［α］フルオラン、３－（Ｎ－エチル－Ｎ－イソペンチルアミノ）－６－メチル－７－アニリノフルオラン、３－ジエチルアミノ－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－（ｏ，ｐ－ジメチルアニリノ）フルオラン、３－（Ｎ－エチル－Ｎ－ｐ－トルイジノ）－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－ジブチルアミノ－６－メチル－７－アニリノフルオラン、３－（Ｎ－シクロヘキシル－Ｎ－メチルアミノ）－６－メチル－７－アニリノフルオラン、３－ジエチルアミノ－７－（ｏ－クロロアニリノ）フルオラン、３－ジエチルアミノ－７－（ｍ－トリフロロメチルアニリノ）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－［Ｎ－（３－エトキシプロピル）－Ｎ－エチルアミノ］６－メチル－７－アニリノフルオラン、３－（Ｎ－ｎ－ヘキシル－Ｎ－エチルアミノ）－７－（ｏ－クロロアニリノ）フルオラン、３－（Ｎ－エチル－Ｎ－２－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－ジブチルアミノ－７－（ｏ－クロロアニリノ）フルオラン、３，６－ジメトキシフルオラン、３－ピロリジノ－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、３－ジエチルアミノ－７，８－ジベンゾフルオラン、３－ジエチルアミノ－６，７－ジメチルフルオラン、３－（Ｎ－メチル－ｐ－トルイジノ）－７－メチルフルオラン、３－（Ｎ－メチル－Ｎ－イソアミルアミノ）－７，８－ベンゾフルオラン、３－（Ｎ－メチル－Ｎ－イソアミルアミノ）－７－フェノキシフルオラン、３－（Ｎ－エチル－Ｎ－ｐ－トリルアミノ）－７－（Ｎ－フェニル－Ｎ－メチルアミノ）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－ベンジルアミノフルオラン、３－ピロリジノ－７－ジベンジルアミノフルオラン等が挙げられる。 Examples of fluoran compounds include 3-diethylamino-7-dibenzylaminobenzo[α]fluoran, 3-(N-ethyl-N-isopentylamino)-6-methyl-7-anilinofluoran, and 3-diethylamino-7-dibenzylaminobenzo[α]fluoran. Diethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-(o,p-dimethylanilino)fluoran, 3-(N-ethyl-Np-toluidino)-6- Methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, 3-(N-cyclohexyl-N-methyl amino)-6-methyl-7-anilinofluorane, 3-diethylamino-7-(o-chloroanilino)fluorane, 3-diethylamino-7-(m-trifluoromethylanilino)fluorane, 3-di(n- pentyl)amino-6-methyl-7-anilinofluorane, 3-[N-(3-ethoxypropyl)-N-ethylamino]6-methyl-7-anilinofluorane, 3-(N-n- hexyl-N-ethylamino)-7-(o-chloroanilino)fluorane, 3-(N-ethyl-N-2-tetrahydrofurfurylamino)-6-methyl-7-anilinofluorane, 3-dibutylamino- 7-(o-chloroanilino)fluorane, 3,6-dimethoxyfluorane, 3-pyrrolidino-6-chlorofluorane, 3-diethylamino-6-methyl-7-chlorofluorane, 3-diethylamino-7-chlorofluorane , 3-diethylamino-7,8-dibenzofluorane, 3-diethylamino-6,7-dimethylfluorane, 3-(N-methyl-p-toluidino)-7-methylfluorane, 3-(N-methyl- N-isoamylamino)-7,8-benzofluorane, 3-(N-methyl-N-isoamylamino)-7-phenoxyfluorane, 3-(N-ethyl-Np-tolylamino)-7-( N-phenyl-N-methylamino)fluorane, 3-diethylamino-7-anilinofluorane, 3-diethylamino-7-benzylaminofluorane, 3-pyrrolidino-7-dibenzylaminofluorane, and the like.
これらの塩基性染料は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 These basic dyes may be used alone or in combination of two or more.
本実施形態の感熱記録材料は、必要に応じて増感剤を用いることができる。増感剤としては、従来公知の増感剤を用いることができる。増感剤としては、例えば、ステアリン酸アミド、ビスステアリン酸アミド、パルミチン酸アミド等の脂肪酸アミド、ｐ－トルエンスルホンアミド、ステアリン酸、ベヘン酸やパルミチン酸等のカルシウム、亜鉛あるいはアルミニウム等の脂肪酸金属塩、ｐ－ベンジルビフェニル、ジフェニルスルホン、ベンジルオキシ安息香酸ベンジル、２－ベンジルオキシナフタレン、１，２－ビス（ｐ－トリルオキシ）エタン、１，２－ビス（フェノキシ）エタン、１，２－ビス（３－メチルフェノキシ）エタン、１，３－ビス（フェノキシ）プロパン、シュウ酸ジベンジル、シュウ酸ｐ－メチルベンジル、ｍ－ターフェニル、１－ヒドロキシ－２－ナフトエ酸等が挙げられる。 A sensitizer can be used in the heat-sensitive recording material of this embodiment, if necessary. As the sensitizer, conventionally known sensitizers can be used. Examples of sensitizers include fatty acid amides such as stearamide, bisstearamide, and palmitic acid amide, p-toluenesulfonamide, stearic acid, calcium such as behenic acid and palmitic acid, and fatty acid metals such as zinc or aluminum. Salt, p-benzylbiphenyl, diphenylsulfone, benzyl benzyloxybenzoate, 2-benzyloxynaphthalene, 1,2-bis(p-tolyloxy)ethane, 1,2-bis(phenoxy)ethane, 1,2-bis( Examples include 3-methylphenoxy)ethane, 1,3-bis(phenoxy)propane, dibenzyl oxalate, p-methylbenzyl oxalate, m-terphenyl, and 1-hydroxy-2-naphthoic acid.
さらに、本実施形態の感熱記録材料は、従来公知の保存安定剤を併用することができる。
保存安定剤としては、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）、１，１，３－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、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、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、トリス（２，６－ジメチル－４－ｔｅｒｔ－ブチル－３－ヒドロキシベンジル）イソシアヌレート、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－メチルグリシルオキシ）ジフェニルスルホン、テレフタル酸グリシジル、ビスフェノールＡ型エポキシ樹脂型、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塩または多価金属塩、ビス（４－エチレンイミンカルボニルアミノフェニル）メタン、さらに、下記式（８）で表されるジフェニルスルホン架橋型化合物等が挙げられる。
Furthermore, the heat-sensitive recording material of this embodiment can be used in combination with a conventionally known storage stabilizer.
Examples of storage stabilizers include 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), and 2,2'-ethylidene. Bis(4,6-di-tert-butylphenol), 4,4'-thiobis(2-methyl-6-tert-butylphenol), 4,4'-butylidene bis(6-tert-butyl m-cresol), 1, 1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,1,3-tris(2-methyl-4-hydroxy-5-cyclohexylphenyl)butane, 4,4' -bis[(4-methyl-3-phenoxycarbonylaminophenyl)ureido]diphenylsulfone, tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl)isocyanurate, 4,4'-thiobis(3 -methylphenol), 4,4'-dihydroxy-3,3',5,5'-tetrabromodiphenylsulfone, 4,4'-dihydroxy3,3',5,5'-tetramethyldiphenylsulfone, 2, 2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethyl) Hindered phenol compounds such as phenyl)propane, 1,4-diglycidyloxybenzene, 4,4'-diglycidyloxydiphenylsulfone, 4-benzyloxy-4'-(2-methylglycyloxy)diphenylsulfone, terephthal Epoxy compounds such as glycidyl acid, bisphenol A type epoxy resin type, cresol novolak type epoxy resin, phenol novolac type epoxy resin, N,N'-di-2-naphthyl-p-phenylenediamine, 2,2'-methylenebis(4 , 6-di-tert-butylphenyl) phosphate, sodium salt or polyvalent metal salt, bis(4-ethyleneiminecarbonylaminophenyl)methane, and a diphenylsulfone crosslinked compound represented by the following formula (8), etc. Can be mentioned.
上記保存安定剤のなかでも、特に、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、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、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および下記式（８）で表されるジフェニルスルホン架橋型化合物がさらなる保存性改良に好適である。 Among the above storage stabilizers, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,1,3-tris(2-methyl-4-hydroxy -5-cyclohexylphenyl)butane, 4,4'-bis[(4-methyl-3-phenoxycarbonylaminophenyl)ureido]diphenylsulfone, and the diphenylsulfone crosslinked compound represented by the following formula (8) provide further storage stability. Suitable for improvement.
本実施形態の感熱記録材料は、感熱記録層がバインダーを含んでいてもよい。バインダーとしては、例えば、酸化澱粉、エステル化澱粉、エーテル化澱粉等の澱粉類、メチルセルロース、カルボキシメチルセルロース、メトキシセルロース、ヒドロキシエチルセルロース等のセルロース類、カゼイン、ゼラチン、完全（または部分）鹸化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、アミド変性ポリビニルアルコール、スルホン酸変性ポリビニルアルコール、ブチラール変性ポリビニルアルコール等のポリビニルアルコール類、スチレン－無水マレイン酸共重合体、スチレンーブタジエン共重合体樹脂並びに、酢酸ビニル樹脂、ウレタン樹脂、アクリルアミド樹脂、アクリル酸エステル樹脂、ビニルブチラール・スチロールおよびそれらの共重合体樹脂、アミド樹脂、シリコーン樹脂、石油樹脂、テルペン樹脂、ケトン樹脂、クロマン樹脂等が挙げられる。これらのバインダーは、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。これらのバインダーは、溶剤に溶解して使用するほか、水または他の媒体中に乳化あるいはペースト状に分散した状態で使用することもできる。 In the heat-sensitive recording material of this embodiment, the heat-sensitive recording layer may contain a binder. Examples of binders include starches such as oxidized starch, esterified starch, and etherified starch; celluloses such as methylcellulose, carboxymethylcellulose, methoxycellulose, and hydroxyethylcellulose; casein, gelatin, fully (or partially) saponified polyvinyl alcohol, and carboxylic acid. Polyvinyl alcohols such as modified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, silicon-modified polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, butyral-modified polyvinyl alcohol, styrene-maleic anhydride copolymer, styrene-butadiene copolymer Polymer resins, vinyl acetate resins, urethane resins, acrylamide resins, acrylic ester resins, vinyl butyral styrene and their copolymer resins, amide resins, silicone resins, petroleum resins, terpene resins, ketone resins, chroman resins, etc. Can be mentioned. These binders may be used alone or in combination of two or more. These binders can be used not only by being dissolved in a solvent, but also by being emulsified or dispersed in a paste form in water or other medium.
本実施形態の感熱記録材料は、感熱記録層が顔料を含んでいてもよい。顔料としては、例えば、非晶性シリカ、非晶性珪酸カルシウム、重質炭酸カルシウム、軽質炭酸カルシウム、カオリン、焼成カオリン、ケイソウ土、タルク、二酸化チタン、酸化亜鉛、水酸化アルミニウム、水酸化マグネシウム、硫酸バリウム、コロイダルシリカ、ポリスチレンパウダー、ナイロンパウダー、尿素－ホルマリン樹脂フィラー、スチレン－メタクリル酸共重合体、スチレン－ブタジエン共重合体や中空プラスチックピグメント等の無機あるいは有機顔料等が挙げられる。これらの顔料は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 In the heat-sensitive recording material of this embodiment, the heat-sensitive recording layer may contain a pigment. Examples of pigments include amorphous silica, amorphous calcium silicate, heavy calcium carbonate, light calcium carbonate, kaolin, calcined kaolin, diatomaceous earth, talc, titanium dioxide, zinc oxide, aluminum hydroxide, magnesium hydroxide, Examples include inorganic or organic pigments such as barium sulfate, colloidal silica, polystyrene powder, nylon powder, urea-formalin resin filler, styrene-methacrylic acid copolymer, styrene-butadiene copolymer, and hollow plastic pigment. These pigments may be used alone or in combination of two or more.
本実施形態の感熱記録材料は、感熱記録層が助剤を含んでいてもよい。助剤としては、例えば、ジオクチオル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および高級脂肪酸金属塩、ステアリン酸アミド等の高級脂肪酸アミド、パラフィン、ポリエチレンワックス、酸化ポリエチレンワックス、カスターワックス、エステルワックス等のワックス類、アジピン酸ジヒドラジド等のヒドラジド化合物、グリオキザール、ホウ酸、ジアルデヒドスターチ、メチロール尿素、グリオキシル酸塩、エポキシ系化合物等の耐水化剤、消泡剤、着色染料、蛍光染料等が挙げられる。これらの助剤は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 In the heat-sensitive recording material of this embodiment, the heat-sensitive recording layer may contain an auxiliary agent. Examples of auxiliary agents include dispersants such as sodium dioctiolsuccinate, sodium dodecylbenzenesulfonate, sodium lauryl alcohol sulfate, fatty acid metal salts, zinc stearate, calcium stearate, higher fatty acid metal salts, stearamide, etc. Higher fatty acid amides, paraffin, polyethylene wax, waxes such as oxidized polyethylene wax, castor wax, and ester wax, hydrazide compounds such as adipic acid dihydrazide, glyoxal, boric acid, dialdehyde starch, methylol urea, glyoxylate, epoxy type Waterproofing agents such as compounds, antifoaming agents, colored dyes, fluorescent dyes, and the like can be mentioned. These auxiliaries may be used alone or in combination of two or more.
本実施形態の感熱記録材料では、感熱記録層に含まれる顕色剤、塩基性染料、顕色剤、増感剤、バインダー、顔料およびその他助剤等の添加剤の種類や使用量は、感熱記録層に要求される品質性能に応じて適宜調節される。 In the heat-sensitive recording material of this embodiment, the types and amounts of additives such as color developer, basic dye, color developer, sensitizer, binder, pigment, and other auxiliary agents contained in the heat-sensitive recording layer are It is adjusted as appropriate depending on the quality performance required of the recording layer.
感熱記録層の形成方法は、上記の感熱記録層に含まれる顕色剤、塩基性染料、顕色剤、増感剤、バインダー、顔料、その他助剤等の添加剤および溶媒等を含む感熱記録層用塗料を調製する工程と、支持体上に感熱記録層用塗料を塗工する工程と、を有する。 The method for forming the heat-sensitive recording layer is to form a heat-sensitive recording layer containing additives such as a color developer, a basic dye, a color developer, a sensitizer, a binder, a pigment, and other auxiliaries, and a solvent contained in the heat-sensitive recording layer. The method includes a step of preparing a coating material for the layer, and a step of coating the coating material for the heat-sensitive recording layer on a support.
感熱記録層用塗料を調製する工程では、感熱記録層に要求される品質性能に応じて、顕色剤、塩基性染料、顕色剤、増感剤、バインダー、顔料、その他助剤等の添加剤および溶媒の種類や使用量を適宜調節し、これらを混合することにより、感熱記録層用塗料を得る。 In the process of preparing the paint for the heat-sensitive recording layer, color developers, basic dyes, color developers, sensitizers, binders, pigments, and other auxiliary agents are added depending on the quality performance required for the heat-sensitive recording layer. A paint for a heat-sensitive recording layer is obtained by appropriately adjusting the types and amounts of the agent and solvent and mixing them.
支持体上に感熱記録層用塗料を塗工するための塗工方法は、特に限定されるものではなく、例えば、エアーナイフコーティング、バリバーコーティング、ピュアーブレードコーティング、ロッドブレードコーティング、カーテンコーティング、ダイコーティング、スライドビロードコーティング、オフセットグラビアコーティング、５本ロールコーティング等が用いられる。 The coating method for coating the heat-sensitive recording layer coating on the support is not particularly limited, and examples include air knife coating, varibar coating, pure blade coating, rod blade coating, curtain coating, and dye coating. Coating, slide velvet coating, offset gravure coating, five-roll coating, etc. are used.
支持体上に感熱記録層用塗料を塗工する工程では、支持体上に感熱記録層用塗料を直接塗工することにより、支持体上に感熱記録層を形成してもよいし、支持体上に下塗り層を形成した後、形成された下塗り層上に感熱記録層を形成してもよい。
支持体上に下塗り層の設けることにより、感熱記録層における感度、画質の改善、印字粕吸収機能等を改善することができる。
In the step of coating the heat-sensitive recording layer coating material on the support, the heat-sensitive recording layer may be formed on the support by directly coating the heat-sensitive recording layer coating on the support, or the heat-sensitive recording layer may be formed on the support. After forming an undercoat layer thereon, a heat-sensitive recording layer may be formed on the formed undercoat layer.
By providing an undercoat layer on the support, it is possible to improve the sensitivity, image quality, printing sludge absorption function, etc. in the heat-sensitive recording layer.
下塗り層の組成は、目的により適宜選択することができる。下塗り層は、例えば、バインダー、顔料（無機顔料、有機顔料）等を含む。 The composition of the undercoat layer can be appropriately selected depending on the purpose. The undercoat layer includes, for example, a binder, pigments (inorganic pigments, organic pigments), and the like.
下塗り層に含まれるバインダーは、感熱記録層に用いられるバインダーを用いることができる。すなわち、バインダーとしては、例えば、酸化澱粉、エステル化澱粉、エーテル化澱粉等の澱粉類、メチルセルロース、カルボキシセルロース、メトキシセルロース、メトキシセルロース、ヒドロキシエチルセルロース等のセルロース樹脂、カゼイン、ゼラチン、完全（または部分）鹸化ポリビニアルコール、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、アミド変性ポリビニルアルコール、スルホン酸変性ポリビニルアルコール、ブチラール変性ポリビニルアルコール等のポリビニルアルコール類、スチレン－無水マレイン酸共重合体系ラテックス、スチレンーブタジエン共重合体系ラテックス、酢酸ビニル樹脂系ラテックス、ウレタン樹脂系ラテックス及びアクリル樹脂系ラテックス等を用いることができる。 As the binder contained in the undercoat layer, a binder used in the heat-sensitive recording layer can be used. That is, examples of the binder include starches such as oxidized starch, esterified starch, and etherified starch, cellulose resins such as methylcellulose, carboxycellulose, methoxycellulose, methoxycellulose, and hydroxyethylcellulose, casein, gelatin, complete (or partial) Polyvinyl alcohols such as saponified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, silicon-modified polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, butyral-modified polyvinyl alcohol, styrene-maleic anhydride copolymer system Latex, styrene-butadiene copolymer latex, vinyl acetate resin latex, urethane resin latex, acrylic resin latex, etc. can be used.
下塗り層に含まれる無機顔料としては、例えば、水酸化アルミニウム、水酸化マグネシウム、硫酸バリウム、珪酸アルミニウム、炭酸カルシウム等の金属酸化物、金属水酸化物、硫酸塩、炭酸塩等の金属化合物、無定形シリカ、焼成カオリン、タルク等の無機白色顔料等が挙げられる。これらのなかでも、特に、焼成カオリンは、感熱記録層における発色感度と画質および印字粕吸収性に優れていることから、好適に用いられる。
無機顔料の平均粒子径は、０．５μｍ～３．０μｍであることが好ましい。
Examples of inorganic pigments contained in the undercoat layer include metal oxides such as aluminum hydroxide, magnesium hydroxide, barium sulfate, aluminum silicate, and calcium carbonate; metal compounds such as metal hydroxides, sulfates, and carbonates; Examples include inorganic white pigments such as regular silica, calcined kaolin, and talc. Among these, calcined kaolin is particularly preferably used because it is excellent in color development sensitivity, image quality, and print sludge absorbability in the heat-sensitive recording layer.
The average particle diameter of the inorganic pigment is preferably 0.5 μm to 3.0 μm.
また、下塗り層に含まれる有機顔料としては、例えば、球状樹脂粒子（所謂、密実型樹脂粒子）、中空樹脂粒子、貫通孔を有する樹脂粒子、中空樹脂粒子の一部を変面で裁断して得られるような開口部を有する樹脂等が挙げられる。感熱記録層における記録濃度を高めるには、中空樹脂粒子が好適に用いられる。 In addition, examples of the organic pigments contained in the undercoat layer include spherical resin particles (so-called dense resin particles), hollow resin particles, resin particles having through holes, and hollow resin particles cut by cutting a part of the hollow resin particles with a deformed surface. Examples include resins having openings such as those obtained by Hollow resin particles are preferably used to increase the recording density in the heat-sensitive recording layer.
感熱記録層における感度と印字粕吸収性を両立させるためには、無機顔料と有機顔料を併用することが好ましい。
無機顔料と有機顔料の配合比は、質量比で９０：１０～３０：７０であることが好ましく、７０：３０～５０：５０であることがより好ましい。
In order to achieve both sensitivity and printing sludge absorbability in the heat-sensitive recording layer, it is preferable to use an inorganic pigment and an organic pigment in combination.
The blending ratio of the inorganic pigment and the organic pigment is preferably 90:10 to 30:70 in mass ratio, more preferably 70:30 to 50:50.
さらに、感熱記録層における感度の向上を図るために、下塗り層は発泡系樹脂を含んでいてもよい。 Further, in order to improve the sensitivity of the heat-sensitive recording layer, the undercoat layer may contain a foamed resin.
下塗り層は、下塗り層塗料を、支持体上に塗布した後、乾燥して形成される。
下塗り層塗料は、分散媒体である水に、無機顔料および有機顔料の少なくとも１種とバインダーとを混合、攪拌して調製したものである。
支持体上への下塗り層塗料の塗布量は、下塗り層塗料の乾燥後の塗布量が１ｇ／ｍ２～２０ｇ／ｍ２であることが好ましく、５ｇ／ｍ２～１５ｇ／ｍ２であることがより好ましい。
The undercoat layer is formed by applying an undercoat layer paint onto a support and then drying it.
The undercoat layer paint is prepared by mixing at least one of an inorganic pigment and an organic pigment and a binder in water, which is a dispersion medium, and stirring the mixture.
The coating amount of the undercoat layer paint on the support is preferably 1 g/m 2 to 20 g/
下塗り層塗料におけるバインダーの含有量は、下塗り層全固形分１００質量％中、５質量％～４０質量％となる量であることが好ましい。
下塗り層塗料における顔料の含有量は、下塗り層全固形分１００質量％中、１０質量％～９５質量％となる量であることが好ましい。
The content of the binder in the undercoat layer paint is preferably 5% by mass to 40% by mass based on 100% by mass of the total solid content of the undercoat layer.
The pigment content in the undercoat layer paint is preferably 10% by mass to 95% by mass based on 100% by mass of the total solid content of the undercoat layer.
下塗り層用塗料には、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、パラフィンワックス等の滑剤、蛍光染料、着色染料、界面活性剤、架橋剤等の各種助剤を添加することもできる。 If necessary, various auxiliary agents such as lubricants such as zinc stearate, calcium stearate, and paraffin wax, fluorescent dyes, colored dyes, surfactants, and crosslinking agents may be added to the coating for the undercoat layer.
下塗り層は、１層であってもよく、２層以上であってもよい。 The number of undercoat layers may be one layer, or two or more layers.
本実施形態の感熱記録材料では、感熱記録層上に、成膜性を有するバインダーを主成分とする保護層を設けてもよい。
保護層の形成方法は、溶媒である水に、バインダー、顔料、および、必要に応じてその他助剤を混合、撹拌して保護層用塗料を調製する工程と、感熱記録層上に保護層用塗料を塗工する工程と、を有する。
In the heat-sensitive recording material of this embodiment, a protective layer containing a binder having film-forming properties as a main component may be provided on the heat-sensitive recording layer.
The method for forming the protective layer consists of a process of preparing a coating for the protective layer by mixing and stirring a binder, a pigment, and other auxiliaries as necessary with water as a solvent, and a process of preparing a coating for the protective layer on the heat-sensitive recording layer. and a step of applying paint.
保護層用塗料に用いられるバインダー、顔料、助剤は、上記の感熱記録層用塗料に含まれるもの８が用いられる。 As the binder, pigment, and auxiliary agent used in the coating for the protective layer, those included in the coating for the heat-sensitive recording layer are used.
また、保護層上に光沢層を設けてもよい。
光沢層の形成方法としては、例えば、保護層上に電子線または紫外線硬化性化合物を主成分とする塗料（光沢層用塗料）を塗布した後、その塗液に電子線または紫外線を照射して硬化させて光沢層を得る方法や、保護層上に超微粒子のコアシェル型アクリル樹脂を塗布した後、その塗液を硬化させて光沢層を得る方法等が挙げられる。
Furthermore, a glossy layer may be provided on the protective layer.
A method for forming a glossy layer is, for example, by applying a paint containing an electron beam or ultraviolet ray curing compound as a main component (gloss layer paint) on the protective layer, and then irradiating the coating liquid with an electron beam or ultraviolet rays. Examples include a method of curing to obtain a glossy layer, and a method of coating an ultrafine core-shell type acrylic resin on a protective layer and then curing the coating liquid to obtain a glossy layer.
さらに、支持体の裏面側に帯電防止層を設けてもよい。 Furthermore, an antistatic layer may be provided on the back side of the support.
下塗り層用塗料、保護層用塗料および光沢層用塗料は、感熱記録層用塗料と同様に、ピュアーブレードコーティング、ロッドブレードコーティング、カーテンコーティング、オフセットグラビアコーティング等の適宜の塗工方法により塗工することができる。これらの塗工方法によって、前記の各塗料によって形成した塗膜を乾燥することにより、下塗り層、保護層および光沢層が形成される。 The paint for the undercoat layer, the paint for the protective layer, and the paint for the glossy layer are applied by an appropriate coating method such as pure blade coating, rod blade coating, curtain coating, offset gravure coating, etc., in the same way as the paint for the heat-sensitive recording layer. be able to. By drying the coating film formed with each of the above-mentioned paints by these coating methods, an undercoat layer, a protective layer, and a glossy layer are formed.
下塗り層、保護層および光沢層を形成した後、または感熱記録材料を構成する全ての層を形成した後、スーパーキャレンダー処理する等の感熱記録材料製造分野における各種の公知処理技術を適宜付加してもよい。 After forming the undercoat layer, protective layer and gloss layer, or after forming all the layers constituting the heat-sensitive recording material, various known processing techniques in the field of heat-sensitive recording material manufacturing, such as supercalender treatment, are added as appropriate. It's okay.
本実施形態の感熱記録材料の感熱記録層において、増感剤の含有量は、感熱記録層に含まれる塩基性染料１００質量部に対して、０質量部～４００質量部であることが好ましい。
本実施形態の感熱記録材料の感熱記録層において、バインダーの含有量は、感熱記録層全固形分１００質量％中、５質量％～５０質量％であることが好ましい。
In the heat-sensitive recording layer of the heat-sensitive recording material of the present embodiment, the content of the sensitizer is preferably 0 to 400 parts by weight based on 100 parts by weight of the basic dye contained in the heat-sensitive recording layer.
In the heat-sensitive recording layer of the heat-sensitive recording material of this embodiment, the content of the binder is preferably 5% by mass to 50% by mass based on 100% by mass of the total solid content of the heat-sensitive recording layer.
本実施形態では、塩基性染料、顕色剤、増感剤および保存安定剤等は、例えば、水を分散媒体として、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って平均粒子径が２μｍ以下になるように微分散した分散液として用いられる。
このように微分散された分散液に、必要に応じて、顔料、バインダー、助剤等を混合、撹拌することにより、感熱記録層用塗料を調製する。
In this embodiment, basic dyes, color developers, sensitizers, storage stabilizers, etc. are reduced to an average particle size of 2 μm or less using a stirring pulverizer such as a ball mill, attritor, or sand mill using water as a dispersion medium. It is used as a finely dispersed dispersion liquid.
A paint for a heat-sensitive recording layer is prepared by mixing and stirring a pigment, a binder, an auxiliary agent, etc., as necessary, into the finely dispersed dispersion liquid.
このようにして得られた感熱記録層用塗料を、支持体上に塗布した後、乾燥することにより、支持体上に感熱記録層を形成し、本実施形態の感熱記録材料を得る。
支持体上への感熱記録層用塗料の塗布量は、感熱記録層用塗料の乾燥後の塗布量が１．０ｇ／ｍ２～２０ｇ／ｍ２であることが好ましく、２．０ｇ／ｍ２～７．０ｇ／ｍ２であることがより好ましい。
The heat-sensitive recording layer coating material thus obtained is applied onto a support and then dried to form a heat-sensitive recording layer on the support, thereby obtaining the heat-sensitive recording material of this embodiment.
The coating amount of the heat-sensitive recording layer coating material on the support is preferably 1.0 g/m 2 to 20 g/ m 2 , and 2.0 g/m 2 after drying. More preferably, it is 7.0 g/m 2 .
支持体としては、例えば、紙、再生紙、合成紙、プラスティックフィルム、不織布、金属箔等が挙げられる。また、これらを組み合せた複合シートも支持体として用いることができる。
支持体の厚さは、特に限定されず、本実施形態の感熱記録材料の用途に応じて適宜調整される。
Examples of the support include paper, recycled paper, synthetic paper, plastic film, nonwoven fabric, metal foil, and the like. Moreover, a composite sheet made by combining these can also be used as a support.
The thickness of the support is not particularly limited, and is appropriately adjusted depending on the use of the heat-sensitive recording material of this embodiment.
本実施形態の感熱記録材料によれば、発色濃度、白色度、および印字部の耐熱性、耐水性、耐油性、保存性等の感熱記録材料としての要求性能を満たす感熱記録材料を提供することができる。 According to the heat-sensitive recording material of this embodiment, it is possible to provide a heat-sensitive recording material that satisfies the required performance as a heat-sensitive recording material, such as color density, whiteness, and heat resistance, water resistance, oil resistance, and preservability of the printed portion. I can do it.
以下、実施例および比較例により本発明をさらに具体的に説明するが、本発明は以下の実施例に限定されるものではない。
なお、実施例および比較例中、「部」および「％」は、「質量部」および「質量％」を表わす。
EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
In the examples and comparative examples, "parts" and "%" represent "parts by mass" and "% by mass."
（合成例１）Ｎ，Ｎ’－ビス（３－［｛４－メチルフェニル｝スルホニルアミノ］フェニル）尿素の合成
滴下ロート、温度計、窒素導入管、冷却器を付置した２００ｍＬの四ツ口フラスコに、ｍ－フェニレンジアミン５．４ｇ（５０ｍＭ）、酢酸エチル７０ｍＬ、トリエチルアミン５．６ｇ（５５ｍＭ）を仕込み窒素置換をした後、内温を３０℃にした。
次いで、四ツ口フラスコの内温を保持しながら、酢酸エチル４０ｍＬに溶解したｐ－トルエンスルホニルクロライド９．５ｇ（５０ｍＭ）を滴下した。
反応を２時間継続した後、四ツ口フラスコの内温を加温して５０℃にし、有機相を塩酸水、重曹水、水の順に水洗分液した。
この有機相に、酢酸エチルに懸濁したカルボニルジイミダゾール４．１ｇ（２５ｍＭ）を間欠的に注加した。
反応を２時間継続した後、有機相を塩酸水、重曹水、水の順に水洗分液し、有機相を減圧濃縮し、濃縮残渣を得た。
得られた濃縮残渣に酢酸エチルを加えて、濃縮残渣を結晶化した。
結晶を濾別、乾燥し、得られた結晶について、核磁気共鳴スペクトル（１Ｈ－ＮＭＲスペクトル）、電解離脱質量スペクトル（ＦＤ－ＭＳスペクトル）および赤外吸収スペクトル（ＩＲスペクトル）を測定した。
１Ｈ－ＮＭＲスペクトルの測定には、ブルカー・バイオスピン社製のＡＶＡＮＣＥ ＮＥＯ ｃｒｙｏ ５００型（商品名）を用いた。
ＦＤ－ＭＳスペクトルの測定には、日本電子社製のＪＴＳ－Ｔ１００ ＧＣＡｃｃｏ ＴＯＦＧＣ（商品名）を用いた。
ＩＲスペクトルの測定には、島津製作所社製の島津フーリエ変換赤外分光光度計ＩＲ Ａｆｆｉｎｉｔｙ－１（商品名）を用いた。
図１に１Ｈ－ＮＭＲスペクトル、図２にＦＤ－ＭＳスペクトル、図３にＩＲスペクトルを示す。
図１～図３の結果から、Ｎ，Ｎ’－ビス（３－［｛４－メチルフェニル｝スルホニルアミノ］フェニル）尿素が得られていることが確認された。
(Synthesis Example 1) Synthesis of N,N'-bis(3-[{4-methylphenyl}sulfonylamino]phenyl)
Next, while maintaining the internal temperature of the four-necked flask, 9.5 g (50 mM) of p-toluenesulfonyl chloride dissolved in 40 mL of ethyl acetate was added dropwise.
After the reaction was continued for 2 hours, the internal temperature of the four-necked flask was raised to 50° C., and the organic phase was washed and separated in the order of hydrochloric acid, sodium bicarbonate, and water.
4.1 g (25 mM) of carbonyldiimidazole suspended in ethyl acetate was added intermittently to this organic phase.
After continuing the reaction for 2 hours, the organic phase was washed and separated in this order with aqueous hydrochloric acid, aqueous sodium bicarbonate, and water, and the organic phase was concentrated under reduced pressure to obtain a concentrated residue.
Ethyl acetate was added to the obtained concentrated residue to crystallize it.
The crystals were filtered and dried, and the resulting crystals were subjected to nuclear magnetic resonance spectra ( 1 H-NMR spectra), electrolytic desorption mass spectra (FD-MS spectra), and infrared absorption spectra (IR spectra).
1 H-NMR spectrum was measured using AVANCE NEO cryo 500 model (trade name) manufactured by Bruker Biospin.
For the measurement of the FD-MS spectrum, JTS-T100 GCAcco TOFGC (trade name) manufactured by JEOL Ltd. was used.
For the measurement of the IR spectrum, a Shimadzu Fourier transform infrared spectrophotometer IR Affinity-1 (trade name) manufactured by Shimadzu Corporation was used.
FIG. 1 shows the 1 H-NMR spectrum, FIG. 2 shows the FD-MS spectrum, and FIG. 3 shows the IR spectrum.
From the results shown in FIGS. 1 to 3, it was confirmed that N,N'-bis(3-[{4-methylphenyl}sulfonylamino]phenyl)urea was obtained.
（合成例２）Ｎ，Ｎ’－ビス（４－［｛４－メチルフェニル｝スルホニルアミノ］フェニル）尿素の合成
合成例１のｍ－フェニレンジアミン５．４ｇ（５０ｍＭ）を、ｐ－フェニレンジアミン５．４ｇ（５０ｍＭ）に代えたこと以外は合成例１と同様の操作を行い、結晶を得た。
得られた結晶について、合成例１と同様にして、１Ｈ－ＮＭＲスペクトル、ＦＤ－ＭＳスペクトルおよびＩＲスペクトルを測定した。
図４に１Ｈ－ＮＭＲスペクトル、図５にＦＤ－ＭＳスペクトル、図６にＩＲスペクトルを示す。
図４～図６の結果から、Ｎ，Ｎ’－ビス（４－［｛４－メチルフェニル｝スルホニルアミノ］フェニル）尿素が得られていることが確認された。
(Synthesis Example 2) Synthesis of N,N'-bis(4-[{4-methylphenyl}sulfonylamino]phenyl)urea 5.4 g (50 mM) of m-phenylenediamine of Synthesis Example 1 was mixed with p-phenylenediamine 5 Crystals were obtained by carrying out the same operation as in Synthesis Example 1 except that the amount was changed to .4 g (50 mM).
The 1 H-NMR spectrum, FD-MS spectrum, and IR spectrum of the obtained crystals were measured in the same manner as in Synthesis Example 1.
FIG. 4 shows the 1 H-NMR spectrum, FIG. 5 shows the FD-MS spectrum, and FIG. 6 shows the IR spectrum.
From the results shown in FIGS. 4 to 6, it was confirmed that N,N'-bis(4-[{4-methylphenyl}sulfonylamino]phenyl)urea was obtained.
（合成例３）Ｎ，Ｎ’－ビス（４－［｛４－メチルフェニル｝スルホニルアミノ］フェニル）尿素の合成
合成例２と同様の操作を行い、ｐ－フェニレンジアミンのモノトシル化物の酢酸エチル溶液を得た。
この溶液から酢酸エチルを減圧除去した後、濃縮残渣に尿素１．５ｇ（２５ｍＭ）、濃塩酸４．７ｇ（４５ｍＭ）、ジエチレングリコールジメチルエーテル７０ｍＬを仕込み加熱した。
この混合溶液を加熱して、四ツ口フラスコの内温を１４５℃とし、反応を８時間継続した。
反応終了後、冷却して、トルエン５０ｇを加え、結晶を析出させ、さらに水５０ｇを加えて、結晶を濾別した。
得られた結晶について、合成例１と同様にして、１Ｈ－ＮＭＲスペクトル、ＦＤ－ＭＳスペクトルおよびＩＲスペクトルを測定した。その結果、Ｎ，Ｎ’－ビス（４－［｛４－メチルフェニル｝スルホニルアミノ］フェニル）尿素が得られていることが確認された。
(Synthesis Example 3) Synthesis of N,N'-bis(4-[{4-methylphenyl}sulfonylamino]phenyl)urea The same operation as in Synthesis Example 2 was carried out to prepare a solution of monotosylated p-phenylenediamine in ethyl acetate. I got it.
After removing ethyl acetate from this solution under reduced pressure, 1.5 g (25 mM) of urea, 4.7 g (45 mM) of concentrated hydrochloric acid, and 70 mL of diethylene glycol dimethyl ether were added to the concentrated residue and heated.
This mixed solution was heated to bring the internal temperature of the four-necked flask to 145°C, and the reaction was continued for 8 hours.
After the reaction was completed, the mixture was cooled, and 50 g of toluene was added to precipitate crystals. Further, 50 g of water was added, and the crystals were separated by filtration.
The 1 H-NMR spectrum, FD-MS spectrum, and IR spectrum of the obtained crystals were measured in the same manner as in Synthesis Example 1. As a result, it was confirmed that N,N'-bis(4-[{4-methylphenyl}sulfonylamino]phenyl)urea was obtained.
（合成例４）Ｎ，Ｎ’－ビス（３－［｛フェニルスルホニル｝アミノ］フェニル）尿素の合成
合成例１のｐ－トルエンスルホニルクロライド９．５ｇ（５０ｍＭ）を、ベンゼンスルホニルクロライド８．８ｇ（５０ｍＭ）に代えたこと以外は合成例１と同様の操作を行い、結晶を得た。
得られた結晶について、合成例１と同様にして、ＩＲスペクトルを測定した。
図７にＩＲスペクトルを示す。
図７の結果から、Ｎ，Ｎ’－ビス（３－［｛フェニルスルホニル｝アミノ］フェニル）尿素が得られていることが確認された。
(Synthesis Example 4) Synthesis of N,N'-bis(3-[{phenylsulfonyl}amino]phenyl)urea 9.5 g (50 mM) of p-toluenesulfonyl chloride of Synthesis Example 1 was mixed with 8.8 g of benzenesulfonyl chloride ( Crystals were obtained by carrying out the same operation as in Synthesis Example 1 except that 50 mM) was used.
The IR spectrum of the obtained crystal was measured in the same manner as in Synthesis Example 1.
Figure 7 shows the IR spectrum.
From the results shown in FIG. 7, it was confirmed that N,N'-bis(3-[{phenylsulfonyl}amino]phenyl)urea was obtained.
（合成例５）Ｎ，Ｎ’－ビス（３－［｛２，４，６－トリメチルフェニル｝スルホニルアミノ］フェニル）尿素の合成
合成例１のｐ－トルエンスルホニルクロライド９．５ｇ（５０ｍＭ）を、メシチレンスルホニルクロライド１０．９ｇ（５０ｍＭ）に代えたこと以外は合成例１と同様の操作を行い、結晶を得た。
得られた結晶について、合成例１と同様にして、ＩＲスペクトルを測定した。
図８にＩＲスペクトルを示す。
図８の結果から、Ｎ，Ｎ’－ビス（３－［｛２，４，６－トリメチルフェニル｝スルホニルアミノ］フェニル）尿素が得られていることが確認された。
(Synthesis Example 5) Synthesis of N,N'-bis(3-[{2,4,6-trimethylphenyl}sulfonylamino]phenyl)urea 9.5g (50mM) of p-toluenesulfonyl chloride of Synthesis Example 1, Crystals were obtained by performing the same operation as in Synthesis Example 1 except that 10.9 g (50 mM) of mesitylene sulfonyl chloride was used instead.
The IR spectrum of the obtained crystal was measured in the same manner as in Synthesis Example 1.
Figure 8 shows the IR spectrum.
From the results shown in FIG. 8, it was confirmed that N,N'-bis(3-[{2,4,6-trimethylphenyl}sulfonylamino]phenyl)urea was obtained.
（合成例６）Ｎ，Ｎ’－ビス（３－［｛ベンジルスルホニル｝アミノ］フェニル）尿素の合成
合成例１のｐ－トルエンスルホニルクロライド９．５ｇ（５０ｍＭ）を、ベンジルスルホニルクロライド９．５ｇ（５０ｍＭ）に代えたこと以外は合成例１と同様の操作を行い、結晶を得た。
得られた結晶について、合成例１と同様にして、ＩＲスペクトルを測定した。
図９にＩＲスペクトルを示す。
図９の結果から、Ｎ，Ｎ’－ビス（３－［｛ベンジルスルホニル｝アミノ］フェニル）尿素が得られていることが確認された。
(Synthesis Example 6) Synthesis of N,N'-bis(3-[{benzylsulfonyl}amino]phenyl)urea 9.5 g (50 mM) of p-toluenesulfonyl chloride of Synthesis Example 1 was mixed with 9.5 g of benzylsulfonyl chloride ( Crystals were obtained by carrying out the same operation as in Synthesis Example 1 except that 50 mM) was used.
The IR spectrum of the obtained crystal was measured in the same manner as in Synthesis Example 1.
Figure 9 shows the IR spectrum.
From the results shown in FIG. 9, it was confirmed that N,N'-bis(3-[{benzylsulfonyl}amino]phenyl)urea was obtained.
（合成例７）Ｎ，Ｎ’－ビス（３－［｛２－ナフチルスルホニル｝アミノ］フェニル）尿素の合成
合成例１のｐ－トルエンスルホニルクロライド９．５ｇ（５０ｍＭ）を、２－ナフタレンスルホニルクロライド１４．９ｇ（５０ｍＭ）に代えたこと以外は合成例１と同様の操作を行い、結晶を得た。
得られた結晶について、合成例１と同様にして、ＩＲスペクトルを測定した。
図１０にＩＲスペクトルを示す。
図１０の結果から、Ｎ，Ｎ’－ビス（３－［｛２－ナフチルスルホニル｝アミノ］フェニル）尿素が得られていることが確認された。
(Synthesis Example 7) Synthesis of N,N'-bis(3-[{2-naphthylsulfonyl}amino]phenyl)urea 9.5 g (50 mM) of p-toluenesulfonyl chloride of Synthesis Example 1 was mixed with 2-naphthalenesulfonyl chloride. Crystals were obtained by carrying out the same operation as in Synthesis Example 1 except that the amount was changed to 14.9 g (50 mM).
The IR spectrum of the obtained crystal was measured in the same manner as in Synthesis Example 1.
FIG. 10 shows the IR spectrum.
From the results shown in FIG. 10, it was confirmed that N,N'-bis(3-[{2-naphthylsulfonyl}amino]phenyl)urea was obtained.
合成例１～合成例７の合成物の水に対する安定性を確認するために、アセトニトリルと水との混合液（アセトニトリル／水＝８０／２０（質量比））に、合成物を０．５％溶解して５０℃で５時間攪拌して、合成物の分解量を嶋津製作所社製の高速液体クロマトグラフィー（検出波長：２０５ｎｍ）で測定した。
分解量が１％以上あれば「×」、１％以下であれば「〇」とした。結果を表１に示す。
In order to confirm the stability of the compounds of Synthesis Examples 1 to 7 in water, 0.5% of the compounds were added to a mixture of acetonitrile and water (acetonitrile/water = 80/20 (mass ratio)). The mixture was dissolved and stirred at 50° C. for 5 hours, and the amount of decomposition of the compound was measured using high performance liquid chromatography (detection wavelength: 205 nm) manufactured by Shimazu Seisakusho.
If the amount of decomposition was 1% or more, it was marked "×", and if it was 1% or less, it was marked "○". The results are shown in Table 1.
下記操作により、感熱記録材料を作製した。 A heat-sensitive recording material was produced by the following operation.
［下塗り層用塗料の調製］
プラスチック中空粒子（商品名：ローペイクＳＮ－１０５５、中空率：５５％、固形分２６．５％、ダウ・ケミカル社製）１００部、焼成カオリンの５０％分散液１００部、スチレン－ブタジエン系ラテックス（商品名：Ｌ－１５７１、固形分４８％、旭化成ケミカルズ社製）２５部、酸化澱粉の１０％水溶液５０部および水２０部を混合して、下塗り層用塗料を調製した。
[Preparation of paint for undercoat layer]
100 parts of plastic hollow particles (trade name: Lowpeke SN-1055, hollow rate: 55%, solid content 26.5%, manufactured by Dow Chemical Company), 100 parts of a 50% dispersion of calcined kaolin, styrene-butadiene latex ( A paint for the undercoat layer was prepared by mixing 25 parts of L-1571 (trade name: L-1571, solid content: 48%, manufactured by Asahi Kasei Chemicals), 50 parts of a 10% aqueous solution of oxidized starch, and 20 parts of water.
（実施例１）
［感熱記録層用塗料の調製］
Ａ液（染料分散液の調製）
３－（Ｎ，Ｎ－ジブチルアミノ）－６－メチル－７－アニリノフルオラン １０部
１０％ポリビニルアルコール水溶液 １０部
水 １６．７部
(Example 1)
[Preparation of paint for heat-sensitive recording layer]
Solution A (preparation of dye dispersion)
3-(N,N-dibutylamino)-6-methyl-7-
Ｂ液（顕色剤分散液の調製）
Ｎ，Ｎ’－ビス（３－［｛４－メチルフェニル｝スルホニルアミノ］フェニル）尿素 ３０部
１０％ポリビニルアルコール水溶液 ３０部
水 ５０．０部
Solution B (preparation of developer dispersion)
N,N'-bis(3-[{4-methylphenyl}sulfonylamino]phenyl)
Ｃ液（増感剤分散液の調製）
１，２－ビス（ｍ－トリルオキシ）エタン ７．５部
１０％ポリビニルアルコール水溶液 ７．５部
水 １２．５部
Solution C (preparation of sensitizer dispersion)
1,2-bis(m-tolyloxy)ethane 7.5
上記Ａ液、Ｂ液およびＣ液の分散液をサンドグラインダーで平均粒子径が１μｍ以下になるまで粉砕し、下記割合で分散液を混合して塗布液とした。
Ａ液（染料剤分散液） ３６．７部
Ｂ液（顕色剤分散液） １１０部
Ｃ液（増感剤分散液） ２７．５部
The above dispersions of liquids A, B, and C were ground with a sand grinder until the average particle diameter was 1 μm or less, and the dispersions were mixed in the following proportions to prepare a coating liquid.
Solution A (dye dispersion) 36.7 parts Solution B (developer dispersion) 110 parts Solution C (sensitizer dispersion) 27.5 parts
上記の塗布液に、水酸化アルミニウム（商品名：ハイジライトＨ－４２、昭和電工社製）２７部、無定形シリカ（商品名：ミズカシルＰ－５２７、水澤化学工業社製）１０部、酸化澱粉の１０％溶解物１００部、ステアリン酸亜鉛分散液：（商品名：ハイドリンＺ－８－３６、中京油脂社製）１９．４部および水５０部からなる組成分を混合して、感熱記録層用塗料を調製した。 To the above coating solution, 27 parts of aluminum hydroxide (trade name: Hygilite H-42, manufactured by Showa Denko Co., Ltd.), 10 parts of amorphous silica (trade name: Mizukashiru P-527, manufactured by Mizusawa Chemical Industry Co., Ltd.), and oxidized starch. A thermosensitive recording layer was prepared by mixing 100 parts of a 10% solution of Zinc stearate, 19.4 parts of zinc stearate dispersion (trade name: Hydrin Z-8-36, manufactured by Chukyo Yushi Co., Ltd.), and 50 parts of water. A paint for this purpose was prepared.
［感熱記録材料の作製］
支持体として坪量が５３ｇの上質紙（酸性紙）上に、上記の下塗り層用塗料を、乾燥後の面積当たりの質量が８ｇ／ｍ２となるように塗布、乾燥し、下塗り層を形成した。
その後、下塗り層上に、上記の感熱記録層用塗料を、乾燥後の面積当たりの質量が４．２ｇ／ｍ２となるように塗布、乾燥し、感熱記録層を形成し、上質紙および感熱記録層を備えるシートを得た。
得られたシートを、スーパーカレンダーで平滑度が９００ｓ～１２００ｓになるように処理して、感熱記録材料を作製した。
なお、平滑度は、ＪＩＳ Ｐ８１５５：２０１０「紙及び板紙－平滑度試験方法－王研法」に準ずる方法により測定した。
[Preparation of heat-sensitive recording material]
The above paint for undercoat layer was applied onto a high-quality paper (acidic paper) with a basis weight of 53 g as a support so that the mass per area after drying was 8 g/m 2 and dried to form an undercoat layer. did.
Thereafter, the above paint for heat-sensitive recording layer was applied onto the undercoat layer so that the mass per area after drying was 4.2 g/ m2 , and dried to form a heat-sensitive recording layer. A sheet provided with a recording layer was obtained.
The obtained sheet was treated with a supercalender to give a smoothness of 900s to 1200s to produce a heat-sensitive recording material.
The smoothness was measured by a method according to JIS P8155:2010 "Paper and paperboard - Smoothness test method - Oken method".
［評価］
（感熱記録試験）
得られた感熱記録材料について、感熱記録紙印字試験機（商品名：ＴＨ－ＰＭＤ、大倉電気社製）を用い、印加エネルギー０．３８ｍＪ／ｄｏｔで印加した。未印字部および記録部の印字濃度をマクベス反射濃度計（商品名：ＲＤ－９１４、グルタグマクベス社製）で測定した。これをサンプル（ブランク）とした。
[evaluation]
(thermal recording test)
An applied energy of 0.38 mJ/dot was applied to the obtained heat-sensitive recording material using a heat-sensitive recording paper printing tester (trade name: TH-PMD, manufactured by Okura Electric Co., Ltd.). The print density of the unprinted area and the recorded area was measured using a Macbeth reflection densitometer (trade name: RD-914, manufactured by Glutag Macbeth). This was used as a sample (blank).
（地肌耐熱性試験）
得られた感熱記録材料を６０℃～１４０℃まで１０℃単位で各環境下に１時間放置して
未印字部の濃度を上記のマクベス反射濃度計で測定した。各測定濃度をプロットして、未印字部の濃度が０．２に達する温度を地肌耐熱温度とした。結果を表１に示す。
(Skin heat resistance test)
The obtained heat-sensitive recording material was left for 1 hour in each environment from 60°C to 140°C in 10°C increments, and the density of the unprinted area was measured using the Macbeth reflection densitometer described above. Each measured density was plotted, and the temperature at which the density of the unprinted area reached 0.2 was defined as the background heat resistance temperature. The results are shown in Table 1.
（耐水性試験）
感熱記録性試験で記録した感熱記録材料を水中に２４時間浸漬した後、サンプルを風乾させ、画像（印字部）濃度と未印字部（地肌部）濃度を上記のマクベス反射濃度計で測定した。結果を表１に示す。
(Water resistance test)
After the heat-sensitive recording material recorded in the heat-sensitive recording property test was immersed in water for 24 hours, the sample was air-dried, and the image (printed area) density and unprinted area (background area) density were measured using the Macbeth reflection densitometer described above. The results are shown in Table 1.
（耐油性試験）
感熱記録性試験で記録した感熱記録材料をサラダオイル中に１０分間浸漬した後、サンプルの油を拭き取り、画像（印字部）濃度と未印字部（地肌部）濃度を上記のマクベス反射濃度計で測定した。結果を表１に示す。
(Oil resistance test)
After immersing the heat-sensitive recording material recorded in the heat-sensitive recording property test in salad oil for 10 minutes, the oil on the sample was wiped off, and the image (printed area) density and unprinted area (background area) density were measured using the Macbeth reflection densitometer mentioned above. It was measured. The results are shown in Table 1.
（実施例２）
実施例１のＢ液のＮ，Ｎ’－ビス（３－［｛４－メチルフェニル｝スルホニルアミノ］フェニル）尿素を、Ｎ，Ｎ’－ビス（４－［｛４－メチルフェニル｝スルホニルアミノ］フェニル）尿素に代えたこと以外は実施例１と同様の操作を行い、実施例２の感熱記録材料を作製した。
実施例２による感熱記録材料の各種試験結果を表１に示す。
(Example 2)
The N,N'-bis(3-[{4-methylphenyl}sulfonylamino]phenyl)urea in Solution B of Example 1 was converted into N,N'-bis(4-[{4-methylphenyl}sulfonylamino] A heat-sensitive recording material of Example 2 was prepared in the same manner as in Example 1 except that phenyl)urea was used.
Table 1 shows the results of various tests on the heat-sensitive recording material according to Example 2.
（実施例３）
実施例１のＢ液のＮ，Ｎ’－ビス（３－［｛４－メチルフェニル｝スルホニルアミノ］フェニル）尿素を、Ｎ，Ｎ’－ビス（３－［｛フェニルスルホニル｝アミノ］フェニル）尿素に代えたこと以外は実施例１と同様の操作を行い、実施例３の感熱記録材料を作製した。
実施例３による感熱記録材料の各種試験結果を表１に示す。
(Example 3)
The N,N'-bis(3-[{4-methylphenyl}sulfonylamino]phenyl)urea in Solution B of Example 1 was replaced with N,N'-bis(3-[{phenylsulfonyl}amino]phenyl)urea. A heat-sensitive recording material of Example 3 was produced by carrying out the same operation as in Example 1 except that .
Table 1 shows the results of various tests on the heat-sensitive recording material according to Example 3.
（実施例４）
実施例１のＢ液のＮ，Ｎ’－ビス（３－［｛４－メチルフェニル｝スルホニルアミノ］フェニル）尿素を、Ｎ，Ｎ’－ビス（３－［｛２，４，６－トリメチルフェニル｝スルホニルアミノ］フェニル）尿素に代えたこと以外は実施例１と同様の操作を行い、実施例４の感熱記録材料を作製した。
実施例４による感熱記録材料の各種試験結果を表１に示す。
(Example 4)
The N,N'-bis(3-[{4-methylphenyl}sulfonylamino]phenyl)urea in Solution B of Example 1 was replaced with N,N'-bis(3-[{2,4,6-trimethylphenyl) A heat-sensitive recording material of Example 4 was prepared in the same manner as in Example 1 except that urea was used instead.
Table 1 shows the results of various tests on the heat-sensitive recording material according to Example 4.
（実施例５）
実施例１のＢ液のＮ，Ｎ’－ビス（３－［｛４－メチルフェニル｝スルホニルアミノ］フェニル）尿素を、Ｎ，Ｎ’－ビス（３－［｛ベンジルスルホニル｝アミノ］フェニル）尿素に代えたこと以外は実施例１と同様の操作を行い、実施例５の感熱記録材料を作製した。
実施例５による感熱記録材料の各種試験結果を表１に示す。
(Example 5)
The N,N'-bis(3-[{4-methylphenyl}sulfonylamino]phenyl)urea in Solution B of Example 1 was replaced with N,N'-bis(3-[{benzylsulfonyl}amino]phenyl)urea. A heat-sensitive recording material of Example 5 was produced by carrying out the same operation as in Example 1 except that .
Table 1 shows the results of various tests on the heat-sensitive recording material according to Example 5.
（実施例６）
実施例１のＢ液のＮ，Ｎ’－ビス（３－［｛４－メチルフェニル｝スルホニルアミノ］フェニル）尿素を、Ｎ，Ｎ’－ビス（３－［｛２－ナフチルスルホニル｝アミノ］フェニル）尿素に代えたこと以外は実施例１と同様の操作を行い、実施例６の感熱記録材料を作製した。
実施例６による感熱記録材料の各種試験結果を表１に示す。
(Example 6)
N,N'-bis(3-[{4-methylphenyl}sulfonylamino]phenyl)urea in Solution B of Example 1 was replaced with N,N'-bis(3-[{2-naphthylsulfonyl}amino]phenyl ) A heat-sensitive recording material of Example 6 was prepared by carrying out the same operation as in Example 1 except that urea was used.
Table 1 shows the results of various tests on the heat-sensitive recording material according to Example 6.
（比較例１）
実施例１のＢ液のＮ，Ｎ’－ビス（３－［｛４－メチルフェニル｝スルホニルアミノ］フェニル）尿素を、４，４’－イソプロピリデンジフェノール（ビスフェノールＡ）に代えたこと以外は実施例１と同様の操作を行い、比較例１の感熱記録材料を作製した。
比較例１による感熱記録材料の各種試験結果を表１に示す。
(Comparative example 1)
Except that N,N'-bis(3-[{4-methylphenyl}sulfonylamino]phenyl)urea in Solution B of Example 1 was replaced with 4,4'-isopropylidenediphenol (bisphenol A). The same operation as in Example 1 was performed to produce a heat-sensitive recording material of Comparative Example 1.
Table 1 shows the results of various tests on the heat-sensitive recording material according to Comparative Example 1.
（比較例２）
実施例１のＢ液のＮ，Ｎ’－ビス（３－［｛４－メチルフェニル｝スルホニルアミノ］フェニル）尿素を、４，４’－ビスヒドロキシジフェニルスルホン（ビスフェノールＳ）に代えたこと以外は実施例１と同様の操作を行い、比較例２の感熱記録材料を作製した。
比較例２による感熱記録材料の各種試験結果を表１に示す。
(Comparative example 2)
Except that N,N'-bis(3-[{4-methylphenyl}sulfonylamino]phenyl)urea in Solution B of Example 1 was replaced with 4,4'-bishydroxydiphenylsulfone (bisphenol S). The same operation as in Example 1 was performed to produce a heat-sensitive recording material of Comparative Example 2.
Table 1 shows the results of various tests on the heat-sensitive recording material according to Comparative Example 2.
（比較例３）
実施例１のＢ液のＮ，Ｎ’－ビス（３－［｛４－メチルフェニル｝スルホニルアミノ］フェニル）尿素を、４－アリルオキシ－４’－ヒドロキシジフェニルスルホンに代えたこと以外は実施例１と同様の操作を行い、比較例３の感熱記録材料を作製した。
比較例３による感熱記録材料の各種試験結果を表１に示す。
(Comparative example 3)
Example 1 except that N,N'-bis(3-[{4-methylphenyl}sulfonylamino]phenyl)urea in Solution B of Example 1 was replaced with 4-allyloxy-4'-hydroxydiphenylsulfone. A heat-sensitive recording material of Comparative Example 3 was prepared in the same manner as in the above.
Table 1 shows the results of various tests on the heat-sensitive recording material according to Comparative Example 3.
（比較例４）
実施例１のＢ液のＮ，Ｎ’－ビス（３－［｛４－メチルフェニル｝スルホニルアミノ］フェニル）尿素を、４－ヒドロキシ－４’－イソプロピルオキシ－ジフェニルスルホンに代えたこと以外は実施例１と同様の操作を行い、比較例４の感熱記録材料を作製した。
比較例４による感熱記録材料の各種試験結果を表１に示す。
(Comparative example 4)
The same procedure was carried out except that N,N'-bis(3-[{4-methylphenyl}sulfonylamino]phenyl)urea in Solution B of Example 1 was replaced with 4-hydroxy-4'-isopropyloxy-diphenylsulfone. The same operation as in Example 1 was performed to produce a heat-sensitive recording material of Comparative Example 4.
Table 1 shows the results of various tests on the heat-sensitive recording material according to Comparative Example 4.
（比較例５）
実施例１のＢ液のＮ，Ｎ’－ビス（３－［｛４－メチルフェニル｝スルホニルアミノ］フェニル）尿素、Ｎ－３－〔（ｐ－トルエンスルホニルオキシ）フェニル〕－Ｎ’－（ｐ－トルエンスルホニル）－尿素に代えたこと以外は実施例１と同様の操作を行い、比較例５の感熱記録材料を作製した。
比較例５による感熱記録材料の各種試験結果を表１に示す。
(Comparative example 5)
N,N'-bis(3-[{4-methylphenyl}sulfonylamino]phenyl)urea, N-3-[(p-toluenesulfonyloxy)phenyl]-N'-(p A heat-sensitive recording material of Comparative Example 5 was prepared in the same manner as in Example 1 except that urea (toluenesulfonyl) was used instead.
Table 1 shows the results of various tests on the heat-sensitive recording material according to Comparative Example 5.
（比較例６）
実施例１のＢ液のＮ，Ｎ’－ビス（３－［｛４－メチルフェニル｝スルホニルアミノ］フェニル）尿素を、Ｎ－［２－（３－フェニルウレイド）フェニル］－ベンゼンスルホンアミドに代えたこと以外は実施例１と同様の操作を行い、比較例６の感熱記録材料を作製した。
比較例６による感熱記録材料の各種試験結果を表１に示す。
(Comparative example 6)
N,N'-bis(3-[{4-methylphenyl}sulfonylamino]phenyl)urea in Solution B of Example 1 was replaced with N-[2-(3-phenylureido)phenyl]-benzenesulfonamide. A heat-sensitive recording material of Comparative Example 6 was prepared in the same manner as in Example 1 except for the above.
Table 1 shows the results of various tests on the heat-sensitive recording material according to Comparative Example 6.
実施例および表１より新規フェニレンジアミンアミン誘導体から作成される感熱記録材料は、高い地肌耐熱温度を有し、耐水性および耐油性の保存性試験に於いても良好であった。 From Examples and Table 1, the heat-sensitive recording material prepared from the new phenylenediamine amine derivative had a high background heat resistance temperature and was good in the water resistance and oil resistance storage tests.
本発明の感熱記録材料は、感熱記録層が顕色剤としてフェニレンジアミン尿素誘導体を含むため、内分泌攪乱の懸念がなく、さらに水に対する分解性もなく、しかも地肌耐熱性に優れ、さらに耐水性および耐油性の保存性試験で良好な保存性が得られ、従来の感熱記録材料に代わるものとして産業上の利用可能性は極め有望である。 In the heat-sensitive recording material of the present invention, since the heat-sensitive recording layer contains a phenylenediamine urea derivative as a color developer, there is no fear of endocrine disruption, there is no decomposition to water, and there is excellent skin heat resistance. Good storage stability was obtained in the oil resistance storage test, and its industrial applicability as an alternative to conventional heat-sensitive recording materials is extremely promising.
Claims (10)
前記感熱記録層は、常温で無色ないし淡色の塩基性染料と、加熱により前記塩基性染料と反応して呈色し得る顕色剤と、を含有し、
前記顕色剤は、下記式（１）～（４）で表される化合物からなる群から選ばれる少なくとも１種のフェニレンジアミン尿素誘導体である、感熱記録材料。
The heat-sensitive recording layer contains a basic dye that is colorless or light-colored at room temperature, and a color developer that can react with the basic dye and develop a color when heated,
The heat-sensitive recording material, wherein the color developer is at least one phenylenediamine urea derivative selected from the group consisting of compounds represented by the following formulas (1) to (4).
前記顕色剤が、下記式（１）で表される化合物からなるフェニレンジアミン尿素誘導体、又は、請求項３若しくは４に記載のフェニレンジアミン尿素誘導体を含有する、感熱記録層。
A heat-sensitive recording layer, wherein the color developer contains a phenylenediamine urea derivative consisting of a compound represented by the following formula (1), or the phenylenediamine urea derivative according to claim 3 or 4.
前記感熱記録材料が、感熱記録紙、感熱記録プラスティックフィルム、又は、感熱記録加工紙である、請求項８に記載の感熱記録材料。 The support is paper, plastic film, or processed paper,
The heat-sensitive recording material according to claim 8, wherein the heat-sensitive recording material is a heat-sensitive recording paper, a heat-sensitive recording plastic film, or a heat-sensitive recording processed paper.
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| JP2019043005A (en) | 2017-08-31 | 2019-03-22 | 三光株式会社 | Heat-sensitive recording material |
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| Claudia Caltagirone, et.al，Anion binding vs. sulfonamide deprotonation in functionalised ureas，Chemical Communications，英国，Royal Society of Chemistry，2007年10月15日，volumeyear: 2008，61-63，DOI:10.1039/b713431b |
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