JP7365480B2 - heat sensitive recording material - Google Patents
heat sensitive recording material Download PDFInfo
- Publication number
- JP7365480B2 JP7365480B2 JP2022167288A JP2022167288A JP7365480B2 JP 7365480 B2 JP7365480 B2 JP 7365480B2 JP 2022167288 A JP2022167288 A JP 2022167288A JP 2022167288 A JP2022167288 A JP 2022167288A JP 7365480 B2 JP7365480 B2 JP 7365480B2
- Authority
- JP
- Japan
- Prior art keywords
- heat
- color developer
- sensitive recording
- recording material
- lignin
- 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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- 239000000463 material Substances 0.000 title claims description 40
- 229920005610 lignin Polymers 0.000 claims description 39
- 229920005611 kraft lignin Polymers 0.000 claims description 37
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- -1 urea urethane compound Chemical class 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 6
- BGLZECVIKIGPIF-UHFFFAOYSA-N 1-[2-(benzenesulfonamido)phenyl]-3-phenylurea Chemical compound C=1C=CC=C(NS(=O)(=O)C=2C=CC=CC=2)C=1NC(=O)NC1=CC=CC=C1 BGLZECVIKIGPIF-UHFFFAOYSA-N 0.000 claims description 4
- BXGWKSJDQKSXDR-UHFFFAOYSA-N 1-phenyl-3-(3-sulfamoylphenyl)urea Chemical compound NS(=O)(=O)C1=CC=CC(NC(=O)NC=2C=CC=CC=2)=C1 BXGWKSJDQKSXDR-UHFFFAOYSA-N 0.000 claims description 3
- ZTILAOCGFRDHBH-UHFFFAOYSA-N 4-(4-propan-2-yloxyphenyl)sulfonylphenol Chemical compound C1=CC(OC(C)C)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 ZTILAOCGFRDHBH-UHFFFAOYSA-N 0.000 claims description 3
- HEVGMYPGMWZOBU-UHFFFAOYSA-N [3-[(4-methylphenyl)sulfonylcarbamoylamino]phenyl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)NC(=O)NC1=CC=CC(OS(=O)(=O)C=2C=CC(C)=CC=2)=C1 HEVGMYPGMWZOBU-UHFFFAOYSA-N 0.000 claims description 3
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
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Landscapes
- Heat Sensitive Colour Forming Recording (AREA)
Description
この発明は、無色ないし淡色の電子供与性ロイコ染料（以下、「ロイコ染料」ともいう。）と電子受容性顕色剤（以下、「顕色剤」ともいう。）との発色反応を利用した感熱記録体であって、顕色剤として単離リグニンを使用する感熱記録体に関する。 This invention utilizes a color-forming reaction between a colorless or light-colored electron-donating leuco dye (hereinafter also referred to as "leuco dye") and an electron-accepting color developer (hereinafter also referred to as "color developer"). The present invention relates to a heat-sensitive recording material that uses isolated lignin as a color developer.
一般に、感熱記録体は通常無色ないし淡色のロイコ染料と顕色剤とを含有する塗工液を、紙、合成紙、フィルム、プラスチック等の支持体に塗工したものであり、サーマルヘッド、ホットスタンプ、熱ペン、レーザー光等の加熱による瞬時の化学反応により発色し、記録画像が得られる。感熱記録体は、ファクシミリ、コンピューターの端末プリンタ、自動券売機、計測用レコーダー、スーパーマーケットやコンビニなどのレシート等の記録媒体として広範囲に使用されている。
この顕色剤として、一般に、ビスフェノール類、アルキルフェノール類、ノボラック型フェノール樹脂、芳香族カルボン酸の誘導体やその金属塩、ヒドロキシ安息香酸エステル、スルホニル尿素系化合物、活性白土などが用いられている。
感熱記録体の使用者からはこのような従来のフェノール系材料等より環境に優しい顕色剤の要求があり、顕色剤としてアスコルビン酸（特許文献１、２等）、サッカリン（特許文献３等）、グルコノラクトン（特許文献４）等を使用した感熱記録体が公開されている。
In general, thermal recording materials are made by coating a support such as paper, synthetic paper, film, or plastic with a coating solution containing a colorless or light-colored leuco dye and a color developer. Color develops through an instant chemical reaction caused by heating with a stamp, thermal pen, laser beam, etc., and a recorded image is obtained. Thermosensitive recording media are widely used as recording media for facsimiles, computer terminal printers, automatic ticket vending machines, measurement recorders, receipts at supermarkets, convenience stores, etc.
As the color developer, bisphenols, alkylphenols, novolac type phenol resins, aromatic carboxylic acid derivatives and metal salts thereof, hydroxybenzoic acid esters, sulfonylurea compounds, activated clay, and the like are generally used.
Users of heat-sensitive recording media are demanding color developers that are more environmentally friendly than conventional phenolic materials, and as the color developer, ascorbic acid (Patent Documents 1, 2, etc.) and saccharin (Patent Document 3, etc.) are used as color developers. ), gluconolactone (Patent Document 4), and the like have been disclosed.
本発明は、環境に優しい顕色剤を用いた感熱記録体を提供することを目的とする。 An object of the present invention is to provide a heat-sensitive recording material using an environmentally friendly color developer.
本発明者らは、上記の課題を解決するために、広範囲の環境に優しい化合物を検討した結果、驚くべきことに、単離リグニンが顕色剤として機能することを見出し、本発明を完成させるに至った。
即ち、本発明は、支持体上に、無色ないし淡色の電子供与性ロイコ染料及び電子受容性顕色剤を含有する感熱記録層を設けた感熱記録体において、該電子受容性顕色剤として単離リグニン、及び該単離リグニン以外の電子受容性顕色剤を含有し、該単離リグニン以外の電子受容性顕色剤が、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、又はウレア構造（－ＮＨＣＯＮＨ－）を有する顕色剤である、感熱記録体である。
In order to solve the above problems, the present inventors investigated a wide range of environmentally friendly compounds and surprisingly discovered that isolated lignin functions as a color developer, thereby completing the present invention. reached.
That is, the present invention provides a heat-sensitive recording material in which a heat-sensitive recording layer containing a colorless or light-colored electron-donating leuco dye and an electron-accepting color developer is provided on a support. It contains released lignin and an electron-accepting color developer other than the isolated lignin, and the electron-accepting color developer other than the isolated lignin is 4,4'-dihydroxydiphenylsulfone, 4-hydroxy-4'- It is a heat-sensitive recording material that is a color developer having isopropoxy diphenyl sulfone or a urea structure (-NHCONH-).
本発明の感熱記録体においては顕色剤として単離リグニンを使用する。植物細胞の細胞壁に存在する天然リグニンはセルロース等の多糖類と複合化しており、単離することが困難である。そのため、通常、化学変性を施すことにより単離される。単離リグニンは、工業リグニンとも呼ばれ、単離リグニンには、リグノスルホン酸塩、クラフトリグニン、ソーダリグニン、ソーダ・アントラキノンリグニン、オルガノリグニン、爆砕リグニン、硫酸リグニン等が含まれる。本発明においては、これらの単離リグニンの中で、クラフトリグニンが好ましく使用される。クラフトリグニンは、チオリグニン、サルフェートリグニンとも呼ばれる。クラフトリグニンは、ヒドロキシフェニルプロパンを基本単位とし、フェノール製ヒドロキシ基やアルコール性ヒドロキシ基、チオール基などの官能基を有する化合物である。クラフトリグニンは、通常、木材に、水酸化ナトリウムと硫化ナトリウムとの混合水溶液を作用させて得られ、水に不溶である。クラフトリグニンの使用形態としては、クラフトリグニンのアルカリ溶液や、クラフトリグニンのアルカリ溶液をスプレードライして粉末化した粉末クラフトリグニン、クラフトリグニンのアルカリ溶液を酸で沈殿させた酸沈殿クラフトリグニンを用いることができる。
クラフトリグニンのアルカリ溶液は、例えば、特開２０００－３３６５８９に記載されているような公知の方法により得られるが、これらの方法に限定されるものではない。
In the heat-sensitive recording material of the present invention, isolated lignin is used as a color developer. Natural lignin present in the cell walls of plant cells is complexed with polysaccharides such as cellulose and is difficult to isolate. Therefore, it is usually isolated by chemical modification. Isolated lignin is also called industrial lignin, and includes lignosulfonate, kraft lignin, soda lignin, soda anthraquinone lignin, organolignin, blasted lignin, sulfuric lignin, and the like. In the present invention, among these isolated lignins, kraft lignin is preferably used. Kraft lignin is also called thiolignin or sulfate lignin. Kraft lignin is a compound whose basic unit is hydroxyphenylpropane and has functional groups such as phenolic hydroxy groups, alcoholic hydroxy groups, and thiol groups. Kraft lignin is usually obtained by treating wood with a mixed aqueous solution of sodium hydroxide and sodium sulfide, and is insoluble in water. Kraft lignin can be used in an alkaline solution of kraft lignin, a powdered kraft lignin obtained by spray-drying an alkaline solution of kraft lignin, and acid-precipitated kraft lignin obtained by precipitating an alkaline solution of kraft lignin with an acid. I can do it.
The alkaline solution of kraft lignin can be obtained, for example, by a known method as described in JP-A No. 2000-336589, but is not limited to these methods.
本発明においては、顕色剤として単離リグニンを使用するが、単離リグニン以外の顕色剤を併用してもよい。これにより、発色性能（印字濃度）等の性能面でより優れた効果をもたらすことができる。但し、単離リグニン以外の顕色剤を併用する場合、単離リグニンの環境に優しいという利点はその割合に従って減少する。
このような顕色剤としては、例えば、活性白土、アタパルジャイト、コロイダルシリカ、珪酸アルミニウムなどの無機酸性物質、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）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、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、２，４'-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、４-ヒドロキシ-４'-ｎ-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、１-［４-（４-ヒドロキシフェニルスルホニル）フェノキシ］-４-［４-（４-イソプロポキシフェニルスルホニル）フェノキシ］ブタン、特開２００３-１５４７６０号公報記載のフェノール縮合組成物、特開平８-５９６０３号公報記載のアミノベンゼンスルホンアミド誘導体、ビス（４-ヒドロキシフェニルチオエトキシ）メタン、１，５-ジ（４-ヒドロキシフェニルチオ）-３-オキサペンタン、ビス（ｐ-ヒドロキシフェニル）酢酸ブチル、ビス（ｐ-ヒドロキシフェニル）酢酸メチル、１，１-ビス（４-ヒドロキシフェニル）-１-フェニルエタン、１，４-ビス［α-メチル-α-（４'-ヒドロキシフェニル）エチル］ベンゼン、１，３-ビス［α-メチル-α-（４'-ヒドロキシフェニル）エチル］ベンゼン、ジ（４-ヒドロキシ-３-メチルフェニル）スルフィド、２，２'-チオビス（３-tert-オクチルフェノール）、２，２'-チオビス（４-tert-オクチルフェノール）、ＷＯ９７／１６４２０号に記載のジフェニルスルホン架橋型化合物等のフェノール性化合物、ＷＯ０２／０８１２２９号あるいは特開２００２-３０１８７３号公報記載の化合物、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、３-（３-トシルウレイド）フェニル-ｐ-トルエンスルホナート、ウレアウレタン化合物、３-｛[（フェニルアミノ）カルボニル]アミノ｝ベンゼンスルホンアミド、また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、ｐ-クロロ安息香酸、没食子酸ステアリル、ビス［４-（ｎ-オクチルオキシカルボニルアミノ）サリチル酸亜鉛］２水和物、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］サリチル酸の芳香族カルボン酸、及びこれらの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塩との塩、さら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、等が挙げられる。これらの顕色剤は、単独で又は２種以上混合して使用することもできる。この他、特開平１０-２５８５７７号公報記載の高級脂肪酸金属複塩や多価ヒドロキシ芳香族化合物などの金属キレート型発色成分を含有することもできる。
In the present invention, isolated lignin is used as a color developer, but color developers other than isolated lignin may be used in combination. This can bring about better effects in terms of performance such as color development performance (print density). However, when a color developer other than isolated lignin is used in combination, the environmentally friendly advantage of isolated lignin is reduced in proportion to its proportion.
Examples of such color developers include activated clay, attapulgite, colloidal silica, inorganic acidic substances such as aluminum silicate, 4,4'-isopropylidenediphenol, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 4,4'-dihydroxydiphenyl sulfide, hydroquinone monobenzyl ether, benzyl 4-hydroxybenzoate, 4,4'-dihydroxydiphenyl sulfone, 2,4 '-Dihydroxydiphenylsulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone, 4-hydroxy-4'-n-propoxydiphenylsulfone, bis(3-allyl-4-hydroxyphenyl)sulfone, 4-hydroxy-4' -Methyldiphenylsulfone, 4-hydroxyphenyl-4'-benzyloxyphenylsulfone, 3,4-dihydroxyphenyl-4'-methylphenylsulfone, 1-[4-(4-hydroxyphenylsulfonyl)phenoxy]-4-[ 4-(4-isopropoxyphenylsulfonyl)phenoxy]butane, the phenol condensation composition described in JP-A-2003-154760, the aminobenzenesulfonamide derivative described in JP-A-8-59603, bis(4-hydroxyphenylthio ethoxy)methane, 1,5-di(4-hydroxyphenylthio)-3-oxapentane, butyl bis(p-hydroxyphenyl)acetate, methyl bis(p-hydroxyphenyl)acetate, 1,1-bis(4- Hydroxyphenyl)-1-phenylethane, 1,4-bis[α-methyl-α-(4'-hydroxyphenyl)ethyl]benzene, 1,3-bis[α-methyl-α-(4'-hydroxyphenyl) )ethyl]benzene, di(4-hydroxy-3-methylphenyl) sulfide, 2,2'-thiobis(3-tert-octylphenol), 2,2'-thiobis(4-tert-octylphenol), WO97/16420 Phenolic compounds such as diphenylsulfone crosslinked compounds described in WO02/081229 or JP2002-301873A, N-(2-(3-phenylureido)phenyl)benzenesulfonamide, 3-( 3-tosylureido) phenyl-p-toluenesulfonate, urea urethane compounds, 3-{[(phenylamino)carbonyl]amino}benzenesulfonamide, and thiourea compounds such as N,N'-di-m-chlorophenylthiourea; p-chlorobenzoic acid, stearyl gallate, bis[4-(n-octyloxycarbonylamino)zinc salicylate] dihydrate, 4-[2-(p-methoxyphenoxy)ethyloxy]salicylic acid, 4-[3- Aromatic carboxylic acids such as (p-tolylsulfonyl)propyloxy]salicylic acid, 5-[p-(2-p-methoxyphenoxyethoxy)cumyl]salicylic acid, and zinc, magnesium, aluminum, calcium, Examples include salts with polyvalent metal salts such as titanium, manganese, tin, and nickel, as well as antipyrine complexes of zinc thiocyanate, and composite zinc salts of terephthalaldehydic acid and other aromatic carboxylic acids. These color developers can be used alone or in combination of two or more. In addition, metal chelate type coloring components such as higher fatty acid metal double salts and polyvalent hydroxy aromatic compounds described in JP-A-10-258577 can also be contained.
このような顕色剤の中で、単離リグニンと併用する顕色剤として、発色性能（印字濃度）、保存性等の性能のバランスが良好となるため、４，４'-ジヒドロキシジフェニルスルホン又はウレア構造（－ＮＨＣＯＮＨ－）を有する顕色剤が好ましい。ウレア構造を有する顕色剤としては、例えば、次のような顕色剤が挙げられる。
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（日本曹達株式会社製ＮＫＫ１３０４、下式）
N-(2-(3-phenylureido)phenyl)benzenesulfonamide (NKK1304 manufactured by Nippon Soda Co., Ltd., formula below)
本発明において、感熱記録層中の単離リグニンの含有量（固形分）は、好ましくは０．５～２０重量％、より好ましくは１～１５重量％、更に好ましくは２～１２重量％である。
本発明において、顕色剤は全量単離リグニンであることが好ましいが、顕色剤として単離リグニンと単離リグニン以外の顕色剤とを併用する場合、単離リグニンと単離リグニン以外の顕色剤の重量比（単離リグニン／単離リグニン以外の顕色剤）は、好ましくは９０／１０～１０／９０、より好ましくは８０／２０～２０／８０、更に好ましくは６０／４０～２５／７５である。
In the present invention, the content (solid content) of isolated lignin in the heat-sensitive recording layer is preferably 0.5 to 20% by weight, more preferably 1 to 15% by weight, and still more preferably 2 to 12% by weight. .
In the present invention, it is preferable that the entire amount of the color developer is isolated lignin, but if isolated lignin and a color developer other than isolated lignin are used together as the color developer, isolated lignin and a color developer other than isolated lignin may be used together. The weight ratio of the color developer (isolated lignin/color developer other than isolated lignin) is preferably 90/10 to 10/90, more preferably 80/20 to 20/80, even more preferably 60/40 to It is 25/75.
本発明の感熱記録体は、顕色剤として単離リグニンを使用する以外の点については、従来の構成を利用できる。
即ち、本発明の感熱記録体は、支持体上に感熱記録層を必須に有し、任意に、感熱記録層上に保護層を有してもよく、支持体と感熱記録層との間に下塗り層を有してもよく、また、支持体の感熱記録層とは反対面にバックコート層を設けてもよい。その他これらの層間に使用目的に応じて適宜構成した塗工層を設けてもよい。
この支持体は、所望する感熱記録体の品質に合わせて、紙、再生紙、合成紙、フィルム、プラスチックフィルム、発泡プラスチックフィルム、不織布など、従来公知の支持体から適宜選択可能であり、特に限定されるものではない。また、これらを組み合わせた複合シートを支持体として使用してもよい。
The heat-sensitive recording material of the present invention can utilize a conventional structure except that isolated lignin is used as a color developer.
That is, the heat-sensitive recording material of the present invention essentially has a heat-sensitive recording layer on the support, and may optionally have a protective layer on the heat-sensitive recording layer, and there is no heat-sensitive recording layer between the support and the heat-sensitive recording layer. It may have an undercoat layer, and a back coat layer may be provided on the opposite side of the support from the heat-sensitive recording layer. In addition, a coating layer configured as appropriate depending on the purpose of use may be provided between these layers.
This support can be appropriately selected from conventionally known supports such as paper, recycled paper, synthetic paper, film, plastic film, foamed plastic film, and nonwoven fabric, depending on the quality of the desired heat-sensitive recording material, and is not particularly limited. It is not something that will be done. Moreover, a composite sheet obtained by combining these may be used as a support.
本発明の感熱記録層は、上記顕色剤以外に、ロイコ染料を必須に含有し、更に任意に、増感剤、バインダー、顔料、架橋剤、画像安定剤、その他の成分を含有してもよい。 In addition to the color developer described above, the heat-sensitive recording layer of the present invention essentially contains a leuco dye, and may optionally contain a sensitizer, a binder, a pigment, a crosslinking agent, an image stabilizer, and other components. good.
本発明で使用するロイコ染料としては、従来の感圧あるいは感熱記録紙分野で公知のものは全て使用可能であり、特に制限されるものではないが、トリフェニルメタン系化合物、フルオラン系化合物、フルオレン系、ジビニル系化合物等が好ましい。以下に代表的な無色ないし淡色のロイコ染料（染料前駆体）の具体例を示す。また、これらのロイコ染料は単独で又は２種以上混合して使用してもよい。 As the leuco dye used in the present invention, all those known in the field of conventional pressure-sensitive or heat-sensitive recording paper can be used, and there are no particular restrictions on the leuco dye, including triphenylmethane compounds, fluoran compounds, fluorene compounds, etc. and divinyl-based compounds are preferred. Specific examples of typical colorless to light-colored leuco dyes (dye precursors) are shown below. Further, these leuco dyes may be used alone or in combination of two or more.
＜トリフェニルメタン系ロイコ染料＞
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〔別名クリスタルバイオレットラクトン〕； ３，３－ビス（ｐ－ジメチルアミノフェニル）フタリド〔別名マラカイトグリーンラクトン〕
<Triphenylmethane-based leuco dye>
3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide [also known as crystal violet lactone]; 3,3-bis(p-dimethylaminophenyl) phthalide [also known as malachite green lactone]
＜フルオラン系ロイコ染料＞
３－ジエチルアミノ－６－メチルフルオラン； 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－ジエチルアミノ－６－メチル－７－クロロフルオラン； ３－ジエチルアミノ－６－メチル－７－（ｍ－トリフルオロメチルアニリノ）フルオラン； ３－ジエチルアミノ－６－メチル－７－（ｏ－クロロアニリノ）フルオラン； ３－ジエチルアミノ－６－メチル－７－（ｐ－クロロアニリノ）フルオラン； ３－ジエチルアミノ－６－メチル－７－（ｏ－フルオロアニリノ）フルオラン； ３－ジエチルアミノ－６－メチル－７－（ｍ－メチルアニリノ）フルオラン； ３－ジエチルアミノ－６－メチル－７－ｎ－オクチルアニリノフルオラン； ３－ジエチルアミノ－６－メチル－７－ｎ－オクチルアミノフルオラン； ３－ジエチルアミノ－６－メチル－７－ベンジルアミノフルオラン； ３－ジエチルアミノ－６－メチル－７－ジベンジルアミノフルオラン；３－ジエチルアミノ－６－クロロ－７－メチルフルオラン； ３－ジエチルアミノ－６－クロロ－７－アニリノフルオラン； ３－ジエチルアミノ－６－クロロ－７－ｐ－メチルアニリノフルオラン； ３－ジエチルアミノ－６－エトキシエチル－７－アニリノフルオラン； ３－ジエチルアミノ－７－メチルフルオラン； ３－ジエチルアミノ－７－クロロフルオラン； ３－ジエチルアミノ－７－（ｍ－トリフルオロメチルアニリノ）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－（ｐ－クロロアニリノ）フルオラン； ３－ジエチルアミノ－７－（ｏ－フルオロアニリノ）フルオラン； ３－ジエチルアミノ－ベンゾ〔ａ〕フルオラン； ３－ジエチルアミノ－ベンゾ〔ｃ〕フルオラン； ３－ジブチルアミノ－６－メチル－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－ジブチルアミノ－６－メチル－７－（ｏ，ｐ－ジメチルアニリノ）フルオラン； ３－ジブチルアミノ－６－メチル－７－（ｏ－クロロアニリノ）フルオラン； ３－ジブチルアミノ－６－メチル－７－（ｐ－クロロアニリノ）フルオラン； ３－ジブチルアミノ－６－メチル－７－（ｏ－フルオロアニリノ）フルオラン； ３－ジブチルアミノ－６－メチル－７－（ｍ－トリフルオロメチルアニリノ）フルオラン； ３－ジブチルアミノ－６－メチル－クロロフルオラン； ３－ジブチルアミノ－６－エトキシエチル－７－アニリノフルオラン； ３－ジブチルアミノ－６－クロロ－７－アニリノフルオラン； ３－ジブチルアミノ－６－メチル－７－ｐ－メチル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－ジブチルアミノ－７－（ｏ－フルオロアニリノ）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－ｎ－ペンチルアミノ－６－メチル－７－（ｐ－クロロアニリノ）フルオラン； ３－ジ－ｎ－ペンチルアミノ－７－（ｍ－トリフルオロメチルアニリノ）フルオラン； ３－ジ－ｎ－ペンチルアミノ－６－クロロ－７－アニリノフルオラン； ３－ジ－ｎ－ペンチルアミノ－７－（ｐ－クロロアニリノ）フルオラン； ３－ピロリジノ－６－メチル－７－アニリノフルオラン； ３－ピペリジノ－６－メチル－７－アニリノフルオラン； ３－（Ｎ－メチル－Ｎ－プロピルアミノ）－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－（Ｎ－エチル－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－（Ｎ－エチル－Ｎ－キシルアミノ）－６－メチル－７－（ｐ－クロロアニリノ）フルオラン； ３－（Ｎ－エチル－ｐ－トルイディノ）－６－メチル－７－アニリノフルオラン； 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－エチル－Ｎ－イソアミルアミノ）－６－クロロ－７－アニリノフルオラン； 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－（Ｎ－エチル－Ｎ－イソブチルアミノ）－６－メチル－７－アニリノフルオラン； ３－（Ｎ－エチル－Ｎ－エトキシプロピルアミノ）－６－メチル－７－アニリノフルオラン； ３－シクロヘキシルアミノ－６－クロロフルオラン； ２－（４－オキサヘキシル）－３－ジメチルアミノ－６－メチル－７－アニリノフルオラン； ２－（４－オキサヘキシル）－３－ジエチルアミノ－６－メチル－７－アニリノフルオラン； ２－（４－オキサヘキシル）－３－ジプロピルアミノ－６－メチル－７－アニリノフルオラン； ２－メチル－６－ｐ－（ｐ－ジメチルアミノフェニル）アミノアニリノフルオラン； ２－メトキシ－６－ｐ－（ｐ－ジメチルアミノフェニル）アミノアニリノフルオラン； ２－クロロ－３－メチル－６－ｐ－（ｐ－フェニルアミノフェニル）アミノアニリノフルオラン； ２－クロロ－６－ｐ－（ｐ－ジメチルアミノフェニル）アミノアニリノフルオラン； ２－ニトロ－６－ｐ－（ｐ－ジエチルアミノフェニル）アミノアニリノフルオラン； ２－アミノ－６－ｐ－（ｐ－ジエチルアミノフェニル）アミノアニリノフルオラン； ２－ジエチルアミノ－６－ｐ－（ｐ－ジエチルアミノフェニル）アミノアニリノフルオラン； ２－フェニル－６－メチル－６－ｐ－（ｐ－フェニルアミノフェニル）アミノアニリノフルオラン； ２－ベンジル－６－ｐ－（ｐ－フェニルアミノフェニル）アミノアニリノフルオラン； ２－ヒドロキシ－６－ｐ－（ｐ－フェニルアミノフェニル）アミノアニリノフルオラン； ３－メチル－６－ｐ－（ｐ－ジメチルアミノフェニル）アミノアニリノフルオラン； ３－ジエチルアミノ－６－ｐ－（ｐ－ジエチルアミノフェニル）アミノアニリノフルオラン； ３－ジエチルアミノ－６－ｐ－（ｐ－ジブチルアミノフェニル）アミノアニリノフルオラン； ２，４－ジメチル－６－〔（４－ジメチルアミノ）アニリノ〕－フルオラン
<Fluorane-based leuco dye>
3-diethylamino-6-methylfluorane; 3-diethylamino-6-methyl-7-anilinofluorane; 3-diethylamino-6-methyl-7-(o,p-dimethylanilino)fluorane; 3-diethylamino- 6-Methyl-7-chlorofluoran; 3-diethylamino-6-methyl-7-(m-trifluoromethylanilino)fluoran; 3-diethylamino-6-methyl-7-(o-chloroanilino)fluoran; 3- Diethylamino-6-methyl-7-(p-chloroanilino)fluoran; 3-diethylamino-6-methyl-7-(o-fluoroanilino)fluoran; 3-diethylamino-6-methyl-7-(m-methylanilino)fluoran ; 3-diethylamino-6-methyl-7-n-octylanilinofluorane; 3-diethylamino-6-methyl-7-n-octylaminofluorane; 3-diethylamino-6-methyl-7-benzylaminofluorane ; 3-diethylamino-6-methyl-7-dibenzylaminofluorane; 3-diethylamino-6-chloro-7-methylfluorane; 3-diethylamino-6-chloro-7-anilinofluorane; 3-diethylamino- 6-chloro-7-p-methylanilinofluorane; 3-diethylamino-6-ethoxyethyl-7-anilinofluorane; 3-diethylamino-7-methylfluorane; 3-diethylamino-7-chlorofluorane; 3-diethylamino-7-(m-trifluoromethylanilino)fluorane; 3-diethylamino-7-(o-chloroanilino)fluorane; 3-diethylamino-7-(p-chloroanilino)fluorane; 3-diethylamino-7-( o-fluoroanilino)fluorane; 3-diethylamino-benzo[a]fluorane; 3-diethylamino-benzo[c]fluorane; 3-dibutylamino-6-methyl-fluorane; 3-dibutylamino-6-methyl-7- Anilinofluoran; 3-dibutylamino-6-methyl-7-(o,p-dimethylanilino)fluoran; 3-dibutylamino-6-methyl-7-(o-chloroanilino)fluoran; 3-dibutylamino- 6-Methyl-7-(p-chloroanilino)fluoran; 3-dibutylamino-6-methyl-7-(o-fluoroanilino)fluoran; 3-dibutylamino-6-methyl-7-(m-trifluoromethyl 3-dibutylamino-6-methyl-chlorofluoran; 3-dibutylamino-6-ethoxyethyl-7-anilinofluoran; 3-dibutylamino-6-chloro-7-anilinofluoran ; 3-dibutylamino-6-methyl-7-p-methylanilinofluorane; 3-dibutylamino-7-(o-chloroanilino)fluoran; 3-dibutylamino-7-(o-fluoroanilino)fluoran; 3-di-n-pentylamino-6-methyl-7-anilinofluorane; 3-di-n-pentylamino-6-methyl-7-(p-chloroanilino)fluoran; 3-di-n-pentylamino -7-(m-trifluoromethylanilino)fluorane; 3-di-n-pentylamino-6-chloro-7-anilinofluorane; 3-di-n-pentylamino-7-(p-chloroanilino) Fluoran; 3-pyrrolidino-6-methyl-7-anilinofluorane; 3-piperidino-6-methyl-7-anilinofluorane; 3-(N-methyl-N-propylamino)-6-methyl-7 -anilinofluorane; 3-(N-methyl-N-cyclohexylamino)-6-methyl-7-anilinofluorane; 3-(N-ethyl-N-cyclohexylamino)-6-methyl-7-ani Linofluorane; 3-(N-ethyl-N-xylamino)-6-methyl-7-(p-chloroanilino)fluoran; 3-(N-ethyl-p-toluidino)-6-methyl-7-anilinofluoran Orane; 3-(N-ethyl-N-isoamylamino)-6-methyl-7-anilinofluorane; 3-(N-ethyl-N-isoamylamino)-6-chloro-7-anilinofluorane; 3-(N-ethyl-N-tetrahydrofurfurylamino)-6-methyl-7-anilinofluorane; 3-(N-ethyl-N-isobutylamino)-6-methyl-7-anilinofluorane; 3-(N-ethyl-N-ethoxypropylamino)-6-methyl-7-anilinofluorane; 3-cyclohexylamino-6-chlorofluorane; 2-(4-oxahexyl)-3-dimethylamino- 6-Methyl-7-anilinofluorane; 2-(4-oxahexyl)-3-diethylamino-6-methyl-7-anilinofluorane; 2-(4-oxahexyl)-3-dipropylamino- 6-Methyl-7-anilinofluorane; 2-methyl-6-p-(p-dimethylaminophenyl)aminoanilinofluorane; 2-methoxy-6-p-(p-dimethylaminophenyl)aminoanilino Fluoran; 2-chloro-3-methyl-6-p-(p-phenylaminophenyl)aminoanilinofluoran; 2-chloro-6-p-(p-dimethylaminophenyl)aminoanilinofluoran; 2 -nitro-6-p-(p-diethylaminophenyl)aminoanilinofluorane; 2-amino-6-p-(p-diethylaminophenyl)aminoanilinofluorane; 2-diethylamino-6-p-(p- diethylaminophenyl)aminoanilinofluorane; 2-phenyl-6-methyl-6-p-(p-phenylaminophenyl)aminoanilinofluorane; 2-benzyl-6-p-(p-phenylaminophenyl)amino Anilinofluoran; 2-hydroxy-6-p-(p-phenylaminophenyl)aminoanilinofluoran; 3-methyl-6-p-(p-dimethylaminophenyl)aminoanilinofluoran; 3-diethylamino -6-p-(p-diethylaminophenyl)aminoanilinofluorane; 3-diethylamino-6-p-(p-dibutylaminophenyl)aminoanilinofluorane; 2,4-dimethyl-6-[(4- dimethylamino)anilino]-fluorane
＜フルオレン系ロイコ染料＞
３，６，６'－トリス（ジメチルアミノ）スピロ〔フルオレン－９，３'－フタリド〕； ３，６，６'－トリス（ジエチルアミノ）スピロ〔フルオレン－９，３'－フタリド〕
＜ジビニル系ロイコ染料＞
３，３－ビス－〔２－（ｐ－ジメチルアミノフェニル）－２－（ｐ－メトキシフェニル）エテニル〕－４，５，６，７－テトラブロモフタリド； ３，３－ビス－〔２－（ｐ－ジメチルアミノフェニル）－２－（ｐ－メトキシフェニル）エテニル〕－４，５，６，７－テトラクロロフタリド； ３，３－ビス－〔１，１－ビス（４－ピロリジノフェニル）エチレン－２－イル〕－４，５，６，７－テトラブロモフタリド； 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
<Fluorene-based leuco dye>
3,6,6'-tris(dimethylamino)spiro[fluorene-9,3'-phthalide];3,6,6'-tris(diethylamino)spiro[fluorene-9,3'-phthalide]
<Divinyl leuco dye>
3,3-bis-[2-(p-dimethylaminophenyl)-2-(p-methoxyphenyl)ethenyl]-4,5,6,7-tetrabromophthalide; 3,3-bis-[2- (p-dimethylaminophenyl)-2-(p-methoxyphenyl)ethenyl]-4,5,6,7-tetrachlorophthalide; 3,3-bis-[1,1-bis(4-pyrrolidinophenyl) ) ethylene-2-yl]-4,5,6,7-tetrabromophthalide; 3,3-bis-[1-(4-methoxyphenyl)-1-(4-pyrrolidinophenyl)ethylene-2- ]-4,5,6,7-tetrachlorophthalide
＜その他＞
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－（４－ジエチルアミノ－２－エトキシフェニル）－３－（１－オクチル－２－メチルインドール－３－イル）－４－アザフタリド； ３－（４－シクロヘキシルエチルアミノ－２－メトキシフェニル）－３－（１－エチル－２－メチルインドール－３－イル）－４－アザフタリド； ３，３－ビス（１－エチル－２－メチルインドール－３－イル）フタリド； ３，６－ビス（ジエチルアミノ）フルオラン－γ－（３'－ニトロ）アニリノラクタム； ３，６－ビス（ジエチルアミノ）フルオラン－γ－（４'－ニトロ）アニリノラクタム； １，１－ビス－〔２'，２'，２''，２''－テトラキス－（ｐ－ジメチルアミノフェニル）－エテニル〕－２，２－ジニトリルエタン； １，１－ビス－〔２'，２'，２''，２''－テトラキス－（ｐ－ジメチルアミノフェニル）－エテニル〕－２－β－ナフトイルエタン； １，１－ビス－〔２'，２'，２''，２''－テトラキス－（ｐ－ジメチルアミノフェニル）－エテニル〕－２，２－ジアセチルエタン； ビス－〔２，２，２'，２'－テトラキス－（ｐ－ジメチルアミノフェニル）－エテニル〕－メチルマロン酸ジメチルエステル
<Others>
3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide; 3-(4-diethylamino-2-ethoxyphenyl)-3-( 1-octyl-2-methylindol-3-yl)-4-azaphthalide; 3-(4-cyclohexylethylamino-2-methoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)- 4-Azaphthalide; 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide; 3,6-bis(diethylamino)fluoran-γ-(3'-nitro)anilinolactam; 3,6 -bis(diethylamino)fluoran-γ-(4'-nitro)anilinolactam;1,1-bis-[2',2',2'',2''-tetrakis-(p-dimethylaminophenyl)- ethenyl]-2,2-dinitrile ethane; 1,1-bis-[2',2',2'',2''-tetrakis-(p-dimethylaminophenyl)-ethenyl]-2-β-naphthoylethane ; 1,1-bis-[2',2',2'',2''-tetrakis-(p-dimethylaminophenyl)-ethenyl]-2,2-diacetylethane; bis-[2,2,2 ',2'-tetrakis-(p-dimethylaminophenyl)-ethenyl]-methylmalonic acid dimethyl ester
本発明で使用可能な増感剤としては、ジフェニルスルホン、ステアリン酸アミド、パルミチン酸アミド等の脂肪酸アマイド、ベンジルオキシナフタレン、１，２－ジ－（３－メチルフェノキシ）エタン、シュウ酸ジ（ｐ－メチルベンジル）剤などを例示することができる。これらの増感剤は、単独で又は２種以上混合して使用してもよい。
これらの増感剤の中で、顕色剤として単離リグニンを使用した場合の発色性能（印字濃度）を補うため、ジフェニルスルホンを使用することが好ましい。
Sensitizers that can be used in the present invention include fatty acid amides such as diphenylsulfone, stearamide, and palmitic acid amide, benzyloxynaphthalene, 1,2-di-(3-methylphenoxy)ethane, and di(p-oxalate). -methylbenzyl) agents and the like. These sensitizers may be used alone or in combination of two or more.
Among these sensitizers, diphenyl sulfone is preferably used in order to supplement the coloring performance (print density) when isolated lignin is used as a color developer.
本発明で使用可能なバインダーとしては、完全ケン化ポリビニルアルコール、部分ケン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、ジアセトン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、アマイ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、オレフィン変性ポリビニルアルコール、ニトリル変性ポリビニルアルコール、ピロリドン変性ポリビニルアルコール、シラノール変性ポリビニルアルコール、カチオン変性ポリビニルアルコール、末端アルキル変性ポリビニルアルコールなどのポリビニルアルコール類、ヒドロキシエチルセルロース、メチルセルロース、エチルセルロース、カルボキシメチルセルロース、アセチルセルロースなどのセルロースエーテル及びその誘導体、澱粉、酵素変性澱粉、熱化学変性澱粉、酸化澱粉、エステル化澱粉、エーテル化澱粉（例えば、ヒドロキシエチル化澱粉など）、カチオン化澱粉などの澱粉類、ポリアクリルアミド、カチオン性ポリアクリルアミド、アニオン性ポリアクリルアミド、両性ポリアクリルアミドなどのポリアクリルアミド類、ポリエステルポリウレタン系樹脂、ポリエーテルポリウレタン系樹脂、ポリウレタン系アイオノマー樹脂などのウレタン系樹脂、（メタ）アクリル酸及び、（メタ）アクリル酸と共重合可能な単量体成分（オレフィンを除く）からなるアクリル系樹脂、スチレン－ブタジエン共重合体、スチレン－ブタジエン－アクリロニトリル共重合体、スチレン－ブタジエン－アクリル共重合体などのスチレン－ブタジエン系樹脂、ポリ酢酸ビニル、塩化ビニル－酢酸ビニル共重合体、エチレン－酢酸ビニル共重合体などのポリオレフィン系樹脂、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリアクリル酸エステル、アラビヤゴム、ポリビニルブチラール、ポリスチロース及びそれらの共重合体、シリコーン樹脂、石油樹脂、テルペン樹脂、ケトン樹脂、クマロン樹脂などを例示することができる。これらは単独で又は２種以上混合して使用してもよい。 Binders that can be used in the present invention include fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, and butyral. Polyvinyl alcohols such as modified polyvinyl alcohol, olefin-modified polyvinyl alcohol, nitrile-modified polyvinyl alcohol, pyrrolidone-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, terminal alkyl-modified polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, Starches such as cellulose ether and its derivatives such as acetyl cellulose, starch, enzyme-modified starch, thermochemically modified starch, oxidized starch, esterified starch, etherified starch (for example, hydroxyethylated starch, etc.), cationized starch, polyester Polyacrylamides such as acrylamide, cationic polyacrylamide, anionic polyacrylamide, and amphoteric polyacrylamide, urethane resins such as polyester polyurethane resin, polyether polyurethane resin, and polyurethane ionomer resin, (meth)acrylic acid and ( Acrylic resins consisting of monomer components (excluding olefins) that can be copolymerized with meth)acrylic acid, styrene-butadiene copolymers, styrene-butadiene-acrylonitrile copolymers, styrene-butadiene-acrylic copolymers, etc. Polyolefin resins such as styrene-butadiene resin, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polyacrylic acid ester, gum arabic, polyvinyl butyral, Examples include polystyrose and copolymers thereof, silicone resins, petroleum resins, terpene resins, ketone resins, coumaron resins, and the like. These may be used alone or in combination of two or more.
本発明で使用可能な顔料としては、シリカ、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、酸化チタン、水酸化アルミニウムなどの無機又は有機充填剤などを例示することができる。これらは単独で又は２種以上混合して使用してもよい。 Examples of pigments that can be used in the present invention include inorganic or organic fillers such as silica, calcium carbonate, kaolin, calcined kaolin, diatomaceous earth, talc, titanium oxide, and aluminum hydroxide. These may be used alone or in combination of two or more.
本発明で使用可能な架橋剤としては、グリオキザール、メチロールメラミン、メラミンホルムアルデヒド樹脂、メラミン尿素樹脂、ポリアミンエピクロロヒドリン樹脂、ポリアミドエピクロロヒドリン樹脂、過硫酸カリウム、過硫酸アンモニウム、過硫酸ソーダ、塩化第二鉄、塩化マグネシウム、ホウ砂、ホウ酸、ミョウバン、塩化アンモニウム剤などを例示することができる。 Crosslinking agents that can be used in the present invention include glyoxal, methylolmelamine, melamine formaldehyde resin, melamine urea resin, polyamine epichlorohydrin resin, polyamide epichlorohydrin resin, potassium persulfate, ammonium persulfate, sodium persulfate, chloride Examples include ferric iron, magnesium chloride, borax, boric acid, alum, and ammonium chloride agents.
また、本発明においては、前記課題に対する所望の効果を阻害しない範囲で、記録画像の耐油性効果などを示す画像安定剤として、４，４'－ブチリデン（６－ｔ－ブチル－３－メチルフェノール）、２，２'－ジ－ｔ－ブチル－５，５'－ジメチル－４，４'－スルホニルジフェノール、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－ｔ－ブチルフェニル）ブタン、４－ベンジルオキシ－４'－（２，３－エポキシ－２－メチルプロポキシ）ジフェニルスルホン等を使用することもできる。
このほかにベンゾフェノン系やトリアゾール系の紫外線吸収剤、分散剤、消泡剤、酸化防止剤、蛍光染料等を使用することができる。
In the present invention, 4,4'-butylidene (6-t-butyl-3-methylphenol ), 2,2'-di-t-butyl-5,5'-dimethyl-4,4'-sulfonyldiphenol, 1,1,3-tris(2-methyl-4-hydroxy-5-cyclohexylphenyl) Butane, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 4-benzyloxy-4'-(2,3-epoxy-2-methylpropoxy)diphenylsulfone, etc. You can also use
In addition, benzophenone-based or triazole-based ultraviolet absorbers, dispersants, antifoaming agents, antioxidants, fluorescent dyes, and the like can be used.
本発明では、顕色剤を、ロイコ染料１重量部に対して、好ましくは０．０５～４．０重量部、より好ましくは０．１～３．０重量部の割合で使用する。
また、増感剤、バインダー、顔料、架橋剤、画像安定剤、その他の任意成分の種類及び量は、要求される性能及び記録適性に従って決定され、特に限定されるものではないが、通常、増感剤０．１～１０重量部、顔料０．５～５０重量部、画像安定剤０．０１～１０重量部、その他の成分０．０１～１０重量部程度が使用され、バインダーは感熱記録層（固形分）１００重量部に対し固形分で５～５０重量部程度が適当である。滑剤の含有量は感熱記録層（固形分）１００重量部に対し固形分で５～１０重量部程度が適当である。
In the present invention, the color developer is preferably used in an amount of 0.05 to 4.0 parts by weight, more preferably 0.1 to 3.0 parts by weight, per 1 part by weight of the leuco dye.
In addition, the types and amounts of sensitizers, binders, pigments, crosslinking agents, image stabilizers, and other optional components are determined according to the required performance and recording suitability, and are not particularly limited. Approximately 0.1 to 10 parts by weight of sensitizer, 0.5 to 50 parts by weight of pigment, 0.01 to 10 parts by weight of image stabilizer, and 0.01 to 10 parts by weight of other components are used, and the binder is used in the heat-sensitive recording layer. (Solid content) Appropriately, the solid content is about 5 to 50 parts by weight per 100 parts by weight. The content of the lubricant is suitably about 5 to 10 parts by weight in terms of solid content per 100 parts by weight of the heat-sensitive recording layer (solid content).
ロイコ染料、顕色剤並びに必要に応じて添加する材料は、ボールミル、アトライター、サンドグライダーなどの粉砕機あるいは適当な乳化装置によって数ミクロン以下の粒子径になるまで微粒化し、バインダー及び目的に応じて各種の添加材料を加えて塗液とする。この塗液に用いる溶媒としては水あるいはアルコール等を用いることができ、その固形分は２０～４０重量％程度である。 The leuco dye, color developer, and other materials to be added as necessary are atomized to a particle size of several microns or less using a pulverizer such as a ball mill, attritor, or sand glider, or an appropriate emulsifying device, and then mixed according to the binder and purpose. Then, various additive materials are added to make a coating liquid. Water or alcohol can be used as a solvent for this coating liquid, and the solid content thereof is about 20 to 40% by weight.
保護層は、上記の感熱記録層に使用可能なバインダー、顔料、架橋剤、その他の成分を所望の効果を阻害しない範囲で使用することができるが、バインダーと顔料を含むことが好ましく、必要に応じて界面活性剤や粘度調整剤等のその他の成分を含んでもよい。 The protective layer may contain binders, pigments, crosslinking agents, and other components that can be used in the heat-sensitive recording layer, as long as they do not impede the desired effect, but preferably contain binders and pigments. Depending on the situation, other components such as surfactants and viscosity modifiers may also be included.
保護層に使用するバインダーとしては、上記の感熱記録層に使用可能なバインダーの中で、ポリビニルアルコール類及びアクリル系樹脂が好ましい。
ポリビニルアルコール類としては、完全ケン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、ジアセトン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が好ましい。
アクリル系樹脂の（メタ）アクリル酸と共重合可能な成分（オレフィンを除く）としては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸－２－エチルへキシル、（メタ）アクリル酸オクチルなどのアクリル酸アルキル樹脂及びエポキシ樹脂、シリコーン樹脂、スチレン又はその誘導体によって変性されたアクリル酸アルキル樹脂などの変性アクリル酸アルキル樹脂、（メタ）アクリロニトリル、アクリル酸エステル、ヒドロキシアルキルアクリル酸エステル等が挙げられ、好ましくは（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸－２－エチルへキシル、（メタ）アクリル酸オクチルなどのアクリル酸アルキル樹脂及びエポキシ樹脂、シリコーン樹脂、スチレン又はその誘導体によって変性されたアクリル酸アルキル樹脂などの変性アクリル酸アルキル樹脂、（メタ）アクリロニトリル、アクリル酸エステル、ヒドロキシアルキルアクリル酸エステルである。特に（メタ）アクリロニトリル及び／又はメタクリル酸メチルが好ましい。アクリル系樹脂は、好ましくは非コアシェル型アクリル系樹脂である。
As the binder used for the protective layer, polyvinyl alcohols and acrylic resins are preferred among the binders that can be used for the heat-sensitive recording layer.
As polyvinyl alcohols, fully saponified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol, and acetoacetyl-modified polyvinyl alcohol are preferable.
Components of acrylic resins that can be copolymerized with (meth)acrylic acid (excluding olefins) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. , alkyl acrylate resins and epoxy resins such as isobutyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, -2-ethylhexyl (meth)acrylate, and octyl (meth)acrylate; Examples include silicone resins, modified alkyl acrylate resins such as alkyl acrylate resins modified with styrene or derivatives thereof, (meth)acrylonitrile, acrylic esters, hydroxyalkyl acrylates, etc., preferably methyl (meth)acrylate. , ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, (meth)acrylic acid-2 - Alkyl acrylate resins such as ethylhexyl, octyl (meth)acrylate, and modified alkyl acrylate resins such as epoxy resins, silicone resins, alkyl acrylate resins modified with styrene or derivatives thereof, (meth)acrylonitrile, acrylic acid ester, hydroxyalkyl acrylic acid ester. Particularly preferred are (meth)acrylonitrile and/or methyl methacrylate. The acrylic resin is preferably a non-core-shell type acrylic resin.
また、保護層は、耐水性等を改善するために、バインダーとしてカルボキシル基含有樹脂を含有してもよく、更にポリアミン／ポリアミド系樹脂を含有してもよい。
このカルボキシル基含有樹脂としては、上記のカルボキシ変性ポリビニルアルコール、アクリル系樹脂、酸化澱粉、カルボキシメチルセルロースなどが挙げられる。
このポリアミン／ポリアミド系樹脂としては、ポリアミド尿素樹脂、ポリアルキレンポリアミン樹脂、ポリアルキレンポリアミド樹脂、ポリアミンポリ尿素樹脂、変性ポリアミン樹脂、変性ポリアミド樹脂、ポリアルキレンポリアミン尿素ホルマリン樹脂、ポリアルキレンポリアミンポリアミドポリ尿素樹脂などが挙げられる。
Further, the protective layer may contain a carboxyl group-containing resin as a binder and may further contain a polyamine/polyamide resin in order to improve water resistance and the like.
Examples of the carboxyl group-containing resin include the above-mentioned carboxy-modified polyvinyl alcohol, acrylic resin, oxidized starch, and carboxymethyl cellulose.
Examples of this polyamine/polyamide resin include polyamide urea resin, polyalkylene polyamine resin, polyalkylene polyamide resin, polyamine polyurea resin, modified polyamine resin, modified polyamide resin, polyalkylene polyamine urea formalin resin, and polyalkylene polyamine polyamide polyurea resin. Examples include.
本発明において、保護層が顔料を含有する場合、感熱記録体の耐水性及び印字走行性が良好となるため、この顔料としては、シリカ、カオリン、焼成カオリン、水酸化アルミニウムが好ましく、カオリン、水酸化アルミニウムがより好ましい。
本発明の保護層が顔料を含まない場合、保護層中のバインダーの配合量は、固形分で、通常７０～１００重量％、好ましくは８５～１００重量％である。
一方、保護層が顔料を含む場合、保護層中のバインダーと顔料の総量は、固形分で、通常８０～１００重量％、好ましくは９０～１００重量％であり、顔料１００重量部に対してバインダーは３０～３００重量部程度であることが好ましい。
バインダー、架橋剤及び顔料以外の成分は、それぞれ保護層中１５重量％、好ましくは１０重量％を超えない。
In the present invention, when the protective layer contains a pigment, the water resistance and print runnability of the heat-sensitive recording medium are improved. Aluminum oxide is more preferred.
When the protective layer of the present invention does not contain a pigment, the amount of binder blended in the protective layer is usually 70 to 100% by weight, preferably 85 to 100% by weight in terms of solid content.
On the other hand, when the protective layer contains a pigment, the total amount of the binder and the pigment in the protective layer is usually 80 to 100% by weight, preferably 90 to 100% by weight in terms of solid content, and the binder and pigment are usually 80 to 100% by weight, preferably 90 to 100% by weight, and the binder and pigment are 100 parts by weight of the pigment. is preferably about 30 to 300 parts by weight.
Components other than the binder, crosslinking agent and pigment each do not exceed 15% by weight, preferably 10% by weight, in the protective layer.
感熱記録層や保護層以外の任意に設けられる各塗工層は、上記のバインダー、顔料、架橋剤、その他の成分を所望の効果を阻害しない範囲で使用することができる。 In each optional coating layer other than the heat-sensitive recording layer and the protective layer, the above-mentioned binder, pigment, crosslinking agent, and other components can be used within a range that does not impede the desired effect.
感熱記録層、保護層その他の塗工層の塗工方法は特に限定されるものではなく、カーテン塗工法、エアーナイフ塗工法、バーブレード塗工法、ロッドブレード塗工法、ベントブレード塗工法、ベベルブレード塗工法、ロール塗工法、スプレー塗工法など、従来公知の方法を採用することができる。 Coating methods for the heat-sensitive recording layer, protective layer, and other coating layers are not particularly limited, and include curtain coating, air knife coating, bar blade coating, rod blade coating, bent blade coating, and bevel blade coating. Conventionally known methods such as a coating method, a roll coating method, and a spray coating method can be employed.
感熱記録層、保護層、その他の塗工層の塗工量は、要求される性能及び記録適性に従って決定され、特に限定されるものではないが、例えば、感熱記録層の一般的な塗工量は固形分で２～１２ｇ／ｍ２程度であり、保護層の一般的な塗工量は固形分で１～５ｇ／ｍ２程度である。
また、各層の塗工後にスーパーカレンダー掛けなどの平滑化処理を施すなど、感熱記録体分野における各種公知の技術を必要適宜付加することができる。
The coating amount of the heat-sensitive recording layer, protective layer, and other coating layers is determined according to the required performance and recording suitability, and is not particularly limited. For example, the coating amount of the heat-sensitive recording layer is The solid content is about 2 to 12 g/m 2 , and the general coating amount of the protective layer is about 1 to 5 g/m 2 in solid content.
Further, various known techniques in the field of heat-sensitive recording materials can be added as necessary, such as performing a smoothing treatment such as super calendering after coating each layer.
以下、実施例にて本発明を例証するが、本発明を限定することを意図するものではない。なお、各実施例及び比較例中、特にことわらない限り「部」は「重量部」、「％」は「重量％」を示す。
各分散液と塗工液を以下のように調製した。
EXAMPLES The present invention will be illustrated below with examples, but they are not intended to limit the present invention. In each of the Examples and Comparative Examples, "part" means "part by weight" and "%" means "% by weight" unless otherwise specified.
Each dispersion liquid and coating liquid were prepared as follows.
下記配合からなる配合物を攪拌分散して、下塗り層用塗工液を調製した。
＜下塗り層用塗工液＞
焼成カオリン（ＢＡＳＦ社製、商品名：アンシレックス９０）
１００．０部
スチレン・ブタジエン共重合体ラテックス（日本ゼオン株式会社製、
商品名：ＳＴ５５２６、固形分４８％） １０．０部
水 ５０．０部
A coating solution for an undercoat layer was prepared by stirring and dispersing a composition having the following composition.
<Coating liquid for undercoat layer>
Calcined kaolin (manufactured by BASF, product name: Ansilex 90)
100.0 parts Styrene-butadiene copolymer latex (manufactured by Nippon Zeon Co., Ltd.,
Product name: ST5526, solid content 48%) 10.0 parts Water 50.0 parts
下記配合の顕色剤分散液（Ａ１～Ａ３液）、ロイコ染料分散液（Ｂ液）、増感剤分散液（Ｃ液）を、それぞれ別々にサンドグラインダーで平均粒子径０．５μｍになるまで湿式磨砕を行い、調製した。クラフトリグニン分散液（Ａ液）については、サンドグラインダーで平均粒子径３．０μｍになるまで湿式磨砕を行い、調製した。 A developer dispersion (Liquid A1 to A3), a leuco dye dispersion (Liquid B), and a sensitizer dispersion (Liquid C) with the following formulations were each separately ground in a sand grinder until the average particle size was 0.5 μm. It was prepared by wet grinding. A kraft lignin dispersion (liquid A) was prepared by performing wet grinding with a sand grinder until the average particle size was 3.0 μm.
クラフトリグニン分散液（Ａ液）
クラフトリグニン（メドウエストバコ（Meadwestbaco）社製、
インジュリンＡＴ（Indulin AT） ６．０部
完全ケン化型ポリビニルアルコール水溶液（株式会社クラレ製、
商品名：ＰＶＡ１１７、固形分１０％） ５．０部
水 １．５部
Kraft lignin dispersion (liquid A)
Kraft lignin (manufactured by Meadwestbaco)
Indulin AT (Indulin AT) 6.0 parts fully saponified polyvinyl alcohol aqueous solution (manufactured by Kuraray Co., Ltd.,
Product name: PVA117, solid content 10%) 5.0 parts Water 1.5 parts
顕色剤分散液（Ａ１液）
４，４'-ジヒドロキシジフェニルスルホン
（小西化学工業株式会社製、商品名：４４ＢＰＳ） ６．０部
完全ケン化型ポリビニルアルコール水溶液（ＰＶＡ１１７） ５．０部
水 １．５部
Color developer dispersion (A1 liquid)
4,4'-Dihydroxydiphenylsulfone (manufactured by Konishi Chemical Industry Co., Ltd., product name: 44BPS) 6.0 parts Completely saponified polyvinyl alcohol aqueous solution (PVA117) 5.0 parts Water 1.5 parts
顕色剤分散液（Ａ２液）
４－ヒドロキシ－４'－イソプロポキシジフェニルスルホン
（三菱ケミカル株式会社製、商品名：ＮＹＤＳ） ６．０部
完全ケン化型ポリビニルアルコール水溶液（ＰＶＡ１１７） ５．０部
水 １．５部
Color developer dispersion (A2 liquid)
4-Hydroxy-4'-isopropoxydiphenylsulfone (manufactured by Mitsubishi Chemical Corporation, trade name: NYDS) 6.0 parts Completely saponified polyvinyl alcohol aqueous solution (PVA117) 5.0 parts Water 1.5 parts
顕色剤分散液（Ａ３液）
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
（日本曹達株式会社製、商品名：ＮＫＫ１３０４） ６．０部
完全ケン化型ポリビニルアルコール水溶液（ＰＶＡ１１７） ５．０部
水 １．５部
Color developer dispersion (A3 liquid)
N-(2-(3-phenylureido)phenyl)benzenesulfonamide (manufactured by Nippon Soda Co., Ltd., trade name: NKK1304) 6.0 parts Completely saponified polyvinyl alcohol aqueous solution (PVA117) 5.0 parts Water 1.5 Department
ロイコ染料分散液（Ｂ液）
３－ジブチルアミノ－６－メチル－７－アニリノフルオラン
（山本化成株式会社製、商品名：ＯＤＢ－２） ６．０部
完全ケン化型ポリビニルアルコール水溶液（ＰＶＡ１１７） ５．０部
水 １．５部
Leuco dye dispersion (liquid B)
3-dibutylamino-6-methyl-7-anilinofluorane (manufactured by Yamamoto Kasei Co., Ltd., product name: ODB-2) 6.0 parts Completely saponified polyvinyl alcohol aqueous solution (PVA117) 5.0 parts Water 1. 5th part
増感剤分散液（Ｃ液）
ジフェニルスルホン（Ｖｏｌａｎｔ社製、商品名：ＤＰＳ） ６．０部
完全ケン化型ポリビニルアルコール水溶液（ＰＶＡ１１７） ５．０部
水 １．５部
Sensitizer dispersion liquid (C liquid)
Diphenylsulfone (manufactured by Volant, trade name: DPS) 6.0 parts Completely saponified polyvinyl alcohol aqueous solution (PVA117) 5.0 parts Water 1.5 parts
次いで、下記の割合で各分散液を混合し、十分に撹拌して感熱記録層用塗工液１～３を調製した。
＜感熱記録層用塗工液１＞
クラフトリグニン分散液（Ａ液） １．５部
ロイコ染料分散液（Ｂ液） １．０５部
シリカ分散液（水澤化学工業株式会社製、商品名：ミズカシルＰ－５３７
、固形分２５％） ５．０部
ステアリン酸亜鉛（中京油脂株式会社製、商品名：ハイドリンＬ５３６、
固形分４０％） ５．０部
完全ケン化型ポリビニルアルコール水溶液（ＰＶＡ１１７） ２０．０部
Next, the respective dispersions were mixed in the proportions shown below and thoroughly stirred to prepare coating solutions 1 to 3 for heat-sensitive recording layers.
<Coating liquid 1 for heat-sensitive recording layer>
Kraft lignin dispersion (liquid A) 1.5 parts Leuco dye dispersion (liquid B) 1.05 parts Silica dispersion (manufactured by Mizusawa Chemical Co., Ltd., product name: Mizukasil P-537)
, solid content 25%) 5.0 parts Zinc stearate (manufactured by Chukyo Yushi Co., Ltd., product name: Hydrin L536,
Solid content 40%) 5.0 parts Completely saponified polyvinyl alcohol aqueous solution (PVA117) 20.0 parts
＜感熱記録層用塗工液２＞
クラフトリグニン分散液（Ａ液） １．５部
ロイコ染料分散液（Ｂ液） １．０５部
増感剤分散液（Ｃ液） １．２部
シリカ分散液（ミズカシルＰ－５３７） ５．０部
ステアリン酸亜鉛（ハイドリンＬ５３６） ５．０部
完全ケン化型ポリビニルアルコール水溶液（ＰＶＡ１１７） ２０．０部
<Coating liquid 2 for heat-sensitive recording layer>
Kraft lignin dispersion (liquid A) 1.5 parts Leuco dye dispersion (liquid B) 1.05 parts Sensitizer dispersion (liquid C) 1.2 parts Silica dispersion (Mizukasil P-537) 5.0 parts Zinc stearate (Hydrin L536) 5.0 parts Completely saponified polyvinyl alcohol aqueous solution (PVA117) 20.0 parts
＜感熱記録層用塗工液３＞
クラフトリグニン分散液（Ａ液） ０．７５部
顕色剤分散液（Ａ１液） ０．７５部
ロイコ染料分散液（Ｂ液） １．０５部
増感剤分散液（Ｃ液） １．２部
シリカ分散液（ミズカシルＰ－５３７） ５．０部
ステアリン酸亜鉛（ハイドリンＬ５３６） ５．０部
完全ケン化型ポリビニルアルコール水溶液（ＰＶＡ１１７） ２０．０部
<Coating liquid 3 for heat-sensitive recording layer>
Kraft lignin dispersion (liquid A) 0.75 parts Color developer dispersion (liquid A1) 0.75 parts Leuco dye dispersion (liquid B) 1.05 parts Sensitizer dispersion (liquid C) 1.2 parts Silica dispersion (Mizukasil P-537) 5.0 parts Zinc stearate (Hydrin L536) 5.0 parts Completely saponified polyvinyl alcohol aqueous solution (PVA117) 20.0 parts
［実施例１］
支持体（坪量４７ｇ／ｍ２の上質紙）の片面に、下塗り層用塗工液を、固形分で塗工量１０．０ｇ／ｍ２となるようにベントブレード法で塗工した後、乾燥を行ない、下塗り層塗工紙を得た。
この下塗り層塗工紙の下塗り層上に、感熱記録層用塗工液１（全顕色剤中のクラフトリグニン＝１００％、感熱記録層中のクラフトリグニン＝１０．９％、顕色剤／ロイコ染料＝１．４３）を、固形分で塗工量６．０ｇ／ｍ２となるようにロッドブレード法で塗工した後、乾燥を行い、スーパーカレンダーで平滑度が５００～１０００秒になるように処理して感熱記録体を作製した。
[Example 1]
After applying the coating solution for the undercoat layer to one side of the support (high-quality paper with a basis weight of 47 g/m 2 ) using a bent blade method so that the coating amount in terms of solid content was 10.0 g/m 2 , It was dried to obtain an undercoat coated paper.
Coating liquid 1 for heat-sensitive recording layer (kraft lignin in total color developer = 100%, kraft lignin in heat-sensitive recording layer = 10.9%, color developer/ Leuco dye = 1.43) was applied using the rod blade method to a coating amount of 6.0 g/ m2 in terms of solid content, then dried, and the smoothness reached 500 to 1000 seconds using a super calender. A heat-sensitive recording medium was prepared by the following treatment.
［実施例２］
感熱記録層塗工液１を感熱記録層塗工液２（全顕色剤中のクラフトリグニン＝１００％、感熱記録層中のクラフトリグニン＝１０．０％、顕色剤／ロイコ染料＝１．４３）に代えた以外は、実施例１と同様にして感熱記録体を作製した。
［実施例３］
感熱記録層塗工液１を感熱記録層塗工液３（全顕色剤中のクラフトリグニン＝５０％、感熱記録層中のクラフトリグニン＝５．０％、顕色剤／ロイコ染料＝１．４３）に代えた以外は、実施例１と同様にして感熱記録体を作製した。
[Example 2]
Heat-sensitive recording layer coating liquid 1 was mixed with heat-sensitive recording layer coating liquid 2 (kraft lignin in total color developer = 100%, kraft lignin in heat-sensitive recording layer = 10.0%, color developer/leuco dye = 1. A heat-sensitive recording material was produced in the same manner as in Example 1 except that 43) was replaced.
[Example 3]
Heat-sensitive recording layer coating liquid 1 was mixed with heat-sensitive recording layer coating liquid 3 (kraft lignin in total color developer = 50%, kraft lignin in heat-sensitive recording layer = 5.0%, color developer/leuco dye = 1. A heat-sensitive recording material was produced in the same manner as in Example 1 except that 43) was replaced.
［実施例４］
感熱記録層塗工液３において、顕色剤分散液（Ａ１液）０．７５部を顕色剤分散液（Ａ２液）０．７５部に代えた以外は、実施例３と同様にして感熱記録体を作製した（全顕色剤中のクラフトリグニン＝５０％、感熱記録層中のクラフトリグニン＝５．０％、顕色剤／ロイコ染料＝１．４３）。
［実施例５］
感熱記録層塗工液３において、顕色剤分散液（Ａ１液）０．７５部を顕色剤分散液（Ａ３液）０．７５部に代えた以外は、実施例３と同様にして感熱記録体を作製した（全顕色剤中のクラフトリグニン＝５０％、感熱記録層中のクラフトリグニン＝５．０％、顕色剤／ロイコ染料＝１．４３）。
[Example 4]
Heat-sensitive recording layer coating solution 3 was prepared in the same manner as in Example 3, except that 0.75 parts of the developer dispersion (Liquid A1) was replaced with 0.75 parts of the developer dispersion (Liquid A2). A recording medium was produced (kraft lignin in total color developer = 50%, kraft lignin in heat-sensitive recording layer = 5.0%, color developer/leuco dye = 1.43).
[Example 5]
Heat-sensitive recording layer coating solution 3 was prepared in the same manner as in Example 3, except that 0.75 parts of the developer dispersion (Liquid A1) was replaced with 0.75 parts of the developer dispersion (Liquid A3). A recording medium was produced (kraft lignin in total color developer = 50%, kraft lignin in heat-sensitive recording layer = 5.0%, color developer/leuco dye = 1.43).
［実施例６］
感熱記録層塗工液３において、顕色剤分散液（Ａ１液）０．７５部を顕色剤分散液（Ａ３液）１．１３部に代え、クラフトリグニン分散液（Ａ液）０．７５部をクラフトリグニン分散液（Ａ液）０．３７部に代えた以外は、実施例３と同様にして感熱記録体を作製した（全顕色剤中のクラフトリグニン＝２４．７％、感熱記録層中のクラフトリグニン＝２．５％、顕色剤／ロイコ染料＝１．４３）。
［実施例７］
感熱記録層塗工液３において、顕色剤分散液（Ａ１液）０．７５部を顕色剤分散液（Ａ３液）０．３７部に代え、クラフトリグニン分散液（Ａ液）０．７５部をクラフトリグニン分散液（Ａ液）１．１３部に代えた以外は、実施例３と同様にして感熱記録体を作製した（全顕色剤中のクラフトリグニン＝７５．３％、感熱記録層中のクラフトリグニン＝７．５％、顕色剤／ロイコ染料＝１．４３）。
[Example 6]
In the heat-sensitive recording layer coating solution 3, 0.75 parts of the color developer dispersion (Liquid A1) was replaced with 1.13 parts of the color developer dispersion (Liquid A3), and 0.75 parts of the kraft lignin dispersion (Liquid A) was added. A heat-sensitive recording material was produced in the same manner as in Example 3, except that 0.37 parts of the kraft lignin dispersion (solution A) was used (kraft lignin in the total color developer = 24.7%, heat-sensitive recording material Kraft lignin in layer = 2.5%, color developer/leuco dye = 1.43).
[Example 7]
In the heat-sensitive recording layer coating liquid 3, 0.75 parts of the color developer dispersion (Liquid A1) was replaced with 0.37 parts of the color developer dispersion (Liquid A3), and 0.75 parts of the kraft lignin dispersion (Liquid A) was added. A heat-sensitive recording material was produced in the same manner as in Example 3, except that 1.13 parts of the kraft lignin dispersion (solution A) was used (kraft lignin in the total developer = 75.3%, heat-sensitive recording material Kraft lignin in layer = 7.5%, color developer/leuco dye = 1.43).
作製した感熱記録体について、下記評価を行った。
＜発色性能（印字濃度）＞
作製した感熱記録体について、大倉電機社製の感熱プリンタ（ＴＨ－ＰＭＤ）を使用して、印加エネルギー０．２７ｍJ／ｄｏｔ及び０．３５ｍＪ／ｄｏｔ、印字速度５０ｍｍ／ｓｅｃで市松模様を印字した。
印字部の濃度をマクベス濃度計（ＲＤ－９１４、アンバーフィルター使用）で測定した。後記表１には各印加エネルギーにおける印字部の濃度を示す。
＜耐光性＞
作製した感熱記録体について、大倉電機社製の感熱プリンタ（ＴＨ－ＰＭＤ）を使用して、印加エネルギー０．３５ｍＪ／ｄｏｔ、印字速度５０ｍｍ／ｓｅｃで市松模様を印字した。印字した感熱記録体を、キセノンフェードメーターで６時間照射処理した後、２３℃、５０％ＲＨ環境下に３時間静置した。
印字部の濃度をマクベス濃度計（ＲＤ－９１４、アンバーフィルター使用）で測定し、下式に従って残存率を算出した。
残存率＝（処理後の印字部の濃度）／（処理前の印字部の濃度）×１００（％）
後記表１には処理後の印字部の濃度と残存率を示す。
The produced heat-sensitive recording material was evaluated as follows.
<Color development performance (print density)>
A checkered pattern was printed on the produced thermal recording material using a thermal printer (TH-PMD) manufactured by Okura Electric Co., Ltd. at an applied energy of 0.27 mJ/dot and 0.35 mJ/dot and a printing speed of 50 mm/sec.
The density of the printed area was measured using a Macbeth densitometer (RD-914, using an amber filter). Table 1 below shows the density of the printed area at each applied energy.
<Light resistance>
A checkered pattern was printed on the produced thermal recording material using a thermal printer (TH-PMD) manufactured by Okura Electric Co., Ltd. at an applied energy of 0.35 mJ/dot and a printing speed of 50 mm/sec. The printed heat-sensitive recording material was irradiated with a xenon fade meter for 6 hours, and then left to stand in an environment of 23° C. and 50% RH for 3 hours.
The density of the printed area was measured using a Macbeth densitometer (RD-914, using an amber filter), and the residual rate was calculated according to the formula below.
Remaining rate = (density of printed area after treatment) / (density of printed area before treatment) x 100 (%)
Table 1 below shows the density and residual rate of the printed area after treatment.
＜印字部の耐熱性＞
作製した感熱記録体について、大倉電機社製の感熱プリンタ（ＴＨ－ＰＭＤ）を使用して、感熱記録材料に印加エネルギー０．３５ｍＪ／ｄｏｔ、印字速度５０ｍｍ／ｓｅｃで市松模様を印字した。印字した感熱記録体を、６０℃の環境下で２４時間処理した後、２３℃、５０％ＲＨ環境下に３時間静置した。
印字部の濃度をマクベス濃度計（ＲＤ－９１４、アンバーフィルター使用）で測定し、上記耐光性と同様に残存率を算出した。後記表１には処理後の印字部の濃度と残存率を示す。
＜非印字部の耐熱性＞
作製した感熱記録体について、ギヤー老化式試験器（（株）東洋精機製作所）を使用して、９０℃、１２０℃、１５０℃の環境下で２４時間処理した後、２３℃、５０％ＲＨ環境下に３時間静置した。
非印字部の濃度をマクベス濃度計（ＲＤ-９１４、アンバーフィルター使用）で測定した。後記表１には処理前の非印字部の濃度と温度ごとの処理後の非印字部の濃度を示す。
<Heat resistance of printed area>
A checkered pattern was printed on the produced thermal recording material using a thermal printer (TH-PMD) manufactured by Okura Electric Co., Ltd. at an applied energy of 0.35 mJ/dot and a printing speed of 50 mm/sec. The printed thermosensitive recording material was treated in an environment of 60° C. for 24 hours, and then left standing in an environment of 23° C. and 50% RH for 3 hours.
The density of the printed area was measured with a Macbeth densitometer (RD-914, using an amber filter), and the residual rate was calculated in the same manner as the light resistance above. Table 1 below shows the density and residual rate of the printed area after treatment.
<Heat resistance of non-printing area>
The produced heat-sensitive recording material was treated in a 90°C, 120°C, and 150°C environment for 24 hours using a gear aging tester (Toyo Seiki Seisakusho Co., Ltd.), and then in a 23°C, 50% RH environment. It was left undisturbed for 3 hours.
The density of the non-printed area was measured using a Macbeth densitometer (RD-914, using an amber filter). Table 1 below shows the density of the non-printed area before treatment and the density of the non-printed area after treatment at each temperature.
＜耐湿熱性＞
作製した感熱記録体について、大倉電機社製の感熱プリンタ（ＴＨ－ＰＭＤ）を使用して、感熱記録材料に印加エネルギー０．３５ｍＪ／ｄｏｔ、印字速度５０ｍｍ／ｓｅｃで市松模様を印字した。印字した感熱記録体を、４０℃、９０％ＲＨ環境下で２４時間処理した後、２３℃、５０％ＲＨ環境下に３時間静置した。
印字部の濃度をマクベス濃度計（ＲＤ－９１４、アンバーフィルター使用）で測定し、上記耐光性と同様に残存率を算出した。後記表１には処理後の印字部の濃度と残存率を示す。
＜耐水性＞
作製した感熱記録体について、大倉電機社製の感熱プリンタ（ＴＨ－ＰＭＤ）を使用して、感熱記録材料に印加エネルギー０．３５ｍＪ／ｄｏｔ、印字速度５０ｍｍ／ｓｅｃで市松模様を印字した。印字した感熱記録体を、２３℃の水に２４時間浸漬処理した後、風乾した。
印字部の濃度をマクベス濃度計（ＲＤ－９１４、アンバーフィルター使用）で測定し、上記耐光性と同様に残存率を算出した。後記表１には処理後の印字部の濃度と残存率を示す。
<Moisture heat resistance>
A checkered pattern was printed on the produced thermal recording material using a thermal printer (TH-PMD) manufactured by Okura Electric Co., Ltd. at an applied energy of 0.35 mJ/dot and a printing speed of 50 mm/sec. The printed thermosensitive recording material was treated in an environment of 40° C. and 90% RH for 24 hours, and then left to stand for 3 hours in an environment of 23° C. and 50% RH.
The density of the printed area was measured with a Macbeth densitometer (RD-914, using an amber filter), and the residual rate was calculated in the same manner as the light resistance above. Table 1 below shows the density and residual rate of the printed area after treatment.
<Water resistance>
A checkered pattern was printed on the produced thermal recording material using a thermal printer (TH-PMD) manufactured by Okura Electric Co., Ltd. at an applied energy of 0.35 mJ/dot and a printing speed of 50 mm/sec. The printed thermosensitive recording material was immersed in water at 23° C. for 24 hours, and then air-dried.
The density of the printed area was measured with a Macbeth densitometer (RD-914, using an amber filter), and the residual rate was calculated in the same manner as the light resistance above. Table 1 below shows the density and residual rate of the printed area after treatment.
＜耐可塑剤性＞
作製した感熱記録体について、大倉電機社製の感熱プリンタ（ＴＨ－ＰＭＤ）を使用して、感熱記録材料に印加エネルギー０．３５ｍＪ／ｄｏｔ、印字速度５０ｍｍ／ｓｅｃで市松模様を印字した。印字した感熱記録体を、紙管に塩ビラップ（三井化学製ハイラップＫＭＡ）を１回巻き付けた上に貼り付け、更にその上に塩ビラップを３重に巻き付けて、２３℃、５０％ＲＨ環境下に２４時間静置した。
印字部の濃度をマクベス濃度計（ＲＤ－９１４、アンバーフィルター使用）で測定し、上記耐光性と同様に残存率を算出した。後記表１には処理後の印字部の濃度と残存率を示す。
<Plasticizer resistance>
A checkered pattern was printed on the produced thermal recording material using a thermal printer (TH-PMD) manufactured by Okura Electric Co., Ltd. at an applied energy of 0.35 mJ/dot and a printing speed of 50 mm/sec. The printed heat-sensitive recording material was pasted on a paper tube wrapped once with PVC wrap (Hi-Lap KMA manufactured by Mitsui Chemicals), and further wrapped with PVC wrap three times on top of that, and placed in an environment of 23°C and 50% RH. It was left standing for 24 hours.
The density of the printed area was measured with a Macbeth densitometer (RD-914, using an amber filter), and the residual rate was calculated in the same manner as the light resistance above. Table 1 below shows the density and residual rate of the printed area after treatment.
評価結果を下表に示す。顕色剤、増感剤の項は感熱記録層中の顕色剤、増感剤の含有量（固形分、重量％）を示す。
Claims (6)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022167288A JP7365480B2 (en) | 2018-12-26 | 2022-10-19 | heat sensitive recording material |
| JP2023172415A JP7498839B2 (en) | 2018-12-26 | 2023-10-04 | Thermal recording medium |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
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| JP7246288B2 (en) * | 2019-09-19 | 2023-03-27 | 株式会社クラレ | Aqueous solution, its production method and its use |
| ES3028248T3 (en) * | 2020-12-28 | 2025-06-18 | Sanko Co Ltd | Colour developer, thermal recording material, and coating material for thermal recording layers |
| EP4365220A4 (en) | 2021-06-30 | 2025-06-11 | Nicca Chemical Co., Ltd. | HEAT-SENSITIVE RECORDING MATERIAL |
| JP7374980B2 (en) * | 2021-12-28 | 2023-11-07 | 日華化学株式会社 | Heat-sensitive recording material and its manufacturing method |
| JP7362694B2 (en) | 2021-06-30 | 2023-10-17 | 日華化学株式会社 | Kraft lignin, color developer for heat-sensitive recording and heat-sensitive recording material |
| JP7803172B2 (en) * | 2022-03-04 | 2026-01-21 | 三菱ケミカル株式会社 | Color developer and thermal recording material |
| EP4559693A1 (en) | 2023-03-31 | 2025-05-28 | Nippon Paper Industries Co., Ltd. | Heat-sensitive recording body |
| WO2025221564A1 (en) * | 2024-04-15 | 2025-10-23 | Dow Global Technologies Llc | Lignin dispersion for seed coating |
| WO2026002826A1 (en) | 2024-06-24 | 2026-01-02 | Ecole Polytechnique Federale De Lausanne (Epfl) | Light-colored lignin fragment |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003154760A (en) | 2001-11-21 | 2003-05-27 | Nippon Paper Industries Co Ltd | Thermal recording medium |
| WO2017069141A1 (en) | 2015-10-23 | 2017-04-27 | 日本製紙株式会社 | Heat-sensitive recording body |
| JP2017528337A (en) | 2014-07-08 | 2017-09-28 | ザイレコ，インコーポレイテッド | Marking of plastic products |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5258611A (en) * | 1975-11-08 | 1977-05-14 | Mitsui Toatsu Chemicals | Colorrdeveloping agent for pressure sensitized copy sheets |
| FR2530191B1 (en) * | 1982-07-16 | 1986-11-21 | Aussedat Rey | NOVEL COLOR DEVELOPERS BASED ON SACCHARIN AND / OR SACCHARIN DERIVATIVES, THERMOGRAPHIC RECORDING COMPOSITIONS CONTAINING THEM AND MATERIALS THEREOF |
| JPS60101171A (en) * | 1983-11-07 | 1985-06-05 | Tanabe Seiyaku Co Ltd | Thermosensitive composition |
| JPS63170080A (en) * | 1987-01-09 | 1988-07-13 | Mitsui Toatsu Chem Inc | Aqueous suspension |
| JP2936550B2 (en) * | 1991-05-09 | 1999-08-23 | 王子製紙株式会社 | Thermal recording medium |
| JP3105354B2 (en) * | 1991-07-03 | 2000-10-30 | 三井化学株式会社 | Developer composition, aqueous suspension, and developer sheet for pressure-sensitive copying paper using the same |
| JPH0553981U (en) * | 1991-12-26 | 1993-07-20 | リンテック株式会社 | Ballot |
| DE19756172A1 (en) * | 1997-12-17 | 1999-06-24 | Stockhausen Chem Fab Gmbh | Process for the grafting of lignin, polymers prepared therefrom and their use |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003154760A (en) | 2001-11-21 | 2003-05-27 | Nippon Paper Industries Co Ltd | Thermal recording medium |
| JP2017528337A (en) | 2014-07-08 | 2017-09-28 | ザイレコ，インコーポレイテッド | Marking of plastic products |
| WO2017069141A1 (en) | 2015-10-23 | 2017-04-27 | 日本製紙株式会社 | Heat-sensitive recording body |
Also Published As
| Publication number | Publication date |
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| JP7498839B2 (en) | 2024-06-12 |
| JP7163173B2 (en) | 2022-10-31 |
| JP2022191430A (en) | 2022-12-27 |
| JP2020104274A (en) | 2020-07-09 |
| JP2023168521A (en) | 2023-11-24 |
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