JP7374980B2 - Heat-sensitive recording material and its manufacturing method - Google Patents
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- JP7374980B2 JP7374980B2 JP2021214415A JP2021214415A JP7374980B2 JP 7374980 B2 JP7374980 B2 JP 7374980B2 JP 2021214415 A JP2021214415 A JP 2021214415A JP 2021214415 A JP2021214415 A JP 2021214415A JP 7374980 B2 JP7374980 B2 JP 7374980B2
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Description
本開示は、感熱記録材料に関する。 The present disclosure relates to heat-sensitive recording materials.
近年、地球温暖化問題や廃棄物問題の両観点から、生物と太陽エネルギーがある限り持続的に再生可能な資源、エネルギー源としてバイオマスが注目されている。そのような中、植物又は植物由来の加工品等のバイオマスを利用する技術や、石油由来の化学品、樹脂製品等をバイオマスに転換する技術の開発が求められている。例えば、林産資源として、間伐材、建築廃材、製紙工場廃材等の木質系廃材などは、燃料として焼却される以外、その多くは廃棄処分されている。しかしながら、地球環境保護の観点から、それら廃材の有効活用、リサイクルが検討されている。 In recent years, biomass has attracted attention as a sustainable and renewable resource and energy source as long as living organisms and solar energy are available, both from the perspective of global warming and waste issues. Under these circumstances, there is a need for the development of technologies that utilize biomass such as plants or plant-derived processed products, and technologies that convert petroleum-derived chemicals, resin products, etc. into biomass. For example, forest resources such as wood waste such as thinned wood, construction waste, and paper mill waste are incinerated as fuel, and most of them are disposed of as waste. However, from the perspective of protecting the global environment, effective use and recycling of these waste materials is being considered.
一般的な木質の主要成分は、セルロース、ヘミセルロース及びリグニンである。そのうち、リグニンは、木質の約３０％の割合で含まれており、地球上でセルロースに次いで多量に存在する天然有機化合物といわれている。リグニンは、芳香環を豊富に含み、ヒドロキシル基などの反応可能な官能基も有しているため、工業的な利用が期待されている。 The main components of common wood are cellulose, hemicellulose and lignin. Among them, lignin is contained in about 30% of wood, and is said to be the second most abundant natural organic compound on earth after cellulose. Lignin is expected to be used industrially because it contains abundant aromatic rings and also has reactive functional groups such as hydroxyl groups.
そのような中、下記の特許文献１には、感熱記録層を設けた感熱記録体において、電子受容性顕色剤として単離リグニンを含有する感熱記録体が開示されている。 Under such circumstances, the following Patent Document 1 discloses a heat-sensitive recording body provided with a heat-sensitive recording layer, which contains isolated lignin as an electron-accepting color developer.
この単離リグニンは、通常、前述したリグニンに化学変性を施すことにより得られる。単離リグニンとしては、その化学変性の違いにより、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、オルガノソルブリグニン、爆砕リグニン、及び硫酸リグニンなどが存在する。 This isolated lignin is usually obtained by chemically modifying the lignin described above. Isolated lignin includes lignosulfonic acid (salt), kraft lignin, soda lignin, soda-anthraquinone lignin, organosol lignin, blasted lignin, and sulfuric lignin, depending on their chemical modification.
その単離リグニンの中でも、クラフトリグニンは、芳香環を豊富に含み、ヒドロキシル基などの反応基を有しているため、感熱記録材料に使用される発色物質を発色させることに適している。そのため、環境に優しい顕色剤として感熱記録材料への応用が期待される。 Among the isolated lignins, kraft lignin contains abundant aromatic rings and has reactive groups such as hydroxyl groups, so it is suitable for coloring the coloring substances used in heat-sensitive recording materials. Therefore, it is expected to be applied to heat-sensitive recording materials as an environmentally friendly color developer.
クラフトリグニンは、木材由来であることから環境に優しい。しかし、顕色剤としてクラフトリグニンを用いた感熱記録材料では、画像部を形成するために加熱すると、単離された状態のクラフトリグニンでは感じられない不快な臭気（以下、「不快臭」ともいう。）が発生することが、本発明者らの検討により明らかになった。 Kraft lignin is environmentally friendly because it is derived from wood. However, when heat-sensitive recording materials that use kraft lignin as a color developer are heated to form image areas, they emit an unpleasant odor (hereinafter also referred to as "unpleasant odor") that cannot be felt with isolated kraft lignin. The present inventors' studies have revealed that .) occurs.
本発明の一側面は、クラフトリグニンを顕色剤として用いながらも画像部を形成するときに不快臭を感じにくい感熱記録材料を提供することを目的とする。 One aspect of the present invention is to provide a heat-sensitive recording material that uses kraft lignin as a color developer and is less likely to cause an unpleasant odor when forming an image area.
本発明者らは上記課題を解決すべく鋭意研究を重ねた結果、画像部を形成するときに感じられる不快臭の原因が、クラフトリグニンに含まれる様々な成分のうち、ジメチルジスルフィドであることを特定した。そして、本発明者らは、クラフトリグニンと、水とを加熱し、ジメチルジスルフィドを水と共沸留去させることでクラフトリグニンを精製し、クラフトリグニンにおけるジメチルジスルフィドの含有量を特定の濃度以下とすることで、得られる感熱記録材料は、画像部を形成するときの不快臭が感じにくいものとなりうることを見出し、この知見に基づいて本発明を完成するに至った。 As a result of extensive research to solve the above problems, the present inventors have discovered that the cause of the unpleasant odor felt when forming the image area is dimethyl disulfide, among the various components contained in kraft lignin. Identified. The present inventors purified kraft lignin by heating kraft lignin and water and azeotropically distilling dimethyl disulfide with the water, thereby reducing the content of dimethyl disulfide in kraft lignin to a specific concentration or less. It has been found that by doing so, the resulting heat-sensitive recording material can be made to have less unpleasant odor when forming an image area, and based on this knowledge, the present invention has been completed.
すなわち、本発明の一側面は、支持体と、支持体上に設けられた感熱発色層と、を備え、感熱発色層が、（Ａ）発色物質と、（Ｂ）ジメチルジスルフィドの含有量が２．５ｐｐｍ以下であるクラフトリグニンと、（Ｃ）下記（Ｃ－１）群の化合物、下記（Ｃ－２）群の化合物、及び下記（Ｃ－３）群の化合物のうちの少なくとも一種の顕色剤と、を含む、感熱記録材料を提供することを目的とする。 That is, one aspect of the present invention includes a support and a thermosensitive coloring layer provided on the support, and the thermosensitive coloring layer has a content of (A) a coloring substance and (B) dimethyl disulfide of 2. .5 ppm or less of kraft lignin, and (C) a color developer of at least one of the following compounds of group (C-1), compounds of group (C-2) below, and compounds of group (C-3) below. An object of the present invention is to provide a heat-sensitive recording material containing a heat-sensitive recording agent.
（Ｃ－１）群：スルホニルウレア基を有する下記一般式（Ｉ）で表される化合物
（Ｃ－２）群：スルホニルアミド基を有する下記一般式（ＩＩ）で表される化合物
（Ｃ－３）群：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、ビス（３－アリル－４－ヒドロキシフェニル）スルホン、４－ヒドロキシ－４’－イソプロポキシジフェニルスルホン、４－ヒドロキシ－４’－アリルオキシジフェニルスルホン、及び４－ベンジルオキシ－４’－ヒドロキシジフェニルスルホン
(C-1) Group: Compounds represented by the following general formula (I) having a sulfonylurea group (C-2) Group: Compounds (C-3) having a sulfonylamido group and represented by the following general formula (II) Group: 4,4'-dihydroxydiphenylsulfone, 2,4'-dihydroxydiphenylsulfone, bis(3-allyl-4-hydroxyphenyl)sulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone, 4-hydroxy-4 '-allyloxydiphenylsulfone, and 4-benzyloxy-4'-hydroxydiphenylsulfone
［式中、Ｒ１及びＲ２は、ハロゲン原子、炭素数１～４のアルキル基、炭素数２～４のアルケニル基、又は、炭素数１～４のアルコキシ基を示し、ｎ１及びｎ２は０～３の整数を示し、Ｒ１及びＲ２が、複数存在する場合には、Ｒ１同士又はＲ２同士は同一であっても異なっていてもよい。］
[In the formula, R 1 and R 2 represent a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and n1 and n2 are 0 Indicates an integer of ˜3, and when a plurality of R 1 and R 2 exist, R 1 or R 2 may be the same or different. ]
［式中、Ｘ１及びＸ２は、それぞれ独立に－Ｏ－又は－ＮＨ－を示し、Ｒ３は水素原子、又は－ＳＯ２－Ｒ４を示し、Ｒ４は置換もしくは無置換のアルキル基、アラルキル基又はアリール基を示し、Ｒ５及びＲ６はそれぞれ独立に水素原子又はアルキル基を示し、ｎ３は０又は１を示し、ｎ４は０～２の整数を示し、Ｒ３が、複数存在する場合には、Ｒ３同士は同一であっても異なっていてもよい。］
[In the formula, X 1 and X 2 each independently represent -O- or -NH-, R 3 represents a hydrogen atom or -SO 2 -R 4 , and R 4 represents a substituted or unsubstituted alkyl group , represents an aralkyl group or an aryl group, R 5 and R 6 each independently represent a hydrogen atom or an alkyl group, n3 represents 0 or 1, n4 represents an integer from 0 to 2, and R 3 is present in plural numbers. In that case, R 3 may be the same or different. ]
上記感熱記録材料は、感熱発色層において、（Ｃ）成分の含有量に対する（Ｂ）成分の含有量の比（（Ｂ）成分／（Ｃ）成分）は、質量比で、２０／８０～９０／１０であってよい。 In the heat-sensitive recording material, in the heat-sensitive coloring layer, the ratio of the content of component (B) to the content of component (C) (component (B)/component (C)) is 20/80 to 90 in terms of mass ratio. /10.
上記感熱記録材料は、顕色剤として、下記構造式（ＩＩＩ）で表される化合物を含んでいてもよい。
上記感熱記録材料は、顕色剤として、下記構造式（IＶ）～（ＶＩ）で表される化合物のうちの1種以上を含んでいてもよい。
本発明の一側面によれば、クラフトリグニンを顕色剤として用いながらも画像部を形成するときに不快臭を感じにくい感熱記録材料を提供することができる。 According to one aspect of the present invention, it is possible to provide a heat-sensitive recording material that uses kraft lignin as a color developer and is less likely to cause an unpleasant odor when forming an image area.
また、上記感熱記録材料は、アルコール及び水への保存性に優れる画像部を形成することができる。 Further, the above-mentioned heat-sensitive recording material can form an image portion having excellent preservability in alcohol and water.
以下、本発明の実施形態について説明する。ただし、本発明は以下の実施形態に限定されるものではない。 Embodiments of the present invention will be described below. However, the present invention is not limited to the following embodiments.
本実施形態に係る感熱記録材料は、支持体と、支持体上に設けられた感熱発色層と、を備える。以下、感熱記録材料について詳述する。 The heat-sensitive recording material according to this embodiment includes a support and a heat-sensitive coloring layer provided on the support. The heat-sensitive recording material will be described in detail below.
［支持体］
支持体としては、特に制限されないが、例えば、中性紙及び酸性紙等の紙、古紙パルプを用いた再生紙、合成紙、フィルム、不織布、並びに織布などを用いることができる。
[Support]
The support is not particularly limited, but for example, paper such as neutral paper and acidic paper, recycled paper using waste paper pulp, synthetic paper, film, nonwoven fabric, woven fabric, etc. can be used.
［感熱発色層］
感熱発色層は、（Ａ）発色物質（以下、「（Ａ）成分」ともいう）と、（Ｂ）ジメチルジスルフィドの含有量が２．５ｐｐｍ以下であるクラフトリグニン（以下、「（Ｂ）成分」ともいう）と、（Ｃ）下記（Ｃ－１）群の化合物、下記（Ｃ－２）群の化合物、及び下記（Ｃ－３）群の化合物のうちの少なくとも一種の顕色剤（以下、「（Ｃ）成分」ともいう）と、を含む。
[Thermosensitive coloring layer]
The thermosensitive coloring layer contains (A) a coloring substance (hereinafter also referred to as "component (A)") and (B) kraft lignin having a dimethyl disulfide content of 2.5 ppm or less (hereinafter referred to as "component (B)"). ), and (C) at least one color developer (hereinafter referred to as (also referred to as "component (C)").
（Ｃ－１）群：スルホニルウレア基を有する下記一般式（Ｉ）で表される化合物
（Ｃ－２）群：スルホニルアミド基を有する下記一般式（ＩＩ）で表される化合物
（Ｃ－３）群：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、ビス（３－アリル－４－ヒドロキシフェニル）スルホン、４－ヒドロキシ－４’－イソプロポキシジフェニルスルホン、４－ヒドロキシ－４’－アリルオキシジフェニルスルホン、及び４－ベンジルオキシ－４’－ヒドロキシジフェニルスルホン
(C-1) Group: Compounds represented by the following general formula (I) having a sulfonylurea group (C-2) Group: Compounds (C-3) having a sulfonylamido group and represented by the following general formula (II) Group: 4,4'-dihydroxydiphenylsulfone, 2,4'-dihydroxydiphenylsulfone, bis(3-allyl-4-hydroxyphenyl)sulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone, 4-hydroxy-4 '-allyloxydiphenylsulfone, and 4-benzyloxy-4'-hydroxydiphenylsulfone
［式中、Ｒ１及びＲ２は、ハロゲン原子、炭素数１～４のアルキル基、炭素数２～４のアルケニル基、又は、炭素数１～４のアルコキシ基を示し、ｎ１及びｎ２は０～３の整数を示し、Ｒ１及びＲ２が、複数存在する場合には、Ｒ１同士又はＲ２同士は同一であっても異なっていてもよい。］
[In the formula, R 1 and R 2 represent a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and n1 and n2 are 0 Indicates an integer of ˜3, and when a plurality of R 1 and R 2 exist, R 1 or R 2 may be the same or different. ]
［式中、Ｘ１及びＸ２は、それぞれ独立に－Ｏ－又は－ＮＨ－を示し、Ｒ３は水素原子、又は－ＳＯ２－Ｒ４を示し、Ｒ４は置換もしくは無置換のアルキル基、アラルキル基又はアリール基を示し、Ｒ５及びＲ６はそれぞれ独立に水素原子又はアルキル基を示し、ｎ３は０又は１を示し、ｎ４は０～２の整数を示し、Ｒ３が、複数存在する場合には、Ｒ３同士は同一であっても異なっていてもよい。］
[In the formula, X 1 and X 2 each independently represent -O- or -NH-, R 3 represents a hydrogen atom or -SO 2 -R 4 , and R 4 represents a substituted or unsubstituted alkyl group , represents an aralkyl group or an aryl group, R 5 and R 6 each independently represent a hydrogen atom or an alkyl group, n3 represents 0 or 1, n4 represents an integer from 0 to 2, and R 3 is present in plural numbers. In that case, R 3 may be the same or different. ]
＜（Ａ）成分＞
（Ａ）成分（発色物質）としては、無色又は淡色のロイコ染料を用いることができる。ロイコ染料としては、例えば、フルオラン誘導体、キナゾリン誘導体、フタリド誘導体、トリフェニルメタン誘導体及びフェノチアジン誘導体を挙げることができる。これらのロイコ染料は、１種を単独で又は２種以上を組み合わせて用いることができる。
<(A) component>
As component (A) (coloring substance), a colorless or light-colored leuco dye can be used. Examples of leuco dyes include fluoran derivatives, quinazoline derivatives, phthalide derivatives, triphenylmethane derivatives, and phenothiazine derivatives. These leuco dyes can be used alone or in combination of two or more.
これらのロイコ染料の中でも、フルオラン構造を有するロイコ染料は、発色性が良好であることから特に好適に用いることができる。フルオラン構造を有するロイコ染料としては、例えば、３－イソアミルエチルアミノ－６－メチル－７－アニリノフルオラン、３－（Ｎ－（４－メチルフェニル）－Ｎ－エチル）アミノ－６－メチル－７－アニリノフルオラン、３－ジアミルアミノ－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－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及び３－シクロヘキシルメチルアミノ－６－メチル－７－アニリノフルオランを挙げることができる。 Among these leuco dyes, leuco dyes having a fluoran structure are particularly suitable for use because they have good coloring properties. Examples of leuco dyes having a fluoran structure include 3-isoamylethylamino-6-methyl-7-anilinofluoran, 3-(N-(4-methylphenyl)-N-ethyl)amino-6-methyl- 7-anilinofluorane, 3-diamylamino-6-methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-anilino Mention may be made of fluorane and 3-cyclohexylmethylamino-6-methyl-7-anilinofluorane.
感熱発色層における発色物質の含有量は、目的とする感熱記録材料の特性に応じて適宜設定することができる。発色物質の含有量は、例えば、感熱発色層の全量を基準として、１～３０質量％であってもよく、５～２０質量％であってもよく、８～１８質量％であってもよい。 The content of the color-forming substance in the heat-sensitive color-forming layer can be appropriately set depending on the characteristics of the intended heat-sensitive recording material. The content of the coloring substance may be, for example, 1 to 30% by mass, 5 to 20% by mass, or 8 to 18% by mass, based on the total amount of the thermosensitive coloring layer. .
＜（Ｂ）成分＞
クラフトリグニンは、クラフト法によりリグニンを処理することで得られる単離リグニンである。クラフト法は、水酸化ナトリウム（ＮａＯＨ）及び硫化ナトリウム（Ｎａ２Ｓ）等によりリグニンを化学変性させて分離する方法である。
<(B) component>
Kraft lignin is isolated lignin obtained by processing lignin by the Kraft method. The Kraft method is a method in which lignin is chemically modified and separated using sodium hydroxide (NaOH), sodium sulfide (Na 2 S), and the like.
ジメチルジスルフィドの含有量の測定方法は、ヘッドスペースガスクロマトグラフ質量分析装置を用いて測定される。 The content of dimethyl disulfide is measured using a headspace gas chromatograph mass spectrometer.
ジメチルジスルフィドの含有量は、本実施形態に係る感熱記録材料の不快な印字時臭気を抑制する観点から、２．５ｐｐｍ以下であり、より不快な印字時臭気を一層抑制できることから、好ましく、２．０ｐｐｍ以下であり、より好ましくは１．５ｐｐｍ以下である。一方、ジメチルジスルフィドの含有量が２．５ｐｐｍを超える場合では、得られる感熱記録材料は、印字時に熱が加わると不快臭が感じられる。 The content of dimethyl disulfide is preferably 2.5 ppm or less from the viewpoint of suppressing the unpleasant odor during printing of the heat-sensitive recording material according to the present embodiment, since it can further suppress the unpleasant odor during printing. It is 0 ppm or less, more preferably 1.5 ppm or less. On the other hand, when the content of dimethyl disulfide exceeds 2.5 ppm, the resulting heat-sensitive recording material gives off an unpleasant odor when heat is applied during printing.
クラフトリグニンにおけるジメチルジスルフィドの含有量を上記範囲とすることで、画像部以外の部分における耐湿熱性及び耐光性の低下を抑制することができる。 By setting the content of dimethyl disulfide in the kraft lignin within the above range, it is possible to suppress deterioration of heat and humidity resistance and light resistance in areas other than the image area.
（Ｂ）成分として用いられるクラフトリグニンの製造方法は、ジメチルジスルフィドの含有量が２．５ｐｐｍ以下となる方法であれば、特に限定されない。このような方法としては、例えば、市販のクラフトリグニンと水とを加熱し、ジメチルジスルフィドを水と共沸留去させることで精製し、クラフトリグニンにおけるジメチルジスルフィドの含有量を２．５ｐｐｍ以下とすることができる。 The method for producing the kraft lignin used as component (B) is not particularly limited as long as the content of dimethyl disulfide is 2.5 ppm or less. Such a method includes, for example, heating commercially available kraft lignin and water and purifying the dimethyl disulfide by azeotropic distillation with the water to reduce the dimethyl disulfide content in the kraft lignin to 2.5 ppm or less. be able to.
＜（Ｃ）成分＞
（（Ｃ－１）群の化合物）
上記式（Ｉ）中、Ｒ１及びＲ２は、得られる感熱記録材料の発色性及び画像部の保存性が一層向上する傾向にあることから、炭素数１～４のアルキル基が好ましく、炭素数１又は２のアルキル基がより好ましく、メチル基がさらに好ましい。
<(C) component>
((C-1) group compound)
In the above formula (I), R 1 and R 2 are preferably alkyl groups having 1 to 4 carbon atoms, since this tends to further improve the coloring properties of the heat-sensitive recording material obtained and the storage stability of the image area. An alkyl group of number 1 or 2 is more preferable, and a methyl group is even more preferable.
上記式（Ｉ）中、ｎ１及びｎ２は、０～２が好ましく。０又は１がより好ましく、１がさらに好ましい。上記範囲であれば、発色性及び画像部の保存性に一層優れる感熱記録材料を得ることができる。 In the above formula (I), n1 and n2 are preferably 0 to 2. 0 or 1 is more preferable, and 1 is even more preferable. Within the above range, it is possible to obtain a heat-sensitive recording material that has better color development and image area storage stability.
（Ｃ－１）群の化合物は、発色性及び画像部の保存性の観点から、下記構造式（ＩＩＩ）で表される化合物（上記式（Ｉ）中、Ｒ１及びＲ２がメチル基でありｎ１及びｎ２が１である化合物）であることが特に好ましい。 The compounds of group (C-1) are compounds represented by the following structural formula (III) (in the above formula (I), R 1 and R 2 are methyl groups) from the viewpoint of color development and image storage stability. A compound in which n1 and n2 are 1 is particularly preferred.
（Ｃ－１）群の化合物の製造方法は特に制限されない。そのような製造方法としては、例えば、特表２００２－５３２４４１号公報に記載の方法が挙げられる。（Ｃ－１）群の化合物は、市販品を用いてもよい。 The method for producing the compound of group (C-1) is not particularly limited. Examples of such a manufacturing method include the method described in Japanese Patent Publication No. 2002-532441. As the compound of group (C-1), commercially available products may be used.
そのような市販品としては、ＢＡＳＦ社製のＰＦ－２０１（商品名、構造式：上記構造式（ＩＩＩ）、化合物名：Ｎ－［ｐ－トルエンスルホニル］－Ｎ’－［３－ｐ－トルエンスルホニルオキシフェニル］尿素）等が挙げられる。 Such commercial products include PF-201 manufactured by BASF (trade name, structural formula: the above structural formula (III), compound name: N-[p-toluenesulfonyl]-N'-[3-p-toluene sulfonyloxyphenyl]urea) and the like.
（Ｃ－１）群の化合物は、１種を単独で又は２種以上を組み合わせて用いてもよい。 The compounds of group (C-1) may be used alone or in combination of two or more.
（（Ｃ－２）群の化合物）
上記式（ＩＩ）中、Ｒ３及びＲ４は、得られる感熱記録材料の発色性及び画像部の保存性が一層向上することから、炭素数１～４のアルキル基が好ましく、炭素数１又は２のアルキル基がより好ましく、メチル基がさらに好ましい。
((C-2) group compound)
In the above formula (II), R 3 and R 4 are preferably alkyl groups having 1 to 4 carbon atoms, and R 3 and R 4 are preferably alkyl groups having 1 to 4 carbon atoms, and R 3 and R 4 are preferably alkyl groups having 1 to 4 carbon atoms, and The alkyl group of 2 is more preferred, and the methyl group is even more preferred.
上記式（ＩＩ）中、ｎ３及びｎ４は、０～２が好ましく、０又は１がより好ましく、０がさらに好ましい。上記範囲であれば、発色性及び画像部の保存性に一層優れる感熱記録材料を得ることができる。 In the above formula (II), n3 and n4 are preferably 0 to 2, more preferably 0 or 1, and even more preferably 0. Within the above range, it is possible to obtain a heat-sensitive recording material that has better color development and image area storage stability.
（Ｃ－２）群の化合物は、発色性及び画像部の保存性の観点から、下記構造式（ＩＶ）～（ＶＩ）で表される化合物であることが好ましい。 The compounds of group (C-2) are preferably compounds represented by the following structural formulas (IV) to (VI) from the viewpoint of color development and storage stability of the image area.
（Ｃ－２）群の化合物の製造方法は特に制限されない。そのような製造方法としては、例えば、国際公開第２０１４／０８０６１５号に記載の方法等が挙げられる。（Ｃ－２）群の化合物は、市販品を用いてもよい。 The method for producing the compound of group (C-2) is not particularly limited. Examples of such a manufacturing method include the method described in International Publication No. 2014/080615. As the compound of group (C-2), commercially available products may be used.
（Ｃ－２）群の化合物の市販品としては、日本曹達株式会社製のＮＫＫ－１３０４（商品名、構造式：上記構造式（ＩＶ）、化合物名：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）、日本化薬株式会社製のＴＧ－ＭＤ（商品名、構造式：上記構造式（Ｖ）、推定される化合物名：Ｎ－［４－［［（４－メチルフェニル）スルホニル］オキシ］フェニル］―Ｎ’－フェニルウレア）が挙げられる。 As a commercially available compound of group (C-2), NKK-1304 manufactured by Nippon Soda Co., Ltd. (trade name, structural formula: the above structural formula (IV), compound name: N-(2-(3-phenylureido) ) phenyl)benzenesulfonamide), TG-MD manufactured by Nippon Kayaku Co., Ltd. (trade name, structural formula: the above structural formula (V), presumed compound name: N-[4-[[(4-methylphenyl) ) sulfonyl]oxy]phenyl]-N'-phenylurea).
（Ｃ－２）群の化合物は、１種を単独で又は２種以上を組み合わせて用いてもよい。 The compounds of group (C-2) may be used alone or in combination of two or more.
（（Ｃ－３）群の化合物）
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、ビス（３－アリル－４－ヒドロキシフェニル）スルホン、４－ヒドロキシ－４’－イソプロポキシジフェニルスルホン、４－ヒドロキシ－４’－アリルオキシジフェニルスルホン及び、４－ベンジルオキシ－４’－ヒドロキシジフェニルスルホンは、それぞれ、下記構造式（ＶＩＩ）～（ＸＩＩ）で表される。
((C-3) group compound)
4,4'-dihydroxydiphenylsulfone, 2,4'-dihydroxydiphenylsulfone, bis(3-allyl-4-hydroxyphenyl)sulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone, 4-hydroxy-4'- Allyloxydiphenylsulfone and 4-benzyloxy-4'-hydroxydiphenylsulfone are represented by the following structural formulas (VII) to (XII), respectively.
（Ｃ－３）群の化合物としては、市販品を用いてもよい。このような市販品としては、例えば、ＢＰ－Ｓ／ＦＦ－１（商品名、構造式：上記構造式（ＶＩＩ）、化合物名：４，４’―ジヒドロキシジフェニルスルホン）、ＢＰＳ－２４Ｃ（商品名、構造式：上記構造式（ＶＩＩＩ）、化合物名：２，４’－ジヒドロキシジフェニルスルホン）、ＢＰＳ－３３ＡＣ（商品名、構造式：構造式（ＩＸ）、化合物名：ビス（３－アリル－４－ヒドロキシフェニル）スルホン）、ＢＰＳ－ＭＡＥ（商品名、構造式：上記構造式（ＸＩ）、化合物名：４－ヒドロキシ－４’－アリルオキシジフェニルスルホン）、ＢＰ－Ｓ／ＭＡ－３（商品名、構造式：上記構造式（ＸＩＩ）、化合物名：４－ベンジルオキシ－４’－ヒドロキシジフェニルスルホン）（以上、いずれも日華化学株式会社製）、及びＤ－８（商品名、構造式：上記構造式（Ｘ）、化合物名：４－ヒドロキシ－４’－イソプロポキシジフェニルスルホン、日本曹達株式会社製）が挙げられる。 As the compound of group (C-3), commercially available products may be used. Such commercial products include, for example, BP-S/FF-1 (trade name, structural formula: the above structural formula (VII), compound name: 4,4'-dihydroxydiphenylsulfone), BPS-24C (trade name). , Structural formula: Structural formula (VIII) above, Compound name: 2,4'-dihydroxydiphenylsulfone), BPS-33AC (Product name, Structural formula: Structural formula (IX), Compound name: Bis(3-allyl-4) -hydroxyphenyl) sulfone), BPS-MAE (trade name, structural formula: above structural formula (XI), compound name: 4-hydroxy-4'-allyloxydiphenyl sulfone), BP-S/MA-3 (trade name , Structural formula: Structural formula (XII) above, Compound name: 4-benzyloxy-4'-hydroxydiphenylsulfone) (both manufactured by NICCA CHEMICAL CO., LTD.), and D-8 (trade name, Structural formula: Examples include the above structural formula (X), compound name: 4-hydroxy-4'-isopropoxydiphenylsulfone, manufactured by Nippon Soda Co., Ltd.).
（Ｃ－３）群の化合物は、１種を単独で又は２種以上を組み合わせて用いてもよい。 The compounds of group (C-3) may be used alone or in combination of two or more.
（感熱発色層における顕色剤配合量）
感熱発色層における（Ｂ）成分及び（Ｃ）成分の含有量の合計は、十分な発色性を有する感熱記録材料を得る観点から、発色物質１００質量部に対して１０～５００質量部であることが好ましく、５０～４００質量部であることがより好ましく、１００～３００質量部であることがさらに好ましく、１４０～２１０質量部であることが特に好ましい。
(Amount of color developer compounded in the heat-sensitive coloring layer)
The total content of component (B) and component (C) in the thermosensitive coloring layer should be 10 to 500 parts by mass based on 100 parts by mass of the coloring substance, from the viewpoint of obtaining a thermosensitive recording material with sufficient coloring properties. The amount is preferably from 50 to 400 parts by weight, even more preferably from 100 to 300 parts by weight, and particularly preferably from 140 to 210 parts by weight.
感熱発色層における（Ｃ）成分の含有量に対する（Ｂ）成分の含有量の比（（Ｂ）成分／（Ｃ）成分）は、質量比で、発色性と画像部の保存性が一層向上することから、２０／８０～９０／１０が好ましく、４０／６０～８５／１５がより好ましく、６０／４０～８０／２０が更に好ましい。上記範囲内であることで、十分な発色性と優れた画像部の保存性を有した感熱記録材料を得ることができる。 The ratio of the content of component (B) to the content of component (C) in the heat-sensitive coloring layer (component (B)/component (C)) is a mass ratio that further improves color development and storage stability of the image area. Therefore, the ratio is preferably 20/80 to 90/10, more preferably 40/60 to 85/15, and even more preferably 60/40 to 80/20. Within the above range, it is possible to obtain a heat-sensitive recording material having sufficient color development and excellent storage stability of the image area.
（その他顕色剤）
感熱発色層は、本実施形態に係る感熱記録材料の効果を損なわない範囲において、（Ｂ）成分及び（Ｃ）成分以外の顕色剤を更に含有することができる。そのような顕色剤として、従来公知のものを用いることができる。
(Other color developers)
The heat-sensitive color forming layer may further contain a color developer other than the component (B) and the component (C) within a range that does not impair the effect of the heat-sensitive recording material according to the present embodiment. As such a color developer, conventionally known ones can be used.
このような顕色剤としては、例えば、特表２０２０－５２０８３３号公報、特開２０２０－１９３１５３号公報、特開２００６－１０４２１９号公報、特開平８－０５９６０３号公報、特開平１０－０２９９６９号公報、特開２００８－３０３２２５号公報、及び特開２００７－３０２６０１号公報に記載の顕色剤を挙げることができる。 Examples of such color developers include those disclosed in Japanese Patent Application Publication No. 2020-520833, Japanese Patent Application Publication No. 2020-193153, Japanese Patent Application Publication No. 2006-104219, Japanese Patent Application Publication No. 8-059603, and Japanese Patent Application Publication No. 10-029969. , JP-A No. 2008-303225, and JP-A No. 2007-302601.
（増感剤）
感熱発色層は、増感剤を更に含有していてもよい。増感剤としては、特に制限はないが、融点が９０～１４０℃の増感剤であることが好ましい。このような増感剤としては、例えば、ステアリン酸アミド等の脂肪酸アミド類、１，２－ビスフェノキシエタン、１，２－ビス（ｍ－トリルオキシ）エタン、２－ベンジルオキシナフタレンなどのエーテル類及びシュウ酸ジ（４－メチルベンジル）等のエステル類、Ｎ－フェニルスルホンアミド等の上記一般式（ＩＩ）で表されるスルホニルアミド基を有する化合物以外のスルホンアミド類、トルエンスルホン酸ナフチルエステル等のスルホン酸エステル類、ｍ－テルフェニル及びｐ－ベンジルビフェニル等の芳香族炭化水素化合物、各種ワックス類、芳香族カルボン酸とアミンとの縮合物、高級直鎖グリコール類、高級ケトン類、ジフェニルスルホン、ｐ－ヒドロキシ安息香酸エステル類並びにフタル酸ジエステル類などを挙げることができる。これらの増感剤は、１種を単独で又は２種以上を組み合わせて用いることができる。
(sensitizer)
The thermosensitive coloring layer may further contain a sensitizer. The sensitizer is not particularly limited, but it is preferably a sensitizer with a melting point of 90 to 140°C. Examples of such sensitizers include fatty acid amides such as stearamide, ethers such as 1,2-bisphenoxyethane, 1,2-bis(m-tolyloxy)ethane, and 2-benzyloxynaphthalene; Esters such as di(4-methylbenzyl) oxalate, sulfonamides other than the compound having a sulfonylamide group represented by the above general formula (II) such as N-phenylsulfonamide, toluenesulfonic acid naphthyl ester, etc. Sulfonic acid esters, aromatic hydrocarbon compounds such as m-terphenyl and p-benzylbiphenyl, various waxes, condensates of aromatic carboxylic acids and amines, higher linear glycols, higher ketones, diphenyl sulfone, Examples include p-hydroxybenzoic acid esters and phthalic acid diesters. These sensitizers can be used alone or in combination of two or more.
（画像安定剤）
感熱発色層は、画像安定剤を更に含有していてもよい。画像安定剤としては、特に制限はないが、例えば、４－ベンジルオキシ－４’－（２－メチルグリシジルオキシ）ジフェニルスルホン、１，１，３－トリス（２－メチル－４－ヒドロキシ－５－シクロヘキシルフェニル）ブタン、１，１，３－トリス（２－メチル－４－ヒドロキシ－５－ｔｅｒｔ－ブチルフェニル）ブタン及び市販品のトミラック２１４（商品名、三菱ケミカル株式会社製）を挙げることができる。これらの画像安定剤は、１種を単独で又は２種以上を組み合わせて用いることができる。
(image stabilizer)
The thermosensitive coloring layer may further contain an image stabilizer. There are no particular limitations on the image stabilizer, but examples include 4-benzyloxy-4'-(2-methylglycidyloxy)diphenylsulfone, 1,1,3-tris(2-methyl-4-hydroxy-5- Examples include cyclohexylphenyl)butane, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, and the commercially available Tomilac 214 (trade name, manufactured by Mitsubishi Chemical Corporation). . These image stabilizers can be used alone or in combination of two or more.
（填料）
感熱発色層は、必要に応じて、填料を更に含有していてもよい。填料としては、例えば、無機充填剤及び有機充填剤を挙げることができる。
(filler)
The thermosensitive coloring layer may further contain a filler, if necessary. Examples of fillers include inorganic fillers and organic fillers.
（添加剤）
感熱発色層は、必要に応じて、更に他の添加剤を含有していてもよい。他の添加剤としては、例えば、滑剤、紫外線吸収剤、耐水化剤、分散剤、消泡剤、酸化防止剤及び蛍光染料を挙げることができる。
(Additive)
The thermosensitive coloring layer may further contain other additives, if necessary. Other additives include, for example, lubricants, ultraviolet absorbers, waterproofing agents, dispersants, antifoaming agents, antioxidants, and fluorescent dyes.
（感熱記録材料の製造方法）
本実施形態に係る感熱記録材料の製造方法は、特に制限されず、例えば、（Ａ）～（Ｃ）成分及び必要に応じて添加するその他の成分を、適当な結合剤と共に、水性媒体などの媒体中に分散させて感熱発色層の塗工液を調製し、この塗工液を支持体上に塗布し、乾燥することにより製造することができる。
(Method for manufacturing heat-sensitive recording material)
The method for producing the heat-sensitive recording material according to the present embodiment is not particularly limited, and for example, components (A) to (C) and other components added as necessary are mixed with an appropriate binder in an aqueous medium or the like. It can be manufactured by dispersing it in a medium to prepare a coating solution for the heat-sensitive coloring layer, applying this coating solution onto a support, and drying it.
（Ａ）～（Ｃ）成分を含有する分散液は、（Ａ）成分を含有する分散液と、（Ｂ）成分及び（Ｃ）成分を含有する分散液とをそれぞれ別々に調製したのち、これらの分散液を混合することにより調製することができる。各分散液中において、（Ａ）～（Ｃ）成分は、微粒子化して分散していることが望ましい。このような分散液の調製には、例えば、サンドミル及びボールミルを用いることができる。 A dispersion containing components (A) to (C) is prepared by separately preparing a dispersion containing component (A) and a dispersion containing components (B) and (C). It can be prepared by mixing dispersions of. In each dispersion, components (A) to (C) are preferably dispersed in fine particles. For example, a sand mill and a ball mill can be used to prepare such a dispersion.
結合剤としては、特に制限はなく、例えば、ヒドロキシエチルセルロース、カルボキシメチルセルロースなどのセルロース誘導体、ポリビニルアルコール、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、ゼラチン、カゼイン、デンプン、ポリアクリル酸、ポリアクリル酸エステル、ポリ酢酸ビニル、ポリアクリルアミド、スチレン－マレイン酸共重合物、スチレン－ブタジエン共重合物、ポリアミド樹脂、石油樹脂及びテルペン樹脂を挙げることができる。これらの結合剤は、１種を単独で又は２種以上を組み合わせて用いることができる。 The binder is not particularly limited, and examples thereof include cellulose derivatives such as hydroxyethyl cellulose and carboxymethyl cellulose, polyvinyl alcohols such as polyvinyl alcohol and modified polyvinyl alcohol, gelatin, casein, starch, polyacrylic acid, polyacrylic ester, and polyvinyl alcohol. Mention may be made of vinyl acetate, polyacrylamide, styrene-maleic acid copolymers, styrene-butadiene copolymers, polyamide resins, petroleum resins and terpene resins. These binders can be used alone or in combination of two or more.
（感熱記録材料の構成）
本実施形態の感熱記録材料においては、必要に応じて、例えば、無機充填剤及び有機充填剤のうち少なくとも一方を含む下塗り層を設けることができる。さらに、必要に応じて、感熱発色層の上に、セルロース誘導体、ポリビニルアルコール類などの水溶性樹脂、スチレン－ブタジエン共重合物などの水溶性エマルジョン樹脂、非水溶性樹脂、又は、それらの樹脂に填料、イソシアネート類、不飽和化合物などのモノマーやオリゴマー、架橋剤を加えた材料から形成されるオーバーコート層を設けることができる。
(Composition of heat-sensitive recording material)
In the heat-sensitive recording material of this embodiment, for example, an undercoat layer containing at least one of an inorganic filler and an organic filler can be provided as necessary. Furthermore, if necessary, a water-soluble resin such as a cellulose derivative, polyvinyl alcohol, a water-soluble emulsion resin such as a styrene-butadiene copolymer, a water-insoluble resin, or any of these resins may be applied on the heat-sensitive coloring layer. An overcoat layer formed from a material to which fillers, isocyanates, monomers and oligomers such as unsaturated compounds, and crosslinking agents are added can be provided.
本実施形態の感熱記録材料は、色調の異なる発色物質が含まれる発色層を多層形成した感熱多色記録材料とすることができる。 The heat-sensitive recording material of this embodiment can be a heat-sensitive multicolor recording material in which multiple color-forming layers containing color-forming substances with different tones are formed.
以下、実施例に基づいて本開示をより具体的に説明するが、本開示は以下の実施例に限定されるものではない。 Hereinafter, the present disclosure will be described in more detail based on Examples, but the present disclosure is not limited to the following Examples.
［クラフトリグニンの精製］
（精製例１）
クラフトリグニンと水とを加熱し、ジメチルジスルフィドを水と共沸留去させる方法により精製した。具体的には、まず、クラフトリグニン（メドウエストバコ社製、インジュリンＡＴ）１６０ｇ及び蒸留水６４０ｇを１Ｌセパラブルフラスコに投入し、処理液を得た。セパラブルフラスコには、留出液の冷却装置及び窒素を混合物中に導入できる窒素導入菅を設置した。セパラブルフラスコは、オイルバス上に設置した。処理液は、オイルバスで加熱することで昇温し、水の留出が始まってから２時間が経過するまで加熱した。オイルバスの温度は、１２０℃とした。加熱中は、窒素を流量２０ｍＬ／分にて処理液中に導入しつつ、処理液を撹拌混合した。２時間の経過後、処理液を５０℃まで空冷した。次いで、空冷した処理液をブフナーロートを用いて吸引濾過し、濾物を得た。得られた濾物を取り出し、乾燥することで精製したクラフトリグニンを得た。乾燥は、パーフェクトオーブンＰＨＨ－２００（商品名、エスペック株式会社製）を用いて行い、温度は６０℃、時間は１８時間とした。
[Purification of kraft lignin]
(Purification example 1)
It was purified by heating kraft lignin and water and azeotropically distilling dimethyl disulfide off with the water. Specifically, first, 160 g of kraft lignin (manufactured by MedWest Baco, Inc., Indulin AT) and 640 g of distilled water were put into a 1 L separable flask to obtain a treatment liquid. The separable flask was equipped with a distillate cooling device and a nitrogen introduction tube capable of introducing nitrogen into the mixture. The separable flask was placed on an oil bath. The temperature of the treatment liquid was increased by heating it in an oil bath, and the temperature was increased until 2 hours had elapsed since the start of distillation of water. The temperature of the oil bath was 120°C. During heating, the treatment liquid was stirred and mixed while nitrogen was introduced into the treatment liquid at a flow rate of 20 mL/min. After 2 hours, the treatment liquid was air cooled to 50°C. Next, the air-cooled treated liquid was suction-filtered using a Buchner funnel to obtain a filtrate. The obtained filtrate was taken out and dried to obtain purified kraft lignin. Drying was performed using Perfect Oven PHH-200 (trade name, manufactured by ESPEC Co., Ltd.) at a temperature of 60° C. for 18 hours.
（精製例２及び３）
混合物の留出が始まってからの混合物の加熱時間、窒素ガス流量及びオイルバスの温度を表１に示す値としたこと以外は、実施例１と同様にして精製したクラフトリグニンを得た。
(Purification Examples 2 and 3)
Purified kraft lignin was obtained in the same manner as in Example 1, except that the heating time of the mixture after the start of distillation of the mixture, the nitrogen gas flow rate, and the temperature of the oil bath were set to the values shown in Table 1.
［未精製クラフトリグニンの準備］
未精製クラフトリグニンとしてクラフトリグニン（メドウエストバコ社製、インジュリンＡＴ）を準備した。
[Preparation of unrefined kraft lignin]
Kraft lignin (Indulin AT, manufactured by MedWest Baco) was prepared as unrefined kraft lignin.
［ジメチルジスルフィドの含有量の測定方法］
（検量線の作成）
電子天秤（ｓａｒｔｏｒｉｕｓ Ａ２００Ｓ、ｓａｒｔｏｒｉｕｓ社製）を用いて、標準物質としてジメチルジスルフィド（純度：９９．０％、富士写真フイルム和光純薬株式会社製）を精秤し、エタノール（純度：９９．５％、富士写真フイルム和光純薬株式会社製）にて順次希釈することで、濃度が、０．２００ｍｇ／ｇ、０．１００ｍｇ／ｇ、０．０２０ｍｇ／ｇ及び０．００４ｍｇ／ｇの標準溶液を作製した。得られた標準溶液を、２２ｍＬバイアル瓶に０．０１ｇ秤量し、ヘッドスペースＧＣ―ＭＳ測定を行った。測定により得られたジメチルジスルフィドに対応する保持時間１１．５～１１．６分のピークの積分値から、検量線を作成した。
[Method for measuring dimethyl disulfide content]
(Creating a calibration curve)
Using an electronic balance (Sartorius A200S, manufactured by Sartorius), dimethyl disulfide (purity: 99.0%, manufactured by Fuji Photo Film Wako Pure Chemical Industries, Ltd.) was accurately weighed as a standard substance, and ethanol (purity: 99.5%) was weighed. , manufactured by Fuji Photo Film Wako Pure Chemical Industries, Ltd.) to prepare standard solutions with concentrations of 0.200 mg/g, 0.100 mg/g, 0.020 mg/g, and 0.004 mg/g. did. 0.01 g of the obtained standard solution was weighed into a 22 mL vial, and headspace GC-MS measurement was performed. A calibration curve was created from the integral value of the peak at a retention time of 11.5 to 11.6 minutes corresponding to dimethyl disulfide obtained by measurement.
（サンプルの測定）
各精製例で得られたクラフトリグニン、又は未精製クラフトリグニン０．４ｇを精秤し、２２ｍＬバイアル瓶に投入した。そして、標準溶液を作製する際に使用したエタノール０．０１ｇをバイアル瓶に加えた上でバイアル瓶を密閉し、標準溶液の測定と同様にヘッドスペースＧＣ－ＭＳ測定を行った。測定により得られたジメチルジスルフィドに対応する保持時間１１．５～１１．６分のピークの積分値と、検量線とを用いて、ジメチルジスルフィドの含有量を算出した。結果を表１に示した。
(Sample measurement)
0.4 g of the kraft lignin or unrefined kraft lignin obtained in each purification example was accurately weighed and poured into a 22 mL vial. Then, 0.01 g of ethanol used in preparing the standard solution was added to the vial, the vial was sealed, and headspace GC-MS measurement was performed in the same manner as the measurement of the standard solution. The content of dimethyl disulfide was calculated using the integrated value of the peak at a retention time of 11.5 to 11.6 minutes corresponding to dimethyl disulfide obtained by the measurement and the calibration curve. The results are shown in Table 1.
［ヘッドスペースＧＣ―ＭＳでの測定条件の詳細］
（測定条件）
装置：Ａｇｉｌｅｎｔ７６９７Ａ－７８９０Ａ／５９７５Ｃ（ヘッドスペース－ＧＣ／ＭＳ）
カラム：製品名ＶＦ－１３０１ｍｓ（６％シアノプロピルフェニル－９４％ジメチルポリシロキサン）
ヘッドスペースバイアル容量：２２ｍＬ
ヘッドスペースオーブン平衡化温度：１００°Ｃ
ループ温度：１２０°Ｃ
トランスファーライン温度：１８０°Ｃ
ヘッドスペース平衡化時間：２０分間
サイクル時間：３２分間
ＧＣ注入口温度：２５０°Ｃ
スプリット比：３０：１
ＧＣ初期温度：４０°Ｃ（３分間保持）
ＧＣ昇温速度：毎分１０°Ｃ
ＧＣ最終温度：２２０°Ｃ（６分間保持）
ＭＳイオン源温度：２３０°Ｃ
ＭＳ四重極温度：１５０°Ｃ
キャリアガス：ヘリウム
キャリアガス流量：１ｍＬ／ｍｉｎ
取り込みＭＳ範囲：３０－３５０
[Details of measurement conditions with headspace GC-MS]
(Measurement condition)
Equipment: Agilent 7697A-7890A/5975C (Headspace-GC/MS)
Column: Product name VF-1301ms (6% cyanopropylphenyl-94% dimethylpolysiloxane)
Headspace vial capacity: 22mL
Headspace oven equilibration temperature: 100°C
Loop temperature: 120°C
Transfer line temperature: 180°C
Headspace equilibration time: 20 minutes Cycle time: 32 minutes GC inlet temperature: 250°C
Split ratio: 30:1
GC initial temperature: 40°C (held for 3 minutes)
GC heating rate: 10°C per minute
GC final temperature: 220°C (held for 6 minutes)
MS ion source temperature: 230°C
MS quadrupole temperature: 150°C
Carrier gas: helium Carrier gas flow rate: 1mL/min
Capture MS range: 30-350
［感熱記録材料の作製］
（１）アンダー層形成用の塗工液
焼成カオリン ２０．０質量部
１０質量％ポリビニルアルコール水溶液 ３０．０質量部
分散剤（アセチレングリコール系非イオン界面活性剤） ０．３質量部
結合剤（ポリ酢酸ビニル乳化液固形分４０質量％） １８．０質量部
蒸留水 ３１．７質量部
計１００．０質量部
[Preparation of heat-sensitive recording material]
(1) Coating liquid for under layer formation Calcined kaolin 20.0 parts by mass 10% by mass polyvinyl alcohol aqueous solution 30.0 parts by mass Dispersant (acetylene glycol nonionic surfactant) 0.3 parts by mass Binder (polyacetic acid Vinyl emulsion solid content 40% by mass) 18.0 parts by mass Distilled water 31.7 parts by mass
Total 100.0 parts by mass
上記組成よりなる混合物を、ホモディスパーを用いて混合攪拌し、アンダー層形成用の塗工液を調製した。 A mixture having the above composition was mixed and stirred using a homodisper to prepare a coating liquid for forming an under layer.
（２）感熱発色層形成用の塗工液
下記に示す組成（質量部）を有するＡ液（第一の顕色剤分散液）、Ｂ液（第二の顕色剤分散液）及びＣ液（発色物質分散液）をそれぞれ調製した。Ａ液～Ｃ液の調製は、サンドミルを用いて平均粒子径が約０．５μｍになるまで湿式分散を行った。
(2) Coating liquid for forming a heat-sensitive coloring layer A liquid (first color developer dispersion), B liquid (second color developer dispersion) and C liquid having the compositions (parts by mass) shown below. (Coloring substance dispersions) were prepared respectively. Solutions A to C were prepared by performing wet dispersion using a sand mill until the average particle size became approximately 0.5 μm.
Ａ液（第一の顕色剤分散液）
表２に記載のクラフトリグニン ２０質量部
１０質量％ポリビニルアルコール水溶液 ２０質量部
蒸留水 ６０質量部
計１００質量部
Solution A (first developer dispersion)
Kraft lignin listed in Table 2 20 parts by mass 10% by mass polyvinyl alcohol aqueous solution 20 parts by mass Distilled water 60 parts by mass
Total 100 parts by mass
Ｂ液（第二の顕色剤分散液）
表３に記載の化合物 ２０質量部
１０質量％ポリビニルアルコール水溶液 ２０質量部
蒸留水 ６０質量部
計１００質量部
Liquid B (second developer dispersion)
Compound listed in Table 3 20 parts by mass 10% by mass aqueous polyvinyl alcohol solution 20 parts by mass Distilled water 60 parts by mass
Total 100 parts by mass
Ｃ液（発色物質分散液）
３－ジブチルアミノ－６－メチル－７－アニリノフルオラン ２０質量部
１０質量％ポリビニルアルコール水溶液 ２０質量部
蒸留水 ６０質量部
計１００質量部
Liquid C (coloring substance dispersion)
3-dibutylamino-6-methyl-7-anilinofluorane 20 parts by mass 10% by mass polyvinyl alcohol aqueous solution 20 parts by mass Distilled water 60 parts by mass
Total 100 parts by mass
なお、Ｂ－４液に配合した構造式（ＶＩ）で表される化合物は、国際公開第２０１９／０４４４６２号に記載された方法で合成した。 In addition, the compound represented by structural formula (VI) blended into B-4 liquid was synthesized by the method described in International Publication No. 2019/044462.
（実施例１）
下記の組成（質量部）よりなる混合物をホモディスパーにて攪拌混合し、感熱発色層形成用の塗工液とした。
(Example 1)
A mixture having the following composition (parts by mass) was stirred and mixed in a homodisper to obtain a coating liquid for forming a heat-sensitive coloring layer.
Ａ液（Ａ－１液） ２２．５質量部
Ｂ液（Ｂ－１液） ７．５質量部
Ｃ液（発色物質分散液） １５．０質量部
焼成カオリン ９．０質量部
２質量％ポリビニルアルコール水溶液 残部
計１００．０質量部
Liquid A (Liquid A-1) 22.5 parts by weight Liquid B (Liquid B-1) 7.5 parts by weight Liquid C (coloring substance dispersion) 15.0 parts by weight Calcined kaolin 9.0 parts by weight 2% by weight Polyvinyl Alcohol aqueous solution remainder
Total 100.0 parts by mass
坪量６５ｇ／ｍ２の上質紙に、アンダー層形成用の塗工液をＷｅｔ塗布量が約２３ｇ／ｍ２になるようにバーコーターにて塗布し、風乾し、カレンダー処理を行い、アンダー層が設けられた支持体を作製した。その後、支持体のアンダー層が設けられた面に対して、感熱発色層形成用の塗工液をＷｅｔ塗布量が約２２ｇ／ｍ２になるように塗布し、風乾し、カレンダー処理を行って感熱発色層を形成し、感熱記録材料を作製した。 A coating solution for forming the under layer is applied to a high-quality paper with a basis weight of 65 g/m 2 using a bar coater so that the wet coating amount is approximately 23 g/m 2 , air-dried, and calendered to form the under layer. A support provided with the following was prepared. Thereafter, a coating solution for forming a heat-sensitive coloring layer was applied to the surface of the support on which the under layer was provided at a wet coating amount of approximately 22 g/m 2 , air-dried, and calendered. A thermosensitive coloring layer was formed to produce a thermosensitive recording material.
（実施例２～６、９～２２及び比較例１～４、７～２２）
感熱発色層形成用の塗布液に配合するＡ液及びＢ液の種類と配合量（質量部）とを表４～１０に示すとおり変更したこと以外は、実施例１と同様にして感熱記録材料をそれぞれ作製した。
(Examples 2-6 , 9-22 and Comparative Examples 1-4, 7-22 )
A heat-sensitive recording material was prepared in the same manner as in Example 1, except that the types and amounts (parts by mass) of liquids A and B mixed in the coating liquid for forming a heat-sensitive coloring layer were changed as shown in Tables 4 to 10. were prepared respectively.
［感熱記録材料の評価］
各実施例及び比較例において作製した感熱記録材料の評価は、次の方法により行った。
[Evaluation of heat-sensitive recording materials]
The heat-sensitive recording materials produced in each Example and Comparative Example were evaluated by the following method.
＜画像部の形成時の臭気の判定＞
感熱紙印字評価試験装置（商品名：「ＴＨ－Ｍ２／ＰＳ」、オオクラエンジニアリング株式会社製）を用いて、印字電圧２０Ｖ、パルス巾３ｍｓにて感熱記録材料を発色させ画像部を形成した。装置から取り出した直後の感熱記録材料の画像部について、感熱記録材料を鼻から約１０ｃｍの距離まで近づけ、臭気を以下の臭気の判定基準に従って官能評価を実施した。評価者６名の各判定結果の数値の平均値を総合判定結果とした。結果を表４～１０に示した。
<Determination of odor during image area formation>
Using a thermal paper printing evaluation test device (trade name: "TH-M2/PS", manufactured by Okura Engineering Co., Ltd.), the thermal recording material was colored to form an image area at a printing voltage of 20 V and a pulse width of 3 ms. Immediately after taking out the heat-sensitive recording material from the apparatus, the image area of the heat-sensitive recording material was brought close to the nose to a distance of about 10 cm, and a sensory evaluation of the odor was performed according to the following odor criteria. The average value of the numerical values of each judgment result of six evaluators was taken as the overall judgment result. The results are shown in Tables 4-10.
（臭気の判定基準）
５：無臭又はほとんど臭いを感じない。
４：わずかに臭いを感じるが、不快臭とは感じない。
３：わずかに不快臭を感じる。
２：不快臭を感じる。
１：かなり強い不快臭を感じる。
（総合判定結果の基準）
Ａ：評価者６名の各判定結果の数値の平均値が５．０
Ｂ：評価者６名の各判定結果の数値の平均値が４．０以上５．０未満
Ｃ：評価者６名の各判定結果の数値の平均値が３．０以上４．０未満
Ｄ：評価者６名の各判定結果の数値の平均値が２．０以上３．０未満
Ｅ：評価者６名の各判定結果の数値の平均値が１．０以上２．０未満
(Odor criteria)
5: No odor or almost no odor.
4: A slight odor is felt, but it is not an unpleasant odor.
3: Slightly unpleasant odor felt.
2: I feel an unpleasant odor.
1: I sense a fairly strong unpleasant odor.
(Criteria for overall judgment results)
A: The average value of the numerical value of each judgment result of 6 evaluators is 5.0
B: The average value of the numerical values of each judgment result of 6 evaluators is 4.0 or more and less than 5.0.
C: The average value of the numerical values of each judgment result of 6 evaluators is 3.0 or more and less than 4.0.
D: The average value of the numerical values of each judgment result of 6 evaluators is 2.0 or more and less than 3.0.
E: The average value of the numerical values of each judgment result of 6 evaluators is 1.0 or more and less than 2.0.
＜発色性＞
感熱紙印字評価試験装置（商品名：「ＴＨ－Ｍ２／ＰＳ」、オオクラエンジニアリング株式会社製）を用いて、パルス巾３ｍｓにて、０．０７ｍＪ／ｄｏｔごとに印字エネルギーを高めて発色を行い、画像部を形成した。形成された画像部の色濃度を、マクベス濃度計（商品名：「ＲＤ－９１８」、マクベス社製）にて測定した。数値が小さいほど画像が薄く、数値が大きくなるほど濃い画像であることを示す。０．４２ｍｊ／ｄｏｔにて発色した場合の画像部の色濃度を、下記判定基準により判定を行った。結果を表４～１０に示した。
<Color development>
Using a thermal paper printing evaluation test device (product name: "TH-M2/PS", manufactured by Okura Engineering Co., Ltd.), coloring was performed by increasing the printing energy in steps of 0.07 mJ/dot with a pulse width of 3 ms. An image portion was formed. The color density of the formed image area was measured using a Macbeth densitometer (trade name: "RD-918", manufactured by Macbeth). The smaller the number, the lighter the image, and the larger the number, the darker the image. The color density of the image area when color was developed at 0.42 mj/dot was determined based on the following criteria. The results are shown in Tables 4-10.
（判定基準）
Ａ：１．２０以上
Ｂ：１．００以上１．２０未満
Ｃ：０．８０以上１．００未満
Ｄ：０．６０以上０．８０未満
Ｅ：０．６０未満
(Judgment criteria)
A: 1.20 or more
B: 1.00 or more and less than 1.20
C: 0.80 or more and less than 1.00
D: 0.60 or more and less than 0.80
E: less than 0.60
＜耐アルコール性＞
感熱紙印字評価試験装置（商品名：「ＴＨ－Ｍ２／ＰＳ」、オオクラエンジニアリング株式会社製）を用いて、印字電圧２０Ｖ、パルス巾３ｍｓにて感熱記録材料を発色させ画像部を形成した。形成した画像部の色濃度をマクベス濃度計（商品名「ＲＤ－９１８」、マクベス社製）にて測定した。次いで、室温（２０℃）のエタノール２５容量部と蒸留水７５容量部との混合液に感熱記録材料を浸して３時間放置した。この後、感熱記録材料を混合液から引き上げ、感熱記録材料の表面を濾紙で押さえながら自然乾燥した。乾燥後の感熱記録材料の画像部の色濃度をマクベス濃度計にて測定した。下記式（１）に基づき残存率（％）を算出し、残存率を下記判定基準に沿って判定した。結果を表４～１０に示した。
残存率（％）＝（混合液に浸漬した後の色濃度／混合液に浸漬する前の色濃度）×１００）・・・式（１）
<Alcohol resistance>
Using a thermal paper printing evaluation test device (trade name: "TH-M2/PS", manufactured by Okura Engineering Co., Ltd.), the thermal recording material was colored to form an image area at a printing voltage of 20 V and a pulse width of 3 ms. The color density of the formed image area was measured using a Macbeth densitometer (trade name "RD-918", manufactured by Macbeth Co., Ltd.). Next, the heat-sensitive recording material was immersed in a mixture of 25 parts by volume of ethanol and 75 parts by volume of distilled water at room temperature (20°C) and left for 3 hours. Thereafter, the heat-sensitive recording material was pulled out of the mixed solution and air-dried while pressing the surface of the heat-sensitive recording material with a filter paper. The color density of the image area of the heat-sensitive recording material after drying was measured using a Macbeth densitometer. The residual rate (%) was calculated based on the following formula (1), and the residual rate was judged according to the following criteria. The results are shown in Tables 4-10.
Residual rate (%) = (color density after immersion in the mixed solution/color density before immersed in the mixed solution) x 100)...Equation (1)
（判定基準）
Ａ：９０％以上
Ｂ：７０％以上９０％未満
Ｃ：５０％以上７０％未満
Ｄ：３０％以上５０％未満
Ｅ：３０％未満
(Judgment criteria)
A: 90% or more
B: 70% or more but less than 90%
C: 50% or more but less than 70%
D: 30% or more but less than 50%
E: Less than 30%
＜耐水性＞
感熱紙印字評価試験装置（商品名：「ＴＨ－Ｍ２／ＰＳ」、オオクラエンジニアリング株式会社製）を用いて、印字電圧２０Ｖ、パルス巾３ｍｓにて感熱記録材料を発色させ画像部を形成した。形成した画像部の色濃度をマクベス濃度計（商品名「ＲＤ－９１８」、マクベス社製）にて測定した。次いで、室温（２０℃）の蒸留水に感熱記録材料を浸して２４時間放置した。この後、感熱記録材料を蒸留水から引き上げ、感熱記録材料の表面を濾紙で押さえながら自然乾燥した。乾燥後の感熱記録材料の画像部の色濃度をマクベス濃度計にて測定した。下記式（２）に基づき残存率（％）を算出し、残存率を下記判定基準に沿って判定した。結果を表４～１０に示した。
残存率（％）＝（蒸留水に浸漬した後の色濃度／蒸留水に浸漬する前の色濃度）×１００・・・式（２）
<Water resistance>
Using a thermal paper printing evaluation test device (trade name: "TH-M2/PS", manufactured by Okura Engineering Co., Ltd.), the thermal recording material was colored to form an image area at a printing voltage of 20 V and a pulse width of 3 ms. The color density of the formed image area was measured using a Macbeth densitometer (trade name "RD-918", manufactured by Macbeth Co., Ltd.). Next, the heat-sensitive recording material was immersed in distilled water at room temperature (20° C.) and left for 24 hours. Thereafter, the heat-sensitive recording material was taken out of the distilled water and air-dried while pressing the surface of the heat-sensitive recording material with a filter paper. The color density of the image area of the heat-sensitive recording material after drying was measured using a Macbeth densitometer. The residual rate (%) was calculated based on the following formula (2), and the residual rate was judged according to the following criteria. The results are shown in Tables 4-10.
Residual rate (%) = (color density after immersion in distilled water/color density before immersion in distilled water) x 100...Formula (2)
（判定基準）
Ａ：９０％以上
Ｂ：８５％以上９０％未満
Ｃ：８０％以上８５％未満
Ｄ：７５％以上８０％未満
Ｅ：７５％未満
(Judgment criteria)
A: 90% or more
B: 85% or more but less than 90%
C: 80% or more but less than 85%
D: 75% or more but less than 80%
E: Less than 75%
＜非画像部地色の耐湿熱性＞
作製した感熱記録体を、４０℃、９０％ＲＨ環境条件下で２４時間静置した。感熱記録体の非画像部（白紙部）のＹｅｌｌｏｗ値濃度をマクベス濃度計（商品名「ＲＤ－９１４」、アンバーフィルター使用）で測定した。Ｙｅｌｌｏｗ値濃度を下記判定基準に沿って判定した。結果を表４～１０に示した。
<Moisture and heat resistance of non-image area ground color>
The produced thermosensitive recording material was left standing under environmental conditions of 40° C. and 90% RH for 24 hours. The yellow value density of the non-image area (blank area) of the thermosensitive recording material was measured using a Macbeth densitometer (trade name "RD-914", using an amber filter). Yellow value density was determined according to the following criteria. The results are shown in Tables 4-10.
（判定基準）
Ａ：０．１未満
Ｂ：０．１以上０．４未満
Ｃ：０．４以上０．５未満
Ｄ：０．５以上０．６未満
Ｅ：０．６以上
(Judgment criteria)
A: Less than 0.1
B: 0.1 or more and less than 0.4
C: 0.4 or more and less than 0.5
D: 0.5 or more and less than 0.6
E: 0.6 or more
＜非画像部地色の耐光性＞
作製した感熱記録体について、キセノンフェードメーター（ＡＴＬＡＳ社製、商品名「Ｃｉ３０００Ｆ」）を用いて照射強度６７Ｗ／ｍ２で６時間照射処理をした。照射処理後の感熱記録材料の非画像部（白紙部）のＹｅｌｌｏｗ値濃度をマクベス濃度計（商品名「ＲＤ－９１４」、アンバーフィルター使用）で測定した。Ｙｅｌｌｏｗ値濃度を下記判定基準に沿って判定した。結果を表４～１０に示した。
<Lightfastness of non-image area background color>
The produced heat-sensitive recording material was irradiated for 6 hours at an irradiation intensity of 67 W/m 2 using a xenon fade meter (manufactured by ATLAS, trade name "Ci3000F"). The yellow value density of the non-image area (blank area) of the heat-sensitive recording material after the irradiation treatment was measured using a Macbeth densitometer (trade name "RD-914", using an amber filter). Yellow value density was determined according to the following criteria. The results are shown in Tables 4-10.
（判定基準）
Ａ：０．２未満
Ｂ：０．２以上０．４未満
Ｃ：０．４以上０．５未満
Ｄ：０．５以上０．６未満
Ｅ：０．６以上
(Judgment criteria)
A: Less than 0.2
B: 0.2 or more and less than 0.4
C: 0.4 or more and less than 0.5
D: 0.5 or more and less than 0.6
E: 0.6 or more
Claims (8)
前記感熱発色層が、（Ａ）発色物質と、（Ｂ）ジメチルジスルフィドの含有量が２．５ｐｐｍ以下であるクラフトリグニンと、（Ｃ）下記（Ｃ－１）群の化合物、下記（Ｃ－２）群の化合物、及び下記（Ｃ－３）群の化合物のうちの少なくとも一種の顕色剤と、を含む、感熱記録材料。
（Ｃ－１）群：スルホニルウレア基を有する下記一般式（Ｉ）で表される化合物
（Ｃ－２）群：スルホニルアミド基を有する下記一般式（ＩＩ）で表される化合物（但し、下記構造式（Ｖ）で表される化合物を除く。）
（Ｃ－３）群：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、ビス（３－アリル－４－ヒドロキシフェニル）スルホン、４－ヒドロキシ－４’－イソプロポキシジフェニルスルホン、４－ヒドロキシ－４’－アリルオキシジフェニルスルホン、及び４－ベンジルオキシ－４’－ヒドロキシジフェニルスルホン
The thermosensitive coloring layer comprises (A) a coloring substance, (B) kraft lignin having a dimethyl disulfide content of 2.5 ppm or less, (C) a compound of the group (C-1) below, and (C-2) below. ), and at least one color developer selected from the compounds of group (C-3) below.
(C-1) group: Compounds represented by the following general formula (I) having a sulfonylurea group (C-2) group: Compounds having a sulfonylamido group and represented by the following general formula (II) (However, the following structure (Excluding compounds represented by formula (V).)
Group (C-3): 4,4'-dihydroxydiphenylsulfone, 2,4'-dihydroxydiphenylsulfone, bis(3-allyl-4-hydroxyphenyl)sulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone, 4-hydroxy-4'-allyloxydiphenylsulfone, and 4-benzyloxy-4'-hydroxydiphenylsulfone
前記（Ａ）成分、前記（Ｂ）成分及び前記（Ｃ）成分を含む塗工液を前記支持体上に塗布して乾燥することで前記感熱発色層を形成する工程を備える、製造方法。 A method for producing a heat-sensitive recording material according to claim 1 or 2, comprising:
A manufacturing method comprising the step of forming the thermosensitive coloring layer by applying a coating liquid containing the component (A), the component (B), and the component (C) onto the support and drying the coating solution.
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| EP22832657.5A EP4365220A1 (en) | 2021-06-30 | 2022-05-25 | Thermosensitive recording material |
| CN202280045692.4A CN117580715A (en) | 2021-06-30 | 2022-05-25 | Thermosensitive recording material |
| PCT/JP2022/021349 WO2023276499A1 (en) | 2021-06-30 | 2022-05-25 | Thermosensitive recording material |
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| JP2003067713A (en) | 2001-08-29 | 2003-03-07 | Oji Paper Co Ltd | Ic mounting body |
| WO2014080615A1 (en) | 2012-11-21 | 2014-05-30 | 日本曹達株式会社 | Recording material produced using non-phenol compound |
| JP2017177627A (en) | 2016-03-31 | 2017-10-05 | 王子ホールディングス株式会社 | Thermosensitive recording linerless label and method for manufacturing the same |
| WO2019044462A1 (en) | 2017-08-31 | 2019-03-07 | 三光株式会社 | N,n'-diarylurea derivative, manufacturing method thereof, and thermosensitive recording material using same |
| JP2020104274A (en) | 2018-12-26 | 2020-07-09 | 日本製紙株式会社 | Thermosensitive recording medium |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3835559A (en) * | 1972-03-27 | 1974-09-17 | G Kotter | Machine for ironing trousers |
| JPS51109304A (en) * | 1975-03-22 | 1976-09-28 | Mitsubishi Paper Mills Ltd | PARUPUKOJONODATSUSHUHOHO |
| JP2936550B2 (en) * | 1991-05-09 | 1999-08-23 | 王子製紙株式会社 | Thermal recording medium |
| FI92726C (en) * | 1991-12-02 | 1994-12-27 | Ahlstroem Oy | Method and apparatus for recovering sulfur dioxide from the chemical cycle of a sulphate pulp mill |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000061449A (en) | 1998-08-17 | 2000-02-29 | Mitsubishi Paper Mills Ltd | Method of removing sulfurous malodorous material in which deodorizing efficiency is improved and stabilized |
| JP2003067713A (en) | 2001-08-29 | 2003-03-07 | Oji Paper Co Ltd | Ic mounting body |
| WO2014080615A1 (en) | 2012-11-21 | 2014-05-30 | 日本曹達株式会社 | Recording material produced using non-phenol compound |
| JP2017177627A (en) | 2016-03-31 | 2017-10-05 | 王子ホールディングス株式会社 | Thermosensitive recording linerless label and method for manufacturing the same |
| WO2019044462A1 (en) | 2017-08-31 | 2019-03-07 | 三光株式会社 | N,n'-diarylurea derivative, manufacturing method thereof, and thermosensitive recording material using same |
| JP2020104274A (en) | 2018-12-26 | 2020-07-09 | 日本製紙株式会社 | Thermosensitive recording medium |
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