JPH08310117A - Thermal recording material - Google Patents
Thermal recording materialInfo
- Publication number
- JPH08310117A JPH08310117A JP7121573A JP12157395A JPH08310117A JP H08310117 A JPH08310117 A JP H08310117A JP 7121573 A JP7121573 A JP 7121573A JP 12157395 A JP12157395 A JP 12157395A JP H08310117 A JPH08310117 A JP H08310117A
- Authority
- JP
- Japan
- Prior art keywords
- heat
- electron
- sensitive recording
- alkyl group
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は感熱記録材料に関し、詳
しくは、感熱記録層に電子供与性無色染料と電子受容性
化合物とを含有する感熱記録材料に関する。FIELD OF THE INVENTION The present invention relates to a heat-sensitive recording material, and more particularly to a heat-sensitive recording material containing an electron-donating colorless dye and an electron-accepting compound in a heat-sensitive recording layer.
【０００２】[0002]
【従来の技術】電子供与性無色染料と電子受容性化合物
（顕色剤）とを使用した感熱記録材料は、既によく知ら
れている。たとえば英国特許２，１４０，４４９、米国
特許４，４８０，０５２、同４，４３６，９２０、特公
昭６０−２３９９２、特開昭５７−１７９８３６、同６
０−１２３５５６、同６０−１２３５５７などに詳し
い。特に、感熱記録材料は特公昭４３−４１６０号等に
詳しく、これら感熱記録システムはファクシミリ、プリ
ンター等の多分野に応用され、ニーズが拡大している。
ニーズ拡大の一例に感熱システムを用いて高画質にする
ため階調性の良好な感熱記録材料が求められている。2. Description of the Related Art Thermal recording materials using an electron-donating colorless dye and an electron-accepting compound (developing agent) are already well known. For example, British Patent 2,140,449, US Patents 4,480,052, 4,436,920, JP-B-60-23992, JP-A-57-179836, and JP-A-57-179836.
Details are 0-123556 and 60-123557. Particularly, the heat-sensitive recording material is detailed in JP-B-43-4160 and the like, and these heat-sensitive recording systems are applied to various fields such as facsimiles and printers, and the needs are expanding.
As an example of expanding needs, a heat-sensitive recording material having good gradation is required to obtain high image quality by using a heat-sensitive system.
【０００３】しかしながら、これを実現するためにはプ
リンター等の印加エネルギーが高エネルギーにシフトし
ているのが現状である。However, in order to realize this, the energy applied to a printer or the like is currently shifting to high energy.
【０００４】従来、感熱記録層の透明性及び層の安定化
を図るため、染料や顕色剤は乳化分散物の形で層中に含
まれ、これらが、例えば、９０ｍｊ／ｍｍ2 以上の高エ
ネルギーの印加を受けると、感熱記録層がただれて画像
の鮮鋭度が低下したり、膜が剥がれたりする原因ともな
っていた。しかしながら、これらの有効な防止手段は未
だ見出されていなかった。Conventionally, in order to improve the transparency of the heat-sensitive recording layer and to stabilize the layer, a dye or a developer is contained in the layer in the form of an emulsified dispersion, and these are contained at a high level of, for example, 90 mj / mm 2 or more. When energy is applied, the heat-sensitive recording layer may be soaked that the sharpness of the image may be deteriorated or the film may be peeled off. However, these effective preventive measures have not been found yet.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、前記
の如く、高エネルギーを印加した場合にも感熱記録層が
影響を受けることなく、良好な画像形成を行なうことが
できる透明な感熱記録材料を提供することにある。SUMMARY OF THE INVENTION As described above, the object of the present invention is to provide a transparent heat-sensitive recording which enables good image formation without being affected by the heat-sensitive recording layer even when high energy is applied. To provide the material.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、鋭意検討
の結果、感熱記録層に特定の構造を有するフェノール系
化合物を添加することによって、高エネルギーの印加に
よる感熱記録層への影響を防止しうるのみならず、感熱
記録層に使用する乳化分散物の安定化にも寄与すること
を見出し、本発明を完成した。As a result of earnest studies, the present inventors have found that the addition of a phenolic compound having a specific structure to the heat-sensitive recording layer reduces the influence of high energy application on the heat-sensitive recording layer. The present invention has been completed based on the finding that not only it can be prevented but also contributes to the stabilization of the emulsion dispersion used in the heat-sensitive recording layer.
【０００７】即ち、本発明の感熱記録材料は、支持体上
に感熱記録層を設けた感熱記録材料において、感熱記録
層が電子供与性無色染料、電子受容性化合物及び下記一
般式（１）で表される化合物の一種又は二種以上を含有
することを特徴とする。That is, the heat-sensitive recording material of the present invention is a heat-sensitive recording material in which a heat-sensitive recording layer is provided on a support, and the heat-sensitive recording layer comprises an electron-donating colorless dye, an electron-accepting compound and the following general formula (1). It is characterized by containing one or more of the compounds represented.
【０００８】[0008]
【化７】 [Chemical 7]
【０００９】式中、Ｒ1 は、水素原子又は炭素数１〜８
のアルキル基を表し、Ｒ2 は、炭素数３〜８の分岐アル
キル基を表し、Ｒ3 は、−（ＣＨ2 ）l −又は−（ＣＨ
2 ） m −Ｏ−（ＣＨ2 ）n −を表し、ｌ、ｍ、ｎはそれ
ぞれ１〜５の整数を表す。Where R1Is a hydrogen atom or 1 to 8 carbon atoms
Represents an alkyl group of R,2Is a branched alkane having 3 to 8 carbon atoms.
Represents a kill group, R3Is-(CH2)l-Or- (CH
2) m-O- (CH2)nRepresents −, and l, m, and n are
Each represents an integer of 1 to 5.
【００１０】さらに本発明の請求項２記載の感熱記録材
料は、前記電子受容性化合物に下記一般式（２）で表さ
れる化合物を含有し、さらに、前記感熱記録層に下記一
般式（３）、下記一般式（４）及び下記一般式（５）で
表される化合物からなる群から選ばれる一種又は二種以
上を含有することを特徴とする。Further, in the heat-sensitive recording material according to claim 2 of the present invention, the electron-accepting compound contains a compound represented by the following general formula (2), and the heat-sensitive recording layer further has the following general formula (3). ), One or more selected from the group consisting of compounds represented by the following general formula (4) and the following general formula (5).
【００１１】[0011]
【化８】 Embedded image
【００１２】式中、ＭｅはＺｎ、Ｃａ又はＡｌを表し、
ｎは２又は３の整数を表す。In the formula, Me represents Zn, Ca or Al,
n represents an integer of 2 or 3.
【００１３】[0013]
【化９】 [Chemical 9]
【００１４】式中、Ｒ4 及びＲ7 はそれぞれ独立に炭素
数３〜８の分岐アルキル基を表し、Ｒ5 及びＲ6 はそれ
ぞれ独立に炭素数１〜８のアルキル基を表し、ｎは０又
は１若しくは２の整数を表す。In the formula, R 4 and R 7 each independently represent a branched alkyl group having 3 to 8 carbon atoms, R 5 and R 6 each independently represent an alkyl group having 1 to 8 carbon atoms, and n is 0. Or represents an integer of 1 or 2.
【００１５】[0015]
【化１０】 [Chemical 10]
【００１６】式中、Ｒ8 及びＲ11はそれぞれ独立に炭素
数３〜８の分岐アルキル基を表し、Ｒ9 及びＲ10はそれ
ぞれ独立に炭素数１〜８のアルキル基を表し、ＸはＳ、
Ｏ、ＳＯ2 、Ｓ2 又は下記一般式（４Ｂ）を表す。In the formula, R 8 and R 11 each independently represent a branched alkyl group having 3 to 8 carbon atoms, R 9 and R 10 each independently represent an alkyl group having 1 to 8 carbon atoms, and X represents S. ,
Represents O, SO 2 , S 2 or the following general formula (4B).
【００１７】[0017]
【化１１】 [Chemical 11]
【００１８】式中、Ｒ12及びＲ13はそれぞれ独立に、水
素原子又は炭素数１〜８のアルキル基を表し、ｎは０又
は１〜３の整数を表す。In the formula, R 12 and R 13 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and n represents 0 or an integer of 1 to 3.
【００１９】[0019]
【化１２】 [Chemical 12]
【００２０】式中、Ｒ14及びＲ15はそれぞれ独立に炭素
数３〜８の分岐アルキル基を表し、Ｒ16は炭素数１〜２
０のアルキル基を表す。In the formula, R 14 and R 15 each independently represent a branched alkyl group having 3 to 8 carbon atoms, and R 16 is 1 to 2 carbon atoms.
Represents an alkyl group of 0.
【００２１】請求項３に係る本発明の感熱記録材料は、
前記電子供与性無色染料がマイクロカプセルに内包さ
れ、前記感熱記録層に含まれる一般式（１）乃至一般式
（５）で表される化合物が乳化分散物として存在し、前
記感熱記録層が実質的に透明であることを特徴とする。The heat-sensitive recording material of the present invention according to claim 3 is
The electron-donating colorless dye is encapsulated in microcapsules, the compounds represented by the general formulas (1) to (5) contained in the heat-sensitive recording layer are present as an emulsion dispersion, and the heat-sensitive recording layer is substantially It is transparent in nature.
【００２２】請求項４に係る本発明の感熱記録材料は、
前記電子受容性化合物に含まれる一般式（２）で表され
る化合物において、式中のＭｅがＺｎであることをを特
徴とする。The heat-sensitive recording material of the present invention according to claim 4 is
In the compound represented by the general formula (2) contained in the electron-accepting compound, Me in the formula is Zn.
【００２３】以下に、本発明を詳細に説明する。本発明
に係る一般式（１）で表される化合物は、フェノール誘
導体の２量体であり、式中、Ｒ1 は、水素原子又は炭素
数１〜８のアルキル基を表し、Ｒ2 は、炭素数３〜８の
分岐アルキル基を表し、Ｒ3 は、−（ＣＨ2 ）l −又は
−（ＣＨ 2 ）m −Ｏ−（ＣＨ2 ）n −を表し、ｌ、ｍ、
ｎはそれぞれ１〜５の整数を表す。The present invention will be described in detail below. The present invention
The compound represented by the general formula (1) according to
R is a dimer of a conductor, where R1Is a hydrogen atom or carbon
Represents an alkyl group of the number 1 to 8, R2Has 3 to 8 carbon atoms
Represents a branched alkyl group, R3Is-(CH2)l-Or
-(CH 2)m-O- (CH2)nRepresents-, m,
n represents an integer of 1 to 5, respectively.
【００２４】Ｒ1 の炭素数１〜８のアルキル基は、直鎖
状であっても、分岐していてもよく、具体的にはメチル
基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−
ブチル基、イソブチル基、sec −ブチル基、tert−ブチ
ル基、ｎ−ペンチル基、イソペンチル基、ｎ−ヘキシル
基、ｎ−オクチル基、２−エチルヘキシル基、シクロヘ
キシル基等が挙げられる。好ましくは、メチル基、エチ
ル基、tert−ブチル基等である。The alkyl group having 1 to 8 carbon atoms represented by R 1 may be linear or branched, and specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group and n. −
Examples thereof include a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, an n-hexyl group, an n-octyl group, a 2-ethylhexyl group and a cyclohexyl group. Preferred are a methyl group, an ethyl group, a tert-butyl group and the like.
【００２５】Ｒ2 の炭素数３〜８の分岐アルキル基は、
イソプロピル基、イソブチル基、sec −ブチル基、tert
−ブチル基、２−エチルヘキシル基等が挙げられ、好ま
しくは、sec −ブチル基、tert−ブチル基、２−エチル
ヘキシル基等である。The branched alkyl group having 3 to 8 carbon atoms of R 2 is
Isopropyl group, isobutyl group, sec-butyl group, tert
-Butyl group, 2-ethylhexyl group and the like can be mentioned, with preference given to sec-butyl group, tert-butyl group and 2-ethylhexyl group.
【００２６】また、Ｒ3 としては、−（ＣＨ2 ）3 −、
−（ＣＨ2 ）2 −Ｏ−ＣＨ2 −、−（ＣＨ2 ）3 −Ｏ−
ＣＨ2 −等が好ましい。Further, as R 3 ,-(CH 2 ) 3- ,
- (CH 2) 2 -O- CH 2 -, - (CH 2) 3 -O-
CH 2 - and the like are preferable.
【００２７】以下に、本発明の一般式（１）で表される
化合物のうち好ましいものを下記式（１−Ｉ）、（１−
II）及び（１−III ）として例示するが、これに限定さ
れるものではない。Among the compounds represented by the general formula (1) of the present invention, preferred compounds are represented by the following formulas (1-I) and (1-
II) and (1-III), but the present invention is not limited thereto.
【００２８】[0028]
【化１３】 [Chemical 13]
【００２９】本発明に用いられる電子供与性無色染料に
は、特に制限はなく、公知の化合物を目的に応じて任意
に選択して用いることができる。電子供与性無色染料の
例としては、公知のトリフェニルメタンフタリド系化合
物、フルオラン系化合物、フェノチアジン系化合物、イ
ンドリルフタリド系化合物、ロイコオーラミン系化合
物、ローダミンラクタム系化合物、トリフェニルメタン
系化合物、トリアゼン系化合物、スピロピラン系化合
物、フルオレン系化合物など各種の化合物を挙げること
ができる。フタリド類の具体例は米国再発行特許明細書
第２３，０２４号、米国特許明細書第３，４９１，１１
１号、同第３，４９１，１１２号、同第３，４９１，１
１６号および同第３，５０９，１７４号、フルオラン類
の具体例は米国特許明細書第３，６２４，１０７号、同
第３，６２７，７８７号、同第３，６４１，０１１号、
同第３，４６２，８２８号、同第３，６８１，３９０
号、同第３，９２０，５１０号、同第３，９５９，５７
１号、スピロジピラン類の具体例は米国特許明細書第
３，９７１，８０８号、ピリジン系およびピラジン系化
合物類は米国特許明細書第３，７７５，４２４号、同第
３，８５３，８６９号、同第４，２４６，３１８号、ロ
イコオーラミン系化合物の具体例は特開平４−１２６２
８７号、フルオレン系化合物の具体例は特開昭６３−９
４８７８号等に記載されている。The electron-donating colorless dye used in the present invention is not particularly limited, and known compounds can be arbitrarily selected and used according to the purpose. Examples of the electron-donating colorless dyes include known triphenylmethanephthalide compounds, fluorane compounds, phenothiazine compounds, indolylphthalide compounds, leucoolamine compounds, rhodaminelactam compounds, triphenylmethane compounds. Various compounds such as compounds, triazene compounds, spiropyran compounds, and fluorene compounds can be mentioned. Specific examples of the phthalides include US Reissue Patent Specification No. 23,024 and US Patent Specification No. 3,491,11.
No. 1, No. 3,491, 112, No. 3, 491, 1
No. 16 and No. 3,509,174, and specific examples of fluoranes are U.S. Pat. Nos. 3,624,107, 3,627,787, and 3,641,011.
No. 3,462,828, No. 3,681,390
Issue No. 3,920,510, No. 3,959,57
1, specific examples of spirodipyrans are U.S. Pat. No. 3,971,808, pyridine compounds and pyrazine compounds are U.S. Pat. Nos. 3,775,424 and 3,853,869, No. 4,246,318 and specific examples of leuco auramine compounds are disclosed in JP-A-4-1262.
No. 87, specific examples of fluorene compounds are disclosed in JP-A-63-9.
No. 4878 and the like.
【００３０】本発明に係る電子供与性無色染料の塗布量
は特には限定されないが、０．１〜３．０ｇ／ｍ2 、特
には１．０〜２．５ｇ／ｍ2 が好ましい。The coating amount of the electron-donating colorless dye according to the present invention is not particularly limited, but is preferably 0.1 to 3.0 g / m 2 , and particularly 1.0 to 2.5 g / m 2 .
【００３１】本発明に用いられる電子供与性無色染料の
顕色剤（即ち、電子受容性化合物）には特に制限はな
く、例えば、ビスフェノール類を包含するフェノール誘
導体、サリチル酸誘導体、ヒドロキシ安息香酸エステル
等の電子受容性化合物を用いることができる。公知の電
子受容性化合物としては、フェノール誘導体、サリチル
酸誘導体、芳香族カルボン酸の金属塩、酸性白土、ベン
トナイト、ノボラック樹脂、金属処理ノボラック樹脂、
金属錯体などが挙げられる。The developer of the electron-donating colorless dye used in the present invention (that is, the electron-accepting compound) is not particularly limited, and examples thereof include phenol derivatives including bisphenols, salicylic acid derivatives, hydroxybenzoic acid esters and the like. The electron-accepting compound can be used. Known electron-accepting compounds include phenol derivatives, salicylic acid derivatives, metal salts of aromatic carboxylic acids, acid clay, bentonite, novolac resins, metal-treated novolac resins,
Examples thereof include metal complexes.
【００３２】これらの例は特公昭４０−９３０９号、特
公昭４５−１４０３９号、特開昭５２−１４０４８３
号、特開昭４８−５１５１０号、特開昭５７−２１０８
８６号、特開昭５８−８７０８９号、特開昭５９−１１
２８６号、特開昭６０−１７６７９５号、特開昭６１−
９５９８８号等に記載されている。Examples of these are JP-B-40-9309, JP-B-45-14039 and JP-A-52-140483.
JP-A-48-51510, JP-A-57-2108
86, JP-A-58-87089, and JP-A-59-11.
286, JP-A-60-176795, JP-A-61-176
No. 95988, etc.
【００３３】これらのなかでも、前記の一般式（２）で
表される化合物を電子受容性化合物として用いることが
電子受容性化合物を含む乳化物の安定性付与の観点から
好ましい。一般式（２）において、ＭｅはＺｎ、Ｃａ又
はＡｌを表し、ｎは２又は３の整数を表すが、なかでも
亜鉛塩（Ｍｅ＝Ｚｎ）で、ｎが２である下記式（２−
Ｉ）で表される化合物が好ましい。Among these, it is preferable to use the compound represented by the general formula (2) as the electron-accepting compound from the viewpoint of imparting stability to the emulsion containing the electron-accepting compound. In the general formula (2), Me represents Zn, Ca, or Al, and n represents an integer of 2 or 3. Among them, a zinc salt (Me = Zn), in which n is 2, the following formula (2-
The compounds represented by I) are preferred.
【００３４】[0034]
【化１４】 Embedded image
【００３５】また、本発明の電子受容性化合物において
は、前記一般式（２）で表される化合物に加えて、前記
の如き公知の電子受容性化合物を併用することができ
る。In the electron-accepting compound of the present invention, in addition to the compound represented by the general formula (2), the known electron-accepting compound as described above can be used in combination.
【００３６】使用される電子供与性無色染料と電子受容
性化合物の比は、重量比で１：１０から１：１の間が好
ましく、１：５から２：３の間が特に好ましい。The weight ratio of the electron-donating colorless dye to the electron-accepting compound used is preferably 1:10 to 1: 1 and more preferably 1: 5 to 2: 3.
【００３７】さらに、この前記一般式（２）を電子受容
性化合物に用いた場合、前記の一般式（３）乃至一般式
（５）で表される化合物からなる群から選択される少な
くとも１種の化合物を併用することにより、前記の効果
が一層顕著になるため、特に、好ましい。これらの化合
物は、記録材料の添加剤として知られているフェノール
系の化合物である。When the general formula (2) is used as an electron-accepting compound, at least one selected from the group consisting of the compounds represented by the general formulas (3) to (5). It is particularly preferable to use the compound (1) in combination because the above-mentioned effect becomes more remarkable. These compounds are phenolic compounds known as additives for recording materials.
【００３８】一般式（３）で示される化合物において、
Ｒ4 及びＲ7 はそれぞれ独立に炭素数３〜８の分岐アル
キル基を表すが、具体的には、イソプロピル基、イソブ
チル基、sec −ブチル基、tert−ブチル基、２−エチル
ヘキシル基等が挙げられ、好ましくは、sec −ブチル
基、tert−ブチル基、２−エチルヘキシル基等である。
また、Ｒ5 及びＲ6 はそれぞれ独立に炭素数１〜８のア
ルキル基を表し、一般式（１）のＲ1 におけるアルキル
基と同様のものが例示されるが、特に、メチル基、エチ
ル基、sec −ブチル基、tert−ブチル基等が好ましい。
ｎは０又は１若しくは２の整数を表すが、ｎは０又は１
であるものが好ましい。好ましい具体例としては下記式
（３−Ｉ）で表されるものが挙げられる。In the compound represented by the general formula (3),
R 4 and R 7 each independently represent a branched alkyl group having 3 to 8 carbon atoms, and specific examples thereof include an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and a 2-ethylhexyl group. However, sec-butyl group, tert-butyl group, 2-ethylhexyl group and the like are preferable.
R 5 and R 6 each independently represent an alkyl group having 1 to 8 carbon atoms, and examples thereof include the same as the alkyl group for R 1 in the general formula (1). , Sec-butyl group, tert-butyl group and the like are preferable.
n represents an integer of 0 or 1 or 2, and n is 0 or 1
Are preferred. Preferred specific examples include those represented by the following formula (3-I).
【００３９】[0039]
【化１５】 [Chemical 15]
【００４０】一般式（４）で示される化合物において、
Ｒ8 及びＲ11はそれぞれ独立に炭素数３〜８の分岐アル
キル基を表すが、これは前記一般式（３）で示される化
合物におけるＲ4 及びＲ7 と同義であり、好ましくはse
c −ブチル基、tert−ブチル基等である。また、Ｒ9 及
びＲ10はそれぞれ独立に炭素数１〜８のアルキル基を表
すが、これは前記一般式（３）で示される化合物におけ
るＲ5 及びＲ6 と同義であり、メチル基、エチル基、se
c −ブチル基、tert−ブチル基等が好ましい。ＸはＳ、
Ｏ、ＳＯ2 、Ｓ2 又は前記一般式（４Ｂ）を表すが、好
ましくは、Ｓ、−（ＣＨ2 ）−等である。好ましい具体
例としては、下記式（４−Ｉ）及び（４−II）で表され
るものが挙げられる。In the compound represented by the general formula (4),
R 8 and R 11 each independently represent a branched alkyl group having 3 to 8 carbon atoms, which has the same meaning as R 4 and R 7 in the compound represented by the general formula (3), and preferably se
Examples include c-butyl group and tert-butyl group. R 9 and R 10 each independently represent an alkyl group having 1 to 8 carbon atoms, which has the same meaning as R 5 and R 6 in the compound represented by the general formula (3), a methyl group, an ethyl group. Base, se
A c-butyl group, a tert-butyl group and the like are preferable. X is S,
It represents O, SO 2 , S 2 or the general formula (4B), and is preferably S, — (CH 2 ) — or the like. Preferred specific examples include those represented by the following formulas (4-I) and (4-II).
【００４１】[0041]
【化１６】 Embedded image
【００４２】一般式（５）で示される化合物において、
Ｒ14及びＲ15はそれぞれ独立に炭素数３〜８の分岐アル
キル基を表すが、これは前記一般式（３）で示される化
合物におけるＲ4 及びＲ7 と同義であり、好ましくはse
c −ブチル基、tert−ブチル基等である。また、Ｒ16は
炭素数１〜２０のアルキル基を表すが、具体的には、メ
チル基、エチル基、ｎ−プロピル基、イソプロピル基、
ｎ−ブチル基、イソブチル基、sec −ブチル基、ｎ−ペ
ンチル基、イソペンチル基、ｎ−ヘキシル基、ｎ−オク
チル基、２−エチルヘキシル基、ｎ−デシル基、ｎ−ド
デシル基、シクロペンチル基、シクロヘキシル基、ベン
ジル基、２−フェネチル基、１−フェネチル基、フェニ
ル基等が挙げられる。また、好ましい例示化合物として
は、下記式（５−Ｉ）で表される化合物が挙げられる。In the compound represented by the general formula (5),
R 14 and R 15 each independently represent a branched alkyl group having 3 to 8 carbon atoms, which has the same meaning as R 4 and R 7 in the compound represented by the general formula (3), and preferably se
Examples include c-butyl group and tert-butyl group. R 16 represents an alkyl group having 1 to 20 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
n-butyl group, isobutyl group, sec-butyl group, n-pentyl group, isopentyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-decyl group, n-dodecyl group, cyclopentyl group, cyclohexyl Group, benzyl group, 2-phenethyl group, 1-phenethyl group, phenyl group and the like. Moreover, the compound represented by the following formula (5-I) is mentioned as a preferable exemplary compound.
【００４３】[0043]
【化１７】 [Chemical 17]
【００４４】本発明の感熱記録材料には、前記化合物に
加えて従来より公知の紫外線吸収剤、蛍光増白剤、酸化
防止剤と併用してもよい。In the heat-sensitive recording material of the present invention, in addition to the above compounds, conventionally known UV absorbers, fluorescent brighteners and antioxidants may be used in combination.
【００４５】併用できる紫外線吸収剤として好ましいも
のは、ベンゾフェノン系紫外線吸収剤、ベンゾトリアゾ
ール系紫外線吸収剤、サリチル酸系紫外線吸収剤、シア
ノアクリレート系紫外線吸収剤、オキザリックアシッド
アニリド系紫外線吸収剤などが挙げられる。これらの例
は特開昭４７−１０５３７号、同５８−１１１９４２
号、同５８−２１２８４４号、同５９−１９９４５号、
同５９−４６６４６号、同５９−１０９０５５号、同６
３−５３５４４号、特公昭３６−１０４６６号、同４２
−２６１８７号、同４８−３０４９２号、同４８−３１
２５５号、同４８−４１５７２号、同４８−５４９６５
号、同５０−１０７２６号、米国特許２，７１９，０８
６号、同３，７０７，３７５号、同３，７５４，９１９
号、同４，２２０，７１１号などに記載されている。Preferred UV absorbers that can be used in combination are benzophenone UV absorbers, benzotriazole UV absorbers, salicylic acid UV absorbers, cyanoacrylate UV absorbers, oxalic acid anilide UV absorbers, and the like. Can be mentioned. Examples of these are JP-A-47-10537 and JP-A-58-111942.
No. 58, No. 58-212844, No. 59-19925,
59-46646, 59-109055, 6
3-53544, Japanese Patent Publication No. 36-10466, 42
No. 26187, No. 48-30492, No. 48-31
No. 255, No. 48-41572, No. 48-54965.
No. 50-10726, US Pat. No. 2,719,08
No. 6, No. 3,707,375, No. 3,754,919
No. 4,220,711 and the like.
【００４６】併用できる蛍光増白剤として好ましいもの
は、クマリン系蛍光増白剤などが挙げられる。これらの
例は特公昭４５−４６９９号、同５４−５３２４号など
に記載されている。Preferable examples of the fluorescent whitening agent that can be used in combination include coumarin type fluorescent whitening agents. Examples of these are described in JP-B-45-4699 and JP-A-54-5324.
【００４７】併用できる酸化防止剤として好ましいもの
は、ヒンダードアミン系酸化防止剤、ヒンダードフェノ
ール系酸化防止剤、アニリン系酸化防止剤、キノリン系
酸化防止剤などが挙げられる。これらの例は特開昭５９
−１５５０９０号、同６０−１０７３８３号、同６０−
１０７３８４号、同６１−１３７７７０、同６１−１３
９４８１号、同６１−１６０２８７などに記載されてい
る。Preferred antioxidants that can be used in combination include hindered amine antioxidants, hindered phenol antioxidants, aniline antioxidants, quinoline antioxidants and the like. Examples of these are JP-A-59
-155090, 60-107383, 60-
107384, 61-1377770, 61-13.
No. 9481, 61-160287 and the like.
【００４８】併用できる紫外線吸収剤、蛍光増白剤、酸
化防止剤の使用量としては０．０５〜１．０ｇ／ｍ2 、
特には０．１〜０．４ｇ／ｍ2 が好ましい。The amount of the ultraviolet absorber, fluorescent brightening agent, and antioxidant that can be used in combination is 0.05 to 1.0 g / m 2 ,
Particularly, 0.1 to 0.4 g / m 2 is preferable.
【００４９】電子供与性無色染料および電子受容性化合
物の使用量は所望の塗布厚、感圧記録紙の形態、カプセ
ルの製法、その他の条件によるのでその条件に応じて適
宜選べばよい。当業者がこの使用量を決定することは容
易である。The amount of the electron-donating colorless dye and the electron-accepting compound used depends on the desired coating thickness, the form of the pressure-sensitive recording paper, the capsule manufacturing method, and other conditions, and may be appropriately selected according to the conditions. A person skilled in the art can easily determine this usage amount.
【００５０】感熱紙に用いる場合には、特開昭６２−１
４４９８９号、特開平１−８７２９１号明細書等に記載
されているような形態をとる。具体的には，電子供与性
無色染料および電子受容性化合物は分散媒中で１０μ以
下、好ましくは３μ以下の粒径まで粉砕分散して用い
る。分散媒としては、一般に０．５ないし１０％程度の
濃度の水溶高分子水溶液が用いられ分散はボールミル、
サンドミル、横型サンドミル、アトライタ、コロイダル
ミル等を用いて行われる。When it is used for thermal paper, it is disclosed in JP-A-62-1.
It takes a form as described in Japanese Patent No. 44989 and Japanese Patent Application Laid-Open No. 1-87291. Specifically, the electron-donating colorless dye and the electron-accepting compound are pulverized and dispersed in a dispersion medium to a particle size of 10 μm or less, preferably 3 μm or less. As the dispersion medium, a water-soluble polymer aqueous solution having a concentration of about 0.5 to 10% is generally used, and dispersion is performed by a ball mill,
It is carried out by using a sand mill, a horizontal sand mill, an attritor, a colloidal mill or the like.
【００５１】その際、熱応答性を改良するために熱可融
性物質を感熱発色層に含有させることができる。熱可融
性物質としては、芳香族エーテル、チオエーテル、エス
テル及び又は脂肪族アミド又はウレイドなどがその代表
である。At that time, a thermofusible substance may be contained in the thermosensitive coloring layer in order to improve the thermal response. Typical examples of the heat-fusible substance include aromatic ethers, thioethers, esters and / or aliphatic amides or ureides.
【００５２】これらの例は特開昭５８−５７９８９号、
同５８−８７０９４号、同６１−５８７８９号、同６２
−１０９６８１号、同６２−１３２６７４号、同６３−
１５１４７８号、同６３−２３５９６１号、特開平２−
１８４４８９号、同２−２１５５８５号などに記載され
ている。Examples of these are disclosed in JP-A-58-57989,
58-87094, 61-58789, 62.
-109681, 62-2132674, 63-
151478, 63-235961, JP-A-2-
No. 184489 and No. 2-215585.
【００５３】これらは電子供与性無色染料と同時又は電
子受容性化合物と同時に微分散して用いられる。これら
の使用量、電子受容性化合物に対して、２０％以上３０
０％以下の重量比で添加され、特に４０％以上１５０％
以下が好ましい。These are used at the same time as the electron-donating colorless dye or at the same time as being finely dispersed at the same time as the electron-accepting compound. 20% or more and 30% of the amount of these used and the electron-accepting compound
It is added in a weight ratio of 0% or less, especially 40% or more and 150%
The following are preferred.
【００５４】このようにして得られた塗液には、さらに
種々の要求を満たす為に必要に応じて添加剤が加えられ
る。添加剤の例としては記録時の記録ヘッドの汚れを防
止するために、バインダー中に無機顔料、ポリウレアフ
ィラー等の吸油性物質を分散させておくことが行われ、
さらにヘッドに対する離型性を高めるために脂肪酸、金
属石鹸などが添加される。したがって一般には、発色に
直接寄与する電子供与性無色染料、電子受容性化合物の
他に、熱可融性物質、顔料、ワックス、帯電防止剤、紫
外線吸収剤、消泡剤、導電剤、蛍光染料、界面活性剤な
どの添加剤が支持体上に塗布され、記録材料が構成され
ることになる。さらに必要に応じて感熱記録層の表面に
保護層を設けてもよい。Additives are added to the coating solution thus obtained, if necessary, in order to meet various requirements. As an example of the additive, in order to prevent contamination of the recording head at the time of recording, an inorganic pigment, an oil absorbing substance such as polyurea filler is dispersed in a binder,
Furthermore, fatty acids, metal soaps, etc. are added to enhance the releasability of the head. Therefore, in general, in addition to electron-donating colorless dyes and electron-accepting compounds that directly contribute to color development, heat-fusible substances, pigments, waxes, antistatic agents, ultraviolet absorbers, defoamers, conductive agents, fluorescent dyes. An additive such as a surfactant is applied on the support to form a recording material. Further, if necessary, a protective layer may be provided on the surface of the heat-sensitive recording layer.
【００５５】通常、電子供与性無色染料及び電子受容性
化合物は、バインダー中に分散して塗布される。バイン
ダーとしては水溶性のものが一般的であり、ポリビニル
アルコ−ル、ヒドロキシエチルセルロース、ヒドロキシ
プロピルセルロース、エピクロルヒドリン変性ポリアミ
ド、エチレン−無水マレイン酸共重合体、スチレン−無
水マレイン酸共重合体、イソブチレン−無水マレインサ
リチル酸共重合体、ポリアクリル酸、ポリアクリル酸ア
ミド、メチロール変性ポリアクリルアミド、デンプン誘
導体、カゼイン、ゼラチン等があげられる。またこれら
のバインダーに耐水性を付与する目的で耐水化剤を加え
たり、疎水性ポリマーのエマルジョン、具体的には、ス
チレン−ブタジエンゴムラテックス、アクリル樹脂エマ
ルジョン等を加えることもできる。これらの使用量とし
ては、０．４〜５ｇ／ｍ2 が好ましく、さらには０．８
〜１．６ｇ／ｍ2 が好ましい。Usually, the electron-donating colorless dye and the electron-accepting compound are dispersed and applied in a binder. Water-soluble binders are generally used, and polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, epichlorohydrin-modified polyamide, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, isobutylene-anhydrous. Examples thereof include maleic salicylic acid copolymer, polyacrylic acid, polyacrylic acid amide, methylol-modified polyacrylamide, starch derivative, casein, gelatin and the like. Further, a water-proofing agent may be added to these binders for the purpose of imparting water resistance, or an emulsion of a hydrophobic polymer, specifically, a styrene-butadiene rubber latex, an acrylic resin emulsion or the like may be added. The amount of these used is preferably 0.4 to 5 g / m 2 , more preferably 0.8
˜1.6 g / m 2 is preferred.
【００５６】得られた感熱塗液は、上質紙、下塗り層を
有する上質紙、合成紙、プラスチックフィルム等に塗布
される。この際ＪＩＳ−８１１９で規定される平滑度が
５００秒以上特に８００秒以上の支持体を用いるのがド
ット再現性の点から特に好ましい。The obtained heat-sensitive coating liquid is applied to high-quality paper, high-quality paper having an undercoat layer, synthetic paper, plastic film and the like. At this time, it is particularly preferable from the viewpoint of dot reproducibility to use a support having a smoothness of 500 seconds or more, particularly 800 seconds or more as defined by JIS-8119.
【００５７】本発明の記録材料においてはその必要に応
じて、公知のワックス、帯電防止剤、消泡剤、導電剤、
蛍光染料、界面活性剤、紫外線吸収剤プレカーサーなど
各種添加剤を使用することができる。In the recording material of the present invention, known wax, antistatic agent, defoaming agent, conductive agent,
Various additives such as fluorescent dyes, surfactants, and ultraviolet absorber precursors can be used.
【００５８】本発明の記録材料には必要に応じて記録層
の表面に保護層を設けてもよい。保護層は必要に応じて
二層以上積層してもよい。保護層に用いる材料として
は、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、酢酸ビニル−アクリルアミド共重合体、ケ
イ素変性ポリビニルアルコール、澱粉、変性澱粉、メチ
ルセルロース、カルボキシメチルセルロース、ヒドロキ
シメチルセルロース、ゼラチン類、アラビアゴム、カゼ
イン、スチレン−マレイン酸共重合体加水分解物、スチ
レン−マレイン酸共重合物ハーフエステル加水分解物、
イソブチレン−無水マレイン酸共重合体加水分解物、ポ
リアクリルアミド誘導体、ポリビニルピロリドン、ポリ
スチレンスルホン酸ソーダ、アルギン酸ソーダなどの水
溶性高分子化合物、及びスチレン−ブタジエンゴムラテ
ックス、アクリロニトリル−ブタジエンゴムラテック
ス、アクリル酸メチル−ブタジエンゴムラテックス、酢
酸ビニルエマルジョン等のラテックス類が用いられる。
保護層の水溶性高分子化合物を架橋してより一層保存安
定性を向上させることもでき、その架橋剤としては公知
の架橋剤を使用することができる。具体的にはＮ−メチ
ロール尿素、Ｎ−メチロールメラミン、尿素−ホルマリ
ン等の水溶性初期縮合物、グリオキザール、グルタルア
ルデヒド等のジアルデヒド化合物類、硼酸、硼砂等の無
機系架橋剤、ポリアミドエピクロルヒドリンなどが挙げ
られる。保護層には、さらに公知の顔料、金属石鹸、ワ
ックス、界面活性剤などを使用することもできる。保護
層の塗布量は０．２〜５ｇ／ｍ2 が好ましく、さらには
１．０〜３．０ｇ／ｍ2 が好ましい。またその膜厚は
０．２〜５μｍが好ましく、特に１．０〜３μｍが好ま
しい。In the recording material of the present invention, a protective layer may be provided on the surface of the recording layer, if necessary. Two or more protective layers may be laminated if necessary. Materials used for the protective layer include polyvinyl alcohol, carboxy-modified polyvinyl alcohol, vinyl acetate-acrylamide copolymer, silicon-modified polyvinyl alcohol, starch, modified starch, methyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, gelatins, gum arabic, casein, Styrene-maleic acid copolymer hydrolyzate, styrene-maleic acid copolymer half ester hydrolyzate,
Isobutylene-maleic anhydride copolymer hydrolyzate, polyacrylamide derivative, polyvinylpyrrolidone, water-soluble polymer compound such as sodium polystyrene sulfonate, sodium alginate, and styrene-butadiene rubber latex, acrylonitrile-butadiene rubber latex, methyl acrylate -Latexes such as butadiene rubber latex and vinyl acetate emulsion are used.
The water-soluble polymer compound in the protective layer can be crosslinked to further improve the storage stability, and a known crosslinking agent can be used as the crosslinking agent. Specifically, water-soluble initial condensates such as N-methylol urea, N-methylol melamine, and urea-formalin, dialdehyde compounds such as glyoxal and glutaraldehyde, inorganic cross-linking agents such as boric acid and borax, polyamide epichlorohydrin, etc. Can be mentioned. Further, known pigments, metal soaps, waxes, surfactants and the like can be used in the protective layer. The coating amount of the protective layer is preferably 0.2 to 5 g / m 2 , and more preferably 1.0 to 3.0 g / m 2 . The film thickness is preferably 0.2 to 5 μm, and particularly preferably 1.0 to 3 μm.
【００５９】本発明の記録材料に保護層を使用する場
合、保護層中に公知のＵＶ吸収剤やＵＶ吸収剤プレカー
サーを含有してもよい。When a protective layer is used in the recording material of the present invention, a known UV absorber or UV absorber precursor may be contained in the protective layer.
【００６０】本発明の記録材料に使用できる支持体とし
ては、酸性紙、中性紙、コート紙、プラスチックフィル
ムラミネート紙、合成紙、プラスチックフィルムなどを
使用することができる。さらにこれら支持体に公知の下
塗り層を設けてもよい。この下塗り層は上記保護層と同
様にして設けることができる。As the support that can be used in the recording material of the present invention, acid paper, neutral paper, coated paper, plastic film laminated paper, synthetic paper, plastic film and the like can be used. Further, these supports may be provided with a known undercoat layer. This undercoat layer can be provided in the same manner as the protective layer.
【００６１】支持体のカールバランスを補正するため或
いは、裏面からの耐薬品性を向上させる目的で、バック
コート層を設けてもよく、また裏面に接着剤層を介して
剥離紙を組み合わせてラベルの形態にしてもよい。この
バックコート層についても上記保護層と同様にして設け
ることができる。In order to correct the curl balance of the support or to improve the chemical resistance from the back side, a back coat layer may be provided, and the back side may be combined with a release paper via an adhesive layer to label the label. You may take the form of. This back coat layer can be provided in the same manner as the protective layer.
【００６２】[0062]
【実施例】以下実施例によって本発明を記述するが本発
明はこれにより限定されるものではない。EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto.
【００６３】又、特に断らない限り、以下に記載する部
及び％はそれぞれ重量部及び重量％を表す。 （実施例１）電子供与性無色染料を内包したカプセル液（ＭＣ１）の
調製 下記式（Ｅ−１）（Ｅ−２）（Ｅ−３）（Ｅ−４）（Ｅ
−５）（Ｅ−６）及び（Ｅ−７）で表わされる化合物、
それぞれ１０．０ｇ、１．３ｇ、２．０ｇ、２．７ｇ、
１．３ｇ、０．１ｇ及び０．４ｇを酢酸エチル２０ｇ中
で加熱溶解させ、４０°Ｃまで徐冷させた後、タケネー
トＤ１１０Ｎ（商品名：武田薬品製カプセル壁剤）２．
０ｇ及びタケネートＤ１２７Ｎ（同上：武田薬品製）１
１．６ｇ及びｎ−ブタノール０．４ｇを添加し４０°Ｃ
で４０分間撹拌させた。Unless otherwise specified, the parts and% described below represent parts by weight and% by weight, respectively. (Example 1) of a capsule liquid (MC1) containing an electron-donating colorless dye
Preparation Formulas (E-1) (E-2) (E-3) (E-4) (E
-5) compounds represented by (E-6) and (E-7),
10.0g, 1.3g, 2.0g, 2.7g, respectively
1. After dissolving 1.3 g, 0.1 g and 0.4 g in 20 g of ethyl acetate by heating and slowly cooling to 40 ° C, Takenate D110N (trade name: capsule wall agent manufactured by Takeda Pharmaceutical Co., Ltd.) 2.
0 g and Takenate D127N (same as above: manufactured by Takeda Pharmaceutical Co., Ltd.) 1
1.6 g and 0.4 g of n-butanol were added and the temperature was 40 ° C.
And allowed to stir for 40 minutes.
【００６４】[0064]
【化１８】 Embedded image
【００６５】得られた溶液をポリビニルアルコール８％
溶液（ＰＶＡ２１７Ｃ：商品名、クラレ製）４０ｇと水
１３ｇを混合した水相に添加した後、エースホモジナイ
ザー（商品名：日本精機（株）製）を用い、１００００
ｒｐｍで５分間乳化分散を行った。The obtained solution is made of polyvinyl alcohol 8%
After adding 40 g of the solution (PVA217C: trade name, manufactured by Kuraray) and 13 g of water to the aqueous phase, 10000 using an ace homogenizer (trade name: manufactured by Nippon Seiki Co., Ltd.)
Emulsified and dispersed at rpm for 5 minutes.
【００６６】得られた乳化液に更に水７０ｇ及びテトラ
エチレンペンタミン０．５ｇを添加した後、６０°Ｃで
３時間カプセル化反応を行わせて、平均粒子径が０．６
μｍのカプセル液（ＭＣ１）を得た。After further adding 70 g of water and 0.5 g of tetraethylenepentamine to the obtained emulsion, encapsulation reaction was carried out at 60 ° C. for 3 hours to give an average particle diameter of 0.6.
A μm capsule liquid (MC1) was obtained.
【００６７】なお平均粒子径はレーザー回析粒度分布測
定装置（ＬＡ７００：商品名、（株）堀場製作所製）を
用いて測定した５０％体積平均粒子径である。The average particle size is a 50% volume average particle size measured by using a laser diffraction particle size distribution measuring device (LA700: trade name, manufactured by Horiba Ltd.).
【００６８】以下において、特に断らない限り、平均粒
子径は上記の５０％体積平均粒子径を表す。電子供与性無色染料を内包したカプセル液（ＭＣ２）の
調製 前記式（Ｅ−１）（Ｅ−２）（Ｅ−３）（Ｅ−４）（Ｅ
−５）（Ｅ−６）及び（Ｅ−７）の化合物、それぞれ、
９．５ｇ、１．２ｇ、１．８ｇ、４．６ｇ、１．０ｇ、
１．０ｇ及び０．４ｇを酢酸エチル２０ｇの中で加熱溶
解させ５０°Ｃまで徐冷させた後、タケネートＤ１４０
Ｎ（商品名：武田薬品製カプセル壁剤）１１．４ｇ及び
バーノックＤ７５０（商品名：大日本インキ（株）製カ
プセル壁剤）１．３ｇを添加し撹拌させた。In the following, unless otherwise specified, the average particle diameter represents the above 50% volume average particle diameter. Of the capsule liquid (MC2) containing an electron-donating colorless dye
Preparation Formula (E-1) (E-2) (E-3) (E-4) (E
-5) compounds of (E-6) and (E-7),
9.5g, 1.2g, 1.8g, 4.6g, 1.0g,
1.0 g and 0.4 g were dissolved by heating in 20 g of ethyl acetate and gradually cooled to 50 ° C, and then Takenate D140 was added.
11.4 g of N (trade name: capsule wall agent manufactured by Takeda Pharmaceutical Co., Ltd.) and 1.3 g of Barnock D750 (capsule wall agent manufactured by Dainippon Ink and Chemicals, Inc.) were added and stirred.
【００６９】得られた溶液を、ポリビニルアルコール８
％溶液（ＰＶＡ２１７Ｃ、クラレ製）４０ｇと水１３ｇ
を混合した水相に添加した後、エースホモジナイザーを
用い、１００００ｒｐｍで５分間乳化分散を行った。The obtained solution was treated with polyvinyl alcohol 8
% Solution (PVA217C, made by Kuraray) 40 g and water 13 g
Was added to the mixed aqueous phase, and then emulsified and dispersed at 10000 rpm for 5 minutes using an ace homogenizer.
【００７０】得られた乳化液に更に水８０ｇ及びテトラ
エチレンペンタミン０．８ｇを添加した後、６０°Ｃで
３時間カプセル化反応を行わせて平均粒子径が０．６μ
ｍのカプセル液（ＭＣ２）を得た。電子受容性化合物（顕色剤）乳化分散液（Ａ）の調製 前記式（２−Ｉ）（３−Ｉ）及び（１−Ｉ）で表わされ
る化合物、それぞれ１８．７ｇ、１３．１ｇ及び５．６
ｇをＴＣＰ（商品名：大八化学社製オイル）１．０ｇ、
ＤＥＭ（商品名：大八化学社製オイル）０．５ｇ及び酢
酸エチル２０ｇを混合した溶液に溶解させた。After 80 g of water and 0.8 g of tetraethylenepentamine were added to the obtained emulsion, encapsulation reaction was carried out at 60 ° C. for 3 hours to give an average particle size of 0.6 μm.
m capsule liquid (MC2) was obtained. Preparation of Emulsion Dispersion Liquid (A) of Electron-Accepting Compound (Developer) Compounds represented by the formulas (2-I), (3-I) and (1-I), 18.7 g, 13.1 g and 5 respectively. .6
g is TCP (trade name: Daihachi Chemical Co., Ltd. oil) 1.0 g,
DEM (trade name: oil manufactured by Daihachi Chemical Co., Ltd.) 0.5 g and ethyl acetate 20 g were dissolved in a mixed solution.
【００７１】得られた溶液をポリビコルアルコール１５
％溶液（ＰＶＡ２０５Ｃ：クラレ社製）２５．０ｇ及び
ポリビニルアルコール８％溶液（ＰＶＡ２１７Ｃ：クラ
レ社製）４６ｇ、ドデシルスルホン酸ナトリウム０．５
ｇ及び水７５．０ｇを混合した水相に投入し、エースホ
モジナイザーを使用し１００００ｒｐｍで３分間乳化
し、平均粒子径が０．６μｍの電子受容性化合物（以
下、適宜顕色剤と称する）乳化分散液（Ａ）を得た。保護層用塗布液の調製 水３０ｇ、ポリビニルアルコール６％水溶液（ＰＶＡ１
２４Ｃ：商品名、クラレ株式会社製）２０ｇ、スルホコ
ハク酸ジオクチルのナトリウム塩２％水溶液０．３ｇ、
カオリン分散物（ポリビニルアルコール３ｇを水１００
ｇに混合した液にカオリン３５ｇをポールミルで分散さ
せたもの）３．０ｇ及びハイドリンＺ（商品名：中京油
脂社製）０．５ｇを混合して保護層用塗布液を得た。下塗層を設けた透明支持体の調製 色度座標（ＪＩＳ Ｚ８７０１）が、Ａ（ｘ＝０．２８
０５，ｙ＝０．３００５）、Ｂ（ｘ＝０．２８２０，ｙ
＝０．２９７０）、Ｃ（ｘ＝０．２８８５，ｙ＝０．３
０１５）、Ｄ（ｘ＝０．２８７０，ｙ＝０．３０４０）
の４点を頂点とする四角形の領域内で着色された、厚さ
１７５μｍのポリエチレンテレフタレートの一方の面に
ＳＢＲラテックスを固形分重量で０．３ｇ／ｍ2 となる
ように塗布した後、下記の下塗層用塗布液を片面当たり
の固形分重量が０．１ｇ／ｍ2 となるように塗布して、
下塗層を設けた透明支持体を得た。下塗層用塗布液の調製 ゼラチン５％水溶液（＃８１０：商品名、新田ゼラチン
社製）２００ｇ、粒子径２μｍのポリメチルメタクリレ
ート樹脂粒子を５％分散したゼラチン分散物０．５ｇ、
１，２−ベンゾチアゾリン−３−オン３％水溶液１．０
ｇ、スルフォン酸ジ（２−エチル）ヘキシル２％水溶液
１０ｇを混合して下塗り層塗布液を得た。感熱記録層用塗布液（１）の調製 既に調製したカプセル液（ＭＣ１）１．５ｇ、カプセル
液（ＭＣ２）３．５ｇ顕色剤乳化分散液（Ａ）（乳化分
散後１日放置したもの）１５ｇ及び水１０ｇを混合して
感熱記録用塗布液（１）を得た。感熱記録材料の調製 既に調製した下塗り層を設けた透明支持体の一方の面に
感熱記録用塗布液（１）を固形分重量で１４ｇ／ｍ2 と
なるように塗布・乾燥した後、その上に調製済の保護層
用塗布液を固形分重量で２．５ｇ／ｍ2 となる様に塗布
・乾燥して本発明の感熱記録材料を得た。印字方法及び性能評価 得られた感熱記録材料にサーマルプリンター（ＴＲＴ−
１６：商品名、長野日本無線（株）製）を用い、サーマ
ルヘッドの印加熱エネルギーを変えて画像（以下、ステ
ップエッジと呼ぶ）を記録した。 （実施例２）実施例１で使用した感熱記録様塗布液
（１）中の顕色剤乳化分散液（Ａ）を以下に記す（Ｂ）
液に変えた以外同様の方法で感熱記録用塗布液（２）を
作成した以外同様な方法で本発明の感熱記録材料を得
た。顕色剤乳化分散液（Ｂ）の調製 実施例１中に記載の顕色剤乳化分散液（Ａ）の調製方法
において、前記式（３−Ｉ）で表される化合物を前記式
（４−Ｉ）で表される化合物に変えた以外同様な方法で
平均粒子径０．６μｍの顕色剤乳化分散液（Ｂ）を作成
した。印字方法及び性能評価 実施例２の感熱記録材料も実施例１記載同様の方法、性
能評価を行った。 （実施例３）実施例１で使用した感熱記録用塗布液
（１）中の顕色剤乳化分散液（Ａ）を以下に記す（Ｃ）
液に変えた以外同様の方法で感熱記録用塗布液（３）を
作成した以外同様な方法で本発明の感熱記録材料を得
た。顕色剤乳化分散液（Ｃ）の調製 実施例１中に記載の顕色剤乳化分散液（Ａ）の調製方法
において、前記式（３−Ｉ）で表される化合物を前記式
（４−II）で表される化合物に変えた以外同様な方法で
平均粒子径０．６μｍの顕色剤乳化分散液（Ｃ）を作成
した。印字方法及び性能評価 実施例３の感熱記録材料も実施例１記載同様の方法、性
能評価を行った。 （実施例４）実施例１で使用した感熱記録用塗布液
（１）中の顕色剤乳化分散液（Ａ）を以下に記す（Ｄ）
液に変えた以外同様の方法で感熱記録用塗布液（４）を
作成した以外同様な方法で本発明の感熱記録材料を得
た。顕色剤乳化分散液（Ｄ）の調製 実施例１中に記載の顕色剤乳化分散液（Ａ）の調製方法
において、前記式（３−Ｉ）で表される化合物を前記式
（５−Ｉ）で表される化合物に変えた以外同様な方法で
平均粒子径０．６μｍの顕色剤乳化分散液（Ｄ）を作成
した。印字方法及び性能評価 実施例４の感熱記録材料も実施例１記載同様の方法、性
能評価を行った。 （実施例５）実施例１で使用した感熱記録用塗布液
（１）中の顕色剤乳化分散液（Ａ）を以下に記す（Ｅ）
液に変えた以外同様の方法で感熱記録用塗布液（５）を
使用した以外同様な方法で本発明の感熱記録材料を得
た。顕色剤乳化分散液（Ｅ）の調製 実施例１中に記載の顕色剤乳化分散液（Ａ）の調製方法
において、前記式（２−Ｉ）、（３−Ｉ）及び（１−
Ｉ）で表わされる化合物、それぞれ１８．７ｇ、１３．
１ｇ及び５．６ｇであるのを、前記式（２−Ｉ）、（３
−Ｉ）、（１−Ｉ）、（４−Ｉ）、（４−II）及び（５
−Ｉ）、それぞれ１６．２ｇ、１０．４ｇ、３．６ｇ、
３．５ｇ、２．２ｇ、及び１．４ｇに変えた以外同様な
方法で平均粒子径０．６μｍの顕色剤乳化分散液（Ｅ）
を作成した。印字方法及び性能評価 実施例５の感熱記録材料も実施例１記載同様の方法、性
能評価を行った。 （比較例１）実施例５で使用した感熱記録用塗布液
（５）中の顕色剤乳化分散液（Ｅ）を以下に記す（Ｆ）
液に変えた以外同様の方法で感熱記録用塗布液（６）を
使用した以外同様な方法で本発明の感熱記録材料を得
た。顕色剤乳化分散液（Ｆ）の調製 実施例１中に記載の顕色剤乳化分散液（Ａ）の調製方法
において、前記式（２−Ｉ）、（３−Ｉ）及び（１−
Ｉ）で表わされる化合物、それぞれ１８．７ｇ、１３．
１ｇ及び５．６ｇであるのを、前記式（２−Ｉ）、（３
−Ｉ）、（４−Ｉ）、（４−II）及び（５−Ｉ）、それ
ぞれ１７．９ｇ、１１．６ｇ、３．９ｇ、２．４ｇ及び
１．６ｇに変えた以外同様な方法で平均粒子径０．６μ
ｍの顕色剤乳化分散液（Ｅ）を作成した。印字方法及び性能評価 実施例５の感熱記録材料も実施例１記載同様の方法、性
能評価を行った。 （比較例２）実施例１で使用した感熱記録用塗布液
（１）中の顕色剤乳化分散液（Ａ）を以下に記す（Ｇ）
液に変えて作成した。顕色剤乳化分散液（Ｇ）の調製 実施例１中に記載の顕色剤乳化分散液（Ａ）の調製方法
において、前記式（２−Ｉ）、（３−Ｉ）及び（１−
Ｉ）で表わされる化合物、それぞれ１８．７ｇ、１３．
１ｇ及び５．６ｇであるのを、前記式（２−Ｉ）及び
（３−Ｉ）で表わされる化合物、それぞれ、１８．７
ｇ、１８．７ｇに変えた以外同様な方法で平均粒子径
０．６μｍの顕色剤乳化分散液（Ｇ）を作成した。１日経時後の顕色剤乳化分散液の様子 顕色剤乳化分散液（Ｇ）を室温にて１日静置させておい
たが１日後この液は析出を生じていた。よってこの
（Ｇ）液をカプセル液（ＭＣ１）及び（ＭＣ２）と混ぜ
塗布しても透明な感熱記録材料を提供できず、以降の印
字及び性能評価を打ち切った。 （比較例３）実施例１で使用した感熱記録用塗布液
（１）中の顕色剤乳化分散液（Ａ）を以下に記す（Ｉ）
液に変えて作成した。顕色剤乳化分散液（Ｉ）の調製 実施例１中に記載の顕色剤乳化分散液の調製方法におい
て、前記式（２−Ｉ）、（３−Ｉ）及び（１−Ｉ）で表
わされる化合物、それぞれ、１８．７ｇ、１３．１ｇ及
び５．６ｇであるのを、前記式（２−Ｉ）及び（４−
Ｉ）で表わされる化合物、それぞれ、１８．７ｇ、１
８．７ｇに変えた以外同様な方法で平均粒子径０．６μ
ｍの顕色剤乳化分散液（Ｉ）を作成した。１日経時後の顕色剤乳化分散液の様子 顕色剤乳化分散液（Ｉ）を室温にて１日静置させておい
たが１日後この液は析出を生じていた。よってこの
（Ｉ）液をカプセル液（ＭＣ１）及び（ＭＣ２）と混ぜ
塗布しても透明な感熱記録材料を提供できず、以降の印
字及び性能評価を打ち切った。 （比較例４）実施例１で使用した感熱記録用塗布液
（１）中の顕色剤乳化分散液（Ａ）を以下に記す（Ｊ）
液に変えて作成した。顕色剤乳化分散液（Ｊ）の調製 実施例１中に記載の顕色剤乳化分散液の調製方法におい
て、前記式（２−Ｉ）、（３−Ｉ）及び（１−Ｉ）で表
わされる化合物、それぞれ、１８．７ｇ、１３．１ｇ及
び５．６ｇであるのを、前記式（２−Ｉ）及び（４−I
I）で表わされる化合物、それぞれ、１８．７ｇ、１
８．７ｇに変えた以外同様な方法で平均粒子径０．６μ
ｍの顕色剤乳化分散液（Ｊ）を作成した。１日経時後の顕色剤乳化分散液の様子 顕色剤乳化分散液（Ｊ）を室温にて１日静置させておい
たが１日後この液は析出を生じていた。よってこの
（Ｊ）液をカプセル液（ＭＣ１）及び（ＭＣ２）と混ぜ
塗布しても透明な感熱記録材料を提供できず、以降の印
字及び性能評価を打ち切った。 （比較例５）実施例１で使用した感熱記録用塗布液
（１）中の顕色剤乳化分散液（Ａ）を以下に記す（Ｋ）
液に変えて作成した。顕色剤乳化分散液（Ｋ）の調製 実施例１中に記載の顕色剤乳化分散液の調製方法におい
て、前記式（２−Ｉ）、（３−Ｉ）及び（１−Ｉ）で表
わされる化合物、それぞれ、１８．７ｇ、１３．１ｇ及
び５．６ｇであるのを、前記式（２−Ｉ）及び（５−
Ｉ）で表わされる化合物、それぞれ、１８．７ｇ、１
８．７ｇに変えた以外同様な方法で平均粒子径０．６μ
ｍの顕色剤乳化分散液（Ｋ）を作成した。１日経時後の顕色剤乳化分散液の様子 顕色剤乳化分散液（Ｋ）を室温にて１日静置させておい
たが１日後この液は析出を生じていた。よってこの
（Ｋ）液をカプセル液（ＭＣ１）及び（ＭＣ２）と混ぜ
塗布しても透明な感熱記録材料を提供できず、以降の印
字及び性能評価を打ち切った。The obtained solution was treated with polybicol alcohol 15
% Solution (PVA205C: Kuraray Co., Ltd.) 25.0 g and polyvinyl alcohol 8% solution (PVA217C: Kuraray Co., Ltd.) 46 g, sodium dodecyl sulfonate 0.5
g and water (75.0 g) were mixed, and the mixture was emulsified by using an ace homogenizer at 10000 rpm for 3 minutes to emulsify an electron-accepting compound having an average particle size of 0.6 μm (hereinafter, referred to as a developer). A dispersion liquid (A) was obtained. Preparation of coating liquid for protective layer 30 g of water, polyvinyl alcohol 6% aqueous solution (PVA1
24C: trade name, manufactured by Kuraray Co., Ltd.) 20 g, 0.3 g of 2% aqueous solution of dioctyl sulfosuccinate sodium salt,
Kaolin dispersion (polyvinyl alcohol 3 g in water 100
To the liquid mixed with g, 3.0 g of kaolin 35 g dispersed by a pole mill) and 0.5 g of hydrin Z (trade name: manufactured by Chukyo Yushi Co., Ltd.) were mixed to obtain a coating liquid for protective layer. The prepared chromaticity coordinate (JIS Z8701) of the transparent support provided with the undercoat layer is A (x = 0.28).
05, y = 0.3005), B (x = 0.2820, y
= 0.2970), C (x = 0.2885, y = 0.3)
015), D (x = 0.2870, y = 0.3040)
The SBR latex was coated on one surface of polyethylene terephthalate having a thickness of 175 μm, which was colored in a rectangular area having four points as apexes, so that the solid content was 0.3 g / m 2, and The undercoat layer coating solution is applied so that the solid content weight per one side is 0.1 g / m 2, and
A transparent support provided with an undercoat layer was obtained. Preparation of coating liquid for undercoat layer 200% of 5% gelatin aqueous solution (# 810: trade name, manufactured by Nitta Gelatin Co., Ltd.), 0.5 g of gelatin dispersion in which 5% of polymethylmethacrylate resin particles having a particle diameter of 2 μm are dispersed,
1,2-benzothiazolin-3-one 3% aqueous solution 1.0
g, and 10 g of a 2% aqueous solution of di (2-ethyl) hexyl sulfonate were mixed to obtain a coating solution for undercoat layer. Preparation of coating liquid (1) for heat-sensitive recording layer 1.5 g of the capsule liquid (MC1) and 3.5 g of the capsule liquid (MC2) that have been prepared in advance. A thermosensitive recording coating solution (1) was obtained by mixing 15 g of water and 10 g of water. Preparation of heat-sensitive recording material The heat-sensitive recording coating solution (1) was applied to one surface of a transparent support provided with an undercoating layer, which had been prepared previously, to a solid content of 14 g / m 2 and dried. The prepared protective layer coating solution was applied and dried to a solid content of 2.5 g / m 2 to obtain a heat-sensitive recording material of the present invention. Printing method and performance evaluation The thermal recording material obtained was printed with a thermal printer (TRT-
16: An image (hereinafter referred to as a step edge) was recorded by using a trade name, manufactured by Nagano Japan Radio Co., Ltd., while changing the thermal energy applied to the thermal head. (Example 2) The developer dispersion (A) of the developer in the heat-sensitive recording-like coating liquid (1) used in Example 1 is described below (B).
A heat-sensitive recording material of the present invention was obtained by the same method except that the coating liquid (2) for heat-sensitive recording was prepared by the same method except that the liquid was changed. Preparation of Developer Emulsion Dispersion Liquid (B) In the method for preparing developer emulsion dispersion (A) described in Example 1, the compound represented by Formula (3-I) is replaced by Formula (4- A developer emulsified dispersion liquid (B) having an average particle diameter of 0.6 μm was prepared in the same manner except that the compound represented by I) was used. Printing Method and Performance Evaluation For the thermal recording material of Example 2, the same method and performance evaluation as in Example 1 were performed. (Example 3) An emulsion dispersion (A) of the developer in the coating liquid (1) for heat-sensitive recording used in Example 1 is described below (C).
The heat-sensitive recording material of the present invention was obtained by the same method except that the heat-sensitive recording coating liquid (3) was prepared by the same method except that the liquid was changed. Preparation of Developer Emulsion Dispersion Liquid (C) In the method for preparing developer emulsion dispersion (A) described in Example 1, the compound represented by Formula (3-I) is replaced by Formula (4- A developer emulsion dispersion (C) having an average particle diameter of 0.6 μm was prepared in the same manner except that the compound represented by II) was used. Printing Method and Performance Evaluation The thermal recording material of Example 3 was also subjected to the same method and performance evaluation as described in Example 1. (Example 4) The developer dispersion (A) of the developer in the coating liquid (1) for heat-sensitive recording used in Example 1 is described below (D).
A heat-sensitive recording material of the present invention was obtained by the same method except that the coating liquid (4) for heat-sensitive recording was prepared by the same method except that the liquid was changed. Preparation of Developer Emulsion Dispersion Liquid (D) In the method for preparing developer emulsion dispersion (A) described in Example 1, the compound represented by Formula (3-I) is replaced by Formula (5- A developer emulsion dispersion (D) having an average particle diameter of 0.6 μm was prepared in the same manner except that the compound represented by I) was used. Printing Method and Performance Evaluation The thermal recording material of Example 4 was also subjected to the same method and performance evaluation as in Example 1. (Example 5) The developer dispersion (A) of the developer in the coating liquid (1) for heat-sensitive recording used in Example 1 is described below (E).
A heat-sensitive recording material of the present invention was obtained by the same method except that the heat-sensitive recording coating liquid (5) was used in the same manner except that the liquid was changed. Preparation of Developer Emulsion Dispersion Liquid (E) In the method for preparing developer emulsion dispersion (A) described in Example 1, the formulas (2-I), (3-I) and (1-
Compounds represented by I), 18.7 g and 13.
1 g and 5.6 g correspond to the formulas (2-I) and (3
-I), (1-I), (4-I), (4-II) and (5
-I), 16.2 g, 10.4 g, 3.6 g, respectively.
Emulsion dispersion of developer (E) having an average particle diameter of 0.6 μm by the same method except that the amounts were changed to 3.5 g, 2.2 g and 1.4 g.
It was created. Printing Method and Performance Evaluation For the thermal recording material of Example 5, the same method and performance evaluation as in Example 1 were performed. (Comparative Example 1) The developer dispersion (E) of the developer in the coating liquid (5) for heat-sensitive recording used in Example 5 is described below (F).
A heat-sensitive recording material of the present invention was obtained by the same method except that the heat-sensitive recording coating liquid (6) was used in the same manner except that the liquid was changed. Preparation of Developer Emulsion Dispersion Liquid (F) In the method for preparing developer emulsion dispersion (A) described in Example 1, the formulas (2-I), (3-I) and (1-
Compounds represented by I), 18.7 g and 13.
1 g and 5.6 g correspond to the formulas (2-I) and (3
-I), (4-I), (4-II) and (5-I) in the same manner except that they were changed to 17.9 g, 11.6 g, 3.9 g, 2.4 g and 1.6 g, respectively. Average particle size 0.6μ
A developer emulsified dispersion (E) of m was prepared. Printing Method and Performance Evaluation For the thermal recording material of Example 5, the same method and performance evaluation as in Example 1 were performed. (Comparative Example 2) The developer dispersion (A) of the developer in the coating liquid (1) for heat-sensitive recording used in Example 1 is described below (G).
Created by changing to liquid. Preparation of Developer Emulsion Dispersion (G) In the method for preparing developer emulsion dispersion (A) described in Example 1, the formulas (2-I), (3-I) and (1-
Compounds represented by I), 18.7 g and 13.
1 g and 5.6 g are the compounds represented by the formulas (2-I) and (3-I), respectively, 18.7.
g and 18.7 g were used to prepare a color developer emulsion dispersion (G) having an average particle diameter of 0.6 μm by the same method. State of developer emulsion dispersion after 1 day of aging The developer emulsion dispersion (G) was allowed to stand at room temperature for 1 day, but after 1 day, this liquid was causing precipitation. Therefore, even if this liquid (G) was mixed with the capsule liquids (MC1) and (MC2) and applied, a transparent heat-sensitive recording material could not be provided, and the subsequent printing and performance evaluation were terminated. (Comparative Example 3) The color developer emulsified dispersion (A) in the thermal recording coating liquid (1) used in Example 1 is described below (I).
Created by changing to liquid. Preparation of Developer Emulsion Dispersion Liquid (I) In the method for preparing a developer emulsion dispersion described in Example 1, it is represented by the above formulas (2-I), (3-I) and (1-I). The compounds represented by the formulas (2-I) and (4-) are 18.7 g, 13.1 g and 5.6 g, respectively.
Compounds represented by I), 18.7 g, 1 respectively
The average particle size was 0.6μ in the same manner except that the average particle size was changed to 8.7g.
m developer dispersion (I) was prepared. State of color developer emulsion dispersion after 1 day of aging The color developer emulsion dispersion (I) was allowed to stand at room temperature for 1 day, but after 1 day, this liquid had precipitated. Therefore, even if this liquid (I) was mixed with the capsule liquids (MC1) and (MC2) and applied, a transparent heat-sensitive recording material could not be provided, and the subsequent printing and performance evaluation were terminated. (Comparative Example 4) The developer dispersion (A) of the developer in the coating liquid (1) for heat-sensitive recording used in Example 1 is described below (J).
Created by changing to liquid. Preparation of Developer Emulsion Dispersion Liquid (J) In the method for preparing a developer emulsion dispersion described in Example 1, it is represented by the formula (2-I), (3-I) and (1-I). The compounds represented by the above formulas (2-I) and (4-I) are 18.7 g, 13.1 g and 5.6 g, respectively.
Compounds represented by I), 18.7 g, 1 respectively
The average particle size was 0.6μ in the same manner except that the average particle size was changed to 8.7g.
m developer dispersion (J) was prepared. State of color developer emulsion dispersion after 1 day of aging The color developer emulsion dispersion (J) was allowed to stand at room temperature for 1 day, but after 1 day, this liquid had precipitated. Therefore, even if this liquid (J) was mixed with the capsule liquids (MC1) and (MC2) and applied, a transparent heat-sensitive recording material could not be provided, and the subsequent printing and performance evaluation were terminated. (Comparative Example 5) The developer emulsified dispersion liquid (A) in the thermal recording coating liquid (1) used in Example 1 is described below (K).
Created by changing to liquid. Preparation of Developer Emulsion Dispersion Liquid (K) In the method for preparing a developer emulsion dispersion described in Example 1, it is represented by the formula (2-I), (3-I) and (1-I). The compounds represented by the formulas (2-I) and (5-) are 18.7 g, 13.1 g and 5.6 g, respectively.
Compounds represented by I), 18.7 g, 1 respectively
The average particle size was 0.6μ in the same manner except that the average particle size was changed to 8.7g.
m developer dispersion (K) was prepared. State of color developer emulsion dispersion after 1 day of aging The color developer emulsion dispersion (K) was allowed to stand at room temperature for 1 day, but after 1 day, this liquid had precipitated. Therefore, even if this liquid (K) was mixed with the capsule liquids (MC1) and (MC2) and applied, a transparent heat-sensitive recording material could not be provided, and the subsequent printing and performance evaluation were terminated.
【００７２】顕色剤乳化分散液の安定性評価 実施例１〜５及び比較例１〜６の顕色剤乳化分散液を作
成した後、経時１日における状態を目視で観察した結果
を下記表１に示す。 Evaluation of Stability of Developer Emulsion Dispersion Solution After the developer emulsion dispersions of Examples 1 to 5 and Comparative Examples 1 to 6 were prepared, the results obtained by visually observing the state one day later were shown in the table below. Shown in 1.
【００７３】[0073]
【表１】 [Table 1]
【００７４】表１に明らかなように、本発明の一般式
（１）で表される化合物を顕色剤（電子受容性化合物）
とともに添加した実施例１〜５の顕色剤乳化物は、乳化
安定性が良好で析出を生じなかったが、本発明の一般式
（１）で表される化合物を添加していない比較例２〜６
の顕色剤乳化物は１日経時後に析出が生じたため、染料
含有カプセル液と混ぜて塗布しても透明な感熱記録材料
を提供できず、使用に適さないことがわかった。As is clear from Table 1, the compound represented by the general formula (1) of the present invention is a developer (electron-accepting compound).
The developer emulsions of Examples 1 to 5 added together with the emulsion had good emulsion stability and did not cause precipitation, but Comparative Example 2 in which the compound represented by the general formula (1) of the present invention was not added. ~ 6
It was found that since the emulsion of the developer of No. 1 was precipitated after a lapse of one day, a transparent heat-sensitive recording material could not be provided even when mixed with the dye-containing capsule liquid and applied, and was not suitable for use.
【００７５】次に、１日経時した後に析出を生じていな
い顕色剤乳化分散液（実施例１〜５及び比較例１）を用
いた感熱記録材料について、サーマルプリンター（ＴＲ
Ｔ−１６）を用いて、印加エネルギー９０又は１００ｍ
ｊ／ｍｍ2 として印字した場合のステップエッジの様子
を下記表２に示す。Next, a thermal printer (TR) was used for thermal recording materials using the developer dispersion liquids (Examples 1 to 5 and Comparative Example 1) which did not cause precipitation after one day.
T-16), applied energy 90 or 100 m
The state of the step edge when printed as j / mm 2 is shown in Table 2 below.
【００７６】[0076]
【表２】 [Table 2]
【００７７】表２に明らかなように、本発明の一般式
（１）で表される化合物を電子受容性化合物とともに添
加した実施例１〜５の感熱記録材料は、９０ｍｊ／ｍｍ
2 で印字したところ塗膜状態は良好であった。また、１
００ｍｊ／ｍｍ2 で印字したところ実施例５感熱記録材
料の塗膜状態は良好であり、実施例１〜４の感熱記録材
料にもほとんどはがれは見られず実用上問題のない印字
レベルであったが、比較例１の感熱記録材料は前記いず
れの条件においても塗膜にはがれが発生し、良好な印字
は得られなかった。As is clear from Table 2, the heat-sensitive recording materials of Examples 1 to 5 to which the compound represented by the general formula (1) of the present invention was added together with the electron-accepting compound were 90 mj / mm.
When printed with 2 , the state of the coating film was good. Also, 1
When printed at 00 mj / mm 2 , the coating state of the heat-sensitive recording materials of Example 5 was good, and almost no peeling was observed in the heat-sensitive recording materials of Examples 1 to 4, and the print level was practically no problem. However, in the heat-sensitive recording material of Comparative Example 1, peeling occurred in the coating film under any of the above conditions, and good printing could not be obtained.
【００７８】[0078]
【発明の効果】本発明の感熱記録材料は、前記の如く、
高エネルギーを印加した場合にも感熱記録層が影響を受
けることなく、良好な画像形成を行なうことができ、電
子受容性化合物の乳化状態が長期間安定であるという優
れた効果を示した。The heat-sensitive recording material of the present invention, as described above,
Even when a high energy was applied, the heat-sensitive recording layer was not affected and good image formation could be performed, and the excellent effect that the emulsified state of the electron-accepting compound was stable for a long time was shown.
Claims (4)
材料において、 感熱記録層が電子供与性無色染料、電子受容性化合物及
び下記一般式（１）で表される化合物の一種又は二種以
上を含有することを特徴とする感熱記録材料。 【化１】 式中、Ｒ1 は、水素原子又は炭素数１〜８のアルキル基
を表し、Ｒ2 は、炭素数３〜８の分岐アルキル基を表
し、Ｒ3 は、−（ＣＨ2 ）l −又は−（ＣＨ2 ） m −Ｏ
−（ＣＨ2 ）n −を表し、ｌ、ｍ、ｎはそれぞれ１〜５
の整数を表す。1. A thermosensitive recording comprising a thermosensitive recording layer provided on a support.
In the material, the thermosensitive recording layer contains an electron-donating colorless dye, an electron-accepting compound and
And one or more compounds represented by the following general formula (1)
A heat-sensitive recording material containing the above. [Chemical 1]Where R1Is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
Represents R2Represents a branched alkyl group having 3 to 8 carbon atoms.
Then R3Is-(CH2)l-Or- (CH2) m-O
-(CH2)nRepresents −, and l, m, and n are each 1 to 5
Represents the integer.
（２）で表される化合物を含有し、さらに、前記感熱記
録層に下記一般式（３）、下記一般式（４）及び下記一
般式（５）で表される化合物からなる群から選ばれる一
種又は二種以上を含有することを特徴とする請求項１記
載の感熱記録材料。 【化２】 式中、ＭｅはＺｎ、Ｃａ又はＡｌを表し、ｎは２又は３
の整数を表す。 【化３】 式中、Ｒ4 及びＲ7 はそれぞれ独立に炭素数３〜８の分
岐アルキル基を表し、Ｒ5 及びＲ6 はそれぞれ独立に炭
素数１〜８のアルキル基を表し、ｎは０又は１若しくは
２の整数を表す。 【化４】 式中、Ｒ8 及びＲ11はそれぞれ独立に炭素数３〜８の分
岐アルキル基を表し、Ｒ9 及びＲ10はそれぞれ独立に炭
素数１〜８のアルキル基を表し、ＸはＳ、Ｏ、ＳＯ2 、
Ｓ2 又は下記一般式（４Ｂ）を表す。 【化５】 式中、Ｒ12及びＲ13はそれぞれ独立に、水素原子又は炭
素数１〜８のアルキル基を表し、ｎは０又は１〜３の整
数を表す。 【化６】 式中、Ｒ14及びＲ15はそれぞれ独立に炭素数３〜８の分
岐アルキル基を表し、Ｒ16は炭素数３〜２０のアルキル
基を表す。2. The electron-accepting compound contains a compound represented by the following general formula (2), and the thermosensitive recording layer further contains the following general formula (3), the following general formula (4) and the following general formula. The heat-sensitive recording material according to claim 1, containing one or more selected from the group consisting of the compounds represented by (5). Embedded image In the formula, Me represents Zn, Ca or Al, and n is 2 or 3
Represents the integer. Embedded image In the formula, R 4 and R 7 each independently represent a branched alkyl group having 3 to 8 carbon atoms, R 5 and R 6 each independently represent an alkyl group having 1 to 8 carbon atoms, and n is 0 or 1 or Represents an integer of 2. [Chemical 4] In the formula, R 8 and R 11 each independently represent a branched alkyl group having 3 to 8 carbon atoms, R 9 and R 10 each independently represent an alkyl group having 1 to 8 carbon atoms, and X represents S, O, SO 2 ,
It represents S 2 or the following general formula (4B). Embedded image In the formula, R 12 and R 13 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and n represents 0 or an integer of 1 to 3. [Chemical 6] In the formula, R 14 and R 15 each independently represent a branched alkyl group having 3 to 8 carbon atoms, and R 16 represents an alkyl group having 3 to 20 carbon atoms.
セルに内包され、前記感熱記録層に含まれる一般式
（１）乃至一般式（５）で表される化合物が乳化分散物
として存在し、前記感熱記録層が実質的に透明であるこ
とを特徴とする請求項１又は２記載の感熱記録材料。3. The electron-donating colorless dye is encapsulated in microcapsules, and the compounds represented by the general formulas (1) to (5) contained in the heat-sensitive recording layer are present as an emulsified dispersion. The heat-sensitive recording material according to claim 1, wherein the heat-sensitive recording layer is substantially transparent.
般式（２）で表される化合物において、式中のＭｅがＺ
ｎであることを特徴とする請求項２記載の感熱記録材
料。4. In the compound represented by the general formula (2) contained in the electron-accepting compound, Me in the formula is Z.
The thermal recording material according to claim 2, wherein the thermal recording material is n.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12157395A JP3691543B2 (en) | 1995-05-19 | 1995-05-19 | Thermal recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12157395A JP3691543B2 (en) | 1995-05-19 | 1995-05-19 | Thermal recording material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08310117A true JPH08310117A (en) | 1996-11-26 |
| JP3691543B2 JP3691543B2 (en) | 2005-09-07 |
Family
ID=14814586
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12157395A Expired - Fee Related JP3691543B2 (en) | 1995-05-19 | 1995-05-19 | Thermal recording material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3691543B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190113782A (en) * | 2017-02-17 | 2019-10-08 | 소시에떼 빅 | Novel thermosensitive pigment compositions comprising a compound of formula (I) as a reaction medium |
-
1995
- 1995-05-19 JP JP12157395A patent/JP3691543B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190113782A (en) * | 2017-02-17 | 2019-10-08 | 소시에떼 빅 | Novel thermosensitive pigment compositions comprising a compound of formula (I) as a reaction medium |
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| Publication number | Publication date |
|---|---|
| JP3691543B2 (en) | 2005-09-07 |
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