JPH0472866B2 - - Google Patents
Info
- Publication number
- JPH0472866B2 JPH0472866B2 JP7181684A JP7181684A JPH0472866B2 JP H0472866 B2 JPH0472866 B2 JP H0472866B2 JP 7181684 A JP7181684 A JP 7181684A JP 7181684 A JP7181684 A JP 7181684A JP H0472866 B2 JPH0472866 B2 JP H0472866B2
- Authority
- JP
- Japan
- Prior art keywords
- methyl
- fluoroanilino
- dibutylamino
- parts
- type
- 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.)
- Expired
Links
- 238000012986 modification Methods 0.000 claims description 15
- 230000004048 modification Effects 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 10
- 238000002441 X-ray diffraction Methods 0.000 claims description 8
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 claims description 7
- 238000010586 diagram Methods 0.000 claims description 4
- 229910017488 Cu K Inorganic materials 0.000 claims 1
- 229910017541 Cu-K Inorganic materials 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000007788 liquid Substances 0.000 description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 10
- 238000004040 coloring Methods 0.000 description 10
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 10
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 7
- 230000009466 transformation Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003086 colorant Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000004383 yellowing Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001555 benzenes Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000029052 metamorphosis Effects 0.000 description 2
- DMLQZTMMXYDSAV-UHFFFAOYSA-N n,4-difluoroaniline Chemical compound FNC1=CC=C(F)C=C1 DMLQZTMMXYDSAV-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- QPNFUBAIQZJEPO-UHFFFAOYSA-N 2-[4-(dibutylamino)-2-hydroxybenzoyl]benzoic acid Chemical compound OC1=CC(N(CCCC)CCCC)=CC=C1C(=O)C1=CC=CC=C1C(O)=O QPNFUBAIQZJEPO-UHFFFAOYSA-N 0.000 description 1
- -1 3-(4-dibutylamino-2-hydroxyphenyl)-3-[5- (p-fluoroanilino)-2-methoxy-4-methylphenyl]phthalide Chemical compound 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- WPYMKLBDIGXBTP-VQEHIDDOSA-N benzoic acid Chemical compound OC(=O)C1=CC=C[13CH]=C1 WPYMKLBDIGXBTP-VQEHIDDOSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000005506 phthalide group Chemical class 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 230000016776 visual perception Effects 0.000 description 1
Description
本発明は３−ジブチルアミノ−６−メチル−７
−（4′−フルオロアニリノ）フルオランの結晶変
態に関する。更に詳しくはCu−Kα線によるＸ線
回折法における回折角（2θ）6.9°及び19.1°に強い
ピーク、11.1°、17.5°、18.5°、18.7°、22.3°、22
.8°
及び23.9°に中間強度のピークを示すＸ線回折図
により特徴づけられる３−ジブチルアミノ−６−
メチル−７−（4′−フルオロアニリノ）フルオラ
ンの結晶変態（以下これをβ型変態と称する）に
関するものである。
従来より、電子供与性無色染料（発色剤）と電
子受容性物質（顕色剤）とを物理的な力または熱
により接触せしめて起る呈色反応を利用し発色画
像を得る感圧複写法または感熱記録法は良く知ら
れており、本発明で扱う３−ジブチルアミノ−６
−メチル−７−（4′−フルオロアニリノ）フルオ
ランはそれらのうちの発色剤として用いられるも
のである。かかる感圧複写または感熱記録用発色
剤としては発色感度、発色濃度、地発色性等の発
色特性及びい発色後の諸堅牢度に優れていること
が要求されるがこれらの性能のすべてを満足させ
る発色剤は少ない。例えば３−ジブチルアミノ−
６−メチル−７−（4′−フルオロアニリノ）フル
オランは通常えられる結晶形のものを感熱記録用
発色剤として用いたのでは前記したような発色特
性、殊に自己発色性及び経時における黄変性の点
で十分満足出来る結果がえられない。
本発明者らは３−ジブチルアミノ−６−メチル
−７−（4′−フルオロアニリノ）フルオランの結
晶型とそれを用いた感熱記録材の発色特性及び経
時黄変性との関係を鋭意検討した結果、本化合物
には２種類の結晶変態が存在することを見い出し
た。即ち淡桃色の結晶で、感熱記録用発色剤とし
て使用した場合、発色感度、発色画像の諸堅牢度
等には優れているが、自己発色性及び地肌の日光
による経時黄変性が大きいという欠点をもつ結晶
変態（以下これをα型変態と称する）と、白桃色
を呈し、発色感度、発色画像の諸堅牢度はα型変
態と同等であるが、自己発色性並びに地肌の日光
による経時黄変性が非常に小さい結晶（β型変
態）の２種である。
３−ジブチルアミノ−６−メチル−７−（4′−
フルオロアニリノ）フルオランは通常の方法に従
い例えば次の様にして製造される。即ち、２−
（4′−ジブチルアミノ−2′−ヒドロキシベンゾイ
ル）安息香酸と4′−フルオロ−４−メトキシ−２
−メチル−ジフエニルアミンとを硫酸（脱水縮合
剤）の存在で−10〜150℃好ましくは０〜30℃で
数時間乃至数10時間反応させる。次いで反応液を
氷水中に注入し、生じた沈澱を必要に応じて別
した後、苛性カリ、苛性ソーダ等のアルカリ水溶
液とトルエン等の有機溶媒との混合液中で80〜85
℃、１〜３時間加熱することにより閉環する。次
に反応液を静置し分液後、有機溶媒層を濃縮し、
その濃縮液にメタノール又はエタノールを添加し
て結晶を析出させることによりα型変態がえられ
る。
このようなα型変態を２〜10倍量のモノクロル
ベンゼン、ジクロロベンゼン、トリクロロベンゼ
ン等のクロル化ベンゼンで70〜150℃、30分〜３
時間、より好ましくは90℃〜120℃、１〜２時間
処理することによつてβ型変態が得られる。
又３−ブチルアミノ−６−メチル−７−（4′−
フルオロアニリノ）フルオラン合成の中間生成物
であるフタリドを取したあと前記したクロル化
ベンゼンとカセイアルカリ水溶液との混合液で閉
環したあと分液して３−ブチルアミノ−６−メチ
ル−７−（4′−フルオロアニリノ）フルオランを
含んだクロル化ベンゼン溶液を前記したような温
度および時間で処理することによつてもβ型変態
がえられる。
次に３−ジブチルアミノ−６−メチル−７−
（4′−フルオロアニリノ）フルオランのα型変態
及びβ型変態を図面によつて説明する。第１図お
よび第２図は、粉体Ｘ線回折法によるものであ
り、Cu−Kα線による回折状態をプロポーシヨナ
ルカウンターを使用して記録した図である。第１
図はβ型変態のものであり、回折角（2θ）6.9°及
び19.1°に強いピーク、11.1°、17.5°、18.5°、18.7
°、
22.3°、22.8°及び23.9°に中間強度のピークを示し
ている。第２図はα型変態のものであり、回折角
（2θ）11.8°及び20.7°に強いピークを示している他
α型結晶のピークとは明瞭に相違したピークを示
している。（回折角度の表示において±0.2°程度
の誤差は許容されるものとする）そして前記した
処理法においてα型変態が本発明のβ型変態に変
換されたかどうかはＸ線回折図を測定することに
よつて判定されるが、より簡単な識別方法として
は、試料の融点を測定することによつても判定さ
れる。即ち、α型変態がm.p.135〜137℃であるの
に対し、β型変態はm.p.169〜171℃を示す。
次に、実施例並びに比較試験を挙げて本発明を
具体的に説明する。（実施例、比較試験中、部は
重量部を示す）
参考例
３−ブチルアミノ−６−メチル−７−（4′−フ
ルオロアニリノ）フルオランの合成
２−（4′−ジブチルアミノ−2′−ヒドロキシベ
ンゾイル）安息香酸36.9部、4′−フルオロ−４−
メトキシ−２−メチル−ジフエニルアミン23.1部
を濃硫酸200mlに加え、０〜５℃で20時間反応さ
せた後、氷水あけして生じた結晶を過し、水１
で水洗しフタリドケーキ（３−（４−ジブチル
アミノ−２−ヒドロキシフエニル）−３−〔５−
（ｐ−フルオロアニリノ）−２−メトキシ−４−メ
チルフエニル〕フタリド）を得る。このフタリド
ケーキをモノクロルベンゼン200ml、水100mlから
なる混合液に加え28％苛性ソーダで中和後、苛性
ソーダ４部を加えて80〜85℃で３時間撹拌する。
静置後モノクロルベンゼン層を分液して、70℃以
上を保ちつつ、シロツプ状物を得るまで濃縮した
後、メタノール300mlを加えて結晶を析出させる
ことにより、淡桃色の第２図のＸ線回折図を示す
３−ジブチルアミノ−６−メチル−７−（4′−フ
ルオロアニリノ）フルオランのα型変態41部得
た。（mp＝135〜137℃）
実施例 １
前記のα型変態の３−ジブチルアミノ−６−メ
チル−７−（4′−フルオロアニリノ）フルオラン
41部にｏ−ジクロロベンゼン100mlを加え100〜
110℃で１時間処理して乳白色のβ型変態38部を
得た。このものは第１図で示されるようなＸ線回
折図を与えた。（mp＝169〜171℃）
実施例 ２
前記参考例におけるのと同様にしてえられたフ
タリドケーキをモノクロルベンゼン200mlと水100
mlからなる混合液に加え、28％苛性ソーダで中和
後、苛性ソーダ４部を加えて80〜85℃で３時間撹
拌する。静置後分液して減圧下でモノクロルベン
ゼン100mlを留去したあと３−ブチルアミノ−６
−メチル−７−（4′−フルオロアニリノ）フルオ
ランを含むモノクロルベンゼンを110〜120℃で90
分処理して白桃色の第１図のＸ線回折図をβ型変
態の３−ブチルアミノ−６−メチル−７−（4′−
フルオロアニリノ）フルオラン40部を得た。（mp
＝169〜171℃）
比較試験
３−ジブチルアミノ−６−メチル−７−（4′−
フルオロアニリノ）フルオランのα型及びβ型変
態の感熱記録紙に与える効果につて比較する為に
次の比較試験を実施した。
〔Ａ〕液
α型またはβ型変態の３−ジブチルアミノ−６
−メチル−７−（4′−フルオロアニリノ）フル
オラン 15.0部
ゴーセノールGL−0.5H（25％水溶液）（日本合
成） 12.0部
水 33.0部
〔Ｂ〕液
ビスフエノールＡ 34.5部
ゴーセノールGL−0.5H（25％水溶液） 20.0部
水 110.0部
〔Ａ〕、〔Ｂ〕両液をそれぞれ別個にサンドグラ
インダーを用いて平均粒径が１〜3μになる様に
粉砕分散化して〔Ａ〕及び〔Ｂ〕液の分散液を調
製した。また、下記組成物より成る混合分をサン
ドグラインダーで２時間粉砕、分散化して〔Ｃ〕
液の分散液を調製した。
〔Ｃ〕液
アーマイドHT−Ｐ（ライオンアクゾ社製）
29.5部
炭酸カルシウム 60.0部
ゴーセノールGL−0.5H（25％水溶液） 20.0部
水 109.0部
次いで〔Ａ〕液の分散液：〔Ｂ〕液の分散液：
〔Ｃ〕液の分散液を６：47：47の割合で混合して
感熱発色層形成液を調製し、坪量約50ｇ／m2の上
質紙表面に乾燥固形分が５ｇ／m2となるように塗
布、乾燥し、α型変態、β型変態の３−ジブチル
アミノ−６−メチル−７−（4′−フルオロアニリ
ノ）フルオランを含有する感熱記録紙を得た。
α型変態およびβ型変態の感熱記録紙を用いて
比較試験を行つた結果を次表に示した。
The present invention provides 3-dibutylamino-6-methyl-7
- Concerning the crystal modification of (4'-fluoroanilino)fluorane. More details include strong peaks at diffraction angles (2θ) of 6.9° and 19.1° in X-ray diffraction using Cu-Kα rays, 11.1°, 17.5°, 18.5°, 18.7°, 22.3°, 22
.8°
and 3-dibutylamino-6- characterized by an X-ray diffraction diagram showing a peak of intermediate intensity at 23.9°
This invention relates to a crystal modification (hereinafter referred to as β-type modification) of methyl-7-(4'-fluoroanilino)fluorane. Conventionally, a pressure-sensitive copying method is used to obtain colored images using a color reaction that occurs when an electron-donating colorless dye (color former) and an electron-accepting substance (color developer) are brought into contact with each other using physical force or heat. Alternatively, the thermal recording method is well known, and the 3-dibutylamino-6
-Methyl-7-(4'-fluoroanilino)fluorane is used as a coloring agent. Coloring agents for such pressure-sensitive copying or heat-sensitive recording are required to have excellent coloring characteristics such as coloring sensitivity, coloring density, and background coloring, as well as various fastnesses after coloring, all of which are satisfied. There are few coloring agents. For example, 3-dibutylamino-
6-Methyl-7-(4'-fluoroanilino)fluorane, which is normally available in crystalline form, is used as a coloring agent for heat-sensitive recording. Fully satisfactory results cannot be obtained in terms of denaturation. The present inventors have intensively investigated the relationship between the crystal form of 3-dibutylamino-6-methyl-7-(4'-fluoroanilino)fluoran, the coloring characteristics of heat-sensitive recording materials using it, and yellowing over time. As a result, it was found that this compound has two types of crystal modifications. In other words, it is a pale pink crystal, and when used as a coloring agent for heat-sensitive recording, it has excellent coloring sensitivity and various fastnesses of colored images, but it has the drawbacks of self-coloring and large yellowing of the skin over time due to sunlight. It exhibits a white-pink color, and the color sensitivity and color fastness of the color image are the same as the α-type transformation, but it has self-coloring property and yellowing of the skin over time due to sunlight. There are two types of very small crystals (β-type modification). 3-dibutylamino-6-methyl-7-(4'-
Fluoroanilino)fluorane is produced according to a conventional method, for example, as follows. That is, 2-
(4'-dibutylamino-2'-hydroxybenzoyl)benzoic acid and 4'-fluoro-4-methoxy-2
-Methyl-diphenylamine is reacted with sulfuric acid (dehydration condensation agent) at -10 to 150°C, preferably 0 to 30°C for several hours to several tens of hours. Next, the reaction solution was poured into ice water, and after separating the resulting precipitate as necessary, it was heated to 80-85% in a mixture of an aqueous alkali solution such as caustic potash or caustic soda and an organic solvent such as toluene.
C. for 1 to 3 hours to close the ring. Next, the reaction solution was allowed to stand still and the organic solvent layer was concentrated.
α-type modification can be obtained by adding methanol or ethanol to the concentrated solution to precipitate crystals. This α-type transformation is carried out with 2 to 10 times the amount of chlorinated benzene such as monochlorobenzene, dichlorobenzene, trichlorobenzene, etc. at 70 to 150°C for 30 minutes to 30 minutes.
By treating for 1 to 2 hours, preferably at 90°C to 120°C, β-type transformation can be obtained. Also, 3-butylamino-6-methyl-7-(4'-
After removing phthalide, which is an intermediate product in the synthesis of fluoroanilino)fluorane, the ring was closed with the above-mentioned mixture of chlorinated benzene and caustic aqueous solution, and the liquid was separated to obtain 3-butylamino-6-methyl-7-( The β-type transformation can also be obtained by treating a chlorinated benzene solution containing 4'-fluoroanilino)fluorane at the temperature and time described above. Then 3-dibutylamino-6-methyl-7-
The α-type modification and β-type modification of (4'-fluoroanilino)fluorane will be explained with reference to the drawings. FIGS. 1 and 2 are diagrams obtained by powder X-ray diffraction, in which the diffraction state of Cu-Kα rays was recorded using a proportional counter. 1st
The figure shows the β-type transformation, with strong peaks at diffraction angles (2θ) of 6.9° and 19.1°, 11.1°, 17.5°, 18.5°, and 18.7°.
°,
It shows intermediate intensity peaks at 22.3°, 22.8° and 23.9°. Figure 2 shows the α-type modification, which shows strong peaks at diffraction angles (2θ) of 11.8° and 20.7°, as well as peaks that are clearly different from the peaks of the α-type crystal. (An error of approximately ±0.2° is allowed in the display of diffraction angles.) Whether or not the α-type modification has been converted to the β-type modification of the present invention in the above-mentioned treatment method can be determined by measuring the X-ray diffraction pattern. However, a simpler method of identification is to measure the melting point of the sample. That is, while α-type metamorphosis has a mp of 135 to 137°C, β-type metamorphosis has a mp of 169 to 171°C. Next, the present invention will be specifically explained with reference to Examples and comparative tests. (In Examples and Comparative Tests, parts indicate parts by weight) Reference Example 3 Synthesis of 2-(4'-dibutylamino-2'-butylamino-6-methyl-7-(4'-fluoroanilino)fluoran) -hydroxybenzoyl)benzoic acid 36.9 parts, 4'-fluoro-4-
Add 23.1 parts of methoxy-2-methyl-diphenylamine to 200 ml of concentrated sulfuric acid and react at 0 to 5°C for 20 hours.
The phthalide cake (3-(4-dibutylamino-2-hydroxyphenyl)-3-[5-
(p-fluoroanilino)-2-methoxy-4-methylphenyl]phthalide) is obtained. This phthalide cake is added to a mixture of 200 ml of monochlorobenzene and 100 ml of water, neutralized with 28% caustic soda, and then 4 parts of caustic soda are added and stirred at 80-85°C for 3 hours.
After standing still, the monochlorobenzene layer was separated and concentrated until a syrup-like substance was obtained while keeping the temperature above 70°C, and then 300 ml of methanol was added to precipitate crystals. 41 parts of α-modified 3-dibutylamino-6-methyl-7-(4'-fluoroanilino)fluoran having a diffraction pattern were obtained. (mp=135-137°C) Example 1 The α-modified 3-dibutylamino-6-methyl-7-(4′-fluoroanilino)fluoran
Add 100ml of o-dichlorobenzene to 41 parts and add 100~
After treatment at 110° C. for 1 hour, 38 parts of milky-white β-type modified product were obtained. This gave an X-ray diffraction pattern as shown in FIG. (mp=169-171°C) Example 2 A phthalide cake obtained in the same manner as in the reference example above was mixed with 200 ml of monochlorobenzene and 100 ml of water.
After neutralizing with 28% caustic soda, add 4 parts of caustic soda and stir at 80-85°C for 3 hours. After standing still, the liquid was separated and 100ml of monochlorobenzene was distilled off under reduced pressure, and 3-butylamino-6
-Methyl-7-(4'-fluoroanilino)fluorane-containing monochlorobenzene at 110-120℃ at 90℃
After separation, the white-pink X-ray diffraction pattern shown in Figure 1 was obtained from the β-modified 3-butylamino-6-methyl-7-(4'-
40 parts of fluorane (fluoroanilino) were obtained. (mp.
= 169-171℃) Comparative test 3-dibutylamino-6-methyl-7-(4'-
In order to compare the effects of α-type and β-type modifications of fluoroanilino)fluorane on thermal recording paper, the following comparative test was conducted. [A] Liquid α-type or β-type modified 3-dibutylamino-6
-Methyl-7-(4'-fluoroanilino)fluoran 15.0 parts Gohsenol GL-0.5H (25% aqueous solution) (Nippon Gosei) 12.0 parts Water 33.0 parts [B] Liquid Bisphenol A 34.5 parts Gohsenol GL-0.5H ( 25% aqueous solution) 20.0 parts Water 110.0 parts Both [A] and [B] liquids were ground and dispersed separately using a sand grinder so that the average particle size was 1 to 3μ. A dispersion was prepared. In addition, a mixture consisting of the following composition was ground and dispersed using a sand grinder for 2 hours [C]
A liquid dispersion was prepared. [C] Liquid Aramide HT-P (manufactured by Lion Akzo)
29.5 parts Calcium carbonate 60.0 parts Gohsenol GL-0.5H (25% aqueous solution) 20.0 parts Water 109.0 parts Then [A] liquid dispersion: [B] liquid dispersion:
[C] Mix the dispersion of liquid at a ratio of 6:47:47 to prepare a thermosensitive coloring layer forming liquid, and the dry solid content will be 5 g/m 2 on the surface of high-quality paper with a basis weight of about 50 g/m 2 The coating was coated and dried in the same manner as above to obtain a thermosensitive recording paper containing α-modified and β-modified 3-dibutylamino-6-methyl-7-(4'-fluoroanilino)fluoran. The following table shows the results of a comparative test using thermosensitive recording paper of α-type transformation and β-type transformation.
【表】
●地発色濃度：マクベクス濃度計RD−914で測
定。
●黄変性：感熱記録紙を窓際に98時間放置したと
きの感熱記録紙の地色発色度を黄変性とした。
視感により次の判定により評価し、又
○：良い ×：悪い
同じ試料につきマクベス濃度計RD−914で発
色度を測定した。上記表の「黄色性」の欄の
×、○は視感により判定、又（ ）の数値は
RD−914による測定値である。[Table] ●Ground color density: Measured with MacBex Densitometer RD-914. ●Yellowing: The degree of color development of the background color of thermal recording paper when it was left near a window for 98 hours was defined as yellowing. Visual evaluation was made according to the following criteria, and the degree of color development of the same sample was measured using a Macbeth densitometer RD-914. × and ○ in the “yellowness” column of the table above are determined by visual perception, and the numbers in parentheses are
This is a measurement value using RD-914.
第１図および第２図は３−ジブチルアミノ−６
−メチル−７−（4′−フルオロアニリノ）フルオ
ランのβ型変態およびα型変態のＸ線回折図であ
る。図面において、横軸は回折角（2θ）を表わ
し、縦軸は回折強度を表わす。
Figures 1 and 2 show 3-dibutylamino-6
-Methyl-7-(4'-fluoroanilino)fluorane - X-ray diffraction diagrams of β-type modification and α-type modification. In the drawings, the horizontal axis represents the diffraction angle (2θ), and the vertical axis represents the diffraction intensity.
Claims (1)
（2θ）6.9°及び19.1°に強いピーク、11.1°、17.5°
、
18.5°、18.7°、22.3°、22.8°及び23.9°に中間強度
の
ピークを示すＸ線回折図により特徴づけられる３
−ジブチルアミノ−６−メチル−７−（4′−フル
オロアニリノ）フルオランの結晶変態。1 Strong peaks at diffraction angles (2θ) of 6.9° and 19.1°, 11.1° and 17.5° in X-ray diffraction using Cu-K rays
,
3 characterized by an X-ray diffraction diagram showing intermediate intensity peaks at 18.5°, 18.7°, 22.3°, 22.8° and 23.9°.
-Crystal modification of dibutylamino-6-methyl-7-(4'-fluoroanilino)fluoran.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7181684A JPS60217267A (en) | 1984-04-12 | 1984-04-12 | Crystal modification of 3-dibutylamino-6-methyl-7-(4'- fluoroanilino)fluorane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7181684A JPS60217267A (en) | 1984-04-12 | 1984-04-12 | Crystal modification of 3-dibutylamino-6-methyl-7-(4'- fluoroanilino)fluorane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60217267A JPS60217267A (en) | 1985-10-30 |
| JPH0472866B2 true JPH0472866B2 (en) | 1992-11-19 |
Family
ID=13471457
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7181684A Granted JPS60217267A (en) | 1984-04-12 | 1984-04-12 | Crystal modification of 3-dibutylamino-6-methyl-7-(4'- fluoroanilino)fluorane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60217267A (en) |
-
1984
- 1984-04-12 JP JP7181684A patent/JPS60217267A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60217267A (en) | 1985-10-30 |
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