JPH02250879A - Production of fluoran compound - Google Patents
Production of fluoran compoundInfo
- Publication number
- JPH02250879A JPH02250879A JP1073159A JP7315989A JPH02250879A JP H02250879 A JPH02250879 A JP H02250879A JP 1073159 A JP1073159 A JP 1073159A JP 7315989 A JP7315989 A JP 7315989A JP H02250879 A JPH02250879 A JP H02250879A
- Authority
- JP
- Japan
- Prior art keywords
- solvent
- compound
- heat
- anilino
- methyl
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- -1 fluoran compound Chemical class 0.000 title abstract description 3
- 239000013078 crystal Substances 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 239000003849 aromatic solvent Substances 0.000 claims abstract description 10
- 239000012046 mixed solvent Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 11
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 6
- 238000002441 X-ray diffraction Methods 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 15
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 238000004040 coloring Methods 0.000 abstract description 4
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 238000009835 boiling Methods 0.000 abstract description 2
- 230000001476 alcoholic effect Effects 0.000 abstract 2
- 125000001931 aliphatic group Chemical group 0.000 abstract 2
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 238000012986 modification Methods 0.000 description 20
- 230000004048 modification Effects 0.000 description 20
- 229940126062 Compound A Drugs 0.000 description 19
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 19
- 239000000243 solution Substances 0.000 description 14
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YGLYYWZISFBCPU-UHFFFAOYSA-N 4-ethoxy-2-methyl-n-phenylaniline Chemical compound CC1=CC(OCC)=CC=C1NC1=CC=CC=C1 YGLYYWZISFBCPU-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- DYFFAVRFJWYYQO-UHFFFAOYSA-N n-methyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(C)C1=CC=CC=C1 DYFFAVRFJWYYQO-UHFFFAOYSA-N 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0025—Crystal modifications; Special X-ray patterns
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
- Color Printing (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、感熱記録紙、感圧複写紙等の記録体に使用す
る発色性染料として有用な２−アニリノ−３−メチル−
６−Ｎ二ｎ−プロピルメチルアミノフルオラン（以下、
化合物Ａと称する）結晶変態の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention provides 2-anilino-3-methyl-
6-N di-n-propylmethylaminofluorane (hereinafter referred to as
The present invention relates to a method for producing a crystal modification (referred to as Compound A).
〔従来の技術および解決すべき問題点〕感熱記録紙、感
圧複写紙等に使用される発色性染料として、化合物Ａが
優れた性能を有する化合物であることが知られている（
特開昭５９−１２０６５４号）。[Prior art and problems to be solved] Compound A is known to have excellent performance as a color-forming dye used in thermal recording paper, pressure-sensitive copying paper, etc.
JP-A-59-120654).
本発明者らは、該化合物の製造方法について種々検討し
た結果、反応液から目的物を単離するための後処理方法
の違いによって、二種の結晶変態が生成することを見出
した０通常の方法では、反応後、反応液から目的物を有
機溶媒で抽出し、該有機溶媒溶液を−ａ縮して析出させ
た結晶を乾燥して目的物を得るが、安定的に一方の変態
を得ることが難しい。As a result of various studies on manufacturing methods for the compound, the present inventors found that two types of crystal modifications occur depending on the post-treatment method used to isolate the target compound from the reaction solution. In this method, after the reaction, the target product is extracted from the reaction solution with an organic solvent, and the organic solvent solution is subjected to -a condensation to dry the precipitated crystals to obtain the target product, but one modification is stably obtained. It's difficult.
この結晶変態はそれぞれ異なる発色性能を示し、目的に
応じそれぞれを自由に製造することが望まれる。しかし
ながら、前記の如＜、確実に一方の結晶変態を得る処理
方法が明確でなかった。Each of these crystal modifications exhibits different coloring performance, and it is desirable to freely manufacture each of them depending on the purpose. However, as mentioned above, the processing method for reliably obtaining one crystal modification was not clear.
本発明の目的は、化合物Ａの所望する結晶変態を得るた
めの方法を提供するにある。An object of the present invention is to provide a method for obtaining a desired crystal modification of Compound A.
（問題を解決するための手段］
本発明は、化合物Ａを芳香族系溶媒と低級脂肪族アルコ
ール系溶媒との混合溶媒とともに加熱処理することを特
徴とするＣｕ−にα線によるＸ線回折法における回折角
（２θ）１９．６°および２１．７°に最強ピークを有
する化合物Ａ結晶変態の製造方法に関するものである。(Means for Solving the Problem) The present invention provides an X-ray diffraction method using alpha rays for Cu-, which is characterized in that compound A is heat-treated with a mixed solvent of an aromatic solvent and a lower aliphatic alcohol solvent. The present invention relates to a method for producing a crystal modified compound A having the strongest peaks at diffraction angles (2θ) of 19.6° and 21.7°.
化合物Ａの結晶には、第１図および第２図に示す２種の
結晶変態が存在する０両図はＣｕ−にα線によるＸ線回
折図であり、第１図は、発色感度の高い低融点結晶（融
点１７５〜１７７°Ｃ１以下、α型変態と称する）のＸ
線回折図であり、回折角（２θ）１９．６＠および２１
．７″″に最強ピークを有する。第２図は、地肌の白炭
、耐湿熱性の優れた高融点結晶（融点１７８〜１８１
’Ｃ１以下、β型変態と称する）のＸ線回折図であり、
回折角（２θ）２３．６’および２５．６８に強いピー
クを有する。（回折角の誤差：±０．２°）化合物Ａは
、通常の反応方法により合成できる。There are two types of crystal modifications shown in Figures 1 and 2 in the crystal of Compound A. Both figures are X-ray diffraction diagrams using alpha rays for Cu-, and Figure 1 shows a modification with high coloring sensitivity. X of low melting point crystals (melting point 175-177° C1 or lower, referred to as α-type modification)
It is a line diffraction diagram, with diffraction angles (2θ) of 19.6 @ and 21
．． It has the strongest peak at 7″″. Figure 2 shows white charcoal on the ground, high melting point crystals with excellent moisture and heat resistance (melting point 178-181
It is an X-ray diffraction diagram of 'C1 and below, referred to as β-type modification),
It has strong peaks at diffraction angles (2θ) of 23.6' and 25.68. (Diffraction angle error: ±0.2°) Compound A can be synthesized by a conventional reaction method.
即ち、ｏ−（４−Ｎ−ｎ−プロピルメチルアミノ−２−
ヒドロキシベンゾイル）安息香酸と４−エトキシ−２−
メチルジフェニルアミンとを濃硫酸中宅反応させ、反応
液を氷水中に注加することにより得られる析出物を濾取
する。これを水酸化ナトリウム水溶液等のアルカリ水溶
液の存在下、トルエン等の芳香族系溶媒中で加熱し、生
成物を該溶媒で抽出する。That is, o-(4-N-n-propylmethylamino-2-
hydroxybenzoyl)benzoic acid and 4-ethoxy-2-
The reaction mixture is reacted with methyldiphenylamine in concentrated sulfuric acid, and the precipitate obtained by pouring the reaction solution into ice water is collected by filtration. This is heated in an aromatic solvent such as toluene in the presence of an aqueous alkaline solution such as an aqueous sodium hydroxide solution, and the product is extracted with the solvent.
この溶液から目的物を得る通常の方法では、該溶液をｉ
ｌｌ縮し、析出物を濾過、乾燥する。しかしながら、こ
の後処理の方法の僅かな違いによって、α型変態が得ら
れる場合とβ型変態が得られる場合とがある。In the usual method of obtaining the target product from this solution, the solution is
The precipitate is filtered and dried. However, depending on slight differences in the method of this post-treatment, there are cases where α-type transformation is obtained and cases where β-type transformation is obtained.
本発明においては、上記の様にして得られた化合物Ａの
有機溶媒溶液をｆＡｌｌ、析出した結晶を濾過して得ら
れた未乾燥状態の結晶を、芳香族系溶媒と低級脂肪族ア
ルコール系溶媒との混合溶媒とともに加熱処理すること
により確実にα型変態を得ることができる。In the present invention, the organic solvent solution of Compound A obtained as described above is fAll, and the undried crystals obtained by filtering the precipitated crystals are mixed with an aromatic solvent and a lower aliphatic alcohol solvent. α-type transformation can be reliably obtained by heat treatment with a mixed solvent.
また、反応後、本発明の方法を行わずに、有機溶媒溶液
から分離、乾燥して、β型変態が得られた場合にも、こ
のβ型変態を前記の混合溶媒で加熱処理してもよい。In addition, even if the β-type modification is obtained by separating and drying from the organic solvent solution without performing the method of the present invention after the reaction, the β-type modification may be heat-treated with the above-mentioned mixed solvent. good.
更には、反応後の抽出溶媒ががトル主′ン等の芳香族系
溶媒であれば、該溶液に、あるいは該溶液の濃縮液に低
級脂肪族アルコール系溶媒を加え加熱処理してもよい、
即ち、この場合は、反応後の化合物Ａ抽出溶媒が本発明
方法の芳香族系溶媒に相当する。Furthermore, if the extraction solvent after the reaction is an aromatic solvent such as toluene, a lower aliphatic alcohol solvent may be added to the solution or a concentrated solution of the solution and heat-treated.
That is, in this case, the compound A extraction solvent after the reaction corresponds to the aromatic solvent of the method of the present invention.
熱処理の方法は、化合物Ａを混合溶媒で湿潤させた後、
または混合溶媒中に分散した後、６５℃以上の温度、好
ましくは沸点で、３０分以上、好ましくは１〜５時間加
熱する。加熱処理後、溶媒を除去すれば化合物Ａのα型
変態が得られる。溶媒を除去するには、溶媒の量に応じ
、加熱処理後、加熱を継続して溶媒を蒸発させてもよい
し、冷却、濾取した結晶を加熱して溶媒を蒸発させても
よい。The heat treatment method involves moistening compound A with a mixed solvent, and then
Alternatively, after dispersing in a mixed solvent, it is heated at a temperature of 65° C. or higher, preferably at the boiling point, for 30 minutes or more, preferably 1 to 5 hours. After the heat treatment, the α-type modification of compound A can be obtained by removing the solvent. To remove the solvent, depending on the amount of the solvent, after the heat treatment, heating may be continued to evaporate the solvent, or the crystals that have been cooled and filtered may be heated to evaporate the solvent.
本発明で使用する芳香族系溶媒としては、化合物Ａに対
して不活性で、化合物Ａが可溶な溶媒、例えば、化合物
への２５°Ｃでの溶解度が１％以上、好ましくは２％以
上である溶媒が使用され、具体的にはベンゼン、トルエ
ン、キシレン、クロルベンゼン類等のヘンゼン系溶媒が
挙げらｉ、通常トルエンが使用される。低級脂肪族アル
コール系溶媒としては、メタノール、エタノール、ｎ−
プロパツール、１ｓｏ−プロパツール等の化合物ＡＭ溶
性の溶媒が使用される。工業的にはメタノールが好まし
い。The aromatic solvent used in the present invention is a solvent that is inert to Compound A and in which Compound A is soluble, for example, a solvent with a solubility of the compound at 25°C of 1% or more, preferably 2% or more. A solvent is used, and specific examples include henzene-based solvents such as benzene, toluene, xylene, and chlorobenzenes. Usually, toluene is used. Examples of lower aliphatic alcohol solvents include methanol, ethanol, n-
Solvents in which the compound AM is soluble, such as propatool, 1so-propatool, etc., are used. Methanol is industrially preferred.
これらの溶媒の混合比率は、芳香族系溶媒：低級脂肪族
アルコール系溶媒（重量部）が７０：１〜１：８０の範
囲、好ましくは４０：ｌ〜１：５０の範囲である。The mixing ratio of these solvents is aromatic solvent: lower aliphatic alcohol solvent (parts by weight) in the range of 70:1 to 1:80, preferably in the range of 40:l to 1:50.
該混合溶媒の使用量は、化合物Ａが溶媒で湿潤する程度
でも、分散液となる程度でもよく、化合物Ａの０．１重
量部以上であれば特に限定されないが、２重量部以上が
工業的操作上好ましい、上限は特にないが、余り多量で
あると経済的に好ましくないので、工業的観点から適宜
選択すればよい。The amount of the mixed solvent used may be such that Compound A is wetted with the solvent or that it becomes a dispersion, and is not particularly limited as long as it is 0.1 parts by weight or more of Compound A, but 2 parts by weight or more is industrially acceptable. There is no particular upper limit which is preferable for operation, but too large amounts are economically unfavorable, so it may be selected appropriately from an industrial viewpoint.
一方、β型変態を得るには、前記の如く通常の反応を行
い、得られた有機溶媒溶液から析出させた結晶を、トル
エン等の芳香族系溶媒で再結晶すゎばよい、あ、いは、
。型変態。結晶＝％様８、結晶してもよい。On the other hand, in order to obtain the β-type modification, all you have to do is carry out the usual reaction as described above, and then recrystallize the crystals precipitated from the resulting organic solvent solution in an aromatic solvent such as toluene. teeth,
. Type pervert. Crystal = % like 8, may be crystallized.
以下、実施例を挙げ本発明を更に詳細に説明する。Hereinafter, the present invention will be explained in more detail with reference to Examples.
参考例１゜
０− （４−Ｎ−ｎ−プロピルメチルアミノ−２−ヒド
ロキシベンゾイル）安息香酸７．６ｇと４−エトキシ−
２−メチルジフェニルアミン６、Ｉｇとを、濃硫酸４０
ｇ 中に加え、２０〜２５°Ｃの温度で４８時間攪拌し
たのち、反応物を氷水中に性別し、析出物を濾過した。Reference Example 1 7.6 g of 0-(4-N-n-propylmethylamino-2-hydroxybenzoyl)benzoic acid and 4-ethoxy-
2-methyldiphenylamine 6, Ig and concentrated sulfuric acid 40
After stirring at a temperature of 20-25°C for 48 hours, the reaction mixture was poured into ice water and the precipitate was filtered.
得られたケーキをトルエンと２０％水酸化ナトリウム水
溶液と混合し、加熱抽出した０次いでトルエン層を分離
し、濃縮して析出した結晶を濾取し、トルエンで湿潤し
た化合物Ａを得た（トルエン含有率１０％）。The obtained cake was mixed with toluene and a 20% aqueous sodium hydroxide solution, extracted with heat, and then the toluene layer was separated, concentrated, and the precipitated crystals were collected by filtration to obtain Compound A moistened with toluene (toluene content 10%).
実施例１゜
参考例１と同様にして得られた結晶１０．８ｇをトルエ
ン：メタノール（１：３）溶媒３５ｇに加え、２時間、
還流下で加熱した後、冷却、濾過して得られた結晶を、
１１０℃で乾燥して化合物Ａのα型変態（融点１７５〜
１７７℃）の結１．Ｔｈｏを得た。Example 1 10.8 g of crystals obtained in the same manner as in Reference Example 1 were added to 35 g of toluene:methanol (1:3) solvent, and the mixture was stirred for 2 hours.
After heating under reflux, the crystals obtained by cooling and filtering are
By drying at 110°C, the α-type modification of Compound A (melting point 175~
1. Got Tho.
実施例２゜
参考例１と同様にして得られた結晶１０．８ｇを１１０
℃で乾燥したところ、融点１７８〜１８１ ℃の化合物
Ａのβ型変態が得られた。これををトルエン：メタノー
ル（１ｊ １０）溶媒３５ｇに加え、４時間、還流下で
加熱した後、冷却、濾過して得られた結晶を、１１０℃
で乾燥して化合物Ａのα型変態（融点１７５〜１７７℃
）の結晶を得た。Example 2゜10.8g of crystals obtained in the same manner as in Reference Example 1 were
When dried at 0.degree. C., a beta modification of compound A with a melting point of 178-181.degree. C. was obtained. This was added to 35 g of toluene:methanol (1j 10) solvent, heated under reflux for 4 hours, cooled and filtered, and the resulting crystals were heated to 110°C.
to obtain the α-type modification of Compound A (melting point 175-177°C).
) were obtained.
〔効果］
発色性染料として優れた２−アニリノ−３−メチル−６
−Ｎ−ｎ−プロピルメチルアミノフルオランには二種の
結晶変態が存在し、それぞれ特徴を有している。[Effect] 2-anilino-3-methyl-6 excellent as a color-forming dye
-N-n-propylmethylaminofluorane has two types of crystal modifications, each of which has its own characteristics.
本発明によれば、用途に応じ、自由に一方の変態を製造
できる。特に、発色性感度の優れたα型変態を確実に得
ることができるということは、工業的にも極めて有用で
ある。According to the present invention, one of the transformations can be freely produced depending on the application. In particular, the ability to reliably obtain α-type modification with excellent color development sensitivity is extremely useful from an industrial perspective.
第１図は、α型変態の、第２図はβ′＆変態のＸ線回折
図である０図面において、横軸は回折角（２θ）を、縦
軸は回折強度を表す。
第１図FIG. 1 is an X-ray diffraction diagram of the α-type modification, and FIG. 2 is an X-ray diffraction diagram of the β′ & transformation. In the drawings, the horizontal axis represents the diffraction angle (2θ) and the vertical axis represents the diffraction intensity. Figure 1
Claims (1)
ルメチルアミノフルオランを芳香族系溶媒と低級脂肪族
アルコール系溶媒との混合溶媒とともに加熱処理するこ
とを特徴とするＣｕ−にα線によるＸ線回折法における
回折角（２θ）１９．６°および２１．７°に最強ピー
クを有する２−アニリノ−３−メチル−６−Ｎ−ｎ−プ
ロピルメチルアミノフルオラン結晶変態の製造方法。(1) Cu- characterized by heat treating 2-anilino-3-methyl-6-Nn-propylmethylaminofluorane with a mixed solvent of an aromatic solvent and a lower aliphatic alcohol solvent. Production of crystal modified 2-anilino-3-methyl-6-N-n-propylmethylaminofluorane having the strongest peaks at diffraction angles (2θ) of 19.6° and 21.7° in X-ray diffraction using alpha rays Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1073159A JP2676401B2 (en) | 1989-03-24 | 1989-03-24 | Method for producing fluoran compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1073159A JP2676401B2 (en) | 1989-03-24 | 1989-03-24 | Method for producing fluoran compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02250879A true JPH02250879A (en) | 1990-10-08 |
| JP2676401B2 JP2676401B2 (en) | 1997-11-17 |
Family
ID=13510115
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1073159A Expired - Lifetime JP2676401B2 (en) | 1989-03-24 | 1989-03-24 | Method for producing fluoran compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2676401B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05147351A (en) * | 1991-11-28 | 1993-06-15 | Fuji Photo Film Co Ltd | Thermal recording material |
-
1989
- 1989-03-24 JP JP1073159A patent/JP2676401B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05147351A (en) * | 1991-11-28 | 1993-06-15 | Fuji Photo Film Co Ltd | Thermal recording material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2676401B2 (en) | 1997-11-17 |
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