JPS62179984A - Color forming recording material - Google Patents
Color forming recording materialInfo
- Publication number
- JPS62179984A JPS62179984A JP61023569A JP2356986A JPS62179984A JP S62179984 A JPS62179984 A JP S62179984A JP 61023569 A JP61023569 A JP 61023569A JP 2356986 A JP2356986 A JP 2356986A JP S62179984 A JPS62179984 A JP S62179984A
- Authority
- JP
- Japan
- Prior art keywords
- recording material
- color
- pressure
- paper
- sensitive copying
- 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.)
- Pending
Links
- 239000000463 material Substances 0.000 title abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- -1 fluoran compound Chemical class 0.000 abstract description 19
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000003960 organic solvent Substances 0.000 abstract description 6
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical class C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000002775 capsule Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- DXYZIGZCEVJFIX-UHFFFAOYSA-N 2'-(dibenzylamino)-6'-(diethylamino)spiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound C=1C(N(CC)CC)=CC=C(C2(C3=CC=CC=C3C(=O)O2)C2=C3)C=1OC2=CC=C3N(CC=1C=CC=CC=1)CC1=CC=CC=C1 DXYZIGZCEVJFIX-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- QTKIQLNGOKOPOE-UHFFFAOYSA-N 1,1'-biphenyl;propane Chemical group CCC.C1=CC=CC=C1C1=CC=CC=C1 QTKIQLNGOKOPOE-UHFFFAOYSA-N 0.000 description 1
- YGTJOGMCOFZQHN-UHFFFAOYSA-N 2-(dibenzylamino)phenol Chemical class OC1=CC=CC=C1N(CC=1C=CC=CC=1)CC1=CC=CC=C1 YGTJOGMCOFZQHN-UHFFFAOYSA-N 0.000 description 1
- 125000006282 2-chlorobenzyl group Chemical group [H]C1=C([H])C(Cl)=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical class NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZKURGBYDCVNWKH-UHFFFAOYSA-N [3,7-bis(dimethylamino)phenothiazin-10-yl]-phenylmethanone Chemical compound C12=CC=C(N(C)C)C=C2SC2=CC(N(C)C)=CC=C2N1C(=O)C1=CC=CC=C1 ZKURGBYDCVNWKH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 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 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 125000005506 phthalide group Chemical group 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
- B41M5/132—Chemical colour-forming components; Additives or binders therefor
- B41M5/136—Organic colour formers, e.g. leuco dyes
- B41M5/145—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
- B41M5/1455—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring characterised by fluoran compounds
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、発色性記録材料に関し、それ自体はとんど無
色の電子供与性物質を電子受容性物質と接触せしめて発
色させる性質を利用するものであわ、具体的には現在、
感圧複写紙や感熱記録紙などの形で実用される材料であ
る。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a color-forming recording material, which utilizes the property of an electron-donating substance, which itself is mostly colorless, to develop color when brought into contact with an electron-accepting substance. I have a lot of things to do, specifically at the moment.
It is a material that is used in the form of pressure-sensitive copying paper, heat-sensitive recording paper, etc.
〔従来の技術と発明が解決しようとする問題点〕従来か
ら緑ないし黒縁色に発色する化合物としてフルオラン化
合物が知られているが、有機溶剤に対する溶解性が低い
か又はその発色像が光に対して極めて不安定であるか、
いずれかの欠点を有している。例えば２−ジベンジルア
ミノ−６−ジエチルアミノフルオランは、有機溶剤には
よく溶解するが、その発色像は光に対して不安定である
。[Prior art and problems to be solved by the invention] Fluoran compounds have been known as compounds that develop a green or black edge color, but they either have low solubility in organic solvents or their colored image does not stand up to light. is extremely unstable or
It has some drawbacks. For example, 2-dibenzylamino-6-diethylaminofluorane dissolves well in organic solvents, but its color image is unstable to light.
２−ジ（オルトクロルベンジル）−アミノ−６−ジエチ
ルアミノフルオラン（特公昭４９−１８７２７号公報参
照）はその発色像は、光に対して安定であるが、有機溶
剤に対する溶解性が極めて低い。このように公知のフル
オラン化合物は、感圧複写紙等の記録材料用色素として
利用するには充分な性質を有していない。2-di(orthochlorobenzyl)-amino-6-diethylaminofluoran (see Japanese Patent Publication No. 18727/1983) has a color image that is stable to light, but has extremely low solubility in organic solvents. As described above, known fluoran compounds do not have sufficient properties to be used as dyes for recording materials such as pressure-sensitive copying paper.
本発明の発明者等は、これら欠点のない、緑ないし黒縁
色に発色する発色性記録材料を開発すべく鋭意研究した
結果、本発明者等が新規に合成した一般式〔■〕で表わ
されるフルオラン化合物が上記の公知フルオラン化合物
に比べ感圧複写紙用記録材料として極めて利用価値が高
いことを見い出〔式中へは炭素数１〜５のアルキル基を
示し、Ｒ２は炭素数６〜１２のアルキル基を示す。以下
、同符号は同じものを意味する。〕
二 １
−すな
わち一般式ｍで表わされる新規フルオラン化合物は、そ
れ自体はとんど無色であるが、有機溶剤、例えばジアリ
ールエタン、アル・■ルナフタレン、水素化ターフェニ
ル、アルキルピフェニル等によく溶解し、その発色像は
、すぐれた光安定性を示す。本発明のフルオラン化合物
は単独でも２ｆ４以上混合しても用いることができ、又
他の感圧複写紙用記録材料、例えば３．蟻３−ビス（ジ
メチルアミノフェニル）−６−シメチルアミノフタリド
、３，７−ビス（ジメチルアミノ）−１０−ベンゾイル
フェノチアジン、ジ置換フルオラン化合物、例えば英国
特許第１１８２７４３号明細書、ベルギー特許第８１５
２９１号明細書に記載されているもの、及びビスインド
リルフタリド、例えばドイツ特許公告用２２５９７１１
号明細書に記載されているもの等を混合しても用いるこ
とができる。The inventors of the present invention conducted intensive research to develop a color-forming recording material that does not have these drawbacks and develops a green or black edge color. It has been found that fluoran compounds have extremely high utility value as recording materials for pressure-sensitive copying paper compared to the above-mentioned known fluoran compounds. 12 alkyl groups are shown. Hereinafter, the same symbols mean the same things. ] Two 1
-That is, the new fluoran compound represented by the general formula m is mostly colorless itself, but it dissolves well in organic solvents such as diarylethane, al-naphthalene, hydrogenated terphenyl, alkylpiphenyl, etc. , its color image shows excellent photostability. The fluoran compound of the present invention can be used alone or in a mixture of 2f4 or more, and can also be used in other recording materials for pressure-sensitive copying paper, such as 3. 3-bis(dimethylaminophenyl)-6-dimethylaminophthalide, 3,7-bis(dimethylamino)-10-benzoylphenothiazine, disubstituted fluoran compounds, such as British Patent No. 1182743, Belgian Patent No. 815
291, and bisindolyl phthalides, such as German Patent Publication No. 2259711.
It is also possible to use a mixture of those described in the specification.
本発明の一般式〔Ｉ〕で表わされる新規なフルオラン化
合物は、下記の方法によって合成される。The novel fluoran compound represented by the general formula [I] of the present invention is synthesized by the following method.
すなわち一般式〔Ｉ〕で表わされるベンゾフェノンカル
ボン酸誘導体と一般式〔璽〕で表わされるジベンジルア
ミノフェノール誘導体のほぼ等モルを硫酸ポリリン酸等
の脱水剤の存在下に反応させることにより得られる。こ
こで使用されるベンゾフェノンカルボン酸誘導体（１）
は、公知の方法、例えば無水フタル酸とｍ−アミノフェ
ノール誘導体ＣＮ’Ｊのほぼ等モルをテトラクロルエタ
ン、ベンゼン、クロルベンゼン、ニトロベンゼン等の不
活性有機溶剤中で反応させるか又は塩化アルミニウム、
塩化亜鉛、塩化リンなどのフリーデルクラフト触媒存在
下で反応させて得ることができる。 Ｃ，ＩＯ〕
臼１［ｆｆ１
ｒ式中Ｒ５、Ｒ４は水素又は低級アルキル基を示す。〕
〔発明の作用と効果〕
本発明に係るフルオラン化合物は、感圧複写紙や感熱記
録紙用記録材料として用いることができるが、特に感圧
複写紙用記録材料として極めてすぐれた性質を有してい
る。この事実を、本発明のフルオラン化合物の１つであ
る２−ジ（オルトクロルベンジル）アミノ−１ｓ−（Ｎ
−エチル）ヘキシルアミノフルオラン（Ａ）と（Ａ）と
類似の構造を有する２−ジベンジルアミノ−６−ジエチ
ルアミノフルオラン（Ｂ）及び２−ジ（オルトクロルベ
ンジル）アミノ−６−ジエチルアミノフルオラン（Ｃ）
との比較により明らかにする。That is, it can be obtained by reacting approximately equimolar amounts of the benzophenonecarboxylic acid derivative represented by the general formula [I] and the dibenzylaminophenol derivative represented by the general formula [Case] in the presence of a dehydrating agent such as sulfuric acid polyphosphoric acid. Benzophenone carboxylic acid derivative (1) used here
can be carried out by a known method, for example, by reacting approximately equal moles of phthalic anhydride and m-aminophenol derivative CN'J in an inert organic solvent such as tetrachloroethane, benzene, chlorobenzene, nitrobenzene, or by reacting aluminum chloride,
It can be obtained by reaction in the presence of a Friedel-Crafts catalyst such as zinc chloride or phosphorus chloride. C, IO]
Mill 1 [ff1 r In the formula, R5 and R4 represent hydrogen or a lower alkyl group. [Operations and Effects of the Invention] The fluoran compound according to the present invention can be used as a recording material for pressure-sensitive copying paper or heat-sensitive recording paper, and has extremely excellent properties particularly as a recording material for pressure-sensitive copying paper. ing. This fact can be considered as 2-di(orthochlorobenzyl)amino-1s-(N
-ethyl)hexylaminofluorane (A) and 2-dibenzylamino-6-diethylaminofluorane (B) having a similar structure to (A) and 2-di(orthochlorobenzyl)amino-6-diethylaminofluorane (C)
This will be clarified by comparison with
（Ｃ）
（１）感圧複写紙用溶剤に対する溶解性の比較；化合物
（Ａ）及び（Ｃ）（７） Ｋｈ４ｃｍ１１３ （ｔＡ呉
羽化学製アルキルナフタレン）とハイゾールＳＡＳ （
日本石油化学契ジアリールエタン）での２５″Ｃでの溶
解度Ｃ重量％）を示す。(C) (1) Comparison of solubility in solvents for pressure-sensitive copying paper; Compounds (A) and (C) (7) Kh4cm113 (tA Kureha Chemical Co., Ltd. alkylnaphthalene) and Hysol SAS (
The solubility (C weight %) at 25″C in Nippon Petrochemical Co., Ltd. (diarylethane) is shown.
表１゜
表１で示される如く本発明の新規なフルオラン化合物（
Ａ）は公知フルオラン化合物（Ｃ）に比べ溶解度が極め
て高い。これは本発明のフルオラン化合物を用いて感圧
複写紙をつくる際、マイクロカプセル中で結晶析出の恐
れがなく、又マイクロカプセル化に当って高価な芳香族
系の溶剤を少くし、相対的に安価な石油系の溶剤の使用
量を増すことができることを意味する。Table 1゜As shown in Table 1, the novel fluoran compound of the present invention (
A) has extremely high solubility compared to the known fluoran compound (C). This means that when pressure-sensitive copying paper is made using the fluoran compound of the present invention, there is no fear of crystal precipitation in the microcapsules, and the amount of expensive aromatic solvents used during microencapsulation can be reduced, making it relatively easy to use. This means that the amount of inexpensive petroleum-based solvents used can be increased.
（２）発色像の光に対する安定性の比較；化合物（Ａ）
及び（Ｂ）各７９をＫＭＣ−１１３ｑｓｖｅに溶解し、
後述の突施例１の方法においてマイクロカプセル化し紙
にコーテングして上葉紙を得た。発色剤の塗布量は０．
１５９／ばてあった。これを酸性白土を塗布した下葉紙
と重ね合せて発色させ、その発色像に太陽光を照射し、
照射時間毎の発色像の濃度をマクベスＲＤ−５１４反射
濃度計により測定した。(2) Comparison of stability of colored images against light; Compound (A)
and (B) each 79 is dissolved in KMC-113qsve,
The product was microencapsulated and coated on paper using the method of Example 1 described later to obtain top paper. The amount of coloring agent applied is 0.
159/ was there. This is layered with paper coated with acidic clay to develop color, and the colored image is irradiated with sunlight.
The density of the colored image at each irradiation time was measured using a Macbeth RD-514 reflection densitometer.
フィルターはラッテン、ｆ２５を用いた。Wratten f25 was used as a filter.
発色像は強い光安定性を示す。これは、他の感圧複写紙
用色素と混合して用いる場合、色調変化の少い安定した
感圧複写紙が得られることを裏付けるものである。The colored image shows strong photostability. This proves that when used in combination with other dyes for pressure-sensitive copying paper, stable pressure-sensitive copying paper with little change in color tone can be obtained.
次に、本発明の一般式［１’ｌで表わされる新規フルオ
ラン化合物の合成法を具体的に例示する。Next, a method for synthesizing the novel fluoran compound represented by the general formula [1'l] of the present invention will be specifically illustrated.
合成例 １゜
Ｃ］
２−〔２−ヒドロキシ−４−（Ｎ−エチル）へキシルア
ミノベンゾイル〕−安息香酸１８．５ ｇと４−メトキ
シ−Ｎ、 Ｎ−ジ（オルトクロルベンジル）アニリン１
８．８ｇを濃硫酸１５０コ中に徐々に加えて溶解し２０
℃で１００時間反応させた。この反応液を氷水１００口
＝１中に注加しまた後、析出物を戸別し、カセイソーダ
液中に加えてアルカリ性とした。析出物を戸別してｎ−
ブチルアルコールによシ再結晶し、融点１５１−１５２
での無色結晶として２−ジ（オルトクロルベンジル）ア
ミノ−６−（Ｎ−エチル）へキシルアミノフルオラン１
８ｇを得た。Synthesis Example 1゜C] 18.5 g of 2-[2-hydroxy-4-(N-ethyl)hexylaminobenzoyl]-benzoic acid and 4-methoxy-N,N-di(orthochlorobenzyl)aniline 1
Gradually add 8.8 g to 150 g of concentrated sulfuric acid and dissolve.
The reaction was carried out at ℃ for 100 hours. This reaction solution was poured into 100 mouths of ice water, and the precipitates were separated from each other and added to a caustic soda solution to make them alkaline. Separate the precipitates from house to house.
Recrystallized from butyl alcohol, melting point 151-152
2-di(orthochlorobenzyl)amino-6-(N-ethyl)hexylaminofluorane 1 as colorless crystals at
8g was obtained.
２−「２−ヒドロキシ−４−（Ｎ−エチル）へキシルア
ミノベンゾイル〕−安息香酸１８．５ｇト４−メトキシ
ーＮ、Ｎ−ジ（パラクロルベンジル）アニソ７１８．８
ｇを濃硫酸１５０Ｗｊｌ中に徐々に加えて溶解し、２０
でで１００時間反応させた。この反応液を合成例１と同
様な方法で処理し・融点１１３．５−１１５．２℃の無
色結晶として２−ジ（パラクロルベンジル）アミノ−６
−（Ｎ−エチル）ヘキシルアミノフルオラン１５９を得
た。2-2-hydroxy-4-(N-ethyl)hexylaminobenzoyl]-benzoic acid 18.5 g 4-methoxy N,N-di(parachlorobenzyl)aniso 718.8
Gradually add and dissolve 20 g of concentrated sulfuric acid in 150 Wjl of concentrated sulfuric acid.
The reaction was carried out for 100 hours. This reaction solution was treated in the same manner as in Synthesis Example 1 to form colorless crystals with a melting point of 113.5-115.2°C. 2-di(parachlorobenzyl)amino-6
-(N-ethyl)hexylaminofluorane 159 was obtained.
これらフルオラン化合物を用いて感圧複写紙を製造する
には、公知の方法例えげ米国特許第２８００４５８号明
細書、第２８０６４５７号明細書に記載の方法があシ、
又感熱記録紙を製造するには、公知の方法、例えば特公
昭４５−１４０３９号公報に記載の方法がある。To produce pressure-sensitive copying paper using these fluoran compounds, there are known methods such as those described in U.S. Pat. Nos. 2,800,458 and 2,806,457.
In addition, there are known methods for producing heat-sensitive recording paper, such as the method described in Japanese Patent Publication No. 45-14039.
以下新規フルオラン化合物を用いた感圧複写紙及び感熱
記録紙の実施例を示し、本発明を具体的に説明する。The present invention will be specifically explained below by showing examples of pressure-sensitive copying paper and heat-sensitive recording paper using the new fluoran compound.
実施例 １．（感圧複写紙の例）
合成例１の２−ジ（オルトクロルベンジル）アミノ−６
−（Ｎ−エチル）ヘキシルアミノフルオラン７部（以下
Ｘ＝部で示す）をモノイソプロプルビフェニル９６部に
溶解し、この液にゼラチン２４部とアシビアゴム２４部
を水４００部に溶解しＰＨを７に調製した液を加える。Example 1. (Example of pressure-sensitive copying paper) 2-di(orthochlorobenzyl)amino-6 of Synthesis Example 1
Dissolve 7 parts of -(N-ethyl)hexylaminofluorane (hereinafter referred to as X=parts) in 96 parts of monoisopropylbiphenyl, dissolve 24 parts of gelatin and 24 parts of gum asibia in 400 parts of water, and adjust the pH. Add the solution prepared in step 7.
ホモジナイザーで乳化し、温水１０００部を加え５０″
Ｃで３０分間攪拌したのち、１０％カセイソーダ液約１
部を加え、さらに５０℃で３０分間攪拌した。次いで希
酢酸を徐々に加えてＰＨを４．５に調製し、５０℃で約
１時間攪拌し０−５℃に冷却、さらに３０分間攪拌した
。次にグルタルアルデヒド水溶液３５部を徐々に加えて
カプセルを硬化させ、カセイソーダ水溶液でＰ）Ｔを６
に調整し室温で数時間攪拌してカプセル化を完了した。Emulsify with a homogenizer and add 1000 parts of warm water to 50"
After stirring for 30 minutes at C, add about 10% caustic soda solution.
of the mixture was added, and the mixture was further stirred at 50°C for 30 minutes. Next, dilute acetic acid was gradually added to adjust the pH to 4.5, and the mixture was stirred at 50°C for about 1 hour, cooled to 0-5°C, and further stirred for 30 minutes. Next, 35 parts of glutaraldehyde aqueous solution was gradually added to harden the capsules, and P)T was reduced to 6 parts with caustic soda aqueous solution.
The encapsulation was completed by stirring at room temperature for several hours.
このカプセル液をワイヤーパーで均一に塗布し乾燥して
塗布紙（上葉紙）を得た。この紙を顕色剤として酸性白
土又はフェノールホルマリン樹脂を塗布した紙（下葉紙
）に重ね合わせボールペンの筆圧、あるいはタイプライ
タ−の衝撃を加えると下葉紙上に濃い緑色の像が逸やか
に現われた。この像はすぐれた光安定性を示し、カプセ
ル塗布面の光による着色は少なかった。This capsule liquid was applied uniformly with a wire spar and dried to obtain coated paper (top paper). When this paper is overlaid on paper coated with acid clay or phenol-formalin resin as a color developer (lower paper) and pressure from a ballpoint pen or impact from a typewriter is applied, a dark green image will appear on the lower paper. A crab appeared. This image showed excellent photostability, with little coloration of the coated surface of the capsules due to light.
実施例 ２．（感熱記録紙の例）
合成例１の２−ジ（オルトクロルベンジル）アミノ−６
−（Ｎ−エチル）ヘキシルアミノフルオラン３０部（以
下重量部で示す）を１５０部の１０％ポリヒニルアルコ
ール水溶液及び６５部の水とボールミルでｌＯ時間混合
粉砕して成分Ａとする。粉砕後の発色剤の粒子径は３−
５ミクロンであった。他方３５部のビスフェノールＡ１
１５０部のｌｔｌ ％ポリビ・ニルアルコール水溶液及
び６５部の水を同様にボールミルで粒子径が３−５ミク
ロンになる迄混合粉砕して成分Ｂとする。次に３部の成
分Ａと６７部め成分Ｂとを混合し乾燥後の固形分重量が
７ｔｉ／ｒｒｌ’になるよう上質紙にワイｊ七−で塗布
し乾燥して感熱記録紙を得た。この感熱記録紙は熱ペン
等の加熱により速やかに緑色に発色した。Example 2. (Example of thermal recording paper) 2-di(orthochlorobenzyl)amino-6 of Synthesis Example 1
Component A is obtained by mixing and pulverizing 30 parts of -(N-ethyl)hexylaminofluorane (hereinafter expressed in parts by weight) with 150 parts of a 10% polyhinyl alcohol aqueous solution and 65 parts of water in a ball mill for 10 hours. The particle size of the coloring agent after pulverization is 3-
It was 5 microns. and 35 parts of bisphenol A1 on the other hand.
150 parts of ltl% polyvinyl alcohol aqueous solution and 65 parts of water were similarly mixed and ground in a ball mill until the particle size became 3-5 microns to obtain component B. Next, 3 parts of component A and 67 parts of component B were mixed, and the mixture was coated on high-quality paper with a wi-j7-coat so that the solid content weight after drying was 7ti/rrl' and dried to obtain heat-sensitive recording paper. . This thermosensitive recording paper quickly developed a green color when heated with a thermal pen or the like.
Claims (1)
２は炭素数６〜１２のアルキル基を示す〕で表わされる
新規なフルオラン化合物を呈色反応性無色物質として含
有することを特徴とする発色性記録材料。(1) General formula ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 represents an alkyl group having 1 to 5 carbon atoms, and R_
2 represents an alkyl group having 6 to 12 carbon atoms] as a color-forming reactive colorless substance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61023569A JPS62179984A (en) | 1986-02-04 | 1986-02-04 | Color forming recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61023569A JPS62179984A (en) | 1986-02-04 | 1986-02-04 | Color forming recording material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62179984A true JPS62179984A (en) | 1987-08-07 |
Family
ID=12114169
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61023569A Pending JPS62179984A (en) | 1986-02-04 | 1986-02-04 | Color forming recording material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62179984A (en) |
-
1986
- 1986-02-04 JP JP61023569A patent/JPS62179984A/en active Pending
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