JPH0226782A - Color forming recording material - Google Patents
Color forming recording materialInfo
- Publication number
- JPH0226782A JPH0226782A JP63177525A JP17752588A JPH0226782A JP H0226782 A JPH0226782 A JP H0226782A JP 63177525 A JP63177525 A JP 63177525A JP 17752588 A JP17752588 A JP 17752588A JP H0226782 A JPH0226782 A JP H0226782A
- Authority
- JP
- Japan
- Prior art keywords
- color
- paper
- carbazolylmethane
- formula
- blue
- 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 claims abstract description 11
- -1 carbazolylmethane compound Chemical class 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 10
- 239000004927 clay Substances 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 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 abstract description 5
- 230000002378 acidificating effect Effects 0.000 abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract 3
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000975 dye Substances 0.000 description 10
- 238000004040 coloring Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 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
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical class C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical group C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 2
- HIAGSPVAYSSKHL-UHFFFAOYSA-N 1-methyl-9h-carbazole Chemical class N1C2=CC=CC=C2C2=C1C(C)=CC=C2 HIAGSPVAYSSKHL-UHFFFAOYSA-N 0.000 description 2
- SDFLTYHTFPTIGX-UHFFFAOYSA-N 9-methylcarbazole Chemical compound C1=CC=C2N(C)C3=CC=CC=C3C2=C1 SDFLTYHTFPTIGX-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 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
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- JTTMYKSFKOOQLP-UHFFFAOYSA-N 4-hydroxydiphenylamine Chemical class C1=CC(O)=CC=C1NC1=CC=CC=C1 JTTMYKSFKOOQLP-UHFFFAOYSA-N 0.000 description 1
- MNLZGFHCFGWITO-UHFFFAOYSA-N 9-butylcarbazole-3-carbaldehyde Chemical compound O=CC1=CC=C2N(CCCC)C3=CC=CC=C3C2=C1 MNLZGFHCFGWITO-UHFFFAOYSA-N 0.000 description 1
- PNTJHESWOJBCRP-UHFFFAOYSA-N 9-methylcarbazole-3-carbaldehyde Chemical compound O=CC1=CC=C2N(C)C3=CC=CC=C3C2=C1 PNTJHESWOJBCRP-UHFFFAOYSA-N 0.000 description 1
- WRBOHOGDAJPJOQ-UHFFFAOYSA-N 9H-Carbazole-3-carboxaldehyde Chemical class C1=CC=C2C3=CC(C=O)=CC=C3NC2=C1 WRBOHOGDAJPJOQ-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001555 benzenes Chemical group 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical class C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 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
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- PJNPCSKARBTURZ-UHFFFAOYSA-N n-phenyl-4-phenylmethoxyaniline Chemical compound C=1C=CC=CC=1COC(C=C1)=CC=C1NC1=CC=CC=C1 PJNPCSKARBTURZ-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- BHTJEPVNHUUIPV-UHFFFAOYSA-N pentanedial;hydrate Chemical compound O.O=CCCCC=O BHTJEPVNHUUIPV-UHFFFAOYSA-N 0.000 description 1
- 150000002990 phenothiazines Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 150000004961 triphenylmethanes Chemical class 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
- 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
- C09B11/26—Triarylmethane dyes in which at least one of the aromatic nuclei is heterocyclic
-
- 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
- B41M5/1366—Organic colour formers, e.g. leuco dyes characterised solely by tri (aryl or hetaryl)methane derivatives
-
- 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
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/323—Organic colour formers, e.g. leuco dyes
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、それ自体淡黄色または
黄土色にわずかに着色しているにすぎない電子供与性物
質を電子受容性物質と接触せしめて濃青色に発色させる
性質を利用するものである。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a color-forming recording material, in which an electron-donating substance, which itself is only slightly colored pale yellow or ocher, is used as an electron-accepting substance. It utilizes the property of producing a deep blue color when it comes into contact with it.
具体的には感圧複写紙や感熱複写紙などに用いられる。Specifically, it is used for pressure-sensitive copying paper, thermal copying paper, etc.
〔従来の技術と本発明が解決しようとする課題〕青ない
し青紫に発色する呈色性無色物質として、クリスタルバ
イオレットラクトン（ＣＶｔ、）を代表とするフタリド
化合物、スピロピラン化合物。[Prior art and problems to be solved by the present invention] Phthalide compounds and spiropyran compounds, typified by crystal violet lactone (CVt), are color-forming colorless substances that develop a blue to bluish-purple color.
フェノチアジン化合物あるいはトリフェニルメタン化合
物等のロイコ色素が既に実用化されている。Leuco dyes such as phenothiazine compounds or triphenylmethane compounds have already been put into practical use.
しかしながら、各ロイコ色素にはそれぞれ固有の発色色
相９全色濃度２発色速度、耐光堅牢性、自己発色性など
があるため目的に応じて数種の色素を組み合わせて用い
、その効果を高めることが行われている。例えば青発色
性ロイコ色素として著名なりリスタルバイオレフトラク
トン（ＣＶＬ）は迅速発色性であるが耐光堅牢性に乏し
いため、緩発色性ながら耐光性の良い青発色性ロイコ色
素との組み合わせで使用されることが多い。この種の緩
青発色性ロイコ色素として実用されているものは、ベン
ゾイルロイコメチレンブルー（ＢＬＭＢ） 、 ３−
Ｃ４，４°−ビス（Ｎ−メチルアニリノ）うな緩青発
色性ロイコ色素として顕色剤（電子受容物質）との接触
で鮮明かつ濃色に発色し、かつ発色像の耐光堅牢性が優
れ、自己発色性も少ないものを発見し、本発明に到達し
た。However, each leuco dye has its own unique color development hue, total color density, color development speed, light fastness, and self-color development, so it is possible to enhance the effect by using several types of dyes in combination depending on the purpose. It is being done. For example, lystal bioleft lactone (CVL), which is well-known as a blue-coloring leuco dye, has rapid color-forming properties but poor light fastness, so it is used in combination with a blue-coloring leuco dye that is slowly color-forming but has good light fastness. There are many things. This kind of slow blue-coloring leuco dyes that are in practical use include benzoyl leucomethylene blue (BLMB), 3-
C4,4°-bis(N-methylanilino) is a slow blue-coloring leuco dye that develops a clear and deep color when it comes in contact with a color developer (electron-accepting substance), and has excellent light fastness of the colored image. We discovered a material with low color development and arrived at the present invention.
本発明者等は、発色濃度が濃く自己発色性のない、また
１耐光性のある青ないし青紫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
成したカルバゾリルメタン化合物が、感圧複写紙及び感
熱記録紙等の記録材料用色素として極めて利用価値の高
いものであることを見いだした。すなわち本発明は、下
記−数式（１）で表されるカルバゾリルメタン化合物を
呈色反応物質として含有する発色性記録材料に係るもの
である。The inventors of the present invention have conducted extensive research to develop a color-forming recording material that has a high color density, does not have self-coloring property, and is light-fast and develops a blue to bluish-violet color.As a result, the present inventors have newly synthesized It has been found that a carbazolylmethane compound has extremely high utility value as a dye for recording materials such as pressure-sensitive copying paper and heat-sensitive recording paper. That is, the present invention relates to a color-forming recording material containing a carbazolylmethane compound represented by the following formula (1) as a color-forming reactant.
（式中ＲＩ、Ｒ２は水素原子または炭素数１〜５個を持
つアルキル４．ｔであり、環Ａ、Ｂ、Ｃは炭素数１〜５
個を持つアルキル基または炭素数１〜５個を持つアルコ
キシ基で置換され十そよいベンゼン環である。以下、同
符号は同じ意味を有する。）−数式（Ｌ）で表される新
規なカルバゾリルメタン化合物は淡黄色または黄土色に
わずかに着色しているにすぎないが、有機溶剤例えばジ
アリールエタン、アルキルナフタレン、水素化テルフェ
ニル、アルキルビフェニル等によく溶解し、自己発色性
はほとんど示さず、電子受容性物質例えば有機酸、酸性
白土、フェノールホルマリン樹脂。(In the formula, RI and R2 are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and rings A, B, and C each have 1 to 5 carbon atoms.
It is a long benzene ring substituted with an alkyl group having carbon atoms or an alkoxy group having 1 to 5 carbon atoms. Hereinafter, the same symbols have the same meaning. ) - The novel carbazolylmethane compound represented by the formula (L) is only slightly colored pale yellow or ocher, but it can be easily reacted with organic solvents such as diarylethane, alkylnaphthalene, hydrogenated terphenyl, alkyl It dissolves well in biphenyl, etc., shows almost no self-coloring property, and has electron-accepting substances such as organic acids, acid clay, and phenol-formalin resins.
芳香族カルボン酸の金属塩、ビスフェノールＡ等の顕色
剤と緊密に接触させることにより緩やかに青ないし青紫
に発色する。When brought into close contact with a color developer such as a metal salt of an aromatic carboxylic acid or bisphenol A, it slowly develops a blue to bluish-purple color.
本発明の新規なカルバゾリルメタン化合物は単独でも２
種以上混合しても用いる事ができる。また他の公知の発
色性記録材料用色素例えば３．３ビス−（４−ジメチル
アミノフェニル）−６−シメチルアミノフタリド、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８１５２９１号明細書、第８１
５２９４号明細書に記載のもの及びビスインドリルフタ
リド例えばドイツ特許第２２５９７１１号明細書に記載
のものなどとも混合して用いることができる。The novel carbazolylmethane compound of the present invention has two
It can also be used in combination of more than one species. Other known color-forming recording material dyes such as 3.3bis-(4-dimethylaminophenyl)-6-dimethylaminophthalide and di-substituted fluoran compounds such as British Patent No. 1182743 and Belgian Patent No. 815291 Specification, No. 81
5294 and bisindolylphthalides such as those described in German Patent No. 2259711.
本発明の一般式（１）で表される新規なカルバゾリルメ
タン化合物は、下記の方法によって合成される。すなわ
ち一般式（２）で表される４−ベンジルオキシジフェニ
ルアミン＝ｉ体をｐ−トルエンスルホン酸、塩化ホスホ
リルまたは硫酸などノ存在下に有ａ溶剤例えばメチルア
ルコール、エチルアルコール、イソプロピルアルコール
などのアルコール類、塩化エチレン、テトラクロロエチ
レンなどのハロゲン化炭化水素などの中で一般式（３）
で表される３−ホルミルカルバゾール誘導体と縮合反応
させることによって得られる。The novel carbazolylmethane compound represented by the general formula (1) of the present invention is synthesized by the following method. That is, 4-benzyloxydiphenylamine=i-form represented by general formula (2) is mixed with an alcohol such as methyl alcohol, ethyl alcohol, isopropyl alcohol, etc. in the presence of p-toluenesulfonic acid, phosphoryl chloride, sulfuric acid, etc. Among halogenated hydrocarbons such as ethylene chloride and tetrachloroethylene, general formula (3)
It is obtained by a condensation reaction with a 3-formylcarbazole derivative represented by:
Ｒ’
〜
ここで使用される一般式（２）で表される４−ベンジル
オキソジフェニルアミン誘導体は、−Ｃ式（４）で表さ
れる４−ヒドロキシジフェニルアミン誘導体を水酸化ナ
トリウム、水酸化カリウム。R' ~ The 4-benzyloxodiphenylamine derivative represented by the general formula (2) used here is a 4-hydroxydiphenylamine derivative represented by the -C formula (4), sodium hydroxide, potassium hydroxide.
炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム等
のアルカリ存在下に、有機溶剤例えばアルコール類、ジ
エチレングリコールモノメチルエテル、 Ｎ、Ｎ−ジメ
チルホルムアミド、ジメチルスルホキシドなどの中でハ
ロゲン化ベンジルと反応させることによって容易に得ら
れる。It can be easily obtained by reacting with a benzyl halide in an organic solvent such as an alcohol, diethylene glycol monomethyl ether, N,N-dimethylformamide, or dimethyl sulfoxide in the presence of an alkali such as sodium carbonate, sodium hydrogen carbonate, or potassium carbonate. It will be done.
本発明に係る新規なカルバゾリルメタン化合物は発色性
記録材料、特に感圧複写紙及び感熱記録紙用色素として
従来から知られている公知のフタリド化合物には見られ
ない極めて優れた性質を有している。これを本発明の新
規なカルバゾリルメタン化合物の一つである３−（４，
４”−ビス（Ｎ−メチル−４−ベンジルオキシアニリノ
）ベンズヒドリル）−９−ｎブチルカルバゾール（Ａ）
と公知のフタリド化合物であるクリスタルバイオレッ）
ラフ）７ （ＣＶＬ、） 、特公昭５６−５２７５８号
公報に記載のトリフェニルメタン化合物である４、４′
、４”−トリス（メチルフェニルアミノ）トリフェニル
メタン（Ｂ）、特公昭５６−１２５１５号公報に記載の
カルバゾリルメタン化合物である３−（４，４”−ビス
（Ｎ−メチルアニリノ）ベンズヒドリル） −９−ｎブ
チルカルバゾール（Ｃ）との比較により明らかにする。The novel carbazolylmethane compound according to the present invention has extremely excellent properties not found in known phthalide compounds conventionally known as pigments for color-forming recording materials, especially pressure-sensitive copying paper and heat-sensitive recording paper. are doing. This is one of the novel carbazolylmethane compounds of the present invention, 3-(4,
4”-bis(N-methyl-4-benzyloxyanilino)benzhydryl)-9-n butylcarbazole (A)
and crystal violet, a known phthalide compound)
rough) 7 (CVL, ), 4,4' which is a triphenylmethane compound described in Japanese Patent Publication No. 56-52758
, 4"-tris(methylphenylamino)triphenylmethane (B), 3-(4,4"-bis(N-methylanilino)benzhydryl), which is a carbazolylmethane compound described in Japanese Patent Publication No. 12515/1983 This is clarified by comparison with -9-n-butylcarbazole (C).
ｃＪｙ
（１）耐光堅牢性の比較
化合物（Ａ）及びＣＶＬ各７ｇをＫＭＣ−１１３（呉羽
化学製アルキルナフタレン）９３ｍに溶解し、後述の実
施例１の方法によってマイクロカプセル化し、紙の上に
コーティングして上用紙を得た。この紙を酸性電子受容
性吸着剤として酸性白土を塗布した紙に密着させ、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
酸性白土面に青色の像が得られた。マクベスＲＤ−５１
４４反射濃計（マクベス社製）を用いて発色画像の最高
到達濃度と日光照射後（６時間）の画像濃度残存率を測
定したところ表（１）の結果となった。フィルターはラ
フテン＃２５を用いた。cJy (1) Light fastness comparison Compound (A) and CVL (7 g each) were dissolved in 93 m of KMC-113 (alkylnaphthalene manufactured by Kureha Chemical Co., Ltd.), microencapsulated by the method of Example 1 described below, and coated on paper. and obtained the upper paper. This paper was brought into close contact with paper coated with acid clay as an acidic electron-accepting adsorbent, and when pressure from a ballpoint pen or impact from a typewriter was applied, a blue image was obtained on the surface of the acid clay. Macbeth RD-51
The maximum density of the colored image and the remaining image density after sunlight irradiation (6 hours) were measured using a 44 reflection densitometer (manufactured by Macbeth), and the results shown in Table (1) were obtained. Rough Ten #25 was used as the filter.
表（１）
紙上にコーティングする。その中性紙を２５〜３０℃で
２〜８日間放置し、２日目と８日目の発色濃度をマクベ
スＲＤ−５１４反射濃度計（フィルターはラフテン＃２
５）により測定した。Table (1) Coating on paper. The neutral paper was left at 25-30℃ for 2-8 days, and the color density on the 2nd and 8th days was measured using a Macbeth RD-514 reflection densitometer (the filter was Roughten #2).
5).
表（１）で表されるがごとく本発明のカルバゾリルメタ
ン化合物（Ａ）は、ＣＶＬに比べ太陽光による退色は罹
めて少なく、卓越した光堅牢性のある緩発色性ロイコ色
素だということが判る。As shown in Table (1), the carbazolylmethane compound (A) of the present invention is said to be a slowly coloring leuco dye with excellent light fastness and less fading due to sunlight than CVL. I understand that.
（２）自己発色性の比較
化合物（Ａ）及び（Ｂ）各５０■をＫＭＣ−１１３（呉
羽化学製アルキルナフタレン）ｌＨｌとラウリルベンゼ
ン４ｍに溶解し、溶解液数滴を中性表（２）で表される
ごとく本発明のカルバゾリルメタン化合物（Ａ）はトリ
フェニルメタン化合物（Ｂ）に比べ中性紙上での発色が
極めて少ない。(2) Dissolve 50 μm each of self-coloring comparative compounds (A) and (B) in KMC-113 (alkylnaphthalene manufactured by Kureha Chemical) 1H1 and 4 m laurylbenzene, and add a few drops of the dissolved solution to the neutral table (2). As shown, the carbazolylmethane compound (A) of the present invention shows extremely little color development on neutral paper compared to the triphenylmethane compound (B).
これは感圧複写紙及び感熱記録紙として利用する場合、
光による変色が極めて少なく白い紙が得られることを意
味する。When using this as pressure-sensitive copy paper and heat-sensitive recording paper,
This means that white paper can be obtained with extremely little discoloration due to light.
（３）発色速度の比較
化合物（Ａ）及び化合物（Ｃ）各７ｇをＫＭＣ−１１３
（呉羽化学製アルキルナフタレン）９３ｄに溶解し、後
述の実施例１の方法によってマイクロカプセル化し、紙
にコーティングして上用紙を得た。この紙を酸性電子受
容性吸着剤として酸性白土を塗布した紙に密着させ、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
と酸性白土面に青色の像が得られた。すぐさま暗室の中
に放置し、２４時間後の画像の発色濃度をマクベスＲＤ
−５１４反射濃度計（マクベス社製）を用いて測定した
ところ表（３）の結果となった。フィルターはラフテン
＃２５を用いた。(3) Comparison of color development speed 7 g each of compound (A) and compound (C) was added to KMC-113.
(Alkylnaphthalene manufactured by Kureha Chemical) 93d, microcapsules were formed by the method of Example 1 described later, and the mixture was coated on paper to obtain a top paper. This paper was brought into close contact with paper coated with acid clay as an acidic electron-accepting adsorbent, and when pressure from a ballpoint pen or impact from a typewriter was applied, a blue image was obtained on the surface of the acid clay. Immediately leave the image in a dark room and check the color density of the image after 24 hours using Macbeth RD.
-514 reflection densitometer (manufactured by Macbeth), the results are shown in Table (3). Rough Ten #25 was used as the filter.
表（３）
表（３）で表されるかごと（本発明のカルバゾリルメタ
ン化合物（Ａ）はベンジルオキシ基の導入により化合物
（Ｃ）に比べ発色速度が非常に速い。Table (3) The carbazolylmethane compound (A) of the present invention shown in Table (3) has a much faster color development rate than Compound (C) due to the introduction of a benzyloxy group.
次に本発明の一般式（１）で表される新規カルバゾリル
メタン化合物の合成法を具体的に例示する。Next, a method for synthesizing the novel carbazolylmethane compound represented by the general formula (1) of the present invention will be specifically illustrated.
合成例１
Ｎ−メチル−４−ベンジルオキシジフェニルアミン５．
８ｇ中にＮ−メチル−３−ホルミルカルバゾール２．５
ｇ、ｐ−１−ルエンスルホンｆｉ（１水和物）０．８ｇ
、エチルアルコール３０ｍを加え７０°Ｃで２７時間反
応せしめ反応物を氷水１００−中に加え苛性ソーダにて
中和後、トルエン５０−を加えよく混合した。トルエン
層を分離して濃縮し残留物にＮ、Ｎ−ジメチルホルムア
ミド１０ｍを加え溶解し、その溶液をメチルアルコール
２０〇−中に滴下し、沈澱した淡黄色の生成物を濾別し
て３− （４，４’−ビス（Ｎ−メチル−４−ベンジル
オキシアニリノ）ベンズヒドリルゴー９−メチルカルバ
ゾール７．１ｇを得た。このものは酸性白土上で徐々に
６２５ｎｍにλｍａｘを持つ青色に発色し、その発色像
は強い光堅牢性を示した。Synthesis Example 1 N-methyl-4-benzyloxydiphenylamine5.
2.5 N-methyl-3-formylcarbazole in 8g
g, p-1-luenesulfone fi (monohydrate) 0.8g
Then, 30 ml of ethyl alcohol was added, and the mixture was allowed to react at 70° C. for 27 hours. The reaction product was added to 100 ml of ice water, neutralized with caustic soda, and then 50 ml of toluene was added and mixed well. The toluene layer was separated and concentrated, 10 m of N,N-dimethylformamide was added to the residue to dissolve it, the solution was dropped into 200 m of methyl alcohol, and the precipitated pale yellow product was filtered out to give 3- (4 , 4'-bis(N-methyl-4-benzyloxyanilino)benzhydrylgo-9-methylcarbazole (7.1 g) was obtained.This material gradually developed a blue color with λmax at 625 nm on acid clay. , the color image showed strong light fastness.
合成例２
Ｈ３
ｃＪｖ
のは酸性白土上で徐々に６２５ ｎｍにλｍａｘを持つ
青色に発色し、その発色像は強い光堅牢性を示した。Synthesis Example 2 H3 cJv gradually developed a blue color with λmax at 625 nm on acid clay, and the color image showed strong light fastness.
次に一般式（１）において環Ａ、Ｂ、Ｃにそれぞれ置換
基Ｘ ｌ 、 Ｘ ｔ 、 ）ｃ ３の導入されたもの
の例として合成例１．２と同様な方法にて得た新規なカ
ルバゾリルメタン化合物の酸性白土での発色色調を表（
３）に示す。Next, as an example of the general formula (1) in which substituents X l , The color tone of the zolylmethane compound in acid clay is shown in the table (
3).
口Ｃ，１１９
Ｎ−）チル−４−ベンジルオキシジフェニルアミン５．
８ｇ中にＮ−ブチル−３−ホルミルカルバゾール３．０
ｇ、 ρ−トルエンスルホン酸０．８ｇ。Mouth C, 119 N-)Tyl-4-benzyloxydiphenylamine5.
3.0 N-butyl-3-formylcarbazole in 8g
g, 0.8 g of ρ-toluenesulfonic acid.
エチルアルコール３０ｍを加え７０℃で２４時間反応さ
せる。反応物を合成例１と同様な方法で処理し淡黄色の
３− ［４，４’−ビス（Ｎ−メチル−４ベンジルオキ
シアニリノ）ベンズヒドリル〕９−ｎブチルカルバゾー
ル６．９ｇを得た。このもこれらカルバゾリルメタン化
合物を用いて感圧複写紙を製造するには、例えば米国特
許第２８００４５８号明細書、第２８０６４５７号明細
書に記載の公知の方法を用いれば良く、また感熱記録紙
を製造するには、例えば特公昭４５−１４０３９号公報
に記載の公知の方法を用いれば良い。以丁新現カルバゾ
リルメタン化合物を用いた感圧複写紙及び感熱記録紙の
実施例を示す。Add 30ml of ethyl alcohol and react at 70°C for 24 hours. The reaction product was treated in the same manner as in Synthesis Example 1 to obtain 6.9 g of pale yellow 3-[4,4'-bis(N-methyl-4benzyloxyanilino)benzhydryl]9-n-butylcarbazole. In order to produce pressure-sensitive copying paper using these carbazolylmethane compounds, for example, known methods described in U.S. Pat. No. 2,800,458 and U.S. Pat. In order to produce this, for example, a known method described in Japanese Patent Publication No. 45-14039 may be used. Examples of pressure-sensitive copying paper and heat-sensitive recording paper using a carbazolylmethane compound are shown below.
実施例１ （感圧複写紙の例）
合成例１の３−［４，４“−ビス（Ｎ−メチル−４ベン
ジルオキシアニリノ）ベンズヒドリル〕９−メチルカル
バゾールを７部（以下重量部で示す）をモノイソプロピ
ルビフェニル９３部に溶解し、この液にゼラチン２４部
とアラビアゴム２４部を水４００部に溶解しｐＨを７に
調整した液を加える。ホモジナイザーで乳化し、温水１
０００部を加え５０℃で３０分間攪拌したのち、ｌＯ％
苛性ソーダ液約１部を加え、更に５０°Ｃで３０分間攪
拌した。次いで希酢酸を徐々に加えてｐＨ４゜５に調整
し、５０°Ｃで約１時間攪拌し０〜５℃に冷却更に３０
分間攪拌した０次に４％グルタルアルデヒド水ｍｆ！３
５部を徐々に加えてカプセルを硬化させ、苛性ソーダ水
溶液でｐＨを６に調整し室温で数時間攪拌してカプセル
化を終了した。このカプセル液をワイヤーバーで均一に
紙に塗布し乾燥して塗布紙（上用紙）を得た。この紙を
顕色剤として酸性白土、またはフェノールホルマリン樹
脂を塗布した紙（下用紙）に重ね合わせボールペンの１
圧あるいはタイプライタ−の衝撃を加えると下用紙上に
濃い青色の像が徐々に表れた。この像は優れた光安定性
を示した。同じ塗布面を中性紙に転写した場合は中性紙
上でほとんど発色しなかった。Example 1 (Example of pressure-sensitive copying paper) 7 parts of 3-[4,4"-bis(N-methyl-4benzyloxyanilino)benzhydryl]9-methylcarbazole of Synthesis Example 1 (hereinafter expressed in parts by weight) ) in 93 parts of monoisopropylbiphenyl, and to this solution is added a solution prepared by dissolving 24 parts of gelatin and 24 parts of gum arabic in 400 parts of water and adjusting the pH to 7. Emulsify with a homogenizer, and add 1 part of warm water.
After adding 000 parts and stirring at 50°C for 30 minutes, lO%
Approximately 1 part of caustic soda solution 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, stirred at 50°C for about 1 hour, cooled to 0-5°C, and further stirred for 30 minutes.
4% glutaraldehyde water mf after stirring for 0 minutes! 3
5 parts were gradually added to harden the capsules, the pH was adjusted to 6 with an aqueous solution of caustic soda, and the encapsulation was completed by stirring at room temperature for several hours. This capsule liquid was uniformly applied to paper using a wire bar and dried to obtain a coated paper (upper paper). Layer this paper on paper (lower paper) coated with acid clay or phenol-formalin resin as a color developer, and use one of the ballpoint pens.
Upon application of pressure or typewriter impact, a dark blue image gradually appeared on the bottom paper. This image showed excellent photostability. When the same coated surface was transferred to neutral paper, almost no color developed on the neutral paper.
実施例２（感熱記録紙の例）
合成例１の３− （４，４’−ビス（Ｎ−メチル−４−
ベンジルオキシアニリノ）ベンズヒドリル〕９−メチル
カルバゾール３０部を１５０部の１０％ポリビニールア
ルコール水溶液及び６５部の水と一緒にボールミルで１
０時間混合粉砕して成分へとする。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Ａ。Example 2 (Example of thermal recording paper) 3-(4,4'-bis(N-methyl-4-
Benzyloxyanilino)benzhydryl] 30 parts of 9-methylcarbazole were mixed with 150 parts of a 10% polyvinyl alcohol aqueous solution and 65 parts of water in a ball mill.
Mix and grind for 0 hours to obtain ingredients. The particle size of the color former after pulverization was 3 to 5 microns. and 35 parts of bisphenol A on the other hand.
１５０部の１０％ポリビニールアルコール水溶液及び６
５部の水を同様にボールミルで粒子径が３〜５ミクロン
になるまで混合粉砕して成分Ｂとする。次に３部の成分
Ａと６７部の成分Ｂを混合し、乾燥後固形分重量が７
ｇ／ｒｒｃになるように上質紙にワイヤーバーで塗布し
乾燥して感熱記録紙を得た。この感熱記録紙は熱ペン等
の加熱によって青に発色し、自己発色性はほとんどなか
った。150 parts of 10% polyvinyl alcohol aqueous solution and 6
Component B is obtained by mixing and pulverizing 5 parts of water in the same manner using a ball mill until the particle size becomes 3 to 5 microns. Next, 3 parts of component A and 67 parts of component B were mixed, and after drying, the solid content was 7 parts.
The mixture was applied to high-quality paper using a wire bar so as to give g/rrc and dried to obtain heat-sensitive recording paper. This thermosensitive recording paper developed a blue color when heated with a thermal pen or the like, and had almost no self-coloring property.
Claims (1)
を持つアルキル基であり、環Ａ、Ｂ、Ｃは炭素数１〜５
個を持つアルキル基または炭素数１〜５個を持つアルコ
キシ基で置換されていてもよいベンゼン環である。）で
表されるカルバゾリルメタン化合物を呈色反応物質とし
て含有することを特徴とする発色性記録材料。(1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^1 and R^2 are hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, and rings A, B, and C are carbon atoms. Numbers 1-5
It is a benzene ring which may be substituted with an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. ) A color-forming recording material characterized by containing a carbazolylmethane compound represented by the following as a color-forming reactant.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63177525A JPH0226782A (en) | 1988-07-16 | 1988-07-16 | Color forming recording material |
| GB8915963A GB2220671B (en) | 1988-07-16 | 1989-07-12 | Improvements in or relating to colour developing recording materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63177525A JPH0226782A (en) | 1988-07-16 | 1988-07-16 | Color forming recording material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0226782A true JPH0226782A (en) | 1990-01-29 |
Family
ID=16032445
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63177525A Pending JPH0226782A (en) | 1988-07-16 | 1988-07-16 | Color forming recording material |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH0226782A (en) |
| GB (1) | GB2220671B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9313790D0 (en) * | 1993-07-03 | 1993-08-18 | Wiggins Teape Group The Ltd | Pressure-sensitive copying material |
| GB2393352A (en) | 2002-09-23 | 2004-03-24 | Mitel Knowledge Corp | Speaker system with two enclosures having complementary frequency responses |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| LU76074A1 (en) * | 1976-10-26 | 1978-05-16 |
-
1988
- 1988-07-16 JP JP63177525A patent/JPH0226782A/en active Pending
-
1989
- 1989-07-12 GB GB8915963A patent/GB2220671B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| GB2220671A (en) | 1990-01-17 |
| GB8915963D0 (en) | 1989-08-31 |
| GB2220671B (en) | 1992-01-22 |
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