JPS62198494A - Color forming recording material - Google Patents
Color forming recording materialInfo
- Publication number
- JPS62198494A JPS62198494A JP61040695A JP4069586A JPS62198494A JP S62198494 A JPS62198494 A JP S62198494A JP 61040695 A JP61040695 A JP 61040695A JP 4069586 A JP4069586 A JP 4069586A JP S62198494 A JPS62198494 A JP S62198494A
- Authority
- JP
- Japan
- Prior art keywords
- color
- group
- acid
- paper
- triphenylmethanecarboxylic
- 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 10
- -1 triphenylmethanecarboxylic acid ester Chemical class 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000003386 piperidinyl group Chemical group 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 9
- 238000004040 coloring Methods 0.000 abstract description 7
- 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
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000004927 clay Substances 0.000 abstract description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 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 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract 1
- 150000007524 organic acids Chemical class 0.000 abstract 1
- 229920001568 phenolic resin Polymers 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical group C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- DCYGAPKNVCQNOE-UHFFFAOYSA-N 2,2,2-triphenylacetic acid Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(C(=O)O)C1=CC=CC=C1 DCYGAPKNVCQNOE-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 239000002775 capsule Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical class C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 150000004961 triphenylmethanes Chemical class 0.000 description 2
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- FXSFKECPPGDGBN-UHFFFAOYSA-N 3,3-bis(1h-indol-2-yl)-2-benzofuran-1-one Chemical compound C12=CC=CC=C2C(=O)OC1(C=1NC2=CC=CC=C2C=1)C1=CC2=CC=CC=C2N1 FXSFKECPPGDGBN-UHFFFAOYSA-N 0.000 description 1
- XFDUHJPVQKIXHO-UHFFFAOYSA-N 3-aminobenzoic acid Chemical class NC1=CC=CC(C(O)=O)=C1 XFDUHJPVQKIXHO-UHFFFAOYSA-N 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
- 229920000084 Gum arabic Polymers 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 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
- 239000003849 aromatic solvent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 238000002845 discoloration Methods 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
- 150000002148 esters Chemical class 0.000 description 1
- 235000019441 ethanol Nutrition 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
- 238000000227 grinding Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 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
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 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
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
- B41M5/1366—Organic colour formers, e.g. leuco dyes characterised solely by tri (aryl or hetaryl)methane derivatives
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Color Printing (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
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、それ自体殆ど無色の電
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る。具）体的には感圧複写紙
や感熱複写紙などに用いられる。[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 almost colorless, developing color when brought into contact with an electron-accepting substance. . Specifically, it is used for pressure-sensitive copying paper, thermal copying paper, etc.
〔従来の技術と発明が解決しようとする問題点〕背ない
し背紫に発色する呈色性無色物質として、トリフェニル
メタン系化合物が知られている（ケミカルアブストラク
ト６０３−４８−５ ）が、有機溶剤に対する溶解性が
低く、又自己発色性が極めて強く発色前の安定性に著し
く欠けるなどの欠点を有しておシ感圧複写紙および感熱
記録紙等の記録材料用色素として到底実用に耐えるもの
ではない。[Prior art and problems to be solved by the invention] Triphenylmethane compounds are known as color-forming colorless substances that develop a back to back purple color (Chemical Abstract 603-48-5). It has drawbacks such as low solubility in solvents, extremely strong self-coloring properties, and a significant lack of stability before coloring, making it completely unsuitable for practical use as a pigment for recording materials such as pressure-sensitive copying paper and heat-sensitive recording paper. It's not a thing.
本発明者＃は、有機溶剤によく溶解し自己発色性のない
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トリフェ
ニルメタンカルボン酸エステルが、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−・般式（１）
で表される新規なトリフェニルメタンカルボン酸エステ
ル化合物は、それ自体殆ど無色であるが、有機溶剤例え
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、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シ速やかに青ないし青紫に発
色する。As a result of intensive research to develop a color-forming recording material that dissolves well in organic solvents and develops a blue to bluish-purple color without self-coloring property, the present inventors newly synthesized triphenylmethanecarboxylic acid. It has been found that esters are extremely useful as dyes for recording materials such as pressure-sensitive copying paper and heat-sensitive recording paper. That is, - General formula (1)
The novel triphenylmethanecarboxylic acid ester compound represented by When brought into close contact with a color developer such as a metal salt of an aromatic carboxylic acid or bisphenol A, it quickly develops a blue to bluish-purple color.
〔式中Ｒ１、Ｒ２、Ｒ５、Ｒ４、Ｒ５、Ｒ６はそれぞれ
独立にに炭素数１−５の１１アルキル基、シクロアルキ
ル基、ベンジル基、フェニル基よシ選ばれる基を示すか
１又は６とＲ２、Ｒ３とＲ４、Ｒ５とＲ６は互いに結合
して隣接する窒素原子と共にピロジニル基、ピペリジニ
ル基、ヘキサメチレンイミノ基よシ選ばれる基を示し、
Ｒ７は炭素数１−１２のアルキル基又はベンジル基を示
す。以下、同符号は同じ意味を有する。〕
本発明の新規なトリフェニルメタンカルボン酸エステル
は、単独でも２種以上混合しても用いる事ができる。又
他の公知の発色性記録材料用色素、例えば、５．５’−
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８１５２
９１号明細書、＄ ８１５２９４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２２５
９７１１最明＃ｌ書に記載のものとも混合して用いるこ
とができる。[In the formula, R1, R2, R5, R4, R5, and R6 each independently represent a group selected from a C1-5 alkyl group, a cycloalkyl group, a benzyl group, a phenyl group, or 1 or 6. R2, R3 and R4, R5 and R6 are bonded to each other and together with adjacent nitrogen atoms represent a group selected from a pyrodinyl group, a piperidinyl group, a hexamethyleneimino group,
R7 represents an alkyl group having 1 to 12 carbon atoms or a benzyl group. Hereinafter, the same symbols have the same meaning. ] The novel triphenylmethanecarboxylic acid esters of the present invention can be used alone or in combination of two or more. In addition, other known dyes for color-forming recording materials, such as 5.5'-
Bis-(4-dimethylaminophenyl)-6-dimethylaminophthalide, disubstituted fluoran compounds such as British Patent No. 1182743, Belgian Patent No. 8152
No. 91, US Pat. No. 815,294 and bisindolyl phthalide such as German Patent No. 225
It can also be used in combination with those described in 9711 Saimei #l.
本発明の一般式（１）で表される新規なトリフェニルメ
タンカルボン酸エステル化合物は、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２−〔４
，４’−ビス（ジアミノ）ベンズヒドリル〕−５−ジア
ミノ安息香酸誘導体を水酸化ナトリウム、水酸化カリウ
ム、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水溶液中又は有機溶剤例えば、
メチルアルコール、エチルアルコール、中で硫酸ジメチ
ル、硫酸ジエチル及びハロゲン化アルキルと反応させる
か、あるいは一般式（３）で表される４、４′−ビス（
ジアミノ）ベンズヒドロール誘導体と一般式（４）で表
されるｍ−アミン安息香酸エステル銹導体のほぼ等モル
を硫酸、塩酸等の存在下で反応させることによって得ら
れる。The novel triphenylmethanecarboxylic acid ester compound represented by the general formula (1) of the present invention is synthesized by the following method. That is, 2-[4 expressed by general formula (2)
, 4'-bis(diamino)benzhydryl]-5-diaminobenzoic acid derivative in the presence of an alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, etc., in an aqueous solution or in an organic solvent, e.g.
4,4'-bis(
It is obtained by reacting approximately equimolar amounts of a diamino)benzhydrol derivative and the m-amine benzoate ester conductor represented by the general formula (4) in the presence of sulfuric acid, hydrochloric acid, or the like.
、♂＼
Ｒ６（３）
ベンズヒドリル〕−５−ジアミノ安息香酸誘導体は公知
の方法例えば一般式（３）で表される４、４’−ビス（
ジアミノ）ベンズヒドロール銹導体ト一般式（５）で表
されるｍ−アミノ安息香酸誘導体のほぼ等モルを硫酸、
塩酸等の存在下に反応させることによって得られる。,♂＼R6(3) Benzhydryl]-5-diaminobenzoic acid derivatives can be prepared by known methods such as 4,4'-bis(
Diamino)benzhydrol conductor: Approximately equal moles of the m-aminobenzoic acid derivative represented by the general formula (5) are mixed with sulfuric acid,
Obtained by reaction in the presence of hydrochloric acid or the like.
本発明に係る新規なトリフェニルメタンカルボン酸エス
テル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トリフ
ェニルメタン化合物にはみられない極めて優れた性質を
有している０これを本発明の新規なトリフェニルメタン
カルボン酸エステルの一つである２−［４，４’−ビス
（ジメチルアミノ）ベンズヒドリルツー５−ジメチルア
ミノ安息香酸エチルエステル（Ａ）と（Ａ）と９二３１
似の構造を有する公知のトリ７二二ルメタン化合物であ
る。The novel triphenylmethanecarboxylic acid ester compound according to the present invention has extremely superior properties not found in conventional triphenylmethane compounds that have been used as pigments for color-forming recording materials, especially pressure-sensitive copying paper and heat-sensitive recording paper. 2-[4,4'-bis(dimethylamino)benzhydryl-5-dimethylaminobenzoic acid ethyl ester, which is one of the novel triphenylmethanecarboxylic acid esters of the present invention, has the properties of (A) and (A) and 9231
It is a well-known tri72dylmethane compound with a similar structure.
４．４′、４“−トリス（ジメチルアミノ）トリフェニ
ルメタン（Ｅ）との比較によシ明らかにする。This is clarified by comparison with 4.4',4''-tris(dimethylamino)triphenylmethane (E).
（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（Ｉ３）のＫＭＩ：ｊ−１１３（県別化学製ア
ルキルナフタレン）とハイゾールＳＡＳ （日本石油化
学製ジアリールメタン）での２５℃での溶解度。(1) Comparative compounds with solubility in solvents for pressure-sensitive copying paper (
KMI of A) and (I3): Solubility at 25°C in j-113 (alkylnaphthalene manufactured by Kenbetsu Kagaku) and Hysol SAS (diarylmethane manufactured by Nippon Petrochemical).
表１
表１で表されるごとく本発明のトリフェニルメタンカル
ボン酸エステル化合物（Ａ）は、公知のトリフェニルメ
タン化合物ＣＢ）に比べ溶解度が極めて高い。これは、
感圧複写紙を作る際マイクロカプセル中での結晶析出の
恐れがなく、又マイクロカプセル化に当って高価な芳香
族系の溶剤を少なくし、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経＾的に有利であることを意味
する。Table 1 As shown in Table 1, the triphenylmethanecarboxylic acid ester compound (A) of the present invention has extremely high solubility compared to the known triphenylmethane compound CB). this is,
When making pressure-sensitive copying paper, there is no fear of crystal precipitation in microcapsules, and in microencapsulation, the amount of expensive aromatic solvents used can be reduced, and the amount of relatively inexpensive petroleum-based solvents used can be reduced. It means that it is economically advantageous because it can be increased.
（２）自己発色性の比較
化合物（Ａ）及び（Ｂ）各７ｆをＫＭＣ−１１３９３π
ｔ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葉紙を得た。発色前
の塗布量は０−１５ｇ７であった。これら上葉紙を中性
紙と重ね合わせて転写し、その中性紙上の転写像に太陽
光を照射し時間毎の発色濃度をマクベスＲＤ−５１４反
射濃度計（マクベス社製）によシ測定した。フィルター
はラツテン≠２５を用いた０表２
表２で表対有るごとく本発明のトリフ−＝ルメタンカル
ボン酸エステル化合物（Ａ）は、公知のトリフェニルメ
タン化合物（Ｂ）に比べ中性紙上での太陽光による発色
は極めて少ない。これは感圧複写紙及び感熱記録紙とし
て利用する場合、元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。(2) Self-coloring comparative compounds (A) and (B) 7f each with KMC-11393π
The mixture was dissolved in water, microencapsulated by the method of Example 1 described below, and coated on paper to obtain top paper. The amount of coating before color development was 0-15g7. These top sheets were superimposed and transferred onto neutral paper, the transferred image on the neutral paper was irradiated with sunlight, and the color density was measured over time using a Macbeth RD-514 reflection densitometer (manufactured by Macbeth Co., Ltd.). did. As shown in Table 2, the trifluoromethane carboxylic acid ester compound (A) of the present invention has a higher resistance on neutral paper than the known triphenylmethane compound (B). There is very little color development due to sunlight. This means that when used as pressure-sensitive copying paper or heat-sensitive recording paper, white paper can be obtained with extremely little discoloration due to the source.
次に本発明の一般式（１）で表される新規トリフェニル
メタンカルボン酸エステル化合物の合成法を具体的に例
示する。Next, a method for synthesizing the novel triphenylmethanecarboxylic acid ester compound represented by the general formula (1) of the present invention will be specifically illustrated.
合成例 １
ノ、
Ｈ，ＣＧ’Ｈ３
２−［’４．４’−ビス（ジメチルアミノ）ベンズヒド
リル〕−５−ジメチルアミノ安息香酸１６７ｇにメチル
アルコール５００αｔと炭酸カリウム８５．０９を加え
５０℃にて硫酸ジメチル７５．６１Ｆを５時間テ加えた
。さらに６０℃で別時間反応し反応物を氷水２００口ｙ
ｅｔとトルエン５００ｆｆ？中に加えよく混合した。Synthesis Example 1 500αt of methyl alcohol and 85.09 g of potassium carbonate were added to 167 g of 2-['4.4'-bis(dimethylamino)benzhydryl]-5-dimethylaminobenzoic acid at 50°C. Dimethyl sulfate 75.61F was added for 5 hours. The reaction was further carried out at 60°C for another time, and the reaction product was poured into 200 ml of ice water.
et and toluene 500ff? Add to the mixture and mix well.
トルエン層を分離して濃縮し残留物にメチルアルジメチ
ルアミノ）ベンズヒドリル〕−５−ジメチルアミン安息
香酸メチルエステル８２９を得た。The toluene layer was separated and concentrated to give methylaldimethylamino)benzhydryl]-5-dimethylaminebenzoic acid methyl ester 829 as a residue.
合成例 ２゜
Ｈ，Ｃ、ＣＨ３
２−（４１，４’−ビス（ジメチルアミノ）ベンズヒド
リル〕−５−ジメチルアミノ安息香酸１６７ｇにエチル
アルコール５ｏｏＭｔト炭酸カリウム８３．Ｏｆを加え
５０″Ｃにて硫酸ジエチル９２．０ｇを５時間で加えた
。反応物を合成例１と同様な方法で処理（−融点１３０
．５−１３５．５での無色の結晶として２−〔４，４１
−ビス（ジメチルアミノ）ベンズヒドリル〕−５−ジメ
チルアミノ安息香酸エチルエステル８６．９ｆを得た。Synthesis Example 2゜To 167 g of H, C, CH3 2-(41,4'-bis(dimethylamino)benzhydryl]-5-dimethylaminobenzoic acid was added 50 Mt of ethyl alcohol and 83.0 Mt of potassium carbonate, and diluted with sulfuric acid at 50''C. 92.0 g of diethyl was added over 5 hours.The reaction product was treated in the same manner as in Synthesis Example 1 (-melting point 130
．． 2-[4,41 as colorless crystals at 5-135.5
-Bis(dimethylamino)benzhydryl]-5-dimethylaminobenzoic acid ethyl ester 86.9f was obtained.
合成例 ３゜
２−Ｃ４，４’−ビス（ジメチルアミノ）ベンズヒドリ
ルツー５−ジメチルアミフ安息香酸１６７ｇに水５００
１ｑ／と炭酸カリウム８３．Ｏｆを加工８０．０’ｃＫ
て臭化ブチル８０ｇを１０時間で加えた。反応物を合成
例１と同様な同法で処理し融点１３３．５−１３７．５
℃の無色の結晶として２−〔４，４′−ビス（ジメチル
アミノ）ベンズヒドリル〕−５−ジメチルアミノ安息香
酸ブチルエステル６０．０ ｇヲｍｆｃ。Synthesis example 3゜2-C4,4'-bis(dimethylamino)benzhydryl-5-dimethylamifbenzoic acid (167 g) and water (500 g)
1q/ and potassium carbonate 83. Machining Of80.0'cK
80 g of butyl bromide was added over 10 hours. The reactant was treated in the same manner as in Synthesis Example 1 to give a melting point of 133.5-137.5.
2-[4,4'-bis(dimethylamino)benzhydryl]-5-dimethylaminobenzoic acid butyl ester as colorless crystals at 60.0 g mfc.
次に合成例１−３と同様な方法にて得た新規なトリフェ
ニルメタンカルボン酸エステル化合物の酸性白土での発
色色調を表３に示す。Next, Table 3 shows the color tone of the novel triphenylmethanecarboxylic acid ester compound obtained in the same manner as in Synthesis Example 1-3 on acid clay.
これらトリフェニルメタンカルボン酸エステル化合物を
用いて感圧複写紙を製造するには、例えば米国特許第２
８００４５８号明細書、第２８０６４５７号明ａ書に記
載の公知の方法を用いれば良く、又感熱記録紙を製造す
るＫ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。以下新規トリフェニルメタ
ンカルボン酸エステル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。In order to produce pressure-sensitive copying paper using these triphenylmethanecarboxylic acid ester compounds, for example, US Pat.
800458 specification and No. 2806457 specification a may be used, and for K for producing thermal recording paper, for example, the known method described in Japanese Patent Publication No. 14039/1983 may be used. . Examples of pressure-sensitive copying paper and heat-sensitive recording paper using the novel triphenylmethanecarboxylic acid ester compound are shown below.
実施例 １．（感圧複写紙の例）
合成例２の２−（’４．４’−ビス（ジメチルアミノ）
ベンズヒドリル〕−５−ジメチルアミノ安息にゼラチン
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１０００部を加え５０℃で３０分間Ｐζ拌したのち
、１１） ％カセイソーダ液約１部を加えさらに５０′
ｃで３０分間攪拌した。次いで種酢酸を徐々に加えてＰ
Ｈを４．５に調整し、５０”Ｃで約１時間攪拌し０−５
″Ｃに冷却、さらに３０分間攪拌した。Example 1. (Example of pressure-sensitive copying paper) 2-('4.4'-bis(dimethylamino) of Synthesis Example 2
Benzhydryl]-5-dimethylaminobenzate, 24 parts of gelatin and 24 parts of gum arabic were dissolved in 400 parts of water, and the PH
Add the solution adjusted to 7. Emulsify with a homogenizer,
After adding 1000 parts of warm water and stirring at 50°C for 30 minutes, add about 1 part of 11)% caustic soda solution and stir for another 50'.
The mixture was stirred at c for 30 minutes. Then, gradually add seed acetic acid to P.
Adjust the H to 4.5 and stir at 50"C for about 1 hour to 0-5
The mixture was cooled to 30°C and further stirred for 30 minutes.
次に４％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工ｉ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
。このカプセルｉｔ−ワイヤーパーで均一に紙に塗布し
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）Ｋ重ね合わせボールペンの筆圧或はタイプ
ライタ−の衝撃を加えると下葉紙上に濃い青紫の像が徐
々に表われた。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。Next, 35 parts of a 4% glutaraldehyde aqueous solution was gradually added to harden the capsules, the p ratio was adjusted to 6 with a caustic soda aqueous solution, and the mixture was stirred at room temperature for several hours to complete encapsulation. The capsules were uniformly coated on paper using an IT-wire par and dried to obtain coated paper (top paper). This paper is coated with acid clay or phenol-formalin resin as a color developer (lower paper). When the pressure of a ballpoint pen or the impact of a typewriter is applied to this paper, a deep blue-purple image gradually forms on the lower paper. It appeared in 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２の２−（４，４’−ビス（ジメチルアミノ）ベ
ンズヒドリル〕−５−ジメチルアミノ安息香酸エチルエ
ステル３０部（以下重量部で示す）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５−５ミクロンであった。他方３５部の
ビスフェノールＡ、１５０部の１０％ポリビニールアル
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７９／ゴになるよう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速やかにＴ９に発色し、自己
発色社殆んどなかった。Example 2. (Example of thermal recording paper) 10% of 150 parts of 2-(4,4'-bis(dimethylamino)benzhydryl]-5-dimethylaminobenzoic acid ethyl ester of Synthesis Example 2 (hereinafter expressed in parts by weight)
Component A is obtained by mixing and grinding an aqueous polyvinyl alcohol solution and 65 parts of water in a ball mill for 10 hours. The particle size of the color former after pulverization was 5-5 microns. On the other hand, 35 parts of bisphenol A, 150 parts of a 10% polyvinyl alcohol aqueous solution, and 65 parts of water were similarly mixed and ground in a ball mill until the particle size became 3 to 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 wire bar so that the solid content weight after drying was 79/g and dried to obtain heat-sensitive recording paper. This thermosensitive recording paper quickly developed a color of T9 when heated with a thermal pen or the like, and there was almost no self-coloring.
Claims (1)
６はそれぞれ独立に炭素数１−５のアルキル基、シクロ
アルキル基、ベンジル基、フェニル基より選ばれる基を
示すか、又はＲ＾１とＲ＾２、Ｒ＾３とＲ＾４、Ｒ＾５
とＲ＾６は互いに結合して隣接する窒素原子と共にピロ
ジニル基、ピペリジニル基、ヘキサメチレンイミノ基よ
り選ばれる基を示し、Ｒ＾７は炭素数１−１２のアルキ
ル基、又はヘンジル基を示す。〕で表されるトリフェニ
ルメタンカルボン酸エステルを呈色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。[Claims] [1] General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) [In the formula, R^1, R^2, R^3, R^4, R^5, R^
6 each independently represents a group selected from an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group, a benzyl group, a phenyl group, or R^1 and R^2, R^3 and R^4, R^ 5
and R^6 are bonded to each other and represent a group selected from a pyrodinyl group, a piperidinyl group, and a hexamethyleneimino group together with an adjacent nitrogen atom, and R^7 represents an alkyl group having 1 to 12 carbon atoms or a henzyl group. A color-forming recording material characterized by containing triphenylmethanecarboxylic acid ester represented by ] as a color-forming colorless substance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61040695A JPS62198494A (en) | 1986-02-25 | 1986-02-25 | Color forming recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61040695A JPS62198494A (en) | 1986-02-25 | 1986-02-25 | Color forming recording material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62198494A true JPS62198494A (en) | 1987-09-02 |
Family
ID=12587688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61040695A Pending JPS62198494A (en) | 1986-02-25 | 1986-02-25 | Color forming recording material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62198494A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0486749A1 (en) * | 1990-11-22 | 1992-05-27 | Hodogaya Chemical Co., Ltd. | Triarylmethane compounds and pressure sensitive recording material |
| US6485552B2 (en) | 2000-02-29 | 2002-11-26 | Asahi Kogaku Kogyo Kabushiki Kaisha | Ink composition for thermal ink jet printer or thermal ink permeation printer |
-
1986
- 1986-02-25 JP JP61040695A patent/JPS62198494A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0486749A1 (en) * | 1990-11-22 | 1992-05-27 | Hodogaya Chemical Co., Ltd. | Triarylmethane compounds and pressure sensitive recording material |
| US6485552B2 (en) | 2000-02-29 | 2002-11-26 | Asahi Kogaku Kogyo Kabushiki Kaisha | Ink composition for thermal ink jet printer or thermal ink permeation printer |
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