JPS62243652A - Divinyl compound and coloring record material using same - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I(X is heterocyclic group containing N atom; X<1> and X<2> are 1-8C alkyl, 1-8C alkoxy, F, Cl or Br; X<3> is Cl or Br; m and n are 0-3). EXAMPLE:3, 3-Bis[2-(p-pyrrolidinophenyl)-2-(p-methylphenyl)ethenyl]-4,5,6,7-tetra chlorophthalide. USE:A blackening record material or a coupler for infrared light reading record material. PREPARATION:For example, 1-(p-methylphenyl)-1-(p-pyrrolidinophenyl)ethylene is reacted with tetrachlorophthalic anhydride in acetic anhydride, the reaction product is added to water and alkalized with NaOH. Then, the reaction product is extracted with toluene, toluene is distilled away and a solid substance is recrystallized.

Description

Detailed Description of the Invention "Industrial Application Field" [In the formula, X represents a nitrogen atom-containing heterocyclic group, Xl,
X2 represents an alkyl group having 8 or less carbon atoms, an alkoxy group having 8 or less carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, or a combination thereof; x3 represents a chlorine atom, a bromine atom, or a combination thereof; m and n each represent 0.1.2 or 3. Hereinafter, the same symbols have the same meaning. ] The present invention relates to a divinyl compound represented by the following and a recording material using the divinyl compound as a coloring agent.

The fluoran compound represented by the above general formula (1) is a new compound synthesized for the first time by the present inventors, and is almost colorless in itself, extremely stable in the atmosphere, and has excellent sublimation and natural coloring properties (background capri). There is no organic solution. Furthermore, since colored images have strong absorption in the visible region and in the range 700 to 11,000 nm, optical character reading equipment (OCR) using near-infrared rays
lortR), which can be read by a barcode reading device. Therefore, it is an extremely valuable new compound that can be used as a coloring agent for infrared reading recording materials, in addition to ordinary black coloring recording materials, the demand for which has been increasing rapidly in recent years.

Examples of recording materials include pressure-sensitive copying paper, thermal recording paper, electrically conductive thermal recording paper, color-forming thermal transfer recording paper, ultrasonic recording paper, laser recording paper, temperature-indicating material, stamp ink, type ribbon, ballpoint pen ink, etc. It will be done.

"Prior art" and "Problems to be solved by the present invention" The colored image of the following black-coloring fluoran compound (A), which has been conventionally used as a coloring agent for color-forming recording materials, has no absorption in the near-infrared region. Therefore, the optical character reading device could not read the characters. (See Figure 2) In addition, in recent years, the special public interest
8-5940, JP-A-60-21890, JP-A-59
-j 99757, various compounds are proposed.

However, each of them has the following drawbacks, and at present no satisfactory color former has yet been obtained. That is, the compounds (E) and (C) of Japanese Patent Publication No. 58-5940 and Japanese Patent Publication No. 60-230890 are strongly yellow in color and have strong natural coloring (background capri). These drawbacks are extremely inconvenient in the production of recording materials. Japanese Patent Publication No. 59-1
Although the fluoran compound φ) of No. 99757 is colorless, it has poor color development and has weaker absorption in the near-infrared region than in the visible region.

Furthermore, the coloring hues of (B), (C), and (D) are all green, and in order to produce a black color, a large amount of other coloring agent that produces a red or black color must be mixed. When mixed, the color formers have different coloring properties, coloring speeds, etc., and the red coloring agent in particular has poor light resistance, so problems such as an imbalance in color development and a decrease in light resistance cannot be avoided.

The present invention was arrived at as a result of intensive studies aimed at improving these drawbacks.

``Means for solving the problems'' and ``effects'', that is, the present invention provides that the divinyl compound of the general formula (1) has unexpected solubility, coloring of the compound itself, coloring hue, coloring property, and near-infrared absorbance. We have discovered that the compound has excellent properties such as image stability, and have arrived at this as a result of further research.The present invention provides a compound of the general formula (1) and a color-forming recording material containing the compound as a color-forming agent. be.

Specific examples of the divinyl compound of the present invention include the following.

All of them are almost colorless solids, which quickly develop a black to blue-black color with activated clay.

13.3-BisC2-Cp-pyrrolidinophenyl)-
2-phenylethynyl)-4,5゜6.7-titrachlorophthalide 23.3-bisC2-Cp-pyrrolidinophenyl)-2
-(p-methylphenyl)ethynyltwo 4.5,6. Thitrachlorophthalide 33. 3-Bis[2-(p-pyrrolidinophenyl)-2-Cp-methoxyphenyl)ethynyl)-4,5,6,7-thitrachlorophthalide 43.
3-bis[2-(p-pyrrolidinophenyl)-2-Cp
-chlorophenyl)ethynyltwo 4.5,6. fuchtrachlorophthalide 53.3-bisC2-(p-pyrrolidinophenyl)-2-(1)-1fruphenyl)ethynyl]-5-chloro-4,6,7-)lipromophthalide 3.3-bis [z-(p-pyrrolidinophenyl)2
-(p-methoxyphenyl)ethynyl-5,6-dichloro-4,7-dipromophthalidore 3.3-bis[2-(p-pyrrolidinophenyl)-
2-(1)-methylphenyl)ethynyl]-4.5.6
．． 7-Chitrapromophthalide 83.3-bisC2-Cp
-pyrrolidinophenyl)-2-(0-methyl-p-methoxyphenyl)ethynyl)-4,5,6,7-titrachlorophthalide93.3-bis(2-(p-pyrrolidino7enyl) -2
(mop-dimethoxyphenyl)ethynyl)-4,5,
6,7-titrachlorophthalide 103.3-bis(2-(p-pyrrolidinophenyl)-
2-(m,p-dimethylphenyl).

(tenyl)-4,5,6,7-titrapromophthalide 115.5-bis[2-(p-pyrrolidinophenyl)-
2-(p-7')xyphenyl)ethynyl n, s
, 6,7-titrachlorophthalide 123.3-bis[2-(p-pyrrolidinol-methylphenyl)-2-
(p-methylphenyl)ethynyl)-4,5,6,7-
Titrachlorophthalide 133.3-bis(2-(p-pyrrolidinophenyl)-
2-(p-ethylphenyl)ethynyltwo 4.5,6.
fuchtrachlorophthalide 143.5-bis(”2-(
p-pyrrolidino-〇-chlorophenyl)-2-(p-methoxyphenyl)ethynyl')-4,5,6,7-titrachlorophthalide 153.3-bis(2-(1) 2$5-dimethylpyrroli dinophenyl)-2-(1)-methylphenyl)ethynyl)-4,5,6,7-titrachlorophthalide 165.5-bisC2-Cp-piperidinophenyl)-
2-(p-methoxyphenyl)ethynyl]-4.5,6
．． 7-Titrachlorofuclide 173.3-bis(2-(1)-piperidino-7enyl)
-2-(p-methylphenyl)ethynyltwo 4.5,6
．． fuchtrachlorophthalide 183.3-bisr2-C
p-piperidinophenyl)-2-(p-methylphenyl)ethynyl]-4.5,6.7-titrapromophthalide 193.3-bis(2-(p-2-methylpiperidinophenyl) -2-phenylethynyl]-4.5,6.7-
Tetrachlorophthalide 203.3-bisC2-(p-4
-methylpiperidinophenyl)-2-(p-)toxyphenyl)ethynyl)-4,5,6,7-titrachlorophthalide 213.3-bis[2-(p-”\xamethyleneiminophenyl) -2-(p-methylphenyl)ethynyl]-
4,5,6,7-thitrachlorophtate223.3-bis(2-(p-morpholino7enyl)-
2-(p-methoxyphenyl)ethynyl'l-4.5,
6.7-Titrachlorophthalido-233.3-bis[2-(p-pyrronebuthenyl)-2
-(p-ocF-ruphenyl)ethynyl]-4.5,
6.7-Titrachloro7thallide The divinyl compound of the present invention can be synthesized by the following method.

That is, first, benzophenone derivative (1) is converted into ethylene derivative (
1).

(1) IJ) Next, 2 moles of this ethylene derivative (I) and 1 mol of phthalic acid derivative (■)
The divinyl compound represented by the general formula (1) is obtained as almost colorless crystals by condensing the divinyl compound with a mole of the divinyl compound in the presence of a dehydrating agent such as acetic anhydride or sulfuric acid.

Specific examples of the ethylene compound represented by the general formula (1) include the following.

11-Phenyl-1-(p-pyrrolidinophenyl)ethylene 21-(p-methylphenyl)-1-(p-pyrrolidinophenyl)ethylene s 1-(p-methoxyphenyl)-1-(p-pyrrolidino phenyl)ethylene 4 1-(p-ethoxyphenyl)-1-(p-pyrrolidinophenyl)ethylene 5 1-(p-butoxyphenyl)-1-(p-pyrrolidinophenyl)ethylene 6 1-(p-methoxy phenyl)-1-(p-pyrrolidino-〇-methylphenyl)ethylene 71, -(p-methoxyphenyl)-1-(p-pyrrolicinolomethoxyphenyl)ethylene 8 1-(o,p-dimethylphenyl) -1-(p-pyrrolidinophenyl)ethylene 9 1-(o,p-dimethoxyphenyl)-1-(p-
pyrrolidinophenyl)ethylene 1o 1-(p-chlorophenyl)-1-(p-pyrrolidinophenyl)ethylene 111-(p-methylphenyl)-1-(p-2゜5-
c) f Rubyrolidinophenyl) ethylene 121-(p-
methylphenyl)-1-(p-piperidinophenyl)ethylene 1s 1-(p-methoxyphenyl)-1-Cp-4
-methylpiperidinophenyl)ethylene 14 1-(p
-methylphenyl)-1-(p-hexamethyleneiminophenyl)ethylene 151-(p-methoxyphenyl)
Specific examples of phthalic acid derivatives represented by the general formula -1-(p-morpholinophenyl)ethylene include the following: tetrachlorophthalic anhydride, tetrabromophthalic anhydride, 4-chloro-3, 5, 'T' ribomophthalic anhydride,
4,5-Dichloro-3,6-dibromo-7-talic anhydride In the production of pressure-sensitive copying and heat-sensitive recording paper using the divinyl compound thus obtained, these dyes alone can also be used. Two or more types may be mixed.

Mixing may improve color development and storage stability of images. In addition, in order to improve the color development hue, color immersion, image stability, etc., it is also possible to use known color formers that develop various hues within the range that does not impair the performance of the compound of the present invention.

Examples, 3,3-bis(aminophenyl)-6-aminophthalide, 3,5-bis(indolyl)phthalide, 5-
Aminofluorane, aminobenzofluorane, 2,6-
Diamitsufluorane, 2,6-diamitu-3-methylfluorane, spiropyran, phenoxazine, leukoolamine, carbazolylmethane, 3-indolyl-5-(
It is used in combination with coloring agents such as amine) phenyl 7-thalide, 3-indolyl-3-(aminophenyl) azaphthalide, triaminofluorene phthalide, and tetraaminodivinylphthalide.

When manufacturing pressure-sensitive copying paper, various solvents such as alkylbenzene, alkyl biphenyl, alkylnaphthalene, diallylethane, hydrogenated terphenyl, and chlorinated paraffin are used singly or in combination as a solvent for dissolving coloring agents. For encapsulation, a coacervation method, an interfacial polymerization method, or an in-5itu method can be employed. Color developers include clays such as bentonite, activated clay, and acid clay, naphthol, salicylic acid, salicylic acid esters, metal salts of salicylic acid, and bisphenol A1P.
- hydroxy compounds such as hydroxybenzoic acid esters,
P-phenylphenol formalin resin, P-octylphenol formalin resin, metal salts thereof, etc. are used.

In addition, when producing heat-sensitive recording paper, the binders are polyhinyl alcohol, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, gum arabic, gelatin, casein, starch, polyvinylpyrrolidone, styrene-maleic anhydride copolymer. As the color developer, 4-tert-butylphenol, 4-phenylphenol, 4-hydroxydiphenyl ether, α-naphthol, β-1)-
7) -l, 4-hydroxybenzoic acid methyl ester,
4-hydroxybenzoic acid benzyl ester, bisphenol A, 4.4'-thiodiphenol, 4.4'-didihydroxy 9-enyl sulfone, 4-hydroxy-4
Hydroxy compounds with a melting point of 80 to 180°C, such as '-7'f-diphenylsulfone, 4-hydroxy-41-flopoxydiphenylsulfone, and 4,4'-dihydroxy-5,3''-diallyldiphenyls/lzhon. can be used.

Sensitivity improvers include urea, phthalic anhydride, acetanilide, If rough wax, carnauba wax, higher fatty acids, higher fatty acid esters, higher fatty acid amides, 7-thalic acid esters, terephthalic acid esters, benzyl 4-benzyloxybenzoate, naph)- Rubenzyl ether, 1,4-dialkoxynaphthalene, m-terphenyl, p-benzylpiphenyl, dibenzylbenzene, 1-hydroxy-
2-naphthoic acid ester, 2-hydroxy-3-naphthoic acid ester, 4,4'-dialkoxydiphenylsulfone, penzamide, diphenylamine, benzenesulfonamide, benzenesulfonanilide, carbazole, hydroquinone dibenzyl agent, anti-degradation agent, ultraviolet rays Addition of an absorbent or the like or an overcoat of a polymeric substance or the like is effective.

"Example" Next, the present invention will be specifically explained by presenting an example of synthesis of the compound of general formula (1) and an example of producing a color-forming recording material using the same compound as an example of the present invention.

Synthesis example 1゜3.5-bis[2-(p-pyrrolidinophenyl)-2-
(p-methylphenyl)ethynyl) -4,5.

6. Synthesis of 7-titrachlorophthalide 1c 1-(p-Methylphenyl)-1-(p-pyrolictuphenyl)ethylene in acetic anhydride 25 rails 13.
2. Add 9.3 g of tetrachlorophthalic anhydride to 120
The mixture was stirred at ℃ for 2 hours. The reactant was added to 200 Mt of water, made alkaline with caustic soda, and then added with 70 Jl of toluene.
! Extracted with /. The solid obtained by distilling off the toluene was recrystallized using butanol and activated carbon to obtain pale yellow crystals 1.
3.59 was obtained. mp 152-154°C.

It was confirmed by elemental analysis, infrared absorption spectrum, and 117MR that it was the desired product of the following formula.

This product quickly develops a black color due to activated clay. λmax in methanol/stannic chloride is at 910 nm.

Note that 1-(p-methylphenyl)-1- used here
(p-pyrrolidinophenyl)ethylene was synthesized as follows.

4 g of magnesium was added to 30 z:l of ether, then 0.2 g of methyl iodide was added, and after stirring for a while, a solution of 24.89 methyl iodide dissolved in 4 oz of ether was added dropwise over 2 hours while stirring and refluxing. .

On the other hand, 4-methyl-41-pyrrolidinobenzophenone (
A mixture of 19 g (mp 164-166) and 1001 at of tetrahydrofuran was prepared and gradually added to the above reaction solution at room temperature, followed by stirring at 40-50''C for 1 hour.

The reaction solution was poured into 400 grams of water and 300 grams of toluene, made slightly acidic with dilute hydrochloric acid, and stirred for a while at 80° C. to separate the layers. Carbon was added to the toluene layer, and after filtration while hot, the toluene was distilled off to give a pale yellow 1-(p-methylphenyl)-1-
17.9f of (p-virolinodinophenyl)ethylene was obtained. mp 135-136.

Synthesis Examples 2 to 15 Various ethylene derivatives and 7-talic acid derivatives were reacted in the same manner as in Synthesis Example 1 to synthesize divinyl compounds shown in the following table.

All of them are colorless to pale yellow solids, which quickly develop into the hues shown in the table below when exposed to activated clay.

Pressure-sensitive copying paper may be produced using a known method using the divinyl compound of general formula (1) obtained as described above. For example, U.S. Pat. No. 2,800,458, 280
The coacervation method described in No. 6457 and the like can be adopted. In addition, to produce heat-sensitive recording paper, for example, a known method described in Japanese Patent Publication No. 45-14039 may be employed.Production Example 1 - Production Example of Pressure-Sensitive Copying Paper - Compounds of Synthesis Example 1 3,3 -BisC2-Cp- (same parts by weight below) is dissolved in 95 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, Emulsified with a homogenizer. After adding 100 parts of warm water to this emulsion and stirring at 50°C for 30 minutes, about 1 part of 10% aqueous sodium hydroxide solution was added, and the mixture was further stirred at 50°C for 30 minutes. Then, gradually add dilute acetic acid to adjust the pH to 4.5, and heat at 50″C.
After stirring for about 1 hour, the mixture was cooled to 0 to 5°C and further stirred for 30 minutes. Next, 35 parts of 4tiglutaraldehyde aqueous solution was gradually added to harden the capsules, and the pH was adjusted to 6 with dilute caustic soda aqueous solution, and the encapsulation was completed by stirring at room temperature for several hours.During this operation, coloring occurred. didn't happen at all.

Paper (upper paper) was obtained.

When this paper was superimposed on paper coated with phenol-formalin resin as a color developer (lower paper) and written clearly with a ballpoint pen, dark black letters immediately appeared on the lower paper. This image is resistant to light and moisture. It has a strong absorption in the range of 800 to 11,000 nm, making it possible to read it with an OCN.The capsule surface of the top paper also shows excellent light resistance, and there is no coloration or decline in coloring ability due to sunlight irradiation. 0 Comparative Example 1゜A pressure-sensitive copying paper was obtained in the same manner as in Production Example 1 except that 5 parts of the compound was used as a color former. When this was colored using paper coated with phenol-formalin resin, a pale green image gradually appeared. This image had weak near-infrared absorption, so it was difficult to read by OCR. (See Figure 1) Production example 2 - Production example of thermal recording paper - 1) Preparation of color former dispersion (A) 3.3-bis(2-(1)-pyrrolidicyphenyl)-2
-(p-methoxyphenyl)ethynyl)-4,5,6,
7-Titrachlorophthalide (Synthesis Example 3)
15 parts 10% polyvinyl alcohol aqueous solution 10
0 parts water 8
5 parts The above mixture was pulverized using a paint shaker (manufactured by Toyo Seiki Co., Ltd.) until the average particle size of the color former was 2 microns.

2) Adjustment of developer and sensitizer dispersion (solution B) Bisphenol A 15 parts Zinc stearate
10 parts lO% polyvinyl alcohol aqueous solution
tso part The above mixture was pulverized with a paint shaker until the average particle size was 3 microns. 3) Preparation and coating of heat-sensitive coating liquid 10 parts of liquid A and 6.5 parts of liquid B were mixed and stirred to form a heat-sensitive coating liquid. Obtained. This coating liquid was applied to paper with a wire (-) so that the weight after drying was 6
The same results as shown in FIG. 3 were obtained for metal sensitized objects which were coated evenly and dried to give a ratio of g/ba. ), it quickly developed a black color when heated with a hot pen or the like.

This colored image has excellent light fastness and moisture resistance.
Since it has strong absorption at 1000 nm, it was possible to read it by OCR. The coated surface also had excellent light resistance, and no coloration occurred when exposed to sunlight.

Comparative example 2゜Production example 2 except that 5 parts of the compound substance was used as a coloring agent
Thermal recording paper obtained using the same procedure as 0 develops a black color when heated with a thermal pen, etc., but since it has no absorption in the near-infrared region, it cannot be read by OCR. .

Comparative Example 3 A thermosensitive recording paper was obtained in the same manner as in Production Example 2 except that 5 parts of compound (B) was used as a color former. This thermal recording paper had a yellow-green capri. When heated with a heat pen etc., it turned green. (See Figures 2 and 3) The above production examples and comparative examples confirm that the divinyl compound of the present invention is an excellent coloring agent for recording materials.

"Effects of the Invention" The divinyl compound of the present invention is colorless to pale and quickly develops a black color, and the color image has absorption in the range of 700 to 11,000 nm, so it has industrial value as a recording material for optical character reading devices. It's expensive.

[Brief explanation of drawings]

FIG. 1 shows the reflection spectrum of a colored image on pressure-sensitive copying paper using the compound of the present invention (Synthesis Example 1) and compound (D) as coloring agents. Figure 2 shows the reflection spectrum of the background of thermal recording paper using the compound of the present invention (Synthesis Example 3) and Compound (A), and Figure 3 shows the reflection spectrum of the background of thermal recording paper using the compound of the present invention (Synthesis Example 5) and Compound (E) as color formers. be.

Claims (2)

[Claims] (1) Divinyl compound represented by the following general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (I) [In the formula, X represents a heterocyclic group containing a nitrogen atom, and X^1
, X^2 represents an alkyl group having 8 or less carbon atoms, an alkoxy group having 8 or less carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, or a combination thereof, and X^3 represents a chlorine atom, a bromine atom, or a combination thereof. , m, n are 0, 1, respectively.
Indicates 2 or 3. ] (2) Color-forming recording material characterized by containing a divinyl compound represented by the following general formula (I) as a coloring agent ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (I) [In the formula, X is a nitrogen atom represents a heterocyclic group containing X^1
, X^2 represents an alkyl group having 8 or less carbon atoms, an alkoxy group having 8 or less carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, or a combination thereof, and X^3 represents a chlorine atom, a bromine atom, or a combination thereof. , m, n are 0, 1, respectively.
Indicates 2 or 3. ]