JPS62257969A - Divinyl compound and color-developing recording material using same - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (R<1> is 1-6C alkoxyalkyl; R<2>-R<4> are each 1-4C alkyl or 1-6C alkoxyalkyl; X is Cl or Br). EXAMPLE:3,3-bis[2-bis(p-methyl methoxyethyl aminophenyl)ethyl]-4,5,6,7- tetrachlorophthalide of formula II. USE:Color-developing recording material. Outstanding in solubility, color- developing capability, near infrared absorbance, image stability, etc. Having pale color with quick color development into green, the resulting images having a absorption in a wavelength range 700-1,000nm and being able to be read through e.g. an optical character reading device using near infrared radiation. PREPARATION:A benzophenone derivative of formula III is converted to an ethylene derivative of formula IV through Grignard or Witting reaction. Two moles of this ethylene derivative and one mole of a phthalic acid derivative of formula V are brought to condensation in the presence of a dehydrating agent such as acetic anhydride.

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field" The present invention is directed to the general formula
R2, R3, and R' independently represent an alkyl group having 4 or less carbon atoms or an alkoxyalkyl group having 6 or less carbon atoms, and X represents a bound atom, a bromine atom, or a combination thereof. 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 divinyl compound represented by the general formula (1) is a new fc compound that was first synthesized by the present inventors, and is almost colorless itself, extremely stable in the atmosphere, has no sublimation property, and is compatible with JrlA solvents. It dissolves extremely well in the liquid.It quickly develops a green color with a color developer, and the colored image has excellent light fastness and moisture resistance.Furthermore, the colored image has 700 to 1
Since it has a strong absorption of 000nlIn, it has the characteristic that it can be read by optical character reading devices (OCR, OMR) and bar code reading devices that use near infrared rays.

Therefore, it is an extremely valuable new compound that can be used as the main component of a coloring agent for infrared reading recording materials, in addition to ordinary black coloring recording materials whose w1 requirements have been increasing rapidly in recent years.

Examples of recording materials include pressure-sensitive copy sets, thermal recording paper, 7E thermal recording paper, color-forming thermal transfer recording paper, ultrasonic recording paper, laser recording paper, temperature-indicating materials, stamp inks, type ribbons, ballpoint pen inks, and the like.

"Prior art" and "Problems to be solved by the present invention" The colored image of the following green-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, it could not be read by an optical character reader. (See Figure 2) In addition, in recent years, coloring agents that absorb in the near-infrared region have been
Various compounds have been proposed in JP-A-8-5940 and JP-A-59-199757. However, each of them has the following drawbacks, and at present no satisfactory coloring agent has yet been obtained. That is, the compound (B) disclosed in Japanese Patent Publication No. 58-5940 has poor solubility in organic solvents and insufficient color development. The fluorene compound (C) disclosed in JP-A-59-199757 has poor color development and stability of colored images.

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 shows that the divinyl compound containing an alkoxy group of the general formula 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.

In order to clarify these excellent properties, the results of a comparative test between the compounds CD) and (E) of the present invention and the intellectual compounds (A) to <C> are shown.

(D) 3.3-bis[2-bis(p-methylmethquinethylaminophenyl)ethynyl) -4,5,6゜7
-Tetrapphthalide (E) 3.3-bis[2-bis(p-methylethquinethylaminophenyl)ethynyl) -4,5,6゜7-
Tetrachlorophthalide Comparison Test 1 - Comparison of Solubility - ■ Compounds CB) ~ (En 2,51) were added to KMC-115 (solvent for pressure-sensitive copying paper manufactured by Kureha Chemical Co., Ltd.) 47.59, and the mixture was stirred with force. The bath M temperature was measured under sunlight.

(2) The solubility of compounds (B) to (E) in the above KMC-115 at 25°C was measured by the following method.

Each compound h 5f (i-205F /7) 1MC11
3K2if1 and stirred at 100°C for 30 minutes to prepare a liquid of 20%. This solution was kept in a room at 25°C for 2 weeks, and after the crystals were passed through 0f5, the concentration in the solution was measured by high performance liquid chromatography.

The results of ■ and ■ were as follows.

As mentioned above, the divinyl compound of the present invention has much better solubility in pressure-sensitive copying paper solvents than known compounds.

This shows that capsules with a high degree of scarring can be easily produced when backing pressure-sensitive copying paper, and that a larger amount of diluent such as 111+ kerosene can be used.

Comparison j+ (Experiment 2 - Comparison of color development of heat-sensitive recording A) - Compounds (A) to (D) were used as color-forming agents and heat-sensitive recording paper was placed on the surface by the method of ! Color testing machine (
(manufactured by Matsushita Electronic Components)) was used to develop peta color. (Head voltage 19v, pulse width 1.2ms, main scan 8 lines/M
1, sub-scanning 3.85 lines/MM) The absorbance at 900 nm was measured using a spectrophotometer (Uv365 type manufactured by Shimadzu Corporation). The results were as follows.

As mentioned above, the color development property of the present invention in the near-infrared region is much superior to that of the known fiZu products.

Specific examples of the divinyl compounds of the present invention include the following. All of them are pale yellowish-green solids, which quickly turn to green with activated clay.

1 3.6-His(2-CI)-methylethyneethylaminophenyl)-2-CT)-dimethylaminophenyl)ethynyl) -4,5,6,7-tetrachlorophthalide 25.3- Bis[2-bis(p-methylmethoxyethyl 7-minophenyl)eranil) -4,5,6゜7-tetrachlorophthalide33. phenyl) etheni tv) -4,5,6,7-
Tetrachlorophthalide 43.3-bis[2-bis(p-methylethquinethylaminophenyl)ethynyl) -4,5,6゜7-tetrachlorophthalide 53.3-bis(2-(i)- dimethoyaminophenyl)-2-(p-jethylaminophenyl)ethynyl)-4,5,6,7-tetrachlorophthalide66.3-bis(2-(T)-ethylethoxyethylaminophenyl) -2-(1)-'/menalaminophenyl)ethynyl) -4,5,6,7-tetrachlorophthalide73.6-bis[2-bis(p-ethylethoxyethylaminophenyl)ethynyl) - 4,5,6゜7-tetrachlorophthalide 83.3-bis(2-('9-jethoxyethylaminophenyl)-2-(p-dimethylaminophenyl)ethynyl]-4,5,6,7 -tetofbromophthalide95.6-bis[2-bis(p-ethylethoxyethylaminophenyl)ethynyl':l -4,5,6゜7-
Tetrachlorophthalide 10 3.3-bis[2-bis(p-methylethoxyethylaminophenyl)ethynyl) -4,5゜6.7-
Chitrachlorosotari 1°.

11 3.6-bis[2-bis(p-enalmethoxychlorobylaminophenylnetheni/shi)-4,s.

6.7-Tetrachlorophthalide 12 3.3-bis(2-(p-dimethquinepropylaminophenyl)-2-(p-dimethylaminophenyl)ethynyl) -4,5,6,7-tetrachlorophthalide Do13 3.3-Bis(2-(p-menalethoxychlorobylaminophenyl)-2-Cp-dimethylaminophenyl)ethynyl) -4,5,6,7-? Tofchlorophthalide 14 3.3-Bis(2-(I)-Schedquinpropylaminophenyl)-2-(p-dimethylaminophenyl)ethynyl) -4,5,6,7-titrapromophthalide 15 3 .3-bis[2-bis(p-methylethquinpropylaminophenyIV)ethynyl) -4,5°6.
7-tetrachlorophthalide 16 3.3-bis[2-bis(p-methylmethoxyethylaminophenyl)ethynyl) -5,6-dichloro-4,7-dibromophthalide 17 3.3-bis[2- Bis(p-methylmethoxyethylaminophenyl)ethynylcy-5-chloro-4,6
, 7-) Ribromophthalide The divinyl compound of the present invention can be synthesized by the following method.

That is, first, benzophenone derivative (1) is converted into diethylene derivative (1) by Grignard or Wittig reaction.
厘).

(■)
(12 Next, this ethylene visiting conductor (I) 2
The general formula (+
) is obtained as pale yellow crystals.

λ4 Specific examples of the ethylene compound represented by the general formula (1) include the following.

11.1-bis(p-methylmethoxyethylaminophenyl)ethylene21.1-bis(p-ethylmethoxyethylaminophenyl)ethylene31.1-bis(p-methylethoxyethylaminophenyl)ethylene41.1-bis (p-ethylethoxyethylaminophenyl)ethylene 51.1-bis<p-methifremethoxypropylaminophenyl)ethylene61.1-bis(p-dimethoxyethylaminophenyl)ethylene71.1- Bis(p-jethoxyethylaminophenyl)ethylene 81.1-Bis(p-dimethoxypropylaminophenyl)ethylene 91-('p-methylmethkinethylaminophenyl)
-1-(:9-dimethylaminophenyl)ethylene 101-(1)-ethylmethoxyethylaminophenyl)-1-(p-dimethylaminophenyl)ethylene 111-(p-!/methoxyethylaminophenyl)-
1-(I)-dimethylaminophenyl/L/)ethylene 121-(p-methylmethoxyethylaminophenyl)
Examples of the compound represented by the general formula (ff) of -1-(1)-diethylaminophenyl)ethylene include the following.

Tetrachlorophthalic anhydride, 4-chloro-3゜5,6-
) dibromophthalic anhydride, 4,5-dichloro-3,6
-dibromophthalic anhydride, 4-promo 3.5.6-
) Dichlorophthalic anhydride, 4゜5-dibromo-6,6-
Dichlorophthalic anhydride, tetrabromophthalic anhydride When producing pressure-sensitive copying paper and heat-sensitive recording paper using all of these divinyl compounds, these dyes can be used alone or in combination of two or more. Also good.

Mixing may improve color development and storage stability of images. Further, in order to improve the color development hue, color density, image stability, etc., known color formers that develop colors in various hues can be used in combination within a range that does not impair the performance of the compound of the present invention.

For example, 3.3-bis(aminophenyl)-6-7minophthalide, 3.3-bis(indolyl)phthalide, 6-aminofluorane, aminobenzofluorane, 2,6-cyamitsufluorane, 2.6 -Diami2-3-methylfluorane, spiropyran, phenoxazine, leucoolamine, carba)/'IJ lumethane, 3-indolyl-5
-(amino)phenylphthalide, 3-indolyl-3-
(aminophenyl)azaphthalide, triaminofluorene phthalide, tetrasoaminodivinylphthalide, and other color formers are used in combination.

When manufacturing pressure-sensitive copying paper, t'+' dissolves the coloring agent.
4 As All, various solvents such as alkylbenzene type, alkyl biphenyl type, alkylnaphthalene type, diallylethane type, hydrogenated terphenyl type, and chlorinated paraffin type can be used alone or in combination, and for encapsulation, Coacelvae S/ It is possible to employ the Gn method, the interfacial polymerization method, and the In-5itU method.

Color developers include clays such as bentonite, activated clay, and acid clay, naphthol, salicylic acid, salicylic acid esters, metal salts of salicylic acid, hydroxy compounds such as bisphenol A% P-hydroxybenzoate, p-phenylphenol+l </L' Marine [fat, P-octylphenol formalin resin and their gold! j4
Salt etc. are used.

In addition, when preparing a thermosensitive recording paper, the binder is polyvinyl alcohol, methyl cellulose, hydroquine ethyl cellulose, carboxymethyl cellulose, gum arabic, gelatin, casein, starch, polyvinylpyrrolidone, styrene-maleic anhydride copolymer. As the color developer, a-tert-butylphenol, 4-phenylphenol, 4-hydroxydiphenyl ether, a-naphthol, β-naphthol, 4-hydroxybenzoic acid methyl ester, 4-hydroxybenzoic acid methyl ester, etc. can be used. -Hydroxybenzoic acid benzyl ester, bisphenol A
, 4.4'-thiodiphenol, 4.4'-dihydroxydiphenylsulfone, 4-hydroxy-4'-methyldiphenylsulfone, 4-hydroxy-47-propoxydiphenylsulfone, 4°4'-dihydroxy-3
, 3'-sialyl diphenyl sulfone, 1,5-di(4
-hydroxyphenylthio)-3-oxapentane, 1
．． 7-di(4-hydroxyphenylthio) -3,5-
Hydroxy compounds such as dioxahebutane, 1,8-di(4-hydroxyphenylthio)-3,6-thioxaoctane, etc. can be used.

Sensitivity improvers include urea, phthalic anhydride, acetanilide, paraffin wax, carnauba wax, and high-grade rubber.
Acid, higher fatty acid ester, higher fatty acid amide, phthalic acid ester, terephthalic acid ester, benzyl 4-benzyloxybenzoate, naphthol benzyl ether, 1.
4-dialkoxynaphthalene, m-terphenyl, T)
-benzylbiphenyl, dibenzylbenzene, 1-hydroxy V-2-naphthoic acid ester, 2-hydroxy-3
-Naphthoic acid ester, 4,4-dialkoxydiphenyl sulfone, penzamide, diphenylamine, benzene sulfonamide, benzene sulfonanilide, carbazole, hydroquinone dibenzyl ether, etc. can be used.

In order to improve the light resistance and storage stability of the fine image, it is effective to add various antioxidants, deterioration inhibitors, ultraviolet absorbers, etc., or to overcoat with a molecular substance.

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

Synthesis Example 1 Synthesis of 3.3-bis[2-bis(p-methylmethoxyethylaminophenyl)ethynyl)-4,5,6,7-tetrachlorophthalide 1.1-bis(p -methylmethkinethylaminophenyl)ethylene 171. ? 10.7y of trachlorophthalic anhydride was added and stirred at 120°C for 1 hour. The reactant was added to 200 d of water, made alkaline with soda, and then extracted with 70 d of toluene. The solid material obtained by distilling off the toluene was recrystallized from ethanol using activated carbon to obtain 171 pale yellow crystals. mp112
It was confirmed by elemental analysis at ~114°C, infrared absorption spectrum, and NMR that it was the target product of the following formula.

This product quickly develops a green color due to activated clay. kpnax in methanol/stannic chloride is at 865 nm.

Note that 1,1-bis(p-methylmethquinethylaminophenyl)ethylene used here was synthesized as follows.

4 f of magnesium was added to 30 g of ether, then 0.2 zl of methyl iodide was added, and after stirring for a while, 24.8 f of methyl iodide was dissolved in 40 ml of ether, and the solution was stirred and refluxed for 2 hours. It dripped.

On the other hand, 4,4'-bis(methylmethoxyethylamino)
A mixture of benzophenone (viscous liquid) 25%, Oy and 100B of tetofhydrofuran was mixed to form a mixture, and the mixture was gradually added to the above reaction solution at room temperature, and then stirred at 40-50°C for 1 hour.

For reaction purposes, the mixture was pressurized into 400 tgl of total water and 300 dl of toluene, made slightly acidic with dilute hydrochloric acid, and stirred for a while at 80°C to separate the liquids. Carbon was added to the toluene layer, and after heating for a while, toluene was distilled off to obtain 25.5f of liquid 1,1-bis(p-methylmethoxyethylaminophenyl)ethylene.

Synthesis Examples 2 to 10 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.

Both are pale yellow solids, which quickly turn green with activated clay.

Pressure-sensitive copying paper may be produced using the divinyl compound of general formula (1) obtained as described above by any known method. For example, US Pat. No. 2,800,458, No. 2
The core cell page decryption method described in No. 806457 and the like can be adopted.

In addition, for the production of heat-sensitive recording paper, for example,
A known method described in Japanese Patent No. 039 may be employed.

Production Example 1 - Production Example of Pressure Sensitive Duplicating Paper - Compound of Synthesis Example 1 6,3-bis[2-bis(p-methylethoxyethylaminopheniA/)ethynyl) -4
, 5,6,7-tetrachlorophthalide (ffiti
ft was dissolved in 95 parts of monoisopropylbiphenyl, and 24 parts of gelatin and 24 parts of gum arabic dissolved in 400 parts of water and adjusted to pH 7 were added to this solution and emulsified using a homogenizer. Add 100% warm water to this emulsion.
After 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.
Stir at 50°C for about 1 hour, then cool to 0~5°C and further stir for 1 hour.
Stir for 3 minutes then fc.

Next, gradually add 65 parts of 4% gel tar aldehyde in water to harden the capsule, and then use the hydrocarbon soda water! 8
? The pH was adjusted to 6 (tA) in 1i, and the mixture was stirred at room temperature for several hours to perform photon encapsulation. No coloring phenomenon occurred during this operation.

After drying with a wire bar on this capsule liquid gold paper, the tora is 6
It was coated evenly to give a ratio of 9/ln' and dried to obtain capsule-coated paper (top paper).

When this paper is overlaid on paper coated with phenol-formalin resin as a coloring agent (lower paper) and marked with a ballpoint pen, a green letter ω appears immediately on the lower paper.

This image is resistant to light and moisture and has a rating of 800-100.
Since it has strong absorption at 0 nm, it was possible to read it using ○OH. In addition, the cell surface of the top paper cuff also exhibits excellent light resistance, and is incapable of coloring or deterioration of coloring ability due to sunlight irradiation).
It was.

Comparative Example 1 A pressure-sensitive copying paper was obtained in the same manner as in Production Example 1 except that 5 parts of compound (C) was used as a color former. This was then covered with 7-enol formalinne 1j) la 'c x'm paper.

When the color was developed, a pale green image gradually appeared.

This image was difficult to read using ○OH because near-infrared absorption was weak. (See Figure 1) Production Example 2 - Production Example of Heat-Sensitive Recording Paper - 1) Preparation of color former dispersion (A) liquid 3.3-bis[2-bis(p-methylethoxyethylaminophenyl)ethynyl) - 4,5゜6.7-Titrachlorophthalide (Synthesis Example 4) 5 parts Olin
151ro 10 Tivoli vinyl alcohol soluble in water 100 parts water
85 parts The above mixture was pulverized using a paint shaker (■Toyoya Kirei) until the average particle size of the color former was 2 microns.

2) Adjustment of color developer and sensitizer dispersion (Ba) Bisphenol A 15 parts Zinc stearate
10 parts stearic acid amide
20 parts 10% polyvinyl alcohol water #[15C1
The above mixture was ground in a paint shaker until the average particle size was 3 microns.

5) Adjustment of heat-sensitive coating and coating 10 parts of A and 6.5 parts of B were mixed and stirred to obtain a heat-sensitive coating liquid. After drying this coating a on paper with a wire bar [1 is 6
A heat-sensitive recording paper was obtained by uniformly coating and drying the coating to give f/n/. When this thermal recording paper was printed using a thermal color development tester, it quickly developed a dark green color.

This colored image has excellent light resistance and temperature resistance, and has a rating of 700-1.
Since it had strong absorption at 00 [1 part m, it was possible to read it by CJCR.

Furthermore, the coated surface also had excellent light resistance, and no coloring occurred due to sunlight irradiation.

Comparative Example 2 A thermosensitive recording paper was obtained in the same manner as in Fabrication Example 2 except that 5 parts of compound (A) was used as a coloring agent.

This thermosensitive recording paper cannot be read by OCR because it has a green color but has no absorption in the near-infrared region. (See Figure 2) The above-mentioned production examples and comparative examples confirm that the divinyl compound of the present invention is an excellent optical coloring agent for recording materials.

"Effects of the Invention" The divinyl compound of the present invention is pale in color and quickly develops a VC green color, and the developed image has absorption gold in the range of 700 to 11,000 nm, so it has high industrial utility value as a recording material for optical character reading devices. be.

[Brief explanation of drawings]

FIG. 1 is a reflection vector of a colored image on a pressure sensitive copying paper using the compound of the present invention (Synthetic Reli 1) and Compound (C) as color formers. FIG. 2 is a reflection vector of a colored image of a thermosensitive recording paper using the compound of the present invention (Synthesis Example 4) and compound (A) as color formers.

Claims (2)

[Claims] (1) Divinyl compound represented by the following general formula (I) ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) [In the formula, R^1 is an alkoxyalkyl group with 6 or less carbon atoms, and R^2, R^3, and R^4 are independently alkyl groups with 4 or less carbon atoms. group or an alkoxyalkyl group having 6 or less carbon atoms, and X represents a chlorine atom, a bromine atom, or a combination thereof. ] (2) Color-forming recording material characterized by containing a divinyl compound represented by the following general formula (I) as a coloring agent ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R^1 is An alkoxyalkyl group having 6 or less carbon atoms, R^2, R^3, and R^4 independently represent an alkyl group having 4 or less carbon atoms or an alkoxyalkyl group having 6 or less carbon atoms, and X is a chlorine atom, a bromine atom, Indicates an atom or a combination thereof. ]