JP2548959B2 - Recording material using porphyrin derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a pressure-sensitive recording material, a heat-sensitive recording material, which utilizes a color-forming reaction between a color-forming substance (electron-donating substance) and a developer (electron-accepting substance). The present invention relates to a porphyrin derivative useful as a color-forming substance used for a recording material and a photosensitive recording material, and in particular, a novel porphyrin derivative that forms a color image readable by an optical character reading device having a reading wavelength range in the near infrared region. Regarding the recording material used.

[Conventional technology]

Colorless or light-colored substance (electron-donating substance),
By utilizing the color development reaction with a color developer (electron-accepting substance), energy such as pressure, heat, light, and electricity is applied to change it to a substance that has absorption in the visible part, and records characters and image information. Various forms of recording media have been proposed. Then, the color-developing substance used for a recording body using a pressure-sensitive or heat-sensitive recording paper as a hard copy material is usually dissolved in a non-volatile solvent and microcapsulated or dispersed in a binder. And then applied to the base paper.
As such a color forming substance, a blue color forming phthalide compound,
Although a black color-forming fluoran compound is mainly used, the main purpose of these pressure-sensitive and heat-sensitive recording dyes is to obtain visible information by contact with a color developer.

However, with the recent development and popularization of optical character readers, special ones have been required as pressure-sensitive and heat-sensitive recording dyes. In other words, since inexpensive semiconductor lasers have come to be used as light sources, 700-900 nm
There is an increasing demand for a dye that gives a color image that absorbs near-infrared light, and as such a dye, vinyl-containing phthalide (JP-A-57-
167979, JP-A-58-157779), spirofluorenephthalide (JP-A-60-226871), and the like have been proposed. Further, application examples using a porphyrin compound have been proposed in various forms, but originally, the porphyrin compound is a compound having a physiologically active function, and its use has been limited. For example, JP-B-55-8088, JP-B-55-32714 and JP-B-58-56521 disclose a covalent polymer useful as a redox catalyst, an oxygen immobilization catalyst, an oxygen carrier, and an oxygen carrier. A complex was disclosed, and JP-A-60-152487 merely proposed that it could be used as a photosensitizer for laser treatment.

However, in recent years, porphyrin derivatives have been found to be effective as recording materials of various forms in the field of information recording, and some proposals have been made. For example, JP-A-53-95646 discloses a multicolor electrolytic recording material capable of recording various color tones, and JP-A-59-40647 discloses absorption of light in a specific wavelength range to polarize it. A photosensitive compound having an -n junction characteristic, a photoconductive film material described in JP-A-62-61981,
Application examples of photoconductive elements are disclosed.

However, a recording body or the like using the above-mentioned conventional porphyrin derivative has little light absorption in the near infrared region,
As a result, the processing by the optical character reading device was very difficult.

[Problems to be solved by the invention]

The present invention solves the problems of the prior art, and brings it into contact with a color developer by energy such as pressure, heat, light, and electricity to generate a derivative having absorption in the near-infrared region, thereby reading with an optical character reader. The present invention provides a recording material using a porphyrin derivative having high density and high sensitivity.

[Means for solving problems]

The present invention is a recording material containing at least one porphyrin derivative represented by the following general formula [1] as a color-forming substance.

[In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ may be the same or different from each other, and R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , and R ⁷
And R ⁸ may form a ring having a substituent, a hydrogen atom,
Halogen atom, cyano group, nitro group, substituted or unsubstituted alkyl group, vinyl group, -R ⁹ COOH group, -R ⁹ COOR ¹⁰ group (R ⁹ is an alkylene group having 0 to 4 carbon atoms, R ¹⁰ is carbon Q is a bridging group of N ²¹ and N ²² , and is> CH ₂ group,> CHOR ¹¹ group, > CHCOOR ¹¹ group (R ¹¹ is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms which may be the same or different from each other),> C═C (Ar) ₂ group (Ar is a substituted or An unsubstituted aryl group), {A and A'may be the same as or different from each other, and are a hydrogen atom, a cyano group, a formyl, an acyl group, a substituted or unsubstituted alkyl group, an aryl group, a -COOR ¹² group (R ¹² is a hydrogen atom, a substituted or Unsubstituted alkyl group, aryl group)}, Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ are hydrogen atom, halogen atom, cyano group, nitro group, substituted or unsubstituted alkyl group and aryl group. Show. ] As R ^{1 to} R ⁸ in the above general formula [1], a hydrogen atom, a nitro group, a cyano group, a halogen atom such as Cl, Br, I and F, —CH ₃ , —CH ₂ CH ₃ , —CH ₂ CH ₂ CH (CH ₃ ) _{2 and} other alkyl groups, -CHClCH ₂ Cl, -CH ₂ CH ₂ OH, -CH ₂ CH ₂ OCH _{3 and} other substituted alkyl groups, as well as -CH = CH ₂ , -CH ₂ CH ₂ COOH, −CH ₂ CH
₂ COOCH ₃ , R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , and R ⁷ and R ⁸ form a benzene ring. As the bridging group Q,
From acetylene derivatives Eteno groups such as, and> CH ₂ groups,> CHOCH ₃ groups,> CHCOOCH
_{3,> C = C (C} 6 H 5) 2 group, 1,2-naphthylene group, 1,2
Examples thereof include a phenylene group. Also, as Z ^{1 to} Z ⁵ ,
Hydrogen atom, a nitro group, a cyano group, Cl, Br, I, halogen atom such as _{F, -CH 3, -CH 2 CH 3} , -CH 2 CH 2 CH (CH 3) 2,
Alkyl groups such as _{-CH 2 CH 2 CH 2 CH 3} , -CHClCH 2 Cl, -CH 2
_{CH 2 OH, -CH 2 CH 2} OCH 3, -CH 2 COCH 3, -CH 2 COC 6 H 5, -C
_{(C 6 H 5) 3,} -CH (COOCH 3) 2, substituted alkyl groups such as _{-CH 2 NO 2, -C 6 H} 4 Cl, -C 6 H 4 CH 3, substituted, such as -C ₆ H ₅ or unsubstituted aryl group, and _{-CH 2 CH 2 COOH, -CH 2} CH 2 COOC
_{H 3, -COCH 3, -C C-} (C 6 H 5) 3 and the like.

A preferred example of the porphyrin compound according to the present invention is as follows.

In the above table, Et: -CH ₂ CH _{3 group, Ph: -C 6 H 4 CH} 3 group, ACT:
--CH ₂ COCH ₃ group, ACPH: --CH ₂ COC ₆ H ₅ group, Me: --CH ₃ group, Tp: --C
₆ H ₄ OCH ₃ groups, ROMe: -CH ₂ CH ₂ OCH ₃ groups, CN: cyano group, Mp:-
C ₆ H ₅ OCH ₃ group, Bu: representing respectively _{-CH 2 (CH 2) 2 CH} 3 group.

The compound according to the present invention has, for example, the general formula (Wherein R ^{1 to} R ⁸ and Z ^{1 to} Z ⁴ have the same meanings as described above) as a starting material, and the N ²¹ and N ²² crosslinked porphyrin monocations are synthesized by a conventional method. To do. Anions such as various carbanions are reacted with this in a solvent such as acetone.

As a substance that gives the above anion, potassium acetoenolate, lithium acetophenone elenote, n-butyllithium, triphenylmethylenolate, sodium cyanide and the like are preferable. Then, the solvent is removed and the residue is extracted with a petroleum solvent such as hexane to synthesize a porphyrin derivative.

As a result of various spectra and elemental analysis, this porphyrin derivative was found to have a meso position at the 5-position sandwiched between N ²¹ and N ²² -crosslinking groups
N ²¹ , N ^22- Carbanion added from the same side as the bridging group 5
It has the structure of R, 5H florin. The porphyrin derivative is a blue to green-blue oil-soluble compound, and easily reacts with a color developing agent through energy such as light, heat (including heat generated by energization), pressure, and electricity to generate near-infrared rays. The compound changes to a compound having a maximum absorption wavelength in the region and gives a stable color image against oxidation.

That is, as shown in the following formula, it reacts with the acidic developer represented by XH to produce a florin-monocationic compound.

The maximum absorption of the porphyrin derivative according to the present invention is 620n.
Although it is m to 700 nm, the formed florin-monocation compound is changed to a compound having a maximum absorption wavelength in the near infrared region of 700 nm or more.

As the developer, acid clay, activated clay, inorganic acids such as metal salts of perchloric acid, oxalic acid, maleic acid, benzoic acid, salicylic acid, and derivatives thereof, or metal salts,
Preference is given to organic acids such as toluenesulfonic acid, phenolic compounds such as bisphenol A, p-phenylphenol, phenol formalin resins, and the like.
In the case of a photosensitive recording material, carbon tetrabromide, tribromoacetophenone, trifluoroacetic acid ester and the like are preferable.

[Work]

The porphyrin derivative according to the present invention includes pressure, heat, light,
A color image with a large depth of color that can be read by an optical character reader that has a reading wavelength range in the near-infrared region by changing to a compound that absorbs in the near-infrared region by contact with a color developer due to energy such as electricity. To form.

〔The invention's effect〕

The recording material of the present invention can be changed into a compound having absorption in the near infrared region by contact with a color developing agent to form a color image having a large degree of deep coloration, and moreover, it can be applied to acid of recorded characters or images. It has good stability and can be accurately read by an optical character reader. Moreover, since the porphyrin derivative of the present invention has excellent oil solubility, it can be microencapsulated.

〔Example〕

Next, examples of the present invention will be shown, but the present invention is not limited thereto.

Example 1 A solution N ^21, N ²² - (1,2- diphenyl ethenoadenosine) -2,3,7,8,12,13,
17,18-Octaethyl-5-acetonyl-5H-florine (Compound example 1) 20 parts 10% aqueous solution of polyvinyl alcohol 20 parts water 60 parts solution B bisphenol A 15 parts calcium carbonate 5 parts 10% aqueous solution of polyvinyl alcohol 20 parts water 60 parts The solutions A and B were pulverized and dispersed by a paint conditioner. Then, the liquid A and the liquid B were mixed and stirred at a weight ratio of 1: 5 to obtain a thermal recording paper coating liquid. This coating solution for heat-sensitive recording paper was applied to the surface of commercially available high-quality paper using a wire bar so that the coating amount after drying was 6 gm ³ , and dried to obtain heat-sensitive recording paper.

When this heat-sensitive recording paper was pressure-bonded to a hot plate at 120 ° C. under a pressure of ² kg / cm ² for 5 seconds, it changed to an infrared readable monocation of florin (florin salt) having an absorption at about 740 nm.

Example 2 N ^21, N ²² - (1,2- diphenyl ethenoadenosine) -2,3,7,8,12,1
3,17,18- instead of octaethyl-5-acetonyl -5H- Florin (Compound Example ^{1), N 21, N 22} - (1,2- diphenyl ethenoadenosine) 5,10,15,20-tetraphenyl - A thermosensitive recording paper was obtained in the same manner as in Example 1 except that 5H-florin (Compound Example 8) was used.

When this heat-sensitive recording paper was pressed on a hot plate at 120 ° C. for 5 seconds at a pressure of ² kg / cm ² , it changed to a monocation of florin (florin salt) capable of infrared reading having an absorption at about λmax 797 nm.

Example 3 N ^21, N ²² - (1,2- diphenyl ethenoadenosine) -2,3,7,8,12,1
3,17,18-Octaethyl-5-benzoylmethyl-5H-
5 parts of florin (Compound Example 2) was replaced with isopropyl biphenyl.
Dissolve it in 95 parts and add 25 parts of gelatin and gum arabic to this solution.
A liquid prepared by dissolving 25 parts in 400 parts of water was added and emulsified and dispersed. 1000 parts of warm water was added to this emulsion, and the mixture was stirred at 50 ° C for 30 minutes.
Then, dilute acetic acid was gradually added to adjust the pH to 4, 5 and 50 ° C.
After stirring for 1 hour, the mixture was cooled to 0 to 5 ° C, and further stirred for 30 minutes. Next, 35 parts of a 4% butaraldehyde aqueous solution was gradually added to harden the capsule, and then the pH was adjusted to 6 with a dilute caustic soda aqueous solution and stirred at room temperature for several hours to complete encapsulation.

This capsule liquid was applied to paper and dried to obtain a capsule-coated paper (top paper). Phenol-formalin-based resin coated paper (lower paper) using this upper paper as a color developer so that the coated surfaces face each other, and by writing and pressing,
A yellow-green recorded image was obtained. This color image is stable under conditions of heating and humidification, exhibits excellent light resistance, and
It showed absorption in the near infrared region (λmax 745 nm).

Example 4 N ^21, N ²² - (1,2- diphenyl ethenoadenosine) -2,3,7,8,12,1
3,17,18- instead of octaethyl 5 benzoylmethyl -5H- Florin (Compound Example ^{2), N 21, N 22} - (1,2- diphenyl ethenoadenosine) 5,10,15,20 Tetoratoruiru - A pressure sensitive recording paper was obtained in the same manner as in Example 3 except that 5H-florin (Compound Example 10) was used. The color-developed image of this pressure-sensitive recording paper was stable under the conditions of heating and humidification, showed excellent light resistance, and absorbed in the near infrared region (λmax 803 nm).

Example 5 N ^21, N ²² - (1,2- diphenyl ethenoadenosine) 5,10,15,20
5 g of tetraanisyl-5H-florin (Compound Example 11) was added to 5%.
A coating solution prepared by dissolving polyvinyl carbazole in 80 ml of chloroform and adding 5 g of carbon tetrabromide and stirring well was applied to a polyethylene terephthalate film in the dark to obtain a photosensitive recording film. With this 20W ultraviolet light 1
After irradiation and color development for 0 minutes, a yellow-green color image was obtained. The color image was stable under the conditions of heating and humidification, and had absorption in the near infrared region (λmax 830 nm).

Next, each porphyrin derivative shown in Examples 1 to 5,
Also, the absorption spectrum of the monocationic body formed by the reaction of the developer with the developer (electron-accepting substance) was measured.
The results are shown in Table [1].

As is clear from Table [1], it can be seen that the porphyrin derivative of the present invention is converted into a compound having a maximum absorption wavelength in the near infrared region by reacting with the color developer.

Claims (1)

(57) [Claims] 1. A recording material containing at least one porphyrin derivative represented by the following general formula [1] as a color-forming substance. [In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ may be the same or different from each other, and R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , and R ⁷
And R ⁸ may form a ring having a substituent, a hydrogen atom,
Halogen atom, cyano group, nitro group, substituted or unsubstituted alkyl group, vinyl group, -R ⁹ COOH group, -R ⁹ COOR ¹⁰ group (R ⁹ is an alkylene group having 0 to 4 carbon atoms, R ¹⁰ is carbon Number is 1 to 8), Q is a bridging group of N ²¹ and N ²² , and> CH ₂ group,> CHOR ¹¹ group,> > CHCOOR ¹¹ group (R ¹¹ is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms which may be the same or different from each other),> C═C (Ar) ₂ group (Ar is a substituted or An unsubstituted aryl group), {A and A'may be the same or different from each other, and are a hydrogen atom, a cyano group, a formyl group, an acyl group, a substituted or unsubstituted alkyl group, an aryl group, a -COOR ¹² group (R ¹²
Is a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group)}, and Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ are hydrogen atoms, halogen atoms, cyano groups, nitro groups, substituted or unsubstituted An alkyl group and an aryl group are shown. ]