JP2520701B2 - Pentadiene compound and recording material using the compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel pentadiene compound, and a recording material characterized by using at least one of the compounds.

[Problems to be Solved by Prior Art and Invention]

Conventionally, color formers have been used for various recording materials. The main examples thereof include a pressure-sensitive recording material, a heat-sensitive recording material, an electric heat-sensitive recording material, and a photosensitive recording material. The demand for these recording materials is rapidly increasing with the development of the information industry today, which is called the information age. In recent years, computers have come to be used frequently for the purpose of rationalizing office processing associated with office automation, or for various rationalization associated with factory automation. Alternatively, optical bar code readers and the like have been developed and have been remarkably used in recent years.

The present invention relates to a developing material such as an inorganic acid, an organic acid, a phenolic compound, a derivative thereof, a metal salt thereof, or an electron accepting substance such as an oxidizing agent (for example, acid clay, 3,5-diene). -T-butylsalicylic acid, bis (3-
Chlorophenyl) thiourea, 4,4'-isopropylidenediphenol, zinc 4-nitrobenzoate, benzyl 4-hydroxybenzoate, etc.) develops a color and has a strong absorption band in the near infrared region. The present invention provides a pentadiene compound and a recording material characterized by using at least one kind of the compound.

As described above, the novel pentadiene compound of the present invention and a recording material containing at least one of the compounds are conventional pressure-sensitive recording materials, heat-sensitive recording materials, or photosensitive recording materials. It has characteristics not found in color formers used as materials.

Conventionally, typical examples of color formers generally used for recording materials such as pressure-sensitive recording sheets, heat-sensitive recording sheets or photosensitive recording sheets include phthalide-based compounds, fluoran-based compounds, and triphenylmethane-based compounds. Is raised. For example, a typical example of a phthalide compound is crystal violet lactone that develops blue, and a typical example of a fluoran compound is 2- (2-chloroanilino) -6-dibutylaminofluorane that develops black, and triphenylmethane. Representative examples of the compound include leuco crystal violet which emits blue light. However, since these color formers do not have a light absorption property in the near infrared region around 700-900 nm, the recorded images obtained by using these color formers have been remarkably increased in recent years. It is not suitable as a recorded image for an optical character reading device using a light in the near infrared region as a light source or an optical bar code reading device.

[Means for solving problems]

The following general formula of the present invention, (In the formula, R ¹ , R ² , R ³ and R ⁴ represent a lower alkyl group, and R ⁵ represents a halogen atom, an alkyl group, or an aryl group which may be substituted with an alkoxy group, or a naphthyl group. The novel pentadiene compound represented by the formula (1) is an inorganic acid, an organic acid, a phenolic compound, or a derivative thereof, which is used in the production of pressure-sensitive recording materials, heat-sensitive recording materials and photosensitive recording materials, or , Their metal salts,
Alternatively, a color developing material such as an electron accepting substance such as an oxidizing agent (as typical color developing materials, bentonite, zeolite, acid clay, activated clay, silica gel, zinc oxide, zinc chloride,
Aluminum chloride, zinc bromide, salicylic acid, 3-t-butylsalicylic acid, 3,5-di-t-butylsalicylic acid, zinc salicylate, zinc 3-t-butylsalicylate, 3,5-
Zinc di-t-butylsalicylate, bis (3-chlorophenyl) thiourea, bis (3-trifluoromethylphenyl) thiourea, salicylanilide, 4-t-butylphenol, 4-phenylphenol, 4-hydroxydiphenoxide, α -Naphthol, β-naphthol, thymol, 3,5-xylenol, novolac type phenol resin, 4,4'-isopropylidenediphenol, 4,4'-isopropylidenebis (2-chlorophenol), 4,4 '
-Isopropylidene bis (2,6-dibromonofer), 4,4'-isopropylidene bis (2-methylphenol), 4,4'-isopropylidene bis (2,6-dimethylphenol), 4,4 ' -Isopropylidene bis (2-
t-Butylphenol), 4,4'-sec-propylidene diphenol, 4,4'-cyclohexylidene diphenol, 4,4'-cyclohexylidenebis (2-methylphenol), methyl-4-hydroxy Benzoate, 4-
Hydroxybenzophenone, 4-hydroxyacetophenone, catechol, resorcin, hydroquinone, pyrogallol, phloroglysin, phloglycin carboxylic acid,
Benzoic acid, 4-nitrobenzoic acid, zinc 4-nitrobenzoate, ethyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate, butyl 4-hydroxybenzoate, 4
-Benzyl hydroxybenzoate, 4-hydroxybenzoic acid-4'-chlorobenzyl, 4-hydroxybenzoic acid-
2'-chlorobenzyl, 4-hydroxybenzoic acid-4 '
-Methylbenzyl, 4-hydroxybenzoic acid-n-octyl, 2,2'-thiobis (4,6-dichlorophenol),
1-hydroxy-2-naphthoic acid, 2-hydroxy-6
-Zinc naphthoate, zinc 1-hydroxy-2-naphthoate, 2-hydroxy-6-naphthoic acid, 4-hydroxydiphenyl sulfone, 4-hydroxy-4'-chlorodiphenyl sulfone, bis (4-hydroxyphenyl) sulfide, 2-hydroxy-paratoluic acid, oxalic acid, maleic acid, succinic acid, tartaric acid, malic acid, citric acid, stearic acid, biimidazole, hexaphenylbiimidazole, carbon tetrabromide and the like can be mentioned. )
It is a color former that exhibits a green-blue or green-based color tone when contacted with, and develops a high density and vivid color, and is produced using the color former of the present invention, for example, a pressure-sensitive recording sheet or a heat-sensitive recording. The recorded image obtained by the sheet also absorbs light in the near-infrared region around 700-900 nm. It is suitable as a recording material for an optical character reader using a light source or an optical bar code reader.

In the present invention, in producing the pressure-sensitive recording material and the heat-sensitive recording material, one kind selected from these color formers may be used alone, or two or more kinds may be used in combination, and known colorants may be used. Former (for example, crystal violet lactone, 2- (2-chloroanilino) -6-dibutylaminofluorane, 2-anilino-
3-Methyl-6- (N-ethyl-N-tetrahydrofurfurylamino) fluorane, 2-anilino-3-methyl-6-dibutylaminofluorane, 2-anilino-3-
Methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6- (N-methyl-N-cyclohexylamino) fluorane, 2-anilino-3-methyl-6-
(N-ethyl-N-isoamylamino) fluorane, 2
-N, N-dibenzylamino-6-diethylaminofluorane, benzoyl leuco methylene blue, leuco crystal violet, etc.) can also be used as a mixture. By mixing, the color development and storage stability of the image may be further improved.

In the present invention, Hisol SAS-296 (manufactured by Nippon Petrochemical Co., Ltd.), KMC-113 is a typical example of the solvent of the color former used for obtaining the pressure-sensitive recording material.
(Kureha Kagaku Kogyo Co., Ltd.), etc., but monoisopropybiphenyl-based, alkylbenzene-based, alkylbiphenyl-based, alkylnaphthalene-based, diarylethane-based, hydrogenated terphenyl-based, and chlorinated paraffin-based solvents alone It can also be used as a mixture.

Further, in the present invention, as the encapsulation method used for obtaining the pressure-sensitive recording material, a coacervation method, an interfacial polymerization method, an ln-situ method or the like can be used.

Further, in the present invention, as typical examples of the binder used to obtain the heat-sensitive recording material, polyvinyl alcohol, methyl cellulose, methoxy cellulose, ethyl cellulose, hydroxyethyl cellulose, gum arabic, gelatin, casein, starch and derivatives thereof,
Examples thereof include polyvinyl acetate, polyacrylic acid, polyvinylpyrrolidone, polyurethane, polyacrylamide, acrylic acid amide / acrylic acid ester copolymer, and styrene-maleic anhydride copolymer.

Further, in order to further improve the light resistance of the recorded image and the storage stability, higher fatty acid esters, higher fatty acid amides, phthalic acid esters, terephthalic acid esters, benzylphenyls, alkylphenols, benzenesulfonamides, Additives such as various antioxidants such as alkylbenzene sulfonamides and terphenyls, deterioration inhibitors, and ultraviolet absorbers can be used in combination.

The above general formula [1] having excellent properties as described above
The pentadiene compound represented by is Japanese Patent Publication Sho 53-1280.
2, it can be synthesized by the following known representative methods described in JP-A-55-45785 and JP-A-60-231766.

That is, the bisstyryl ketone derivative represented by the general formula [4] (wherein R ¹ , R ² , R ³ , and R ⁴ are as defined above) is represented by the general formula [2]. And a benzaldehyde derivative represented by the general formula [3] can be synthesized by dehydration condensation with acetone using an alkali metal salt such as sodium mercuride as a catalyst.

Further, the bisstyrylcarbinol derivative represented by the general formula [5] is obtained by catalytically reducing the bisstyrylketone derivative represented by the general formula [4] to obtain aluminum lithium hydride or metal powder. It can be synthesized by reduction, and preferably by reduction with sodium borohydride.

Further, the bisstyrylcarbenium perchlorate derivative represented by the general formula [6] is converted into the bisstyrylcarbinol derivative represented by the general formula [5] at 20-100 ° C. in an alcohol solvent such as methanol. It can be synthesized by reacting with perchloric acid.

Further, the pentadiene derivative represented by the general formula [1] is obtained by converting the bisstyrylcarbenium perchlorate derivative represented by the general formula [6] into an alcohol solvent such as methanol at 20-100 ° C. It can be synthesized by reacting with an alkali metal salt of a sulfinic acid such as benzenesulfinic acid represented by [7] (wherein R ⁵ is as defined above).

The pentadiene compound thus obtained is specifically described as follows.

(1) 1,5-bis [4- (N, N-dimethylamino) phenyl] -5-phenylsulfonylpenta-1,3-diene (2) 1,5-bis [4- (N, N-diethylamino) ) Phenyl] -5-phenylsulfonylpenter 1,3-diene (3) 1,5-bis [4- (N, N-di-n-butylamino)
Phenyl] -5-phenylsulfonylpenta-1,3-
Diene (4) 1,5-bis [4- (N, N-di-n-propylamino) phenyl] -5-phenylsulfonylpenta-1,
3-diene (5) 1,5-bis [4- (N, N-dimethylamino) phenyl] -5- (4'-methylphenylsulfonyl) penta-1,3-diene (6) 1,5-bis [4- (N, N-diethylamino) phenyl] -5- (4'-methylphenylsulfonyl) penta-1,3-diene (7) 1,5-bis [4- (N-methyl-N-ethylamino) ) Phenyl] -5-phenylsulfonylpenta-1,
3-diene (8) 1,5-bis [4- (N-methyl-N-ethylamino) phenyl] -5- (4'-methylphenylsulfonyl) penta-1,3-diene (9) 1,5 -Bis [4- (N, N-dimethylamino) phenyl] -5- (β-naphthylsulfonyl) penta-1,3
-Diene (10) 1,5-bis [4- (N, N-diethylamino) phenyl] -5- (β-naphthylsulfonyl) penta-1,3
-Diene (11) 1,5-bis [4- (N, N-di-n-butylamino)
Phenyl] -5- (β-naphthylsulfonyl) penta-1,3-diene (12) 1,5-bis [4- (N, N-di-n-propylamino) phenyl] -5- (β-naphthyl Sulfonyl) penta-1,3-diene (13) 1,5-bis [4- (N, N-dimethylamino) phenyl] -5- (α-naphthylsulfonyl) penta-
1,3-Diene (14) 1,5-Bis [4- (N, N-diethylamino) phenyl] -5- (α-naphthylsulfonyl) penta-1,3
-Diene (15) 1,5-bis [4- (N, N-di-n-butylamino)
Phenyl] -5- (α-naphthylsulfonyl) penta-1,3-diene (16) 1,5-bis [4- (N, N-di-n-propylamino) phenyl] -5- (α-naphthyl Sulfonyl) penta-1,3-diene (17) 1,5-bis [4- (N, N-dimethylamino) phenyl] -5- (4-chlorophenylsulfonyl) penta-1,3-diene (18) 1 , 5-bis [2-ethoxy-4- (N, N-diethylamino) phenyl] -5- (4-methoxyphenylsulfonyl) penta-1,3-diene and the like.

〔Example〕

 Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1 4- (N, N-dimethylamino) benzaldehyde 10.0
Parts (hereinafter, "parts" means "parts by weight", "%" means "% by weight"
Represents ) Is dissolved in 70 ml of ethanol and then acetone is added.
1.95 parts and 13.4 parts of 10% sodium hydroxide aqueous solution were added, and the mixture was reacted at 40-50 ° C. for 8 hours with stirring, and the separated crystals were separated by filtration, washed with 30 ml of ethanol and further with 60 ml of water, After drying, 10.0 parts of orange-yellow crystals were obtained. This one is 189.
It shows a melting point of 0-191.0 ° C and is the result of ¹³ C NMR analysis.
120.5 ppm, and the absorption peak of vinyl carbon substituted to 142.2 ppm, the absorption peak of phenyl carbon bound to the vinyl group at 122.0 ppm, the absorption peak of phenyl carbon bound to the nitrogen atom at 151.2 ppm to 187.9 ppm. Bis [4- (N, N-dimethylamino), which has a symmetrical structure to the carbonyl group while having an absorption peak for the carbonyl carbon
Identified as styryl] ketone.

10 parts of this ketone was dissolved in a mixed solvent of 100 parts of tetrahydrofurfuryl alcohol and 150 parts of THF (tetrahydrofuran), 3.6 parts of sodium borohydride was added, and the mixture was reacted at 30-50 ° C. for 8 hours. 1500 ml of reaction solution
Crystals that had been thrown out into water and were separated by filtration, washed with water, and dried to obtain 8.0 parts of pale yellow crystals.

This product shows a melting point of 80-90 ° C., and as a result of analysis by ¹³ CNMR, the absorption peaks of vinyl carbon substituted at 126.6 ppm and 130.5 ppm are the absorption peaks of phenyl carbon bonded with a vinyl group at 125.2 ppm. , 150.1 ppm has an absorption peak of a phenyl carbon bonded to a nitrogen atom and 74.3 ppm has an absorption peak of a carbinol carbon. Therefore, bis [4- (N , N-Dimethylamino) styryl] carbinol.

After dissolving 5.0 parts of this carbinol in 50 parts of THF, 2.
A mixed solution of 6 parts of 60% perchloric acid and 30 parts of glacial acetic acid was added at room temperature, and the separated crystals were filtered, washed with water and dried to obtain 5.5 parts of black green crystals. This product gradually decomposed at 186 ° C or higher, and as a result of analysis by ¹³ CNMR, the absorption peaks of vinyl carbon substituted at 125.1 ppm and 155.7 ppm,
The absorption peak of phenyl carbon bonded to a vinyl group at 125.1 ppm, the absorption peak of phenyl carbon bonded to a nitrogen atom at 155.1 ppm, and the following structural formula Bis [4- (4), which has a symmetrical structure with respect to carbonium carbon while having an absorption peak of carbon corresponding to carbon carbon in the ultimate structural formula represented by
(N, N-Dimethylamino) styryl] carbenium perchlorate.

After dispersing 5.0 parts of this carbenium perchlorate in 50 parts of methanol, 1.0 part of glacial acetic acid was added, and then 5.0 parts of sodium benzenesulfinate dissolved in 20 parts of methanol was added.
After adding 1 part and reacting under reflux for 1 hour, it was cooled, and the separated crystals were filtered, washed with water and dried to obtain 4.1 parts of pale yellow crystals. It has a melting point of 164.0-166.0 ° C and a ¹³ C NMR
The SP ³ absorption peaks of the carbon in the results 75.0ppm analysis by, an absorption peak of phenyl carbon attached to the SP ³ carbon 119.0Ppm, an absorption peak of phenyl carbon bonded to a vinyl carbon 125.0ppm, 137.7ppm Has an absorption peak of phenyl carbon bound to a sulfonyl group, and further, an absorption peak of phenyl carbon bound to nitrogen is 152.2 ppm, and 15
It was identified as 1,5-bis [4- (N, N-dimethylamino) phenyl] -5-phenylsulfonylpenta-1,3-diene because it appeared after splitting into 0.6 ppm.
In addition, when this product was dissolved in 95% acetic acid and the light absorption characteristics were measured, it showed a maximum absorption at 800 nm.

Example 2 The reaction was performed in the same manner as in Example 1 except that sodium benzenesulfinate was replaced with sodium β-naphthalene sulphinate to obtain 4.1 parts of pale yellow crystals. This product is 152.0-156.0 ℃
Indicates the melting point, ¹³ to the absorption peak of the SP ³ carbon results 75.3ppm analysis by CNMR, also phenyl carbon absorption peak of phenyl carbon attached to the SP ³ carbon 119.2Ppm, bound to vinyl carbon 125.0ppm The absorption peak of phenyl carbon bonded to nitrogen is 150.3p.
pm, and the fact that it splits up to 150.7ppm and appears.
As a result of 1H-NMR analysis, 32 hydrogens were detected. Therefore, 1,5-bis [4- (N, N-dimethylamino) phenyl] -5- (β-naphthylsulfonyl) penta-1,3
-Identified as a diene. In addition, when this product was dissolved in 95% acetic acid and the light absorption characteristics were measured, it showed a maximum absorption at 791 nm.

Example 3 14 parts of gelatin having an isoelectric point of 8.5 and 12 parts of gum arabic are treated at 50 ° C.
Dissolved in 150 parts of deionized water, 3.5 parts of 10% funnel oil as an emulsifier was added, and 1,5-bis [4- (N, N-dimethylamino) phenyl] -5-phenylsulfonylpenta-1,
70 parts of Hisol SAS-296 (diaryl ethane oil, manufactured by Nippon Petroleum Science Co., Ltd.) containing 3% of 3-diene was added, and the mixture was emulsified with a homomixer at 7,000 rpm to obtain an O / W emulsion. Add 40 ° C deionized water to this emulsion.
Add 0 parts to dilute, add 10% acetic acid aqueous solution dropwise with stirring at 350 rpm with a propeller stirrer to adjust pH to 4.3.
Adjusted to.

Then, 13 parts of an aqueous solution of 20% Melment F10 (product of Showa Denko KK) and 40% Newcol 271A (Nippon Emulsifier Co., Ltd.)
3.5 parts of an aqueous solution of (product) was added, and the mixture was cooled from the outside of the vessel while continuing to stir.
5 parts was added and a 10% aqueous sodium hydroxide solution was added dropwise over 15 minutes to adjust the pH to 9.5, and the solution temperature was raised to 50 ° C. for 30 minutes while continuing stirring, and 1,5-bis [4] was added. A microcapsule slurry of-(N, N-dimethylamino) phenyl] -5-phenylsulfonylpenta-1,3-diene dissolved oil was prepared.

After applying this microcapsule slitter on paper and drying it, the microcapsule slitter was brought into close contact with a commercially available pressure-sensitive color developing sheet, and a writing pressure or an impact of a typewriter was applied, and in each case, a green-blue color recorded image was obtained. Further, when the reflection and absorption characteristics of this recorded image were measured, it had a strong electromagnetic wave absorption in the near infrared region.

Example 4 1,5-bis [4- (N, N-dimethylamino) phenyl]
1,5-bis [4- (N, N-dimethylamino) phenyl] -5- (β-naphthylsulfonyl) penta-1,3 instead of -5-phenylsulfonylpenta-1,3-diene
Treated as in Example 3, but using diene, 1,
5-bis [4- (N, N-dimethylamino) phenyl] -5
A microcapsule rally of dissolved oil of-(β-naphthylsulfonyl) penta-1,3-diene was prepared.

This microcapsule slurry was applied on paper and dried, and then closely adhered to a commercially available pressure-sensitive color developing sheet. When a pen pressure or a typewriter impact was applied, a green-blue color recording image was obtained in each case. Further, when the reflection and absorption characteristics of this recorded image were measured, it had a strong electromagnetic wave absorption in the near infrared region.

Example 5 1,5-bis [4- (N, N-dimethylamino) phenyl]
2.0 parts of -5-phenylsulfonylpenta-1,3-diene was dispersed and mixed with 20 parts of an aqueous 10% polyvinyl alcohol solution at room temperature for 24 hours using a ball mill to obtain a colorless slurry as "A liquid". The particle size of the solid material in this slurry was about 3 microns.

On the other hand, 7.5 parts of bisphenol A was dispersed and mixed with 40 parts of 10% aqueous polyvinyl alcohol solution and 10 parts of deionized water at room temperature for 24 hours using a ball mill,
A slurry was prepared as "liquid". The particle size of the solid material in this slurry was about 5 microns.

The above-mentioned "Solution A" and "Solution B" were mixed, stirred at room temperature for 1 hour, uniformly dispersed and mixed to prepare a mixed slurry. This mixed slurry was applied to one side of 50 g / m ² plain paper using a wire bar coater so as to have a uniform film thickness, air-dried at room temperature, and a thermosensitive recording sheet having an almost colorless thermosensitive layer. It was created.

When the heat-sensitive recording sheet thus prepared was colored using a thermal gradient tester, a blue-green color recording image was obtained. Further, when the reflection and absorption characteristics of this recorded image were measured, it had a strong electromagnetic wave absorption in the near infrared region.

Example 6 1,5-bis [4- (N, N-dimethylamino) phenyl]
1,5-bis [4- (N, N-dimethylamino) phenyl] -5- (β-naphthylsulfonyl) penta-1,3 instead of -5-phenylsulfonylpenta-1,3-diene
Treated as in Example 5, but using diene, 1,
5-bis [4- (N, N-dimethylamino) phenyl] -5
A colorless slurry was obtained by using the dispersion liquid of-(β-naphthylsulfonyl) penta-1,3-diene as "C liquid". The particle size of the solid material in this slurry was about 3 microns.

The above-mentioned “Solution C” and the “Solution B” prepared in Example 5 were mixed, stirred at room temperature for 1 hour, and uniformly dispersed and mixed to prepare a mixed slurry. 50 g /
A wire bar coater was used to coat one side of m ² plain paper so as to have a uniform film thickness, and it was air-dried at room temperature to prepare a thermosensitive recording sheet having an almost colorless thermosensitive layer.

When the heat-sensitive recording sheet thus prepared was colored using a thermal gradient tester, a blue-green color recording image was obtained. Further, when the reflection and absorption characteristics of this recorded image were measured, it had a strong electromagnetic wave absorption in the near infrared region.

〔The invention's effect〕

As described above, the present invention has a strong absorption in the near-infrared region in a colored state, and when used in a thermal recording sheet, a novel pentadiene compound having extremely excellent sensitivity characteristics, and at least the compound The present invention provides a recording material containing one kind. Further, the present invention has the effect of expanding the range of use of the recording material.

Claims (2)

(57) [Claims] 1. The following general formula [1] (In the formula, R ¹ , R ² , R ³ and R ⁴ represent a lower alkyl group, and R ⁵ represents a halogen atom, an alkyl group, or an aryl group which may be substituted with an alkoxy group, or a naphthyl group. A novel pentadiene compound represented by 2. A recording material comprising at least one of the compounds described in claim 1.