JPH0611585B2 - Chromogenic recording material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Use of the Invention The present invention is a color-forming recording material that utilizes coloring of an electron-donating color-forming dye (hereinafter, referred to as “color-forming dye”), which is colorless or pale in color, by an acidic substance. Regarding

[Problems to be Solved by Prior Art and Invention]

One of the weaknesses of a color-forming recording material containing a color-forming dye and an acidic substance (developing agent) for developing the color as a main component for coloring is stains caused by fingerprints or cosmetic creams. It has been pointed out that the color-developed image is discolored due to stains, and this defect is particularly remarkable in the heat-sensitive recording paper.

In order to make up for this drawback, attempts have been made to improve color forming dyes and color developers or develop image stabilizers, but satisfactory results have not yet been obtained.

[Means for solving problems]

The present inventors have used a general formula for the reaction system of the color forming dye and the color developing agent. (Where R ¹ is R ² is a hydrogen atom or an alkyl group, and X ¹ and
X ² each independently represent a halogen atom, an alkyl or an alkoxy group, m is 0 or 1, p is an integer of 0 to 5, q is an integer of 0 to 4, and β is an integer of 1 to 5). It has been found that the presence of the represented diphenyl sulfone derivative remarkably improves the above-mentioned weaknesses in a color-developing recording material, particularly a thermosensitive color-developing recording material.

Examples of the diphenyl sulfone derivative represented by the general formula (I) include the following compounds.

1 Two Three Four 5 6 7 8 9 Ten 11 12 13 14 15 16 17 18 19 20 twenty one The first point is that an image obtained by heating a thermal recording paper using a diphenylsulfone derivative represented by the general formula (I) is fast against fingerprint stains and cosmetic cream stains.
Shown in the table. Table 1 shows the results obtained in Example 1, Example 2, Example 3, Example 4 and Comparative Example 1.

Table 1 Examples Fingerprint stain Cosmetic cream stain 1 Almost no change 2 Almost no change 2 Same as above Same as above 3 Same as above 4 Same as above Same as above Comparative Example 1 Obviously fading Obviously fading Diphenyl sulfone derivative represented by the general formula (I) Is
It is used in any color forming recording material utilizing the reaction between a color developing agent which is an acidic substance and a color forming dye, and examples of such a color forming recording material include thermosensitive recording paper and pressure sensitive copying paper. Examples of such systems include heat-sensitive transfer, electric recording, electrophotography, photosensitive recording, ultrasonic recording and electrostatic recording. The amount of the diphenyl sulfone derivative represented by the general formula (1) varies depending on the type and the type of color forming dye used, but usually the color forming dye 1
0.1 to 3 parts, preferably 0.5 to 1.5 parts are used per part.

The chromogenic dye used in these chromogenic recording materials may be of any kind, but as a few of them, crystal violet lettactone, benzoyl rheucomethylene blue, 5 ( Or 7)-(1-octyl-2-methylindol-3-yl) -5 (or 7)-(4-diethylamino-2-ethoxyphenyl) -5,7-dihydrofuro (3,4-b)- 3-Diethylamino-5-as a green color-forming dye such as pyrodisin-7 (or 5) -one
3-Diethylamino-6-as a red color-forming dye such as methyl-7-benzylaminofluorane and 3-N-isobutyl-ethylamino-7-phenylaminofluorane.
3-diethylamino-6-methyl-7-phenylaminofluorane, 3-N-methyl-cyclohexylamino-, etc. as black color-forming dyes such as methyl-7-chlorofluorane and 3-cyclohexylamino-6-chlorofluorane. 6-methyl-7-phenylaminofluorane, 3-N
-Methyl-n-propylamino-6-methyl-7-phenylaminofluorane, 3-N-isopentyl-ethylamino-6-methyl-7-phenylaminofluorane,
3-diethylamino-7-m-trifluoromethylphenylaminofluorane, 3-di-n-butylamino-7
Examples thereof include, but are not limited to, -chlorophenylaminofluorane and 3-N-ethyltoluidino-6-methyl-7-phenylaminofluorane. Further, JP-A-51-121,035 and JP-A-51-121,0
37, JP-A-51-121,038, JP-A-55-115,448, JP-A-55-115,449, JP-A-55-115,450, JP-A-55-
115,451, JP-A-55-115,452, JP-A-55-115,456
JP-A-57-167,979, JP-A-58-157,779, JP-A-60-8,364, JP-A-60-27,589, and JP-A-59-148,6.
95, JP-A-59-199,757, European Patent Application Publication No. 124377, JP-A-60-126149 or Showa 60.
It is described in the patent specification filed by the applicant of the present application on November 6, 2012. It is also possible to use a color forming dye having a property of absorbing an electromagnetic wave from a long wavelength portion of visible light to a near infrared portion during color development. Also, it goes without saying that these color forming dyes can be mixed and used.

The method for producing a heat-sensitive recording paper using the diphenylsulfone derivative represented by the general formula (I) is similar to the ordinary method for producing a heat-sensitive recording paper. For example, JP-B-39-27579.
It can be produced according to the method described in JP-B No. 43-4160, JP-B No. 45-14039 or JP-A No. 59-7087. That is, a suspension in which fine particles of a color forming dye, fine particles of a developer and fine particles of a diphenylsulfone derivative of the general formula (I) are dispersed in an aqueous solution of a water-soluble binder is applied to paper and dried. Therefore, a thermal recording paper can be obtained. The suspension may further contain a filler, a sensitizer, a dispersant, an antioxidant, a desensitizer, an anti-adhesive agent, a defoaming agent, a light stabilizer, a brightening agent and the like. It is also possible to use at least one of the color forming dye and the color developer enclosed in a microcapsule in order to prevent the color forming of the color forming dye during storage of the heat-sensitive memory paper.

Examples of the color developer used for the heat-sensitive recording paper include bisphenol A, 4,4'-cassendariplidene bisphenol, 4,4'-cyclohexylidene bisphenol, 2,2 '.
-Dihydroxydiphenyl, pentamethylene-bis (4
-Hydroxybenzoate) and other bisphenol compounds, 1,7-di (4-hydroxyphenylthio) -3,5-
Sulfur-containing bisphenol compounds such as dioxaheptane, benzyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate, 4
-Isopropyl hydroxybenzoate, butyl 4-hydroxybenzoate, isobutyl 4-hydroxybenzoate, 4
4-Hydroxybenzoic acid esters such as chlorobenzyl hydroxybenzoate, methylbenzyl 4-hydroxybenzoate and diphenylmethyl 4-hydroxybenzoate, 4-hydroxy-4′-methyldiphenyl sulfone, 4-hydroxy-4′- Hydroxysulfones such as isopropoxydiphenyl sulfone and 4-hydroxy-4'-butoxydiphenyl sulfone, 4-hydroxyphthalates such as dimethyl 4-hydroxyphthalate, dicyclohexyl 4-hydroxyphthalate and diphenyl 4-hydroxyphthalate.
Hydroxyphthalic acid diesters, for example ester acids of hydroxynaphthoic acid such as 2-hydroxy-6-carboxynaphthalene, as well as hydroxyacetophenone, p-phenylphenol, benzyl 4-hydroxyphenylacetate, p-benzylphenol, Examples thereof include hydroquinone-monobenzyl ether.

Examples of the water-soluble binder include polyvinyl alcohol, hydroxyethyl cellulose, carboxymethyl cellulose, styrene-maleic anhydride copolymer salt, styrene-
Examples thereof include, but are not limited to, butadiene emulsion, vinyl acetate-maleic anhydride emulsion, polyacrylic acid salt, polyacrylamide, starches, casein, and gum arabic.

Examples of the sensitizer include higher fatty acid amide, benzamide, stearic acid anilide, acetoacetic acid anilide, thioacetanilide, dimethyl phthalate, dibenzyl terephthalate, dibenzyl isophthalate, bis (tert-butylphenol) s, for example 4,4′- Dimethoxydiphenyl sulfone, 4-isc-propoxy-4'-n-butoxydiphenyl sulfone, 4,4'-dibutoxydiphenyl sulfone, 4,4'-di-n- (or isc-) pentyloxydiphenyl sulfone Bisphenol S diethers such as, diphenylamine, carbazole, 2,3
-Di-m-tolylbutane, 4,4 'dimethylbiphenyl,
Examples of the filler include di-β-naphthylphenylenediamine, and examples of the filler include clay, talc, kaolin, satin white, titanium oxide, calcium carbonate, magnesium carbonate, barium sulfate, magnesium silicate, aluminum silicate and the like. it can.

Further, as the dispersant, for example, sulfosuccinates such as dioctyl sodium sulfosuccinate, sodium dodecylbenzenesulfonate, sodium salt of lauryl alcohol sulfate, fatty acid salt, and the like, and as the antioxidant, for example, 2,2′-methylenebis ( 4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,
4'-Propylmethylenebis (3-methyl-6-tert-
Butylphenol), 4,4′-thiobis (2-tert-butyl-5-methylphenol), and the like, desensitizing agents such as aliphatic higher alcohols, polyethylene glycol, guanidine derivatives, and anti-tacking agents. Examples thereof include stearic acid, zinc stearate, calcium stearate, carnauba wax, paraffin wax and ester wax.

To use the diphenyl sulfone derivative represented by the general formula (I) in pressure-sensitive copying paper, U.S. Pat.
Pressure-sensitive copying paper can be produced according to the methods described in 2,548,366, 2,800,457, 2,800458, and JP-A-58-112041 or JP-A-58-139738. it can. At this time, the diphenyl sulfone derivative may be contained in the microcapsule together with the color forming dye,
Alternatively, fine particles of a diphenyl sulfone derivative may be added to a suspension containing microcapsules and applied onto a paper surface,
Alternatively, it may be applied to the paper surface in addition to the developer suspension. The composition of the pressure-sensitive copying paper is as follows: top paper having microcapsules containing an organic solvent solution of a color-forming dye applied and carried on the lower surface and bottom paper having developer (oxidizing substance) applied and carried on the upper surface. A unit consisting of and (medium-leaf paper with a developer on the top and microcapsules on the bottom can also be added to the unit), or the microcapsules and the developer are applied on the same paper surface. It may be so-called self-content paper.

To use the diphenylsulfone derivative represented by the general formula (I) for thermal transfer, for example, JP-A-58-212,985, JP-A-59-33,185, JP-A-59-42,995 or JP-A-59-42,995.
It can be used according to the method described in JP-A-59-225,986.
6,137, JP-A-48-101,935 or JP-A-49-11,3
For use in the method described in JP-A-44, or for use in electrophotography, for example, JP-A-52-24,530 or JP-A-52-56,932
It can be used according to the method described in the publication.

Further, to use the fluorane compound of the present invention for photosensitive recording, for example, JP-B-38-24,188, JP-B-45-10550,
JP-B-49-45978, JP-A-50-80120, JP-A-50-12
6228, JP-A-52-141633 or JP-A-54-147829
It can be used according to the method described in the publication.

For use in ultrasound recording, French Patent No. 2120922
No. 4,39,932 for use in electrostatic recording, and the method described in JP-A No. 48-12104 for use in photosensitive printing materials.

The recording paper produced according to these methods can be provided with a protective layer on the front surface if necessary, and an adhesive layer can be provided on the back surface for convenient use as a label.

Synthesis Example 1 125 g of 4,4′-dihydroxydiphenyl sulfone (bisphenol S), 277.5 g of epichlorohydrin and 1.1 g of sodium acetate were placed in a flask and heated to 115 ° C. with stirring to finely pulverize the hydroxylated product. Sodium 45.4g
And a mixture of 96.7 g of xylene were added dropwise over 30 minutes.
Next, while stirring xylene under reflux for 3 hours, the sodium chloride produced by heating was removed, the crystals precipitated upon cooling were washed and washed with methanol, and 4,4'-diglycidyloxydiph 118 g of ethyl sulfone, melting point 163-16.4
Obtained as white crystals at 0 ° C.

Synthesis Example 2 4-Methyl-4'-hydroxydiphenyl sulfone 19.5
g to 50 ml of ethanol, potassium hydroxide 4.8 g
Was added and completely dissolved. Epichlorohydrin in the next 1
4.5 g was added and heated, and the mixture was refluxed with stirring for 2 hours. After cooling, a small amount of the precipitate was removed, the liquid was concentrated and the precipitate was collected and recrystallized with an ethanol / chloroform mixed solution (50 ml: 15 ml) to melt 15 g of 4-methyl-4′-glycidyloxydiphenyl sulfone. Obtained as white crystals at 136.8 ° to 138.8 ° C.

Synthesis Example 3 4-isopropoxy-4'-hydroxydiphenyl sulfone 29.2 g, sodium hydroxide 5.0 g and water 50 ml
And completely dissolved, and then epichlorohydrin 9.3g
Was added and stirring was continued at room temperature for 10 hours. The precipitated crystals are taken and recrystallized using a mixed solution of ethanol and toluene, and 16 g of 4-isopropoxy-4'-glycidyloxydiphenyl sulfone is melted at 132.5 to 134.3 ° C.
Was obtained as white crystals.

Synthetic Example 4 4,4'-Dihydroxy-3,3 ', 5,5'-tetrabromodiphenyl sulfone 17 g, sodium hydroxide 2.6 g and water 10 ml were mixed and completely dissolved before epibromohydrin 9 Add 0.0 g and 50 ml of ethanol and heat,
Stirring was continued for 5 hours at reflux. 50 ml of Ethanow
Is added and the precipitated crystals are collected and purified to 4,4 ′
-Diglycidyloxy-3,3 ', 5,5'-tetrabromodiphenyl sulfone was obtained as white crystals with a melting point of 210.5-215.0 ° C.

Example 1 10.5 g of bisphenol A, 15% aqueous solution of polyvinyl alcohol (Kuraray Co., Ltd., "Kuraray-105") 41.5
g, Inorganic filler (Engelhard, "UW-90") 8.0 g
And 40.0g of pure water 150g of glass beads (diameter 1-1.5mm)
Put it in a 250 ml polyethylene bottle with a stopper, and seal it with Red De
It was attached to a paint conditioner manufactured by vil and shaken at a frequency of 630 times / min for 8 hours, and then the glass beads were removed to obtain an aqueous suspension of bisphenol A having a particle size of 2 to 3 μ (Liquid A). ).

On the other hand, 7.0 g of 3-N-methylcyclohexylamino-6-methyl-7-phenylaminofluorane, 41.5 g of 15% aqueous solution of polyvinyl alcohol (same as above), inorganic filler (same as above) 11.5 g and pure water 40.0 g. The glass bead
After putting it in a 250 ml polyethylene bottle together with 150 g, sealing it with a paint conditioner at a frequency of 630 times / min for 5 hours and then removing the glass beads, an aqueous suspension of the fluoran compound (particle size 2 to 3 μ) was obtained (B
liquid).

Further, 41.5 g of a 15% aqueous solution of polyvinyl alcohol (same as above), 7.0 g of 4,4'-bis (glycidyloxy) diphenyl sulfone (compound No. 22), 11.5 g of inorganic filler (same as above) and 40.0 of pure water. g glass beads 150
It was put in a 250 ml polyethylene bottle together with g and treated in the same manner as above to obtain an aqueous suspension of 4,4'-bis (glycidyloxy) diphenylsulfone (solution C).

Mix 10g of solution A and 5g each of solution B and solution C, and mix 2
A coating solution was prepared by stirring for 0 minutes.

This coating solution was applied to white base paper using wire rod No. 12 and dried with warm air at 60 ° C for 2 minutes to produce a heat-sensitive recording paper.

This heat-sensitive recording paper was heated on both sides at a temperature of 150 ° C. for 5 seconds using a dry heat tester (Kishino Scientific Machinery Co., Ltd.) to develop color (black). Part of the coloring surface was stained with fingerprints, and the other part was stained with cosmetic cream and stored for 10 days at room temperature, and then observed. Similarly, almost no fading or discoloration was observed.

Example 2 4,4′-bis (glycidyloxy) used in Example 1
4-Methyl-4'-glycidyloxydiphenyl sulfone instead of diphenyl sulfone (Compound No. 11 above)
Was used to carry out the same experiment as in Example 1. 10 at room temperature
After storage for a day, almost no change was observed in the soiled portion as in Example 1.

Example 3 4,4′-bis (glycidyloxy) used in Example 1
Instead of diphenyl sulfone, 4-isopropoxy-
The same experiment as in Example 1 was conducted using 4'-glycidyloxydiphenyl sulfone (Compound No. 20 above). After storage at room temperature for 10 days, almost no change was observed in the soiled portion as in Example 1.

Example 4 4,4′-bis (glycidyloxy) used in Example 1
The same experiment as in Example 1 was carried out by using 4,4'-bis (glycidyloxy) -3,3 ', 5,5'-tetrabromodiphenyl sulfone (Compound No. 25) instead of diphenyl sulfone. I went. After storage at room temperature for 10 days, almost no change was observed in the soiled portion as in Example 1.

Comparative Example 15% aqueous solution of polyvinyl alcohol (same as above) 4
1.5g, inorganic filler (same as above) 18.5g and pure water 4
0.0 g was placed in a 250 ml polyethylene bottle together with 150 g of glass beads, and the bottle was sealed and shaken in the same manner as above to prepare an aqueous suspension of the inorganic filler.

A thermal recording paper was produced in the same manner as in Example 1 except that this aqueous suspension was used instead of the liquid C in Example 1. That is, this heat-sensitive recording paper is a heat-sensitive recording paper containing no diphenyl sulfone derivative. When this heat-sensitive recording paper was subjected to color development, staining and storage in the same manner as in Example 1, discoloration of fingerprint-stained areas and cosmetic cream-stained areas was remarkable.

Claims (1)

[Claims] 1. A color-forming recording material which utilizes the reaction between a colorless or light-colored electron-donating color-forming dye and an acidic substance, the reaction system of which is represented by the general formula: (Where R ¹ is R ² is a hydrogen atom or an alkyl group, and X ¹ and
X ² each independently represent a halogen atom, an alkyl or an alkoxy group, m is 0 or 1, p is an integer of 0 to 5, q is an integer of 0 to 4, and β is an integer of 1 to 5). A chromogenic recording material, characterized in that the diphenyl sulfone derivative represented is present.