JPS60179289A - Recording material - Google Patents

Abstract

PURPOSE:To raise shelf life, by a method wherein an electron accepting compound is the hydroxybenzoate ester having at least not less than 2 hydroxy groups in the recording material using electron donating colorless dyestuff and electron accepting compound, the position neighbouring ester site being substituted and one side thereof is made to be hydroxy group. CONSTITUTION:The titled recording meterial is the recording material using the compound, the hydroxybenzoate ester having at least not less than 2 hydroxy groups as electron donating colourless dyestuff and electron accepting compound, the position neighbouring the ester site of which is substituted and one side thereof is hydroxy group. When electron accepting combining compound is used as electron accepting compound for thermosensitive recording material, said compound should preferably have a melting point of 50 deg.C min. and should especially preferably have a melting point of 70-150 deg.C.

Description

[Detailed description of the invention] <Field of application of the invention> The present invention relates to recording materials.

The recording material according to the present invention utilizes a color-forming reaction between an electron-donating colorless dye and an electron-accepting compound, and particularly relates to a recording material using a novel electron-accepting compound.

The electron-accepting compound according to the present invention is particularly an electron-accepting compound for pressure-sensitive recording materials and heat-sensitive recording materials. It is an extremely useful compound as a chemical compound, and is useful for electrically conductive heat-sensitive recording sheets, photosensitive recording sheets, ultrasonic recording sheets, and electronic recording sheets.

It is a compound that can also be applied to recording sheets for infrared radiation, electrostatic recording sheets, photosensitive pressure-sensitive recording sheets, etc.

<Prior Art> The use of various phenolic compounds as electron-accepting compounds in pressure-sensitive recording materials or heat-sensitive recording materials has been reported in the Japanese Patent Publication No. 3 Theta 3 Theta No. 3 and the Special Publication No. 2003. However, these phenol compounds cannot necessarily be said to be satisfactory electron-accepting compounds. That is, (1) the coloring density when used in combination with an electron-donating colorless dye is not sufficient.

(2) When ,2,x-dihydro L7 xybenzoic acid ester is used in a pressure-sensitive recording material, the humidity and heat resistance of the recording material is poor, and fogging is likely to occur. (3) After recording, there were many problems that needed to be improved, such as the density of the image area decreasing over time and the concentration of white powdery substances on the surface called powder blowing. The object of the present invention is to provide a recording material which has sufficient color density when used in combination with an electron-donating colorless dye and has improved shelf life and storage stability over time.

<Structure of the Invention> The object of the present invention is to use a hydroxybenzoic acid ester having at least a moss or larger hydroxyl group as an electron-donating colorless dye and an electron-accepting compound, the ester moiety (=adjacent position being substituted) One of these was achieved by recording materials using compounds with hydroxyl groups.

The compound of the present invention is preferably represented by the following formula.

H 1 Above formula (=▼-fi, R1 represents alkyl, aralkyl or alkoxy group, R2 represents alkyl or substituted alkyl.

When the electron-accepting compound according to the present invention is used as an electron-accepting compound for heat-sensitive recording materials, it preferably has a melting point of 5.9006 or higher, particularly 7000-/jo"c.
It is preferable to have a melting point of .

The characteristics of the electron-accepting compound according to the present invention include the following.

(1) In combination with an electron-donating colorless dye, a high-density colored image is produced.

(1) Low water solubility.

(Ill) Stable without sublimation.

(1v) It is easy to synthesize and can be obtained with high yield and high purity. The raw materials are also cheap.

For example, a compound in which R1 is a methyl group and R2 is an ethyl group can be synthesized using a very inexpensive and simple synthesis method that uses one mole of diketene, ethanol, and an alkali as raw materials.

Furthermore, the above-mentioned effects of the electron-accepting compound of the present invention are as follows:
It is not yet clear what causes this, but
It can be thought of as follows.

In a recording system that utilizes contact between an electron-accepting compound and an electron-donating compound, ester-based compounds usually exhibit a desensitizing effect and have problems with storage stability after recording, but the electron-accepting compound of the present invention As can be seen from the above formula, the compound is substituted at the position adjacent to the ester moiety, and since one of the two is a hydroxy group, it is easy to form a Z-membered ring hydrogen bond, and the electron pair in the ester moiety is fixed. This is thought to be due to the fact that it becomes difficult to exert other evil influence wisdom.

Next, specific examples of the electron-accepting compound of the present invention are shown, but the present invention is not limited thereto. t-methylbenzoic acid propyl ester (3), 2.Q--dihydroxy-6-ipylbenzoic acid ether ester (4), 2,4t-dihydroxy-2-methylbenzoic acid ether ester (5), 2. .4t-dihydroxy-6- is methylbenzoic acid methyl ester (6), z, &-dihydroxy-t-methoxybenzoic acid butyl ester (7) 2. g-dihydroxy-6-methylbenzoic acid cyclohexyl ester (8) J , 9t-dihydroxy-6-methylbenzoic acid phenyl ester (9)''21Gudihydroxy-2-methylbenzoic acid t
-butyl ester QO), 2. hydroxybenzoic acid amyl ester, etc. These may be used singly or in combination, and furthermore, other compounds such as bisphenol A5 benzyl hydroxybenzoate, λ
, phenethyl q-dihydroxybenzoate, /,/-bis-guhydroxyphenylcyclo-xane and the like. When mixing (2), the ratio is determined by taking into account solubility, color development temperature, solvent resistance, etc.
Zinc salts of fluoric acid derivatives, etc. are used in combination to improve light resistance,
Provides fingerprint resistance.

As the electron-donating colorless dye used in the present invention, triarylmethane compounds, diphenylmethane compounds, xanthine compounds, thiazine compounds, spiropyran compounds, etc. are used.

To illustrate some of these, triarylmethane compounds include 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophenyl, 3゜3-bis(p-
dimethylaminophenyl) phtali Y1. g-(p-dimethylaminophenyl)-3-(/, 3-dimethylindol-3-yl)phthalide1. ? -(p-dimethylaminophenyl)-3-(,2-)delindole-3-
yl) phthalide, and diphenylmethane compounds include <t, l-bis-dimethylaminobenzhydrin benzyl ether, N-herophenyl leuco auramine, N-, z, y, t-trichlorophenyl leuco There are auramines, etc., and xanthine compounds include rhodamine-B-anilinolactam, rhodamine(p-nitroanilino)lactam, rhodamine B(p-chloroaniy))lactam, nodibenzylamino-t-diethylaminofluorane, λ -7nilino-6-dietheraminofluorane, co-anilino-3-methyl-t-diethylaminofluorane, no-anilino-3-methyl-4-N
-cyclohexyl-N-methylaminofluorane, --
Anilino-3-methyl-4-N-ether-N-isoamylaminofluorane 1.2-〇-Chloroanilino 6-
Diethylaminofluorane 1.2-(3,p-dichloroanilino)-6-diethylaminofluorane, -1octylamino-6-ethylaminofluorane, λ-anilino 3-methyl-6-siphenylaminofluorane ,
Koanilinoj -) frou! -chloro0-6-diethylaminofluorane, -1anilino3-mesol-6
-Diethelamino-7-methylfluorane, Cooptylamino-3-chloro-J -Diethylaminofluorane, Coethoxyethylamino-3-chloro[1-6-diethylaminofluorane, Co-anilino-3-chloro-t
-diethylaminofluorane, noanilino-3-methyl-6-sioctylaminofluorane, cordimethylaminocarbonylethylamino-t-diethylaminofluoran 1.2-0-chloroanilino-J -dibutylaminofluorane, noanilino-3- Pentadecyl-6
-diethylaminofluorane, coanilino 3-ethyl-t-dibutylaminofluorane, coanilino 3
-Ethyl-A-N-ethyl-N-isoamylaminofluorane, noanilino-3-methyl-7-N-ethyl-
He-γ-methoxypropylaminofluorane, J-p-
There are chloroanilino-3-phenyl-ot-diethylaminofluoran, copeuniru-t-diethylaminofluoran, etc. Thiazine compounds include benzoylleucomethylene blue, p-nitrobenzylleucomethylene blue, etc., and spiro compounds include 3-methyl Loose Virodinaphthopicune, 3-Ether-Spiro-Dinaphthopyran, 3.3'-Cyclolosespiro-Dinaphthopyran, 3-Benzylspiro-Dinaphthopyran, 3-Metelnaf)-(3-Methoxy-benzo)-Spiropyran1. ? --f ropyrus spirodibensohyran and the like. These may be used alone or in combination.

Next, a specific method for manufacturing the recording material according to the present invention will be described.

Pressure-sensitive copying paper according to the present invention is disclosed in U.S. Pat. No. 2.30, Tough No. 0, Ibid.

jOj, 4t? 9th issue, same co, j da tr, tat issue,
Same, 2,2/i, rθ2, same, 730, 4tt4
No. 2, 23θ, 4ttz, No. 3. +1/l,
Ko! It can take various forms as described in prior patents such as No. θ. Most commonly, it consists of at least one pair of sheets containing separately an electron-donating colorless dye and an electron-accepting compound according to the invention. , alkylated diphenyl, alkylated diphenylmethane, alkylated diarylethane, chlorinated paraffin, etc., and dispersed in a binder or applied to the support after containing it in microcapsules. By dispersing the color former sheet and the electron-accepting compound alone or in combination or together with other electron-accepting compounds in a binder such as sterentadiene latex, polyvinyl alcohol, paper, or plastic sheet. A developer sheet is obtained by applying the color developer to a support such as resin-coated paper.

The amount of the electron-donating colorless dye and the electron-accepting compound to be used depends on the desired coating thickness, the form of the pressure-sensitive copying paper, the capsule manufacturing method, and other conditions, and may be appropriately selected depending on the conditions.

U.S. Pat.

rθθ, 4tt No. 7, 2,700. <The method using coacervation of a hydrophilic colloid sol described in No. TSR, British Patent No. J'A7,797, same! θ,
Google No. 3, same wa/? ,, No. 24, same/.

There are interfacial polymerization methods described in No. 09/, θ7, etc.

The heat-sensitive recording material is prepared by adding an electron-donating colorless dye, an electron-accepting compound according to the present invention, and, if necessary, a thermofusible substance to a liquid in which a binder is dissolved or dispersed, individually or in combination, and sufficiently finely ground. After mixing, an oil-absorbing pigment such as kaolin, calcined kaolin, talc, diatomaceous earth, calcium carbonate, aluminum hydroxide, acid clay, barium sulfate, urea-formalin filler, or cellulose filler is added to form a coating solution. A paraffin wax emulsion, a latex binder, a sensitivity improver, a metal soap, an antioxidant, an ultraviolet absorber, an image storage improver, etc. can be added to this as required.

The coating liquid is applied to a support such as neutral paper, high-quality paper, or plastic film and dried. When preparing a coating liquid, all the components may be mixed and pulverized at the same time from the beginning, or they may be combined in appropriate combinations, pulverized and dispersed separately, and then mixed.

The amounts of each component constituting the heat-sensitive recording material are: 7 to -4 parts by weight of an electron-donating colorless dye, 4 parts by weight of an electron-accepting compound, 0 to 30 parts by weight of a thermofusible substance, and 0 to 73 parts by weight of a pigment. , 7 to 76 parts by weight of binder, antioxidant, fluorescent brightener,
It generally consists of a small amount of a dispersant or the like.

Electron-donating colorless dyes may be used alone or in combination.

Next, examples of binders used in the present invention include styrene-butadiene copolymer, modified acrylamide copolymer, carboxy-modified polyvinyl alcohol,
Examples include acrylic latex, vinyl acetate copolymer, styrene-maleic anhydride copolymer, and hydroxyethyl cellulose.

As the thermofusible substance, erucic acid, stearic acid, benic acid, palmitic acid, stearic acid amide,
Behenic acid amide, stearic acid anilide, stearic acid toluicide, N-myristoyl-p-aningine, N-
Myristoyl-p-phenetidine, /-methoxycarbonyl-cou N-stearylcarbamoylbenzene, N-
Octadecyl flare, N-hexadecyl urea, N・N
'-Didodecyl flare, phenylcarba (yloxycytodecane, pt-butylphenolphenoxyacetate)
-), p-phenylphenol-p-chlorophenoxy acetate, ((,4t'-isopropylidene bismethoxybenyne, β-phenyl eder-p-phenylphenyl ether, col-chlorobenzyloxynaphthalene, cobenzyloxynaphthalene, /-benzyloxynaphthalene, -monophenoxyacetyloxynaphthalene, diphenyl phthalate ester, /-hydroxyconaphthoic acid phenyl ester, cobensoyloxynaphthalene, p-benzyloxybenzoic acid benzyl ester, hydroquinone acetate hydroxynaphthoic acid phenyl ester , p-methoxycarbonylbenzoic acid butyramide, etc. are used.

These substances are colorless solids at room temperature and have sharp melting points at temperatures suitable for copying heating temperatures, that is, around 70 to 30''C.

Examples of waxes include: rhino wax, carnauba wax, microcrystalline wax, polyethylene wax, higher fatty acid amides such as stearic acid amide, ethylene biss, thearoamide, and higher fatty acid esters.

Examples of metal stones include higher fatty acid polyvalent metal salts such as zinc stearate, aluminum stearate, calcium stearate, and zinc oleate.

Phenols or derivatives thereof in which at least 7 or more of the λ or 6-positions are substituted with alkyl groups, preferably branched alkyl groups, are suitable as image storage improvers.

Moreover, those having a plurality of phenol groups in the molecule are preferable, and those having 1 to 3 phenol groups are particularly preferable. Specific examples of these compounds are: bis-[3,3-bis-(2'-methylg'-hydroxyi/j'-tert-butylphenyl)-phtanoic acid] glycol ester-/, /, ! -tris(,2-methyl-couhydroquine-
6-tert-7tylphenyl)butane, <<, g'-
Thiobis(comethyl/I/-4-tert-nibutylphenol), 2,2'-thiobis(4t-methyl-A-tert-butylphenol), co-9,2'-methylenebis(gumethyl-6-tert)
-butylphenol), ri,ri'-butylidenebis(3-methyl-6-tert
-butylphenol), etc.

The amount of these compounds to be used is j to 200% by weight, preferably 20 to 700% by weight, based on the electron-accepting compound.
Weight percentage.

Examples will be shown below, but the present invention is not limited only to these examples.

Examples/■ Preparation of color former sheet Co-anilino 3-methyl- which is an electron-donating colorless dye
/pair/mixture/ of 6-dietheraminofluorane, co-anilino 3-chloro-t-dibutylaminofluorane/
f was dissolved in isopropyldiphenylethane 3θ1.

This solution is water with 4F gelatin and 4TF gum arabic dissolved in it! Add to θ1 with stirring to emulsify, diameter/μ~
/θμ, then add 2jOf water and acetic acid to reduce the pH and cause coacervation.
A wall of gelatin and gum arabic is created around the oil droplet.
After adding formalin, the pH was raised to T and the walls were hardened.

The thus obtained microcapsule dispersion was applied to paper and dried to obtain a color former sheet.

■ Preparation of color developer sheet Co, dihydroxy-6-metherbenzoic acid ester θ2, which is an electron-accepting compound! Chipolyvinyl alcohol aqueous solution, dispersed in 200f, and further kaolin,
Each ioy of synthetic calcium carbonate was added and well dispersed to prepare a coating liquid. The obtained coating liquid was applied to paper and dried to obtain a color developer sheet.

When the thus prepared color former sheet and color developer sheet were brought into contact with each other and pressure was applied, a black printed image was instantaneously obtained. This image had high density and excellent light and heat resistance.

Examples Electron-donating colorless dye 2-anilino-3-methyl-6-N-methyl-N-cyclohexylaminofluorane jfS, 2-anilino-3-A! Tadecyl-6-dietheraminofluorancho? , tenubinpo, oit to j polyvinyl alcohol (Ken's degree of polymerization, degree of polymerization /
θθ0) Aqueous solution! It was processed in a sand mill with 0f to obtain a dispersion with an average particle size of μ. Similarly, co, 4t-dihydroxy-7onte-benzoic acid ether ester 10
After processing f with s% polyvinyl alcohol aqueous solution/θOml in a sand mill and mixing these two types of dispersions, kaolin (Jossia kaolin) aoy was added and well dispersed, and then paraffin wax emulsion! θ
Chi dispersion (Middle East oil cellosol #octopus/)! A coating liquid was prepared by adding f.

The coating solution was applied to a neutral paper having a basis weight of toy/m2 in a coating amount of gt/m2, and dried at 6° 0C for 7 minutes to obtain a coated paper.

Coated paper is heated by facsimile with energy θmJ/
When heated and colored at mm 2 , a black printed image was obtained, and the color density was /, /3. Also, this coated paper is Zθ0Cq
The fog density after being left for 2 hours in ochi RH was 0.
/λ. Further, this recording paper did not cause powder blowing even when it was sandwiched between vinyl sheets (-).

Example 3 An electron-donating colorless dye was used in place of the electron-donating colorless dye in Example 1. Co-anilino-3-chloro-t-diethylaminofluorane! V was used, and as an electron-accepting compound, λ, cudihydroxy-6-methylbenzoic acid ether9. ! ri, 3. ! -Zinc-α-methylbenzylsalicylate resin mixture 0. ! A cloth paper was obtained in the same manner as in Example 1 using V.

Heating coated paper by facsimile Orgieg OmJ
When color was developed at 7 mm 2 , a black impression was obtained.

The color density is i, o,! Met.

Comparative Example/Example 3-1. A coated paper was obtained in the same manner as in Example 3 except that J,,2-bis-(gu-hydroxyphenyl)propane 109 was used as the electron-accepting compound instead of the electron-accepting compound.

Coated paper is heated by facsimile with energy θmJ
When heated and colored at 7 mm 2 , the color density was o and tr.

Comparing Example 2.3 and Comparative Example/1, it is clear that the electron-accepting compound of the present invention has extremely high coloring properties.

Comparative Example λ A coated paper was obtained in the same manner as in Example 3 except that j,4t-dihydroxybenzoic acid hensyl ester 101 was used as the electron-accepting compound instead of the electron-accepting compound in Example 3.

Coated paper is heated by facsimile with energy θm, J
When heated and colored with 7 mm 2, the color density was 0! Met.

Further, this coated paper was left for 24 hours in a temperature of 0''C and θ%RH, and after 7 hours, the density of the coated paper was O1♂/.

Comparing Example C and Comparative Example C, it is clear that the recording paper using the electron-accepting compound of the present invention has excellent moist heat resistance.

Patent applicant: Fuji Photo Film Co., Ltd. Procedural amendment to the Commissioner of the Japan Patent Office 1, Indication of the case: Showa J. J. No. 34790 2,
Name of the invention Recording material 3, Relationship with the person making the amendment Patent applicant Location 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (52
0) Fuji Photo Film Co., Ltd. 4. Subject of amendment 5. We will submit a complete engraving of the amended statement (no changes to the content).

Claims (1)

[Claims] In a recording material using an electron-donating colorless dye and an electron-accepting compound, the electron-accepting compound is a hydroxybenzoic acid ester having at least a moss or larger hydroxyl group, and the position adjacent to the ester moiety is substituted. A recording material characterized in that one of the groups is a hydroxyl group.