JPS62111783A - Recording material - Google Patents

Abstract

PURPOSE:To obtain a recording material developing color in a sufficient density in the presence of an electron donating colorless dye and to enhance shelf stabilities in raw and with time, by using a specific compound as an electron accepting compound. CONSTITUTION:An electron accepting compound shown by a formula is used as an electron accepting compound for a thermal recording material. Bishydroxy phenylalkane carboxylic acid is reacted with dihaloalkane or diol derivative to synthesize the electron accepting compound having 50 deg.C or above melting point. A compound of triarylmethane series, diphenylmethane series, xanthene series, thiazine series, and/or spiropyran series are/is used as an electron donating colorless dye, and singly or mixedly dissolved in a solvent. The obtained solution is dispersed in a binder or contained in a micro-capsule and thereafter coated on a substrate of resin coated paper etc. to obtain a coupler sheet. On the other hand, the electron accepting compound of one or more kind is singly or mixedly dispersed in a binder and thereafter coated on a substrate of resin coated paper etc. to obtain a developer sheet.

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 makes full use of the 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 useful as an electron-accepting compound for pressure-sensitive recording materials and heat-sensitive recording materials. Electron beam recording sheet, static recording sheet 1. - It is a compound that can also be applied to photosensitive printing plate materials, stamping materials, type ribbons, ballpoint pen inks, crayons, etc.

<Prior Art> The use of various phenolic compounds as electron-accepting compounds in total pressure-sensitive recording materials or heat-sensitive recording materials is disclosed in Japanese Patent Publication No. 0-ta 3θri, Tokuko Akihiro J-l≠03-ri, Although disclosed in Kosho J/-27♂30, etc., these phenol compounds $IJ cannot necessarily be said to be satisfactory electron-accepting compounds. In other words, when used in combination with an electron-donating colorless dye, the degree of color development may not be sufficient, or
After recording, there are problems in which the 1 degree of the colored image decreases over time, and white powdery substances concentrate on the surface, which is called powdering.

<Objective of the Invention> Accordingly, an 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 storage stability both raw and over time.

<Structure of the Invention> The object of the present invention has been achieved by a recording material using an electron-donating colorless dye and a compound represented by the following general formula CI) as an electron-accepting compound.

In the above formula, R1 is a hydrogen atom or a lower alkyl group, R2
represents a divalent to chlorinated group having 2 to 10 carbon atoms, X, Y
represents a hydrogen atom, a lower alkyl group, a lower alkenyl group, or a halogen atom, n represents an integer from O to 6, and m represents an integer from λ to Hiroshi.

Among the substituents represented by R1 in the above formula, especially a hydrogen atom,
Methyl group and ethyl group are preferred.

Of the divalent to ≠ valent groups from 2 to IO represented by R2 in the above formula, an alkylene group, an alkylene group containing an ether bond, an alkylene group containing a thionythyl bond, and a carbonyl group containing a carbonyl group. Alkylene groups, alkylene groups containing all halogen atoms, alkylene groups containing unsaturated bonds, and aralkylene groups are preferable, and particularly alkylene groups, alkylene groups containing all 7 to 3 ether bonds, and thioether bonds l to J ′iA are preferable. Preferred are alkylene groups containing 7 to 3 halogen atoms, alkylene groups containing 7 to 3 unsaturated bonds, and aralkylene groups.

Among the substituents represented by X and Y in the above formula, the number of carbon atoms is l~
3 alkyl groups, alkoxy groups having 1-≠ carbon atoms, chlorine atoms, bromine atoms, and alkenyl groups having 2 to 1 carbon atoms, and sometimes alkyl groups having 1 to 3 carbon atoms, carbon Alkenyl group with number of atoms λ~3, carbon atoms a/~3
An alkoxy group, a salt J[child, and an aralkyloxycarbonyl group having from g to IO carbon atoms are preferred.

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 100C or more, particularly 700C~/ro0c.
It is preferable to have a melting point of .

Specific examples of the electron-accepting compound according to the present invention include the following.

By combining (1) with a colorless dye, a colored image with a high degree of clarity can be obtained.

(11) The storage stability of the background and colored images is good.

UiD: Stable without sublimation.

Next, specific examples of the electron-accepting compound of the present invention will be shown, but the present invention is not limited thereto.

/)/, 2-bis(λ, λ-bis(≠-hydroxyphenyl)acetyloxy)ethane λl /, Hiro-bis(u,, 2-bis(≠-hydroxyphenyl)acetyloxy)butanej)/, t-bis(co,2-bis(≠-hydroxyphenyl)acetyloxy)hexane42. j-bis(-
1λ-bis(Hiro-hydroxyphenyl)acetyloxy)butanej)/, 2-bis(Hiro, 4!-bis(≠-hydroxyphenyl)valeryloxy)ethane 41/, ≠-bis(≠, ≠-bis(≠ -hydroxyphenyl)valeryloxy)butane 7) l, t-bis(μ, Hiro-bis(≠-hydroxyphenyl)valeryloxy)hexane Bi, z-bis(Hiro,
≠-bis(≠-hydroxyphenyl)valeryloxy)
-3-oxaheptanta)/, j-bis(Hiro, Hiro-bis(Hiro-hydroxyphenyl)valeryloxy) -J, A-dioxaoctane, etc. These may be used alone or in combination, or in combination with other α-accepting compounds (e.g. , bisphenol A, 4L-hydroxybenzoic acid benzyl ester, /, l-bis-(4L-hydroxyphenyl)cyclohexane, 3,!-bis(α-methylbenzyl)zinc salicylate, activated clay, etc.). .

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

Some of these? For example, triarylmethane compounds include 3,3-bis(p-dimethylaminophenyl)-dimethylaminophthalide (RIJ ticrystal violet lactone), 3゜3-bis(p-dimethylaminophenyl) Phthalide, 3-(p-dimethylaminophenyl)-3-(/, 3-dimethylindole-3-
yl)phthalide, 3-(p-dimethylaminophenyl)
-3-(nomethylindol-3-yl)phthalide, etc., and diphenylmethane compounds include Hiroshi, ≠'
-Bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl-leucoolamine, N-2,4
t,j-)dichlorophenylleucoolamine, etc., and xanthine compounds include rhodamine-B-anilinolactam, rhodamine (p-nitroanilino)lactam, rhodamine B (p-chloroanilino)lactam,
colabenzylamino-6-diethylaminofluorane, λ-anilino-t-diethylaminofluorane, 2-
Anilino-3-methyl-6-diethylaminofluorane, -1anilino-3-methyl-6-N-cyclohexyl-N-methylaminofluorane, λ-anilino-3-methyl-6-N-ethyl-N-isoamylaminofluorane, λ-〇-Chloroanilino-6-dinithylaminofluoran, J-m-chloroanilino-4-diethylaminofluoran, Co(3, Hiro-dichloroanilino)-6-
Diethylaminofluorane, co-octylamino-6-
Diethylaminofluorane, λ-rehexylamino-
6-diethylaminofluoran λ-m-1 Lichloromethylanilino-6-diethylaminofluoran, coptylamino-3-chloro-6-dixf fluoran, λ-ethoxyethylamino-3-chloro-6 -diethylaminofluorane, 2-anilino-3-chloro-6-
Diethylaminofluorane, no-diphenylamino-t
-diethylaminofluorane, co-anilino 3-methyl-6-siphenylaminofluorane, λ-anilino 3-methyl-chloro-2-diethylaminofluorane, λ-anilino 3-methyl-t-diethylamine-
7-Methylfluorane, co-anilino 3-methoxy 2
-dibutylaminofluorane, 2-Q-chloroanilino-6-sibutylaminofluorane, 2-p-chloroanilino-3-ethoxy-2-diethylaminofluorane,
Norphenyl-6-diethylaminofluorane, 2-〇-chloroanilinoA-p-butylanilinofluorane, 2-anilino-3-pentadecyl-6-diethylaminofluorane, -1anilino-3-methyl-4-N- enal-N-tetrahydrofurfurylaminofluorane,
λ-anilino 3-methyl-j-N-butyl-N-tetrahydrofurfurylaminofluorane, λ-anilino 3-methyl-+-N-ethyl-N-isobutylaminofluorane, λ-anilino 3-ethyl-dibutylamino Fluoran, λ-anilino-3-ethyl-AN-ethyl-N-ynamylaminofluorane, 2-anilino-3-methyl-AN-ethyl-Nr-methoxypropylaminofluorane, 2-anilino-3 -phenyl-6
-diethylaminofluorane, λ-diethylamino-3
-Phenyl-6-diethylaminofluorane, etc. are sb Thiazine compounds include pensoyl leucomethylene blue, p-nitrobenzyl leucomethylene blue, etc., and spiro compounds include 3-methyl-spiro-dinaphthopyran, 3-ethyl- Spiracina 7) Piran,
3゜3'-Dichlorosubirodinaphthohyran, 3-benzylspiro-dinaphthopyran, 3-methyl-naphtho-
(3-methoxy-benzo) to spiropyran, 3-propyl-spirogibensohyran, etc. These may be used alone or in combination.

The electron-accepting compound according to the present invention can be easily synthesized by reacting the corresponding bishydroxyphenylalkane carboxylic acid with a dino-10 alkane or diol visiting conductor.

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

The pressure-sensitive copying paper according to the present invention is disclosed in US Pat. j0! ,≠7
No. 0, IW, 12,101. ≠ No. 71, same co.

! 0! ',≠f5' issue, same co, j hiro 1,366, same λ
, 71, j07, 2,730. ≠j4, same No. 2,730. ≠! No. 7, No. 3. It can take various forms as described in prior patents such as ≠it, No. 210. Most commonly, it will consist of at least one pair of sheets separately containing an electron-donating colorless dye and an electron-accepting compound according to the invention. That is, an electron-donating colorless dye, alone or in combination, is dissolved in a solvent (synthetic oil such as alkylated naphthalene, alkylated diphenyl, alkylated diphenylmethane, alkylated diarylethane, or chlorinated paraffin), and this is dispersed in a binder. Or, after containing it in microcapsules, paper, plastic sheet,
A color forming agent sheet can be formed by applying it to a support such as resin-coated paper, and an electron-accepting compound can be used alone or in combination with other electron-accepting compounds in a binder such as styrene-butadiene latex or polyvinyl alcohol. A color developer sheet is obtained by dispersing the colorant in a liquid and applying it to a support such as paper, plastic sheet, or 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. This use is easily determined by one skilled in the art.

For the manufacturing method of the cuff cell, please refer to the US % approval lambda.

100, No. 4117, a method using coacervation of a hydrophilic colloid sol described in J. Too. Art. Hiro≠3
It is described in No. 2A, No. 2A, No. 10yl, No. 074, etc., and describes the electrostatic interfacial polymerization method.

The heat-sensitive recording material is prepared by dissolving the binder in a solvent or dispersion medium, and then adding an electron-donating colorless dye, an electron-accepting compound according to the present invention, and, if necessary, a thermofusible substance to the dispersed liquid in sufficiently fine particles. The oil absorption properties of kaolin, calcined kaolin, talc, waxite, diatomaceous earth, calcium carbonate, aluminum hydroxide, magnesium hydroxide, magnesium carbonate, titanium oxide, barium carbonate, urea-formalin filler, cellulose filler, etc. are crushed and mixed. Add pigment and apply the coating liquid. If necessary, ξ rough-in wax emulsion, latex binder, sensitivity improver, metal soap, antioxidant, ultraviolet absorber, image storage improver, etc. can be added thereto.

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 an appropriate combination, pulverized and dispersed separately, and then mixed.

Further, the coating liquid may be poured into the support.

The support is particularly preferably acid-free paper in terms of raw and aged capri.

The components constituting the heat-sensitive recording material include 7 to 2 parts by weight of an electron-donating colorless dye, 7 to 6 parts by weight of an electron-accepting compound, 0 to 30 parts by weight of a thermofusible substance, and 0 to 1 part by weight of a pigment. part, 7 to /jM parts of binder, and small amounts of additives, dispersants, etc.

One or more electron-donating colorless dyes may be used in combination. Water is most desirable as the dispersion medium (solvent).

Examples of the binder gold used in the present invention include styrene-butadiene copolymer, alkyd resin, acrylamide copolymer, vinyl chloride-vinyl acetate copolymer, styrene-maleic anhydride copolymer, synthetic rubber, arabic polyhinyl alcohol. , hydroxyethylcellulose, and the like.

In particular, water-soluble binders such as gum arabic, polyvinyl alcohol, hydroxymethyl cellulose, and carboxyl methyl cellulose are desirable in relation to the separation medium (solvent).

Thermofusible substances include erucic acid, stearic acid, behenic acid, palmitic acid, stearamide,
Behenic acid amide, stearic acid anilide, stearic acid toluiside, N-myristoyl-p-anisodine, N-
Myristoyl-p-phenetidine, /-methoxy/carbonyl-Hiroshi-N-stearylcarbamoylbenzene, N-
Octadecyl urea, N-hexadecyl urea, N,
N-cytofsilurea, phenylcarbamoyloxydodecane, p-t-butylphenolphenoxyacetate, ly-722phenol-p-chlorophenoxyacetate, ≠, lA'-isoprohyritenebismethoxybenzene, β-phenylethyl-p- Phenyl phenyl ether, 2-p-chlorobenzyloxynaphthalene,
2-benzyloxynaphthalene, /-benzyloxynaphthalene, cophenoxyacetyloxynaphthalene,
Phthalic acid diphenyl ester, l-hydroxy-λ-naphthoic acid phenyl ester, λ-pentyloxynaphthalene, p-benzyloxybenzoic acid indyl ester, hydroquinone acetate, l-phenoxy-2-
p-ethylphenoxyethane, /,44-diphenoxybutane, /-7dinoxyλ-p-methoxyphenoxyethane, etc. are used.

These substances are colorless solids at room temperature, and are suitable for heating temperatures for copying, i.e., 70 to 10 degrees.

It is a substance that has a sharp melting point around 0C.

Examples of waxes include paraffin wax, carnauba wax, microcrystalline wax, polyethylene wax, and higher fatty acid amides such as atearic acid amide, ethylene bisstearamide, 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 lead oleate.

Examples of the image storage stability improving agent include phenol or its derivatives in which at least one of the 2nd or 6th positions is substituted with an alkyl group, and among these, one or more of the 2nd or 3rd positions is substituted with a branched alkyl group. Substituted phenols or derivatives thereof are preferred. Moreover, those having a plurality of phenol groups in the molecule are preferable, and those having from one to three phenol groups are preferable. Specific examples of these compounds include bis-[3,3-bis-(≠'-hydroxy-3'-t
ert-butylphenyl)butanoic acidocoglycol ester, bis-[3,3-bis-(Hiro'-hydroxy-3'Hiro')
-ditert-7'tylphenyl)butanoic acidocoglycol ester, bis-[3,3-bis-(2'-methyl-l'-hydroxy-!'tert-7tylphenyl)-butanoic andoglycol Ester, /, /, J-tris(2-methyl-Hydrox)!-tert-7
tylphenyl)butane, ≠, ≠′-thiobis(3-methyl-&-tert-butylphenol), Hiro, ≠′-thiobis(2-methyl-A-tert-butylphenol), λ, 2′-thiobis(Hiro-methyl -A -tert-
monobutylphenol), 2,2'-methylenebis(≠-methyl-6-tert-
butylphenol), 2,2'-methylenebis(4L-ethyl-6-tert)
-butylphenol), 4t,<z'-butylidenebis(3-methyl-6-te
rt-butylphenol), ≠, g'-methylenebis(2,t-di-tert-butylphenol), 2-tert-butyl-'A tert-butoxyphenol, 2, Kodimethyl-Hiro-improvil-7-tert-
Butyl-6-chromanol, 2,2-dimethyl-A-j
-butyl-yo-benzofuranol, ≠[[day, 6-bis(tertbutylthio)-8-triazine-choyl]amine]λ, 6-tert-butylphenol, and the like.

In order to further improve the storage stability of colored images, powder blowing, etc.
Particularly preferred is the combination with these hindered phenols.

The amount of these compounds used is relative to the electron-accepting compound! -200 M*A-cents, preferably 0 to 100 weight percent.

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
6-dinithylaminofluorane 1t-2 alkylation 7
It was dissolved in Talen 309. In this solution, 6 tons of gelatin and gum arabic were dissolved and added to a Yusui rotor with vigorous stirring to emulsify it to form oil droplets with a diameter of 1 μm to 10 μm, followed by 210 μm of water. added. Add acetic acid little by little to bring the pH to about 10,000 yen to cause coacervation, and the rotation of the oil droplets
A wall of gelatin and gum arabic was made, formalin was added, and the pH was increased to harden the wall.

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

■ Preparation of color developer sheet Electron-accepting compounds /, 2-bis(λ, λ-bis(
4A-hydroxyphenyl)acetyloxy)ethane λ
It was dispersed in 0ff1% polyvinyl alcohol aqueous solution xoot, and further kaolin (Jossia kaolin) 209 was added and well dispersed to prepare a coating liquid. The resulting coating solution was applied to paper and dried to obtain a developer sheet.

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

Example λ 2-anilino-3-methyl- which is an electron-donating colorless dye
4-N-Methyl-N-cyclohexylaminofluorane! The mixture was dispersed in a ball mill overnight with 10 tons of an aqueous solution of 96 polyvinyl alcohol (hydrogen value: 1,000, polymerization degree: 1,000). On the other hand, similarly, these λ-bis(λ, λ-bis(≠-hydroxyphenyl)acetyloxy)butane iot@srs polyvinyl alcohol aqueous solution 1009 was dispersed in a ball mill for a day and night. After mixing the dispersion liquid, kaolin (Jossia kaolin) λOff was added to disperse well, and further, paraffin wax emulsion zo4 dispersion liquid (Chukyo Yushi Cellosol; Ko2♂) st was added to prepare a coating liquid.

The coating liquid was applied to neutral paper having a basis weight of 1097 m2 so that the solid content coating amount was At/m2, and dried at to 0c for 1 minute to obtain a coated paper.

Coated paper is heated by facsimile with energy≠OmJ/
(2) When heated and colored in step 2, a black printed image was obtained. The color density was 1.03.

In addition, during this application M1 Kanehiro o 'C1 R O section RH 2≠
After standing for a period of time, the density of the colored image on the coated paper was up to 0.2, and the density of the non-image area was 0.01.

Example 3 2-anilino-3-chloro-6-dinithylaminofluofone was used as an electron-donating colorless dye instead of the electron-donating colorless dye of Example-2. Jf/ and λ-anilino-3-methyl-A-N-methyl-N-cyclohexylaminofluorane 2.1? using f instead of the ti electron-accepting compound,
As an electron-accepting compound, /, Corbis(2,2-bis(≠-hydroxyphenyl)acetyloxy)ethane 1
A coated paper was obtained in the same manner as in Example A using 0t.

Coated paper is heated by facsimile.
/wr2, a black impression was obtained.

The color density was /,00.

Comparative Example 1 Instead of the electron-accepting compound in Example A, co,2-bis-(≠-hydroxyphenyl) was used as the electron-accepting compound.
Pro/gun10? A coated paper was entirely obtained in the same manner as in Example 3 using F.

Coated paper is heated by facsimile with energy μOm J
/ m2 to heat color and color # to O0!
Comparison of Examples 3 and 3 with Comparative Example/i reveals that the electron-accepting compound of the present invention has extremely high coloring properties.

Comparative Example: In place of the electron-accepting compound in Example λ, as an electron-accepting compound, ≠-hydroxybenzoic acid benzyl ester 10
? A whole coated paper was obtained in the same manner as in Example. When the color was developed in the same manner as in Example /, the color density was /, Oj.

′! After leaving the coated paper in ≠00C20CHRH for 24 hours, the density of the colored image on the coated paper was O.

Ko! A friend of mine.

Comparing Example λ and Comparative Example 2, it is clear that the recording paper using the electron-accepting compound of the present invention has excellent image storage stability.

Procedural amendment (spontaneous) 1985//Mon/i I) E 2. Title of the invention 1. Materials 3. Relationship with the case of the person making the amendment Patent applicant 4. Date of amendment order Spontaneous 5. Amendment We will submit the subject specification 6, the contents of the amendment (no changes to the contents).

Claims (1)

[Scope of Claims] A recording material using an electron-donating colorless dye and an electron-accepting compound, characterized in that the electron-accepting compound is a compound represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the above formula, R_1 is a hydrogen atom or a lower alkyl group,
_2 is a divalent to tetravalent group having 2 to 10 carbon atoms,
, Y represents a hydrogen atom, a lower alkyl group, a lower alkenyl group or a halogen atom, n represents an integer from 0 to 6, and m represents an integer from 2 to 4.