JPS6149888A - Recording material - Google Patents

Abstract

PURPOSE:To obtain a recording material giving a sufficient developed color density and enhanced in preservability, by using a specified benzoic acid ester derivative as an electron-acceptive compound, in a recording material comprising an electron-donative colorless dye and an electron-acceptive compound. CONSTITUTION:A compound of the formula, wherein R is lower alkyl, Ar is aryl and n is an integer of 2-5, is used as an electron-acceptive compound in combination with an electron-donative colorless dye such as a triarylmethane compound, a diphenylmethane compound and a xanthene compound. A compound of the formula having a melting point of 70-150 deg.C is particularly preferred. The components can be applied to both a pressure-sensitive recording material and a thermal recording material. When producing a thermal recording material, 1-2 pts.wt. of the electron-donative dye, 1-6pts.wt. of the electron-acceptive compound, 0-30pts.wt. of a heat-fusible substance and 0-15pts.wt. of a pigment are applied to a base together with a binder and other additives, followed by drying.

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 an extremely useful compound particularly as an electron-accepting compound for pressure-sensitive recording materials and heat-sensitive recording materials. It is a compound that can also be applied to recording sheets, electron beam recording sheets, electrostatic recording sheets, photosensitive printing plates, stamping materials, type ribbons, ballpoint pen inks, crayons, etc.

<Prior Art> The use of various phenolic compounds as electron-accepting compounds in pressure-sensitive recording materials or heat-sensitive recording materials is disclosed in Japanese Patent Publication Shoda No. 0-9309, Japanese Patent Publication No. 4TT-141039, and Japanese Patent Publication No. Sho J-/-29730. However, these phenolic compounds cannot necessarily be said to be satisfactory electron-accepting compounds. In other words, the coloring density was not sufficient when used in combination with an electron-donating colorless dye, the density of the colored image decreased over time after recording, and the concentration of white powder on the surface, so-called powdering. There are some problems that may occur.

<Object of the Invention> Accordingly, an object of the present invention is to provide a recording material that 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 as an electron-accepting compound.

In the above formula, R represents a lower alkyl group, Ar represents an aryl group, and n is 2~! represents an integer.

Among the substituents represented by R in the above general formula, an alkyl group having a carbon atom number/~g is preferable, particularly a methyl group,
Ethyl group and propyl group are preferred.

Among the groups represented by Ar in the above general formula, a phenyl group having a carbon atom number of from .theta. to .theta. is preferred, and a phenyl group having a carbon atom number from .theta.

The group represented by Ar in the above general formula may further have a substituent, examples of which include a lower alkyl group, a lower alkoxy group, a halogen atom, and a hydroxy group.

In the above general formula, n is preferably 1 to Z, particularly preferably -.

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 4000 or more, particularly 7θOC~/! Preferably, the compound has a melting point of θQC.Characteristics of the electron-accepting compound according to the present invention include the following.

(1) When used in combination with an electron-donating colorless dye, a high-density colored image can be produced.

(11) Good storage stability of background and colored images.

(Ill) Stable without sublimation.

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

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

1) 3-Methyl-gu-hydroxybenzoic acid β-phenoxyethyl ester 2) 3-Methyl-gu-hydroxybenzoic acid β-(,2-
)! J ruoxy)ethyl ester 3) 3-Methyl-gu hydroxybenzoic acid β-(3-) + J ruoxy) ethyl ester 4) 3-Methyl-gu hydroxybenzoic acid β-
(p-)lyloxy)ethyl ester 5) 3-methyl-
3-methyl-gu-hydroxybenzoic acid β-(2-I'lorophenyloxy)ethyl ester 6) 3-methyl-gu-hydroxybenzoic acid β-(3-chlorophenyloxy) ethyl ester 7) 3-methyl-gu-hydroxybenzoic acid β-( &-chlorophenyloxy)ethyl ester8) 3-Methyl-guhydroxybenzoic acid-β-β-(,2,<l-dimethylphenyloxy)ethyl ester9) 3-methyl-guhydroxybenzoic acid β-(3, j
--dimethylphenyloxy)ethyl ester 1O) 3-methyl-guhydroxybenzoic acid β-(2,
t-dimethylphenyloxy)ethyl ester 11) 3-methyl-guhydroxybenzoic acid β-(
, z, g-dimethylphenyloxy)ethyl ester 12), ? -Methyl-hydroxybenzoic acid β-(7
! -Methyl-6-chlorophenyloxy)ethyl ester 13) 3-Methyl-guhydroxybenzoic acid β-(2-
Mef router-chlorophenyloxy)ethyl ester 14) 3-methyl-guhydroxybenzoic acid β-(2-
Hydroxyphenyloxy)ethyl ester-1s) 3-methyl-hydroxybenzoic acid β-(3-
methoxyphenyloxy)ethyl ester 16) J-methyl-guhydroxybenzoic acid β-(2-
Methoxyphenyloxy)ethyl ester 17) 3-Ethyl-gu-hydroxybenzoic acid β-phenoxyethyl ester 1B) 3-propyl-gu-hydroxybenzoic acid β-phenoxyethyl ester 19) 3-Hexyl-gu-hydroxybenzoic acid β-phenoxyethyl ester Esters 2)) 3-Methyl-Z-hydroxybenzoic acid γ-phenoxypropyl ester 21) 3-Methyl-Z-hydroxybenzoic acid δ-phenoxybutyl ester, etc. These may be used alone or in combination or with other electron-accepting compounds.
(For example, bisphenol A, g-h)'roxybenzoic acid benzyl ester, /, /-bis-(4t-hydroxyphenyl)cyclohexyl, 3,t-bis-(α-methylbenzyl)zinc salicylate, activated clay, etc.) It is used in combination with

As a method for synthesizing the electron-accepting compound according to the present invention, co-alkylphenol is carboxylated to produce 3-alkyl-
As gu-hydroxybenzoic acid, there are those which are reacted with an alkylating reagent or an alkyl alcohol.

These are all known methods. -Carboxylation of mono-alkylphenols is described, for example, in U.S. Pat.
It is described in the Japanese Society of Organic Synthetic Chemistry, Volume 2z, Page 3, 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.

To illustrate some of these, triarylmethane compounds include 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (i.e., crystal violet lactone), 3゜3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (i.e., crystal violet lactone), -dimethylaminophenyl) phthalide, 3-(p-dimethylaminophenyl) -'! -(/,3-dimethylindole-3
Diphenylmethane-based compounds include p,
4t'-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl-leucoolamine, N-
s, q, t)! Examples of xanthine compounds include J dichloroenyl leuco auramine, and rhodamine.
B-anilinolactam, rhodamine (p-nitroanilino)lactam, rhodamine B (p-chloroanilino)lactam, 2-dibenzylamino-6-diethylaminofluorane, λ-anilino-diethylaminofluorane, λ-anilino-3-methyl -6-dinithylaminofluorane, noanilino-3-methyl-J-N-cyclohexyl-N-methylaminofluorane, noanilino-3-methyl-6-N-ethyl-N-isoamylaminofluorane, λ-O 1 loloanilino≦-diethylaminofluorane, 2-m-chloroanilino-t-diethylaminofluorane 1. z-(3,4t-dichloroanilino)-6-diethylaminofluorane, 2-octylamino-diethylaminofluorane, λ-dihexylamino-diethylaminofluorane 1.2-m-
) dichloromethylanilino-diethylaminofluorane, coptylamino-3-chloro-diethylaminofluorane, co-ethoxyethylamino-3-chloro-6-diethyl aminofluorane, co-anilino-3
- ri o og-diethylaminofluorane, co-diphenylami/-t-diethylaminofluorane, co-anilino-3-methyl-6-diethylaminofluorane, no-anilino-3-methyl-! -4-dibutylaminofluorane, -1-anilino-3-methyl-2-diethylamino-7-methylfluoran, 2-anilino-3-methoxydibutylaminofluorane, -10-chloroanilino-1 dibutylamino 7i /oran, co-p-ri-4-/θ-roayulino-3-ethoxy-fluorane, 2-〇-chloroanilino&-p-butylanilinofluorane, co-anilino-3-(ntadecyyl-g-diethylaminone-fluorane, co-anilino-3-ethyl O-dibutylaminofluoran, λ-anilino 3-ethyl-4-N-ethyl-N-isoamylaminofluoran, Koa Eleanor 3-methyl-methoxypropylaminofluoran, Koaani IJ/
-3-phenyl-6-dinithylaminofluoran, colaethylamino-3-phenyl-6-dinithylaminofluoran, etc. Dithiazine compounds include benzoylleucomethylene blue, p-nitrobenzylleucomethylene blue, etc. , as a spiro compound, 3-
Methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3.3'-cyclospirodinaphthopyran, 3-benzylspiro-dinaphthopyran, 3
-Methyl-naphtho-(3-methoxy-benz)-spiropyran, J--f'ropyru-spirodibenzopyran, 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.

The pressure-sensitive copying paper according to the present invention is disclosed in US Pat. , Gua θ, same λ, Ta 0 evening, Ri 7/, same λ.

! θ! , ri No. 22, same 2 + tolerance + 31 No. 4,
Same, 7/2,! No. 07, No. 730, Gu Jza No. 2,730, Gu! No. 7, No. 3, Ri/Za 1.2! θ
It can take various forms as described in prior patents such as No. 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, electron-donating colorless dyes alone or in combination are dissolved in a solvent (synthetic oil such as alkylated naphtha V/, alkylated diphenyl, alkylated diphenylmethane, alkylated diarylethane, chlorinated paraffin, etc.), and this is dissolved in a binder. After being dispersed or contained in microcapsules, the color former sheet can be prepared by applying it to a support such as paper, plastic sheet, resin-coated paper, etc., and the electron-accepting compound can be used alone or in combination with the electron-accepting compound. Dispersed in binders such as styrene butadiene latex, polyvinyl alcohol, along with other electron-accepting compounds, paper, plastic sheets, etc.
A color developer sheet is obtained by coating it on any support such as resin-coated paper.

The amounts of the electron-donating colorless dye and the electron-accepting compound to be used depend 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. It is easy for one skilled in the art to determine this amount to use.

A method of manufacturing capsules is described in a US patent.

♂Oθ, g! A method using coacervation of a hydrophilic colloid sol described in No. 7, Id., /θθ, 4trr, British Patent No. 7,7, No. 7, J-o, 4
Tgu No. 3, Same ♂9.2 Bug No., Same 109/, 0
There are interfacial polymerization methods such as those described in No. 7.

The heat-sensitive recording material is produced by sufficiently finely pulverizing an electron-donating colorless dye, an electron-accepting compound according to the present invention, and, if necessary, a thermofusible substance, in a liquid in which a binder is dissolved or dispersed in a dispersion medium in a solvent. Further, oil-absorbing pigments such as 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. Add and apply the coating liquid. 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 the 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.

Also, the coating liquid may be poured into the support./4t
- Yes.

Neutral paper is particularly preferred as the support from the viewpoint of fogging during production and over time.

Each component of the heat-sensitive recording material includes an electron-donating colorless dye/~2 parts by weight, an electron-accepting compound 7-3 parts by weight, a thermofusible substance 0-30 parts by weight, and a pigment θ~/! Weight part, binder /~/! It consists of parts by weight and small amounts of other additives, dispersants, etc.

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

Examples of binders used in the present invention include styrene-butadiene copolymers, alkyd resins, acrylamide copolymers, vinyl chloride-vinyl acetate copolymers, styrene-maleic anhydride copolymers, synthetic rubbers, gum arabic, polyvinyl alcohol, hydroxy Examples include ethyl cellulose.

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

The thermofusible substances include cyclic acid, stearic acid, behenic acid, nozorumitic acid, stearic acid amide, behenic acid amide, stearic acid anilide, stearic acid toluide, N-myristoyl-p-aningine, N
-myristoyl-p-pheneticin, /-methoxycarl-Y-N-stearylcarbamoylbenzene,
N-oftadecyl urea, N-hexadecyl urea, N
, N-didodecylurea, phenylcarbamoyloxydodecane, I) t-butylphenolphenoxyacetate, p-phenylphenol-p-chlorophenoxyacetate), "l"'-isopropylidene bismethoxybenzene, β-phenylethyl-p -phenyl phenyl ether, 2-p-chlorobenzyloxynaphthalene, -1penzyloxynaphthalene, /-benzyloxynaphthalene, euphenoxyaceteloxynaphthalene, phthalic acid diphenyl ester, /-hydroxy-2
-Naphthoic acid phenyl ester, -penzoyloxynaphthalene, p-benzyloxybenzoic acid benzyl ester, hydroquinone acetate, etc. are used.

These substances are colorless solids at room temperature and have a sharp melting point at a temperature suitable for heating temperature for copying, that is, around 70 to /g00C.

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

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

Examples of image storage improving agents include phenols or derivatives thereof in which at least 7 or more positions are substituted with alkyl groups, and among these, phenols or derivatives thereof in which at least 7 or more positions are substituted with branched alkyl groups. phenol or its derivatives are preferred. Further, those having a plurality of phenol groups in the molecule are preferred, and those having from one to three phenol groups are particularly preferred. Specific examples of these compounds include bis-[3,3-bis-(Z'-hydroxy-3'-t
ert-butylphenyl)-butanoic acidocoglycol ester, bis-[3,3-bis-(g'-hydroxy-37g')
-di-tert-butylphenyl)butanoic acidocoglycol ester, bis-[3,3-bis=(2'-methylg'-hydroxy-J'-tert-butylphenyl)-butanoic acidocoglycol ester, '+'+3) Squirrel (
2-Methyl-g-hydroxy-j-tert-7'terphenyl)phthane, g,Z'-thiobis(3-methyl-tert-butylphenol), g,g'-thiobis(,2-methyl-/> -tert-
/? - -butylphenol).

j,,2'-f obis(lA-methyl-A-t e
r -butylphenol).

1.2'-methylenebis(a-methyl-tert)
-butylphenol).

2.2'-methylenebis(4-ethyl-tert)
-butylphenol).

Hiroshi, μ′-butyritenebis(3-methyl-&-ter
t-butylphenol), g, lA'-mey-vnbis(2, A-diter
t-butylphenol).

λ-tert-butyl-Hiro-tert-butoxyphenol 2.2-dimethyl-μm isopropyl-7-tert-
Butyl-6-chromanol, co-9,2-dimethyl-x-
t-Butyl-j-benzene furanol.

[[l/-1z-bis(tertbutylthio)-s
-triazine-coyl]amine]2,2-G t
Examples include er t-butylphenol.

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 to be used is approximately 200 cents by weight relative to the electron-accepting compound, preferably 1 + θ to /
θ0 weight percent.

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

Examples / ■ Adjustment of color former sheet Co-anilino 3-methyl- which is an electron-donating colorless dye
One diethylaminofluorane/I was dissolved in alkylated naphthalene 309. This solution was added to water 609 in which f and gum arabic <tg were dissolved in gelatin, and was emulsified with vigorous stirring. After making it into an oil droplet of θμ, -water 2! θf was added. Add acetic acid little by little and p
Coacervation was induced using H as a measure, and a wall of gelatin and gum arabic was created around the oil droplets. After adding formalin, the pH was raised to 9 and the wall was hardened.

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

■ Preparation of color developer sheet 3'% of 3-methyl-hydroxybenzoic acid-β-phenoxyethyl ester 2θf, which is an electron-accepting compound.
It was dispersed in a polyvinyl alcohol aqueous solution, 20Of, and kaolin (Jossia kaolin), 2of, 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 or impact was applied, a black printed image was instantaneously obtained. This image had high density and excellent light resistance and heat resistance.

Example 2 Coalinino 3-methyl-, an electron-donating colorless dye
tN-Methyl-N-cyclohexylaminofluorane jf was dispersed in a ball mill overnight with an aqueous solution Jθ-,2/-f of 3% polyvinyl alcohol (degree of polarization tata%, degree of polymerization/θθθ). On the other hand, similarly, 3-methyl-terhydroxybenzoin powder-β-phenoxyethyl ester/Of, which is an electron-accepting compound, was dispersed with j% polyvinyl alcohol aqueous solution/θ09 in a ball mill for two days and nights, and these two types of dispersions were mixed. After mixing, add 2Of kaolin (Jossia kaolin) and disperse well, then paraffin wax emulsion!
A θ% dispersion liquid (Chukyo Yushi Cellosol #/12r) If was added to prepare a coating liquid.

The coating liquid! The coated paper was coated on a neutron having a basis weight of θf/− so that the solid content coating amount was tf/−, and dried at θ0C for 7 minutes to obtain a coated paper.

Coated paper is heated by facsimile with energy θmT/
ynv? When heated and colored, a black printed image was obtained. The color density was 0.99.

In addition, this coated paper was placed in 4t00C, 90%B, H at 24°C.
Is the density of the colored image on the coated paper 0. after leaving it for a while? 3
The density of the non-image area was 0.01.

Example 3 - λλ - Co-anilino-3-chloro-3-diethylaminofluorane, 2. ! f and 2-anilino-3-methyl-a -N-methyl-N-cyclohexylaluminofluorane, 2. Examples were prepared using 3-methyl-hydroxybenzoic acid β-(,2,4t-dimethylphenyloxy)ethyl ester/θg instead of the electron-accepting compound. Coated paper was obtained in the same manner as in -.

Apply energy to coated paper by facsimile Om17
A black impression was obtained when the color was developed by mixing the mixture with 1 mm''.

The color density is /. /θ.

Comparative Example: Coated paper was obtained in the same manner as in Example 3 using 2,2-bis-(4t-hydroxyphenyl)propane 1011 as the electron-accepting compound instead of the electron-accepting compound in Example A. Ta.

Coated paper is heated by facsimile with energy of OmJ/
When heated and colored with mrd, the color density was 0.! It was f.

Comparing Examples 3 and 3 with Comparative Example 3, it is clear that the electron-accepting compound of the present invention has extremely high coloring properties.

As an electron-accepting compound in place of the electron-accepting compound in Comparative Example Co and Example Co, gu-hydroxybenzoic acid benzyl ester 70
A coated paper was obtained in the same manner as in Example/ using G. When the color was developed in the same manner as in Example /, the color density was /, θ3.

Further, after this coated paper was left in ZO0C 90% RH for 2y hours, the density of the colored image of the coated paper was O1, 2y.

Comparative Example 3 A coated paper was obtained in the same manner as in Example 3 except that λ, tag-hydroxybenzoic acid benzyl ester/θf was used as the electron-accepting compound instead of the electron-accepting compound of Example λ.

When the coated paper was heated and colored using a heating energy bar (OmJ) by facsimile, the color density was /.

θ! Met.

Further, after this coated paper is left in <to0Cqθ%R,H for λ da time, the density of the non-image area of the coated paper is θ.

It was l/.

Comparing Example C and Comparative Examples C and 3, it is clear that the recording paper using the electron-accepting compound of the present invention suffers from poor image preservation.

Patent applicant: Fuji Photo Film Co., Ltd.-, 2j-

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 represents a lower alkyl group, Ar represents an aryl group, and n represents an integer from 2 to 5.