JPS60145882A - Recording material - Google Patents

Abstract

PURPOSE:To obtain a recording material showing a sufficient coloring density when used in combination with an electron-donating colorless dye, by using a cyclohexyl ester hydroxybenzoate derivative as an electron-accepting compound. CONSTITUTION:In a recording material prepared by using an electron-donating colorless dye and an electron-accepting compound, a recording material prepared by a cyclohexyl ester hydroxy-benzoate derivative (e.g. cyclohexyl ester 4-hydroxybenzoate) expressed by the formula (X denotes H, halogen; Y H, lower alkyl, halogen) being contained as the electron-accepting compound. When combined with the electron-donating colorless dye, said electron-accepting compound turns to have such advantages that it gives a color-developed image of high density, has little water-solubility and no subliming property, is stable and easy to compound and enables the preparation of a material of high density with a high yield, and that the raw material therefor is inexpensive.

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. Concerning the recording materials used.

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. Sheets, electron beam recording sheets, electrostatic recording sheets, photosensitive printing plates, stamping materials 1. It is a compound that can also be applied to type ribbons, ballpoint pens/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 No. 4Ao-2302, Japanese Patent Publication No. 4Ao-2302, Japanese Patent Publication No. 4Tj-/μ03, and Japanese Patent Publication No. However, these phenolic compounds cannot necessarily be said to be satisfactory electron-accepting compounds. That is, when used in combination with an electron-donating colorless dye, the color density is not sufficient.

<Object of the Invention> Accordingly, an object of the present invention is to provide a recording material with sufficient color density when used in combination with an electron-donating colorless dye.

<Structure of the Invention> The object of the present invention is achieved by a recording material characterized by using an electron-donating colorless dye and a comparable compound represented by the following general formula (I) as an electron-accepting H substance. .

In the above formula, X represents a hydrogen atom or a halogen atom, and f represents a hydrogen atom, a lower alkyl group, or a halogen atom.

In the above general formula fI), the substituent represented by Y may be substituted at any position on the cyclohexyl ring, but it is particularly preferable that it is substituted at the 2 or ≠ position.

The hydroxybenzoic acid cyclohexyl ester derivative of the present invention has a higher melting point than similar alkyl esters, and is particularly preferred as an electron-accepting compound for heat-sensitive recording materials.

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

(+) By combining with electron-donating colorless dye, high a
Gives a highly colored image.

(11) Low water solubility.

011) Stable without sublimation.

4V) 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.

fi+ Hiro-hydroxybenzoic acid cyclohexyl ester (21J-Chloro-Hiro-hydroxybenzoic acid cyclohexyl ester (3) 4'-hydroxybenzoic acid-(4L~methylcyclohexyl) ester (4) Hiro-hydroxybenzoic acid-(,2- Methylcyclohexyl) ester (5) ≠-Hydroxybenzoic acid-(μmchlorocyclohexyl) ester (6) ≠-Hydroxybenzoic acid-(λ-chlorocyclohexyl) ester These may be used alone or in combination or with other electron-accepting compounds (e.g. Bisphenol A%μm hydroxybenzoic acid benzyl ester, 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 examples of these include triarylmethane compounds such as 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, 3-1p-dimethylaminophenyl)-3-(/,3-dimethylindol-3-yl)phthalide, 3-1p-dimethylaminophenyl)-3
-(2-methylindol-3-yl)phthalide, etc. Diphenylmethane derivatives include ge, μ'-
his-dimethylaminobenzhydro/benzyl ether, N-halophenyl-leucoolamine, N -F,
a, J--4lichlorophenylleucoauramine, etc., and xanthine compounds include rotor i/
-B-anilinolactam, rho-1-mine(p-nitroanilino)raftane, rhodamine B(p-chloroanilino)lactam, J-dibenzylamino-6-jethylaminolluora/, 2-anilino-6-diethylaminofluor oran, no-anilino-3-methyl-t-diethylaminofluorane, co-anilino-3-methyl-J-N-cyclohexyl-N-methylaminofluorane, co-anilino-3-methyl-A-N-ethyl-N-yneamylaminofluoran Ola 7.2-Q-chloroanilino-6-diethylaminofluorane, --m-chloroanilino-t-diethylaminofluoran 1,2-(j, Hiro-dichloroanilino)-t-diethylaminofluorane, 2-octyl Amino-6-dinithylaminofluorane/, cholahexylamino-t-diethylaminofluorane, -2-m
-Trichloromethylanilino-6-dinithylaminolluorane, λ-butylamino-3-chloro-2-diethylaminoflumerane, 2-ethoxyethylamino-3-
Chloro-6-dinithylaminofluorane, -1-anilino-3-chloro-t-diethylaminofluoran, λ-rephenylamino-6-ethylaminofluoran-noanilino-3-methyl-6-siphenylaminofluoran , co-anilino-3-methyl-chloro-6-dinithylaminofluorane, 1-anilino-3-methyl-6
-dinithylamino-7-methylfluorane, coanilino-3-methoxy6-cyptylaminofluorane, λ-
0-Chloroanilino 6-cyptylaminofluorane 1
．． 2-p-chloroanilino-3-ethoxy-6-ethylaminofluorane, nophenyl-6-diethylaminofluorane, etc., and examples of di/based compounds include pensoyl leucomethylene blue, p-nitrobenzyl, etc. Leucomethylene blue, etc., spiro-based analogues include 3-methyl-spiro-dinaphthopyran, 3-ethyl-
Spiro-dinaphthopyran, 3,3'-cyclolose biro-dinaphthopyran, 3-benzylspiro-dinaphthopyran, 3-methyl-nando-(3-methoxy-benzo)-
There are spirovira/, 3-propyl loose virogibe 77'' bira/, etc. These can 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 Patent No. 1. jOj,≠7
No. 0, same co, 103, Hiro 7/no., same 2゜106, μ
g2, same λ,! gu♂, 3t6, same co, 7/2.30
No. 7, No. +2.730.1116, No. J, 730
, Hiroj No. 7, Same mj, <<//ff, J! It can take various forms as described in prior patents such as No. O. 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 is used alone or in combination with a solvent (synthetic oils such as argyl naphthalene, alkyl diphenyl, alkyl diphenylmethane, and alkylated terphenyl; vegetable oils such as cotton oil and castor oil; animal oils; mineral oils). or a mixture thereof), dispersed in a binder, or impregnated in microcapsules, and then applied to a support such as paper, plastic sheet, resin-coated paper, etc. to form a color former sheet. Alternatively, electron-accepting compounds, alone or in combination, or together with other electron-accepting compounds, may be dispersed in a binder such as styrene-butadiene latex or polyvinyl alcohol, and applied to a support such as paper, plastic sheet, or resin-coated paper. A developer sheet is obtained by coating.

The use of electron-donating colorless dyes and fft electron-accepting compounds has a coating thickness of 19 cm, a form of pressure-sensitive copying paper, and a capsule! ! ! It depends on the law and other conditions, so you can choose as appropriate depending on the conditions. It is easy for the customer to determine this usage scenario.

A method for manufacturing capsules is described in US Patent λ.

Method using coacervation of TC hydrophilic colloid sol described in Za00, 4t77, same co, za00, 4'j♂, British Patent No. 67.727, same 60
．． μμ No. 3, Dori Zari, 21 Hiro No. 109/, 07
There are interfacial polymerization methods such as those described in No. 4.

The heat-sensitive recording material 1#+ is prepared by adding an electron-donating colorless dye, an electron-accepting compound according to the present invention, and a thermofusible material, if necessary, to a liquid in which a binder is dissolved or dispersed in a bath medium or a dispersion medium. W! Thoroughly grind and mix, add kaori/,
Oil-absorbing pigments such as calcined kaolin, talc, waxite, cane earth, calcium carbonate, aluminum hydroxide, magnesium hydroxide, magnesium carbonate, titanium oxide, barium carbonate, urea-polumari/filler, cellulose filler, etc. to act. In addition, paraffin wax emulsion, latex binder, sensitivity improver, metal soap, acid and arsenic inhibitor, ultraviolet absorber,
llll111J! Preservability improvers and the like may be added.

It is coated on a support such as paper, plastic sheet, resin-coated paper, etc. and dried. When preparing the cold liquid 1, all the components may be mixed at the same time and crushed and crushed, or they may be mixed in an appropriate combination after being crushed and dispersed separately.

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

Components 11 of each component constituting the heat-sensitive recording material are electron-donating colorless dye/-2 parts by weight, 1 to 2 parts by weight of a bone-tolerant compound, and 30 parts by weight of a thermofusible substance θ to 30't (5 parts by weight). , Kakebe, pigment 0~
13 parts by weight, l-1JRkt part of binder and dispersion medium (
Solvent) 20 to 300 weight tons, tons.

Is electron-donating colorless dye a kind of waste? jI number may be mixed and used. Water is most desirable as the 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, dispersion rubber, gum arabic, polyvinyl alcohol, and hydroxyethyl cellulose. etc. can be mentioned.

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).

Thermofusible substances include erucic acid, stearic acid, behenic acid, palmitic acid, stearamide,
Behenic acid amide, stearic acid anilide, stearic acid toluicide, N-myristoyl-p-aningine, N-
myristoyl-p-phenetidine, /-methoxycarbonyl-u-N-stearylcarbamoylbenzene, N-
Octadefluorurea, N-hexadecyl urea, N,
N-cyto fsilurea, phenylcarbamoyloxydodecane, p-t-7'tylphenol phenoxy acetate, p-phenylphenol-p-chlorophenoxy acetate, Hiroshi, μ'-improhyrite/hismethoxybenzene, β-phenylethyl -p-phenyl phenyl ether, λ-p-chlorobenzyloxynaphthalene, cord/zyloxynaphthalene, l-benzyloxynaphthalene, λ-phenoxyacetyloxina7talene, phthalic acid diphenyl ester, l-hydroxy-λ-
Naphthoic acid phenyl ester, λ-benzoyloxynaphthalene, p-benzyloxybenzoate, hydroquinone acetate, and the like 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 1100C.

Examples of waxes include /ξ mirafin wax, cownapa wax, microcrystalline wax, polyethylene wax, and higher fatty acid amides such as stearic acid amide, ethylene bisstearamide, and higher fatty acid esters.

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

Examples of image storage improvers include phenols or derivatives thereof in which at least one of the co- or 6-positions is substituted with an alkyl group, and among these, one or more of the 412- or 6-positions is a tert-butyl group. Substituted phenols or derivatives thereof are preferred. Further, those having a complex number of phenol groups in the molecule are preferable, and those having from one to three phenol groups are particularly preferable. Specific examples of these compounds include bis-[3,3-bis=(Hiro'-hydroxy-3'-t
ert-7'tylphenyl]-phthanoic acid] glycol ester, bis-[3,3-bis-(I/-'-hydroxy-3'
, j'-di-tert-butylphenyl)butanoic acidocoglycol ester, bis-[3I3-bis-(-'-methyl-μ'-hydroxy!'-tert-ifluphenyl)-butanoic acidocoglycol ester , /, /, 3-) lis(λ-methyl-l-hydroxy-j-tert-butylphenyl)phthane F, F' -fobis(3-methyl-6-1crt-butylphenol), ≠, Hiro'-thiobis (2-methyl-A-ter
t-butylphenol), λ1.2'-thiobis(≠-methyl-4-tert-butylphenol), -'-methylenebis(4A-methyl-1crt
-butylphenol), λlλ'-)-1-lenebis(≠-ethyl-ter
tert-butylphenol),
-butylphenol), Ge, ψ'-methylenebis(λ, t-di-tert-butylphenol), coat-tert-duthoxyphenol, 2,2-dimethyl-≠-inopropyl-7-1crt-
Butyl-t-chromanol, 2, nordimethyl-A-t
-Butyl-! -Benzofuranol, ≠ [[≠, 6-bis(tertbutylthio)-8-triazin-λ-yl]amine] 2・tert-di ter
Examples include t-butylphenol.

The amount of these compounds to be used is J-200 weight percent, preferably J O-70, based on the electron-accepting compound.
0 weight percent.

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

Example 1 ■ Preparation of color former sheet Noanilino-3-methyl- which is an electron-donating colorless dye
6-dinithylaminofluora//9f alkylated 7talene J (dissolved in 7,9).
And 7 Rabiya Gum≠, water in which 9 is dissolved! The mixture was added to θl with vigorous stirring and emulsified to form oil droplets with a chamber diameter of lμ to ioμ, and then water 2jOfi was added. Add acetic acid little by little and p
Coacervation was caused by increasing the H content, and a wall of gelatin and gum arabic was created around the oil droplet. After formalin was added, the pH was raised to t-2 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 compound ≠-hydroxybenzoic acid cyclohexyl ester JO,! 7f1% polyvinyl alcohol aqueous solution λθOIK was dispersed, and kaolin (Jossia kaolin)-2Ofif was further added and dispersed well to prepare a coating liquid. The obtained coating liquid was applied to paper and dried to obtain a color developer 7-t.

When the color forming agent sheet prepared in this manner and the blood coloring agent sheet are brought into contact and pressure or impact is applied, a black image is instantly formed.
I got JJ. This image had high density and excellent light resistance and heat resistance.

Example 2 Electron-donating colorless dye 117 nilino 3-methyl-AN-methyl-N-cyclohexylaminofluoran ry-+ss polyvinyl alcohol (Ken measurement yychi,
Polymerization degree: 1000) The mixture was dispersed in a ball mill with 0 g of an aqueous solution overnight. On the other hand, similarly, the electron-accepting compound V-hydroxybenzoic acid cyclohexyl ester iog
'g (Yochipolyvinyl alcohol aqueous solution / 00.9) was dispersed in a ball mill for a day and night. After mixing these two dispersions, kaolin (Jossia kaolin) 209 was added and well dispersed, and then paraffin wax emulsion! Chi dispersion (Middle East oil cellosol #Hiro-21
)! j; l was added to prepare a coating liquid.

The coating liquid was applied to a base paper having a basis weight of t 09 / m 2 as a solid content coating amount A I! /m'' and dried for 1 minute at to 0c to obtain a coated paper.

Apply heating energy to the coated paper by facsimile.
When heated and colored at am2, a black printed image was obtained. The color density was 0.23.

Example 3 As an electron-donating colorless dye in place of the electron-donating colorless dye of Example 2, λ-anilino-3-chloro-4-diethylaminofluorane! A coated paper was obtained in the same manner as in Example 2 except that 3-chloro-≠-hydroxybenzoic acid cyclohexyl ester lO9 was used as a one-electron-accepting compound in place of the electron-accepting compound.

Coated paper is heated by facsimile with heating energy of 〇mJ/
When color was developed with w2, a colorless impression was obtained.

The color density was /,00.

Comparative Example 1 A coated paper was obtained in the same manner as in Example 3 using lOg of λ,-2-bis-(g-hydroxyphenyl)propane as the electron-accepting compound in place of the electron-accepting compound in Example 3. .

Heat the coated paper by facsimile.
When the color was developed by heating with "my", the color density was 0°.

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.

Example 4 Co-anili/-J-if-4-N-ethyl-N-ynamyl-aminofluorane, 209″fc10 polyvinyl alcohol (saponification degree t polymerization degree too) was dispersed overnight in a 300-ball mill with an aqueous solution of ioog. Similarly, hydroxybenzoic acid cyclohexyl ester was dispersed day and night in a 3001rtl ball mill with 100 g of a log-@1ota polyvinyl alcohol aqueous solution to obtain a dispersion.Similarly, bis-[3
, 20 g of 3-bis-(≠'-hydroxy-j'-tert-butylphenyl)-butanoic acidocoglycol ester in a 10% polyvinyl alcohol aqueous solution ioo
The mixture was dispersed day and night in a 300 ml ball mill with g to obtain a dispersion solution.

Dispersion liquid (8), dispersion liquid 0 and dispersion liquid 0 at 3:20:! The mixture is further mixed at a weight ratio of λoo! 10 for q
/i of calcium carbonate fine powder was added and sufficiently dispersed to prepare a coating liquid.

This coating liquid for thermal recording paper! The mixture was coated with an air knife on a base paper having a basis weight of 0.09/m2 to obtain a coated amount of 417 m2 in terms of solid content, and dried for 10 minutes to obtain a heat-sensitive recording paper.

When the coated paper was colored by facsimile, a black image was obtained.

Moreover, the storage stability of the obtained color image was extremely excellent.

Example 5 In place of the bis-[3,3-bis-(g'-hydroxy-J'-tert-butylphenyl)-butanoic amidocoglycol ester of Example 4, /, /
, 3-tris(2-methyl-≠-hydroxy-〇-1e
Example 4 using ri-butylphenyl)phthane 209
Coated paper was obtained in the same manner as above.

When the coated paper was colored by facsimile, a black impression was obtained. Moreover, the storage stability of the obtained color image was extremely excellent.

Claims (1)

[Claims] A recording material using an electron-donating colorless dye and an electron-accepting compound, wherein the electron-accepting compound has the following general formula +I)
A recording material characterized by being a compound represented by λ In the above formula, X represents a hydrogen atom, tyc represents a halogen atom, and Y represents a hydrogen atom, a lower alkyl group, or a halogen atom.