JPS60176792A - Recording material - Google Patents

Abstract

PURPOSE:To provide a recording material providing a sufficient developed color density and having excellent light resistance and heat resistance, wherein a specified dihydroxybenzoic acid ester is used as an electron-acceptive compound in combination with an electron-donative colorless dye. CONSTITUTION:The compound of the formula, wherein each of R and R' is lower alkyl, lower alkoxy, halogen or H, and (n) is 2-5, e.g., beta-phenethyl 2,4-dihydroxybenzoate or beta-P-chlorophenylethyl 2,4-dihydroxybenzoate, is used as an electron-acceptive compound in a recording material comprising an electron-donative colorless dye, e.g., 2-anilino-3-methyl-6-diethylaminofluoran, and an electron-acceptive compound.

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. In particular, 1. for pressure-sensitive and heat-sensitive recording materials. It is an extremely useful compound as a child-accepting compound, and can also be used as an electrically conductive heat-sensitive recording sheet, a photosensitive recording sheet, an ultrasonic recording sheet, an electron beam recording sheet,
It is a compound that can be applied to electrostatic recording sheets, photosensitive printing sales materials, 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 No. Sho Go-9309, Japanese Patent Publication No. 4TJ-/DA03-2, and No. 5L-2 of 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.

Also, Tokukai Akira! When the benzyl 4t-dihydroxybenzoic acid ester disclosed in No. 1-209!90 is used in a heat-sensitive recording material, the recording material is insufficient in terms of heat and humidity resistance, fogging, etc.

<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 has been achieved by a recording material characterized in that it uses an electron-donating colorless dye and a compound represented by the following general formula as an electron-accepting compound.

In the above formula (2), R and R' may be the same or different and represent a lower alkyl group, a lower alkoxy group, a halogen atom or a hydrogen atom, and n represents an integer from 1 to j.

In the above general formula C''-, the substitution positions of R and R',
OH (on the other hand, when R or R' is a hydrogen atom, the ortho or para position is preferred, and the 7ξ position is particularly preferred.

When both R and R' are other than hydrogen atoms, both are preferably at the niortho or meta position.

In the above general formula, n is preferably co and 3, particularly -
is very talented.

Among the substituents represented by R in the above general formula (2), alkyl groups with carbon atoms/~!, alkoxy groups with carbon atoms/~!, chlorine atoms, bromine atoms, and hydrogen atoms are preferred; Preferred are alkyl groups having 3 carbon atoms, alkoxy groups having 3 to 3 carbon atoms, chlorine atoms, and hydrogen atoms.

When the τ7-accepting compound according to the present invention is used as an electron-accepting compound for a heat-sensitive recording material, it preferably has a melting point of -t00C or higher, particularly 7θ0C~/! θ″
Those having a melting point of C are preferred.

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

(1)! When combined with a child's colorless dye, it gives a highly concentrated colored image.

0) Poor water solubility.

(ill) Stable without sublimation.

(:V) It is easy to synthesize and can be obtained with high yield and high 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),! , 4t-dihydroxybenzoic acid β-phenethyl ester (2)+, , 4t-dihydroxybenzoic acid β-p-
ChloroIff phenylether ester (3), z, g-dihydroxybenzoic acid β-p-t I
J /l' Ethyl ester (4) λ, Kuzihyde V xybenzoic acid β-p-methoxyphenylethyl ester (5) Co, 4t-dihydroxybenzoic acid α-phenethyl ester (6), z, p-dihydroxybenzoic acid α -p-chlorophenyl ester (7) λ, 4t-dihydroxybenzobenzoic acid dinylpropyl ester (s), z+p-dihydroxybenzoic acid α-methyl-α
-phenether ester (9), 2. hydroxybenzoic acid α-meboul-r-phenylpropyl ester, these are used alone or in combination, or mixed with other electron-accepting compounds (eg, bisphenol A, 4t-hydroxybenzoic acid benzyl ester, etc.).

Examples of the electron-donating colorless dye used in the present invention include triarylmethane compounds, diphenylmethane compounds, xanthine compounds, thiazine compounds, and spiropyran compounds.

To illustrate some of these, as triarylmethane compounds, 3.3-bis(p-dimethylaminophenyl)-6-dimetelaminophthalide (i.e., crystal violet lactone), 3. -dimethylaminophenyl)phthalide)', J-(P-dimethylaminophenyl)-J-(/,j-dimethylindol-3-yl)phthalide, J-(p-dimethylaminophenyl)-
There are 3-(,2-methylindol-3-yl)phthalide, etc., which are diphenylmethane-based compounds. Ko+
41. s-)liku-U lophenylleukoolamine, etc., and xanthine compounds include rhogmin-B-anilinolactam, 0-tamine (, p-nitroanilino), etc.
) lactam, rhodamine B (p-chloroanilino)lactam, -1-dibenzylamino-6-dietheraminofluorane, -1-anilino-6-dietheraminofluorane,
-1anilino-3-methyl-6-ethylaminofluorane, noanilino-3-methyl-4-N-cyclohexyl-N-methylaminotourane, noanilino-3
-Methyl-6-dichloro-N-isoamylaminofluorane, 2-0-chloroanilino-6-diethylaminofluorane, -m-dichloroanilino-t-diethylaminofluorane 1,2-(3,p-dichloro Anilino)
-t-diethylaminofluorane, co-octeramino-6-diethylaminofluorane, -1-dihexylamino-t-diethylaminofluorane, 2-m-)licromethylanilino-6-diethylaminofluorane, coptyl Amino-3-chloro-6-diethylaminofluorane, coethoxyethylamino-3-riau -
A-diethylaminofluorane, no-anilino-3-chloro--diethylaminofluorane, no-diphenylamino-6-dietheraminofluorane, co-anilino-3-methyl-t-diphenylaminofluorane, co-anilino-3-methyl-! -ChroIff -Δ-diethylaminofluorane, noanilino-3-methyl-6-
dinitylaminofluoran, 2-anilino-3-methoxy-dibutylaminofluoran 1.2-
0-chloroanilino-6-sibutylaminofluorane,
Examples of thiazine compounds include λ-p-chloroanilino-3-ethoxy-t-diethylaminofluorane and coufenino-t-1-diethylaminoflumerane, and pensoylleucomethylene blue and p-nitrobenzylleucomethylene blue. , as a spiro compound,
3-metelusubiu-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 313'-cyclospirodinaphthopyran, 3-pendylsuubi-U-dinaphthopyran, 3-metelnaf)-(j-methoxy-benzo)-spiropyran, 3-- There are 10 Hirusu biro dibenzohyrans, etc. 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 present invention (-Such pressure-sensitive copying paper is disclosed in U.S. Pat. No. 2.3 Or, 4
t7θ, same! θj, No. 417, same.

! θ! , g/9, same, j4t/, J14, same 2.
7/, No. 2.107, 2.7jθ, Gu! No. 2
, 73θ, 4tj No. 7, same No. 3. Ri/♂,-! Prior patents such as No. θ: It can take various forms as described in 2. Most commonly, it consists of at least one pair of sheets containing the electron-donating colorless dye and the electron-accepting compound according to the invention separately. Synthetic oils such as alkylated diphenyl, alkylated diphenylmethane, and alkylated terphenyl; Vegetable oils such as cotton oil and castor oil; Animal oils; Mineral oils or mixtures thereof, etc.)
By dissolving this in a binder or containing it in microcapsules, and applying it to a support such as paper, plastic sheet, resin-coated paper, etc., a color former sheet can be prepared. alone or in combination or with other electron-accepting compounds, dispersed in a binder such as styrene-butadiene latex, polyvinyl alcohol, paper, plastic sheet,
A developer sheet is obtained by coating a 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.

? Method using coacervation of hydrophilic colloid sol described in 0θ, Guj No. 7, Iθθ1 Clause J, British Patent No. 47.797, Same 9taθ, Gu4t No. 3, Same I 1.26 da issue, same/.

There are interfacial polymerization methods described in No. 09/, No. 07, 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 heat-fusible substance to a liquid in which a binder is dissolved or dispersed in a solvent or a dispersion medium in a sufficiently finely divided manner. The oil absorption properties of kaolin, calcined kaolin, talc, waxite, diatomaceous earth, calcium carbonate, fluminilum 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. 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 solution is applied to a support C such as paper, plastic sheet, resin coated paper, etc. and dried. When preparing a coating liquid, all the components may be mixed and ground simultaneously from the beginning, or they may be combined in a suitable combination and mixed after grinding separately.

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

The amounts of each component constituting the heat-sensitive recording material are: 7 to 2 parts by weight of an electron-donating colorless dye, 0 to 30 parts by weight of an electron-accepting compound, 0 to 30 parts by weight of a thermofusible substance, and θ to /j of a pigment. Weight part, binder /~/! Part by weight and dispersion medium (solvent) -0 to 300
Parts by weight. .

One or more electron-donating colorless dyes may be used in combination. 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, synthetic rubbers, gum arabic, polyvinyl alcohol, and hydroxyethyl cellulose. In particular, water-soluble materials such as gum arabic, polyvinyl alcohol, hydroxymethyl cellulose, and carboxymethyl cellulose are preferred in relation to the dispersion # (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-anisidine, N-
E-ristoyl-p-phenetidine, /-methoxycarbonyl-a-N-stearylcarbamoylbenzene, N-
, t-phtadecyl urea, N-hexadecyl urea, N,
N'-didodecylurea, phenylcarbamoyloxydodecane, p-t-butylphenolphenoxyacetate, p-phenylphenol-p-chlorophenoxyacetate, Q, &'-isopropylidene bismethoxybenzene, β-phenylether-p-phenyl Phenyl ether, 2-p-chlorobenzyloxynaphthalene,
-1-benzyloxynaphthalene, l-benzyloxynaphthalene, cophenoxyacetyloxynaphthalene,
Phthalic acid diphenyl ester, /-hydroxy-λ-naphthoic acid phenyl ester, cobenzoyloxynaphthalene, 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 the heating temperature for copying, that is, around 2θ-/600C.

Examples of waxes include paraffin wax, Kaunaparoku wax, Ma-Fri locrystalline wax, and polyethylene wax, as well as higher fatty acid amides such as stearic 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 zinc oleate.

Examples of image storage improvers include phenols or derivatives thereof in which at least 7 or more of the co- or 4-positions are substituted with alkyl groups, among which 7 or more of the 2- or 6-positions are substituted with tert-butyl groups. phenol or its derivatives are preferred. Those having a plurality of phenol groups in the molecule are preferable, and those having from one to three phenol groups are particularly clever. Specific examples of these compounds include bis-[3,3-bis-(g'-hydroxy-3'-t
ert-butylphenyl)-butanoic acidocoglycol ester, bis-[3,3-bis-(g'-hydroxy-J/
, 4t/-di-tert-butylphenyl)butanoic andcoglycol ester, bis-[3,3-bis-(,2'-methyluda'-hydroxy-!'-ter
t-Butylphenyl)-phtanoic acid] glycol ester- /, / 13Flis(,2-methyl-guhydroxy-〇-tert-butylphenyl)phthane, g, g'-
Thiobis(3-methyl-4-tert-butylphenol), g,g'-thiobis(,2-methyl-A-tert-butylphenol), co,2'-thiobis(g-methyl-A-tert-butylphenol), Tip 2'-methylenebis(gu-methyl-6-tert-
butenophenol), 1,2'-methylenebis(4 to ethyl-ter)
l-butylphenol), g,g'-phthyritin bis(3-methyl-6-tert
-butylphenol), 4t'-methylenebis(2,6-di-tert-butylphenol), λ-tert-butyl-tert-butoxyphenol, tips. 2-dimethyl-a-isopropyl-7-tert
-butyl-6-chromanol,co,2-dimethyl-7-
tert-but-j-benzofuranol,
Butylphenol etc.

The amount of these compounds used is t~200% by weight based on the electron accepting compound, preferably 20~10θ
Weight percentage.

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

Examples/ ③ Preparation of color former sheet Alkylated naphthalene 30? ! =Dissolved. This solution was added to 10 f of water in which 1 gelatin z and 4 tt of gum arabic were dissolved while stirring gently to emulsify it to form oil droplets with a diameter of /μ to 70 μ, and then water and ZjOf were added thereto. Add acetic acid little by little to adjust the pH.
Coacervation was caused by setting the temperature to about y, and a wall of gelatin and gum arabic was created around the oil droplets, formalin was added, and the pH was increased to 9 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
Fragrant acid-β-phenylether ester 2Of jqb polyvinyl alcohol aqueous solution 200? + = dispersed, further (-
Kaolin (Jossia Kaolin) 202 was added and fractionated well to prepare a coating liquid. The resulting coating solution was applied to paper and dried to obtain a developer sheet.

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

EXAMPLE Electron-donating colorless dye no-anilino-3-methyl-
4-N-Methyl-N-cyclohexylaminofluorane! ffj% polyvinyl alcohol (degree of polarization 9tachi, degree of polymerization 10θθ) aqueous solution! In the same way, 10 ml of electron-accepting compound, 41-dihydroxyammonyl, M-β-phenylethyl ester, was dispersed with 10 ml of t% polyvinyl alcohol aqueous solution (in a nibal mill). After mixing these two types of dispersions, kaolin (Jossia kaolin) was added to disperse well, and then paraffin wax emulsion and tO% dispersion (Middle East oil and fat Cellosol #Gukol) were added. A coating liquid was prepared by adding da.

The coating liquid was applied onto a base paper having a basis weight of sow/m2 so that the solid content coating amount was Jf/m2, and at tθ0C 7
A coated paper was obtained by drying for a minute.

Facsimile the coated paper (= more heating energy)
When heated and colored with J 7 mm 2 , a black printed image was obtained. The color density was /.03.

In addition, this coated paper was added to 714
The density of the coated paper after being left for a period of time was θ,/4t.

Example 3 Co-anilino 3-chloro-6-dietheraminofluorane is used as an electron-donating colorless dye instead of the electron-donating colorless dye of Example λ! A coated paper was prepared in the same manner as in Example λ, using f and using an electron-accepting compound, co-dihydroxybenzoic acid-α-phenylethyl ester A//Of, in place of the electron-accepting compound. Obtained.

Coated paper is heated by facsimile with energy θmJ/
When color was developed in mm2, a black impression was obtained.

The color density was θ, rij.

Comparative Example/Instead of the electron-accepting compound of Example 3, 1.2.2-bis-(kuhydrokii/'7:
A coated paper was obtained in the same manner as in Example 3 using propane/θ2.

Facsimile the coated paper (second heating energy
/rnm 2 When the color was heated and developed, the color density θ was obtained.

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

Comparative Example Coated paper was obtained in the same manner as in Example 3 except that 4t-dihydroxybenzoic acid benzyl 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 θmJ/
When color was developed by heating at mm2, the color density was θj.

Further, after this coated paper was left in aooc qo%RH for 24 hours, the density of the coated paper was θ, J'/.

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

Example 100% aqueous solution of gnoanilino-3-methyl-&-N-ethyl-N-isoamylaminofluorane 2Of in polyvinyl alcohol (70% polyvinyl alcohol (degree of polymerization! degree of polymerization! θO))
Dispersed all day and night in a 3θOm nopol mill with dispersion i
(A) was obtained. Similarly, Ko.

Gooji hydroxybenzoic acid-α-phenylether ester 101/(7% polyvinyl alcohol aqueous solution/θθ
A dispersion liquid (B) was obtained by dispersing the mixture together with f in a 30θm Nopol mill for 7 days and nights. Similarly, bis-[3,,? - Bisou (4
t'-hydroxy-3'-tert-butylphenyl)
-Butanoic acid coglycol ester 20f 7
30 with 0% polyvinyl alcohol aqueous solution 1002
(Y m 7 In a ball mill/Dispersed day and night Dispersion liquid (C)
I got it.

Dispersion liquid (A), dispersion liquid (B), and dispersion liquid <C> were mixed at a weight ratio of 3:0:3, and further, 309 carbonate lucicum fine powder was added to the mixed liquid λOθ1, and the mixture was thoroughly mixed. Disperse it and use it as a coating liquid.9.

This coating liquid for thermal recording paper! Coated with an air knife to obtain a coating weight of 4f/m2 of solid content on 1m of base paper with a basis weight of/m2. It was dried at θ0C for 2 minutes to obtain a thermosensitive 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.

Patent Applicant Fuji Photo Film Co., Ltd. Procedural Amendment 1, Case Indication Showa! Special application for the year - 3rd/? Ri No. 2,
Title of the invention Recording material 3, Relationship to the case of the person making the amendment Patent applicant Location 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture Subject of the amendment Description 5, Submit an engraving of the description of the content of the amendment (no change in content) I'll finish it.

Claims (1)

[Scope of Claims] A recording material using an electron-donating colorless dye and an electron-accepting compound (2) A recording material 1 characterized in that the electron-accepting compound is a compound represented by the following general formula ( ' In the above formula, R and R/ may be the same or different and represent a lower alkyl group, a lower alkoxy group, a herogen atom, or a hydrogen atom, and n represents an integer of 2 to !.