JPS6394877A - Recording material - Google Patents

Abstract

PURPOSE:To improve the stability of a coloring image, by employing p- substituted aminophenyl indolylphthalid derivative and p-substituted aminophenyl indolylazaphthalid derivative as a colorless dye in a recording material where coloring through contact between a colorless dye and an acceptor compound is utilized. CONSTITUTION:Preferably, p-substituted aminophenyl indolylphthalid derivative shown by formula (I) and p-substituted aminophenyl indolylazaphthalid derivative shown by formula (II) are employed as a donor colorless dye. Preferably, the acceptor compound has one or more phenolhydroxyl groups and includes salicylic acid derivative, phenol derivative, phenol resin, etc. Coloring matter where these compounds are combined has high stability, and causes no fading due to long time irradiation with light, heating or humidifying, thus enabling long term storage of a record.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to recording materials, and more particularly to a specific recording material with improved stability of colored images.

(Prior Art) Recording materials using an electron-donating colorless dye and an electron-accepting compound are already well known as pressure-sensitive paper, heat-sensitive paper, light-sensitive pressure-sensitive paper, electrically conductive heat-sensitive recording paper, and the like.

For example, British Patent No. 14to, 4t4t, U.S. Patent μ, μto, or, No. 2, Same μ, ≠36. Octopus No. 0, Special Public Showa to-23. Octopus No. 2, JP-A-77-/7-ri,
No. 13, same tO-/23. It! No., same tO-/2
3, J-17, etc.

The performance that a recording material should have is (1) sufficient color density and color development sensitivity, (2) no fogging, (3) sufficient fastness of the color material after color development, (
4) Appropriate color hue and suitability for copying machines, (5)
8/N ratio is high, (6) the color former has sufficient chemical resistance, and (7) it is easily soluble in organic solvents, but currently no product that completely satisfies these requirements is available. Not yet.

Particularly in recent years, with the diversification of requirements for recording systems, research has been intensively conducted to improve these characteristics. Among these, blue color recording materials have particularly strong requirements regarding (3) K.

Conventionally, diphenylmethane-based compounds, triphenylmethane-based compounds, phthalide-based compounds, leucomethylene blue-based compounds, and the like have been known as compounds that develop a color from back to blue-purple. However, each of these compounds has drawbacks.

For example, 3, which is one of the triphenylmethane compounds,
3-bis(p-dimethylaminophenyl)-J-dimethylaminophthalide develops color quickly and exhibits a deep blue color, but the light resistance of the colored image is extremely poor. Leukometylev 7
' A. -The fluorinated adduct 3,7-bis(dimethylamino)-10-benzoylphenothiazine has extremely good light resistance in its color image, but the color development is very slow and cannot be achieved with an organic color developer. It has a very bad flaw.

The present inventors investigated the oil solubility, water solubility, partition coefficient, pKa, polarity of substituents, position of substituents, crystallinity and solubility for each of electron-donating colorless dyes and electron-accepting compounds. We have pursued the development of good materials for recording materials and recording materials, focusing on characteristics such as change.

(Objective of the Invention) Therefore, the object of the present invention is to provide a recording material using a material that has good color development, shelf life, and stability of colored images, and also satisfies other requirements.

(Structure of the Invention) The object of the present invention is to use p-substituted aminophenylindolyl phthalide derivatives and p-substituted aminophenylindolyl azaphthalide derivatives as electron-donating colorless dyes, and a phenolic hydroxyl group as an electron-accepting compound. According to a recording material characterized by using an M organic acid having 7 or more
Among the coupled p-substituted aminophenylindolphthalide derivatives according to the present invention, those represented by the following general formula (1) are preferred.

In the above formula, R and R2 may be the same or different and represent an alkyl group; R and )t4Fi may be the same or different and represent an alkyl group or an aryl group; Y, Y1' and Zl each represent a hydrogen atom, an alkyl group, a halogen atom, a substituted amine group or an alkoxy group.

The aryl group represents a phenyl group, a naphthyl group, or a heteroaromatic ring group, and these include an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a nitro group, a cyano group, a substituted carbamoyl group, a substituted sulfamoyl group, and a substituted amino group. It may have a substituent such as a group, a substituted oxycarbonyl group, or a substituted oxysulfonyl group. Further, the alkyl group represents a saturated or tFi-unsaturated alkyl group or a cycloalkyl group, which may have a substituent such as an aryl group, an alkoxy group, an aryloxy group, or a cyano group spanning a halogen atom.

In the above formula, among the substituents represented by R1 or FL2, an alkyl group, an alkoxyalkyl group, a halogen atom, a substituted alkyl group, and an alkoxyalkyl group having carbon atoms/-10 are preferable, and R3-! Among the substituents represented by -, an alkyl group that may have an aryl group, an alkoxy group, an aryloxy group, or a halogen atom as a substituent, and an alkyl group that has a carbon atom number of t to IO; , an alkoxy group or a phenyl group which may have a halogen atom as a substituent is preferable, and among the substituents represented by R4, an alkyl group having a carbon atom number/-r and a phenyl group having a carbon atom number t to IO are preferable. , among the substituents represented by Xl,
A hydrogen atom, an alkoxy group having a carbon atom number of t to 10, a chlorine atom and a fluorine atom are preferred, and among the substituents represented by Yl, a hydrogen atom, a carbon atom number t to a carbon atom number t to alkyl group, acyloxy group,
Substituted amine groups and alkoxy groups are preferred, and among the substituents represented by Zl, alkyl groups and alkoxy groups having a hydrogen atom number/-4 are preferred.

Some examples of these are 3-(≠-diethylaminocoe)=? diphenyl)-3-(/-ethyl-methylindol-3-yl)phthalide, J-(4(-diethylamino-ethoxyphenyl)-J-(/-isoamyl-methylindole-3) -yl) phthalide, j-(4t-diethylaminocoethoxyphenyl)-J-(/-β-ethoxyethyl-comethylindol-3-yl)phthalide, J-
(4(-diethylamino-2-ethoxyphenyl)-3
-(/-β-phenoxyethyl-2-methylindol-3-yl)phthalide, j-(<4-dibutylamino-
2-Ethoxyphenyl)-J-(/-ethyl-methylindol-3-yl)phthalide, 3-(≠-diethylamino-coethoxyphenyl)-J-(/-ethyl-cophenylindol-3-yl) Phthalide, J-
(≠-N-cyclohexyl-N-ethylamino-coethoxyphenyl)-J-(/-ethyl-nomethylindol-3-yl)phthalide, 3-(der N-ethyl-N-isoamylamino--inamyloxy) Phenyl>-, y-<i-ethyl-comethylindole-3-
yl) phthalide, J-($-diethylamino-methylphenyl)-! -(/-ethyl-4-methylindol-3-yl)phthalide, 3-(μ-N-cyclohexyl-N-zthylaminocoethoxyphenyl)-3-
(i-ethyl-2-methylindol-3-yl)phthalide, 3-(u-N-methyl-N-ethylamino-λ-
methylphenyl)-J-(/-ethyl-2-methylindol-3-yl)phthalide, '-(''-diethylaminophenyl)-3-(/-ethyl-comethylindol-J-yl)phthalide, 3- (U-diethylamino-coethoxyphenyl)-J-(/-hexyl-comethylindol-3-yl)phthalide, J-(4-diethylamino-2-ethoxyphenyl)-J-(/-octyl-2-phenyl) indol-3-yl) phthalide,
3-(μm diethylamino-coethoxyphenyl)-
J-(/-ethyl-J-methylindol-3-yl)
-! or 6-medoxyphthalide, 3-(Hiro-diethylamino-coethoxyphenyl)-3-(/-ethyl-comethylindol-3-yl)-Z or t-chlorophthalide, 3-(''-diethylamino-coethoxyphenyl) -3-(/-ethyl-methylindole-3
-il)-! or A-chlorophthalide, etc.

Among the p-substituted aminophenylindolyl azaphthalide derivatives according to the present invention, those represented by the following general formula (n) are preferred.

In the above formula, fL5 and R6 may be the same or different and represent an alkyl group, R7 and R8 may be the same or different, and Y2, Y2' represent an alkyl group or an aryl group.
and z2 is a water atom, an alkyl group, a halogen atom,
Represents a substituted amino group or alkoxy group.

Ring A represents a pyridine ring.

In addition, the aryl group is a phenyl group, a naphthyl group, Fi
Represents a heteroaromatic ring group, and these include an alkyl group, an alkoxy group, an aryloxy group, a norodane atom, a nitro group, a cyano group, a substituted car-9-moyl group, a substituted sulfamoyl group, a substituted amine group, a substituted oxycarbonyl group, or a substituted It may have a substituent such as an oxysulfonyl group.

Further, the alkyl group refers to a saturated or unsaturated alkyl group, and also refers to a cycloalkyl group, which may have a substituent such as an aryl group, an alkoxy group, an aryloxy group, a halogen atom, or a cyano group.

Among the substituents represented by the above formula, i or R, an alkyl group having 10 carbon atoms, an alkoxyalkyl group, a halogen atom alkyl group, and an alkyl group are preferred, and those represented by R7 Among the substituents, the aryl group having 7 to 10 carbon atoms, an alkoxy group, an aryloxy group, or an aryl group having 7 to 10 carbon atoms, or an alkyl group having 6 to 10 carbon atoms, which may optionally have a halogen atom as a substituent. A phenyl group having an alkoxy group, an alkoxy group, or a halogen atom as a substituent is preferable, and among the substituents represented by R, an alkyl group having a carbon atom number of t and a carbon atom number t
A phenyl group of ~IO is preferred, and among the substituents represented by Y2 and Y2', a hydrogen atom, an alkyl group having ~1/2 carbon atoms, an acyloxy group, a substituted amine group, and an alkoxy group are preferred; Of the substituents represented,
A hydrogen atom, an alkyl group and an alkoxy group having a carbon atom number of 1 to 2 are preferred. Ring A is preferably a pyridine ring in which the nitrogen atom is located at the G or 7 position of the azaphthalide ring, especially ≠-
Azapthalide is preferable because it has less fog.

It is preferable that the sum of the total number of carbon atoms of the substituents represented by R5, R6, Y2, R7, and R8 is r or more because the solubility of the color former in an organic solvent increases. Some examples of these are 3-(μm diethylamino-2-ethoxyphenyl)-
3-(/-ethyl-methylindol-3-yl)
-μm or -7-azaphthalide, 3-(≠-diethylamino, 2-44xyphenyl)-3-(/-etherunophenylindol-3-yl)-μ-or 7-azaphthalide, 3-(II -diethylamino-ethoxyphenyl)-3-(/-isoamyl-cophenylindol-3-yl)-4'-also f17-azaphthalide, J-(II-diethylamino-,2-1), Ii-diphenyl) -J-(/-β-ethoxyethyl-comethylindol-3-yl)-μm or 7-azaphthalide, j-(4-jethylamino-ethoxyphenyl)
-3-(/-β-phenoxyethyl-λ-methylindol-3-yl)-cou or 7-azaphthalide, 3-(
4-dibutylamino-ethoxyphenyl)-3-(
/-ethyl-nophenylindo-3-yl)-ter or -7-azaphthalide, 3-(gaugeethylamino-ethoxyphenyl)-3-(/-methyl-nophenylindol-3-yl)-gu or - 7-Azaphthalide, 3-(l-N-cyclohexyl-N-ethylamino-2-ethoxyphenyl)-J-(/-ethyl-phenylindol-3-yl)-μ-text! -1-7
-Azaphthalide, 3-(≠-N-ethyl-N-isoamylamino-2-ynamyloxyphenyl)-J-(/
-Ethyl-λ-methylindol-3-yl)-cou- or -7-azaphthalide, 3-(4t-diethylamino-ethoxyphenyl)-J-(/-octero-comethylindol-3-yl)-μ- Also, i, l-7-azaphthalide, 3-(II-diethylamino-2-methylphenyl)-3-(/-ethyl-methylindol-3-yl)-μm or -7-azaphthalide, 3-(l
3-(
≠-N-butyl-N-ethylamino-methylphenyl)-j-(/-etherunophenylindole-3
J-(4-diethylaminophenyl)-3-(i-ethyl-2-phenylindol-3-yl)-μm or -7-azaphthalide, J-(4-diethylaminophenyl)-3-yl)-μm or -7-azaphthalide, thylamino-ethoxyphenyl)-3-(/-hexyrunomethylindole-3
-yl)-cou or -7-azaphthalide, 3-(4L-
diethylamino-λ-ethoxyphenyl)-J-(/-
octyl-2-phenylindol-3-yl)-4'
-Also U-7-7 zaftalide, J-(!-diethylamino-coethoxyphenyl)-J-(/-ethyl-2-methylindol-3-yl)-! or t-azaphthalide, 3-(4A-jethylamino-ethoxyphenyl)-J-(/-etherunophenylindole-3-
il)-! Also, azaphthalide, j-(4-dibutylaminoethoxyphenyl)-j-(/-ethylunophenylintol-3-yl)-! Or 6-azaphthalide, 3-('+''-diethylaminephenol)-J(/-ether-methylindol-3-yl)-j-, or 7-azaphthalide.

p-substituted aminophenylindoly/4Z according to the present invention
- Among the luphthalide derivatives, p-substituted aminophenylucophenyl indolyl≠- or -7-azaphthalide is preferred from the viewpoint of its various color development properties.

The usage ratio of p-tWt, FA aminophenylindolylphthalide and p-1ts aminophenylindolyl azaphthalide is determined by performance, coloring hue, and topical properties, but p-substituted aminophenylindolylphthalide It is preferable that the derivative content is 30% or more, especially! It is preferable that the coefficient is θ or higher.

Among the p-substituted aminophenylindolyl phthalide and azaphthalide derivatives according to the present invention, μ-substituted aminococo-alkoxyphenylindolphthalide and azaphthalide are preferable from the viewpoint of color development.

The quantum-receptive adduct used in the recording material of the present invention preferably has a phenolic hydroxyl group, such as salicylic acid derivatives, phenol derivatives, and phenol resins. Among these, salicylic acid derivatives are preferred in terms of color development, color hue, and light resistance of color images.

Some examples of phenol derivatives include hexyluda
Hydroxybenzoate, 2,2'-dihydroxybiphenyl,! ,,2-bis(4t-hydroxyphenyl)pronogne(hisphenol A),French,μ'-isopylidenebis(comethylphenol),/,/-bis-
(3-chloro-μm hydroxyphenyl)cyclohexane, /, /-his(3-chloro-q-hydroxyphenyl)-λ-ethylbutane, μ, j′-secondary-isooctylidene diphenol, Q-tert-octylphenol, μ, ≠′-86C-butylidenediphenol, ≠-p-methylphenylphenol, μ.

l'-Isopentylidene diphenol, <c, II'-
lTylcyclohexylidene diphenol 4t14</
-dihydroquine diphenyl sulfide °, /.

goobis-(lLt'-hydroquincumyl)benzene,
/, 3-bis-(j'-hydroquincumyl)benzene,
g, μ'-thiobis(A-1ert-bunaru-3-J thylphenol), ≠, ll'-thi? )” Roxydiphenyl sulfone, hydroquinone monobenzyl ether,
Hiro-hydroxybenzophenone, J, l-dihydroxybenzophenone, polyvinyl to/siloxycarbonylphenol, j, 4L.

≠′-trihydroxybenzophenone, a2. ．． 2'.

da, μ'-de) 7-hydroxy/benzophenone, μ-hydroquine dimethyl phthalate, g-hydroxymethyl benzoate, λ, ≠ 4t/-trihydroxydiphenylsulfone, l,! -Bis-p-hydroxyphenylpentane, /, 6-bis-p-hydroxyphenoxyhexane, q-human 0ro #7 tolyl benzoate, gouhydroquine benzoate α-phenylbenzyl ester, goohydroxybenzoate phenylfurovir, derhydroxy Annika M Fenenal, Hiro-hydroxybenzoic [-p-chlorobenzyl, Hiro-hydroxybenzoic acid-p-methoxybenzyl,
hydroxybenzoic acid benzyl ester, hydroxybenzoic acid-m-chlorobenzyl ester, ≠-hydroquine benzoic acid β-phenethyl ester, q-hydroquine-2/, 4L/-dimethyldiphenyl sulfone, β-phenethyl orseinate, cinnamon mylolycerinate, orceric acid-o-chlorophenoxyethyl ester, 0-ethylphenoxyethyl orcelinate,
0-Phenylphenoxyethyl orcelinate, m, -
Phenylphenoxyethyl orcelinate,! .

Goudihydrox-7benzoic acid-β-37-1-butyl-μ
'-Hydroxyphenoquine ethyl ester, /-t-7
"Chi-Q-p-hydroxyphenylsulfonyloxybenzene, ≠-N-benzylsulfamoylphenol, 2. Hiro-dihydroxybenzoic [-p~methylbenzyl ester, !, tI-dihydroxybenzoic e-β-phenoquine ethyl ester , co, j-dihydroquine-6-methylbenzoic acid benzyl ester, bis-μm methyl hydroxyphenylacetate, ditolylthiourea, μ, Hiro'-
Examples of phenolic resins include diacetyldiphenylthiourea, p-substituted phenol formaldehyde, p-substituted phenol formaldehyde, and pi-substituted phenol/acetylene jugetsu. Particularly preferred salicylic acid derivatives are those having 73 or more carbon atoms, or -/♂-disubstituted salicylic acid derivatives and metal salts thereof. The substituent of the salicylic acid derivative has carbon number/~7.
It may have a substituent having 2 alkyl groups, an aralkyl group having 7 to 20 carbon atoms, and 1 to 0 carbon atoms. Examples include alkoxy groups and halogen atoms.

Some examples include 3-phenylsalicylic acid, 3-cyclohexylsalicylic e, J + ! - tertiary butylsalicylic acid, 3. ! -didedecylsalicylic acid, 3
-Methyl-j-benzylsalicylic acid, 3-phenyl-j
-(α,α-dimethylbenzyl)salicylic acid, 3. ! −
Di(α-y'fkbenzyl)salicylic acid, J,j-dicyclohexylsalicylic acid, μm Dodecyloxysalicylic acid, Hiro-octadecyloxysalicylic acid, Goubenzyloxysalicylic acid, Gu β-phenethyloxysalicylic acid, μm β-phenoxyethoxysalicylic acid, μm (
4A-phenoquinbutoxy) salicylic acid,! −(p′−
α'-Methylbenzyl-p-α-methylbenzyl)salicylic acid, Hiro-β-p-)lyloxyethoxysalicylic acid, β-p-methoxyphenoxyethoxysalicylic acid, μmβ-p-butylphenoxyethoxysalicylic acid, etc., and these Examples include metal salts (eg, zinc salts, aluminum salts, calcium salts, etc.). These may be used alone or in combination.

The recording material according to the present invention is composed of a combination of a specific electron-donating colorless dye and an electron-accepting compound, and the colored dye is significantly more stable and long-lasting than dyes produced from existing color formers. It is particularly advantageous in terms of long-term preservation of records, as it hardly changes color or fades even when exposed to light, heat, or humidification over time.

In the recording material according to the present invention, p-substituted aminophenylindolylphthalide and p-substituted aminophenylindolyl azaphthalide are already well-known triphenylmethane phthalide-based compounds, fluoran-based compounds, and phenothiazine-based compounds. It is also possible to assemble a recording material by using it in combination with various compounds such as fluorene-based compounds, leuco-olamine-based compounds, rhodamine-lactam-based compounds, triphenylmethane-based compounds, triazene-based compounds, and spiropyran-based compounds.

In this case, it is desirable to use the colorless dye of the present invention in an amount of 20% or more in order to improve properties.

Regarding these existing colorless dyes, for example, specific examples of phthalides include U.S. Reissue Patent No. 02, U.S. Pat.
．． Data/, //// issue, same 3. Tateri/, No. 772, 3.
Data/, //1 No. 3°10, No. 77μ, specific examples of fluorans are US Patent No. 3. tco≠, No. 107, same 3,
No. 427,717, J, 4≠/, 0//, J, I
I4.

rar No. J, At/, No. 390, No. 3. 20.1
No. 10, same 3. Rij? ,! No. 77, specific examples of spiropyrans are given in U.S. Patent No. 3. 7/, rOr, etc. Some examples of these include triarylmethane compounds such as 3゜3-bis(p-dimethylaminophenyl)-1-dimethylaminophthalide, 3-bis(p-dimethylaminophthalide), and 3-bis(p-dimethylaminophthalide).
□-dimethylaminophenyl) phthalide, etc., and examples of the nylmethane compounds include ≠, ri'-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl-leucoolamine, N-, z.

xanthine-based compounds include rhodamine-B-anilinolactam, 3-diethylamino-7, r-benzofluorane, rhodamine (p-nitroanilino)lactam, and rhodamine B (p-nitroanilino)lactam. -chloroanilino)lactam, co-anilino-t-diethylaminofluorane, co-anilino-6-diethylaminofluorane, -mono-anilino-3-methyl-bu-diethylaminofluorane1.
2-7 Nilino 3-methyl-J-N-cyclohexyl N
-methylaminofluorane, 2-o-chloroanilino-
4-diethylaminofluorane, --m-chloroanilino-t-diethylaminofluorane, co(3,gage chloroanilino)-t-diethylaminofluorane, co-octylamino-6-diethylaminofluorane, --
monodihexylamino-4-diethylaminofluorane,
co-+2 +2- -m-)lifchloromethylanilino-t-diethylaminofluorane, -1butylamino-3-chloroo-4-diethylaminofluorane, no-ethoxyethylamino-3
-chloro-t-diethylaminofluorane, co-chloroanilino-3-methyl-t-dibutylaminofluorane, co-anilino-3-methyl-bu-dioctylaminofluorane, -mono-anilino-3-chloro-t-diethylaminofluorane, co-phenylamino-6-diethylaminofluorane, co-anilino-3-methyl-6
-β-diphenylaminoethylaminofluorane, -1-phenyl-6-dietheraminofluorane, co-anilino 3-methyl-4-N-ethyl-N-isoamylaminofluorane, -1-anilino 3-methyl! -Chloro-t-diethylaminofluorane, co-anilino 3-
Methyl-t-diethylamino-7-methylfluorane,
co-anilino-3-methoxy-4-dibutylaminofluorane, j-o-chloroanilino-6-dibutylaminofluorane, 2-p-chloroanilino-3-pentadecyl-4-N-ethyl-N-isoamylaminofluorane, 2-o -chloroanilino-+-p-butylanilinofluorane, noanilino-3-pentadecyl-t-diethylaminofluorane, coanilino-3-ethyl-6
-Cyptylaminofluorane, -1anilino-3-methyl-a',t'-dichlorofluoran, etc. Examples of indolyl heptathalidated adducts include 3,3-bis(/-enal-comethylindole- 3-yl)phthalide, 3,
3-bis(/-octyl-m-methylindole3-
yl) phthalide, etc., and examples of fluorene compounds include 3/, 4/-bisdiethylamino-! -diethylaminospiro(isobenzofuran-7,ri'-fluorene)-
3'-one 3/, 4/-bisdiethylamino-y-dibutylaminospiro(isobenzofuran-/, 2'-fluorene)-3'-o/, 3', t-bis-dibutylamino-! -diethylaminospiro (isohensifuran-
/,ri'-fluorene)-3'-one,3/,t,! −
Bis-N-ethyl-N-ynamylaminospiro(isobenzofuran-/,?'-diphenoxyethylamino!-fluorene)-3'-one, etc., and thiazine compounds include benzoylleucomethylene blue, p
-Nido-abenzoylleucomethylene blue, etc., and spiro compounds include 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3,3
'-Cyclolosespiro-dinaphthopyran, 3-benzylspiro-dinaphthopyran, 3-methyl-naphtho-(3-
Methoxy-benzo)spirothiapyran, 3-propyl-
Examples include spiro-dibenzopyran.

When applied to these colorless dyes and electron-accepting dues recording materials, they are used in the form of fine dispersions or fine droplets.

When used with pressure sensitive paper, U.S. Patent No. 10j, ≠7
No. 0, same, jOj, ≠ No. 77, same, 2°! O! ,≠l
ri number, same number, t4'f, jA number, same, 7/ko, 107
No. 2,730.4t No. 37 Same, 730. Hiro! No. 7, same! , 103. No. 4t-+27-, same 3. II/r, No. 2!0, II, 010,03
It takes various forms as described in prior patents such as No. R. Most commonly, it consists of at least one pair of sheets separately containing a ii) donor-donating colorless dye and an electron-accepting compound.

For the method of manufacturing capsules, see US Pat.
Method using coacervation of hydrophilic colloid sol described in No. 4Az'y, A, too, art, British Patent No. 7,727, same to, ≠ da 3, same t , J4μ issue, same/.

The interfacial polymerization method described in OP/, No. 074, etc. or US Patent No. 3. There is a method described in the io3.4too issue.

In general, electron-donating colorless dyes are used alone or in combination as solvents (alkylated naphthalene, alkylated diphenyl, alkylated diphenylmethane, alkylated terphenyl, alkylated terphenyl, etc.).
Synthetic oils such as chlorinated paraffin; Vegetable oils such as water cotton oil and castor oil; Animal oils; Mineral oils or their mixtures, etc.)
After dissolving this in microcapsules, paper, high-quality paper,
The color former sheet is hung by coating it on a support such as a plastic sheet or resin-coated paper. Neutral paper is particularly preferred as the support.

In addition, the electron-accepting additives described below, alone or in combination, or together with other electron-accepting compounds, are dispersed in a binder such as styrene-butadiene latex or polyvinyl alcohol, and the pigments described below are used in paper, plastic sheets, etc. 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.

When used in thermal paper, the electron-donating colorless dye and the electron-accepting compound are pulverized and dispersed in a dispersion medium to a particle size of IOμ or less, preferably 3μ or less. As a dispersion medium, generally 0. A water-soluble polymer aqueous solution having a concentration of about 10 to 10% is used, and dispersion is carried out using a ball mill, a sand mill, a horizontal sand mill, an attritor, a colloid mill, or the like.

The ratio of the electron-donating colorless dye used to the electron-accepting compound is preferably between l:10 and /:l, and even /:! and Koni 3 are particularly preferred. that time,
Nitrogen-containing organic compounds such as fatty acid amide, stearamide, acetoacetanilide, diphenylamine, penzamide, carbazole, etc.
Rylbutane, 0-fluoropenzoyldielene, phenyl/hydroxyconaphthoate, chlorobenzoylmesitylene, 44.44'-dimethylbiphenyl, or dimethyl isophthalate, diphenyl phthalate,
Carboxylic acid esters such as dimethyl terephthalate, methacryloxybiphenyl, etc., or ether compounds such as di-m-)lyloxyethane, β-naphthol benzyl ether, β-phenoxyethyl tosylate, β-phenoxyethoxyanisole, l-phenoxyno-p- Ethylphenoxyethane, bis-β-(p-
methoxyphenoxy)ethoxymethane, /-1'-methylphenoxy-λ, tI/-ethylphenoxyethane/,
/-tolyloxy-col-methylphenoxyethane,
/, J-diphenoxyethane, /.

≠-diphenoxybutane, bis-β-(p-ethoxyphenokidi)ethyl ether, /-phenoxy-2-p-
Chlorophenoxyethane, /-λ'-methylphenoxy J -a''-ethyloxyphenoquinoethane, /-
! , t/-methylphenoxy2-≠-fluorophenoxyethane, which has a melting point of 7z'C to 730°C, is preferably used in combination with the colorless dye or at the same time as the electron-accepting compound. They are used in a dispersed form.In particular, it is preferable to disperse them at the same time as a colorless dye from the viewpoint of preventing fogging.These are added at a weight ratio of 20% to 300% of the Id-accepting proboscis. and sometimes it is preferable that ≠04 or more/jO=4 or less.

The ffl'd thus obtained is further supplemented with additives in order to meet the requirements of the company.

- Kota - Examples of additives include dispersing oil-absorbing substances such as inorganic pigments and polyurea fillers in the binder in order to prevent the recording head from becoming dirty during recording. Fatty acids, metal soap, etc. are added to improve moldability. Therefore, in addition to colorless dyes and electron-accepting compounds that directly contribute to color development, additives such as pigments, waxes, antistatic agents, ultraviolet absorbers, antifoaming agents, conductive agents, fluorescent dyes, and surfactants are used. is applied onto the support to constitute the recording material.

Specifically, pigments include kaolin, calcined kaolin, talc, lead oxide, diatomaceous earth, calcium carbonate, aluminum hydroxide, magnesium oxide, calcined gypsum, silica, magnesium carbonate, titanium oxide, alumina, barium carbonate, and sulfuric acid. Barium, mica, microballoon, urea-formalin filler, polyethylene particles, cellulose filler, etc. particle size 0. /Naishi/! Selected from μ. Waxes include Nomurafine wax, carboxy-modified paraffin wax, Karte = 30
- Examples include upa wax, microcrystalline wax, polyethylene wax, and higher fatty acid esters.

Examples of the metal soap include polyvalent metal salts of higher fatty acids, ie, zinc, aluminum, and calcium salts of stearic acid, and zinc oleate.

The hindered phenol is at least λ or 4
A phenol derivative in which seven or more positions are substituted with a branched alkyl group is preferred.

For example, /, /-bis(-monomethyl-[mu]mhydroxy-z-t-methylphenyl)methane, l.

/, J-) Lis(3-methyl-Hiro-hydroxy-z-t
--1tylphenyl)methane, bis(,2-hydroxy-Jt-methyl-j-methylphenyl)methane, bis(,2-methyl-4-hydroxyj-1-butylphenyl)sulfide, and the like.

Examples of ultraviolet absorbers include cinnamic acid derivatives, benzophenone derivatives, benzotriazolylphenol derivatives, such as α-cyano-β-phenylbutyl cinnamate, 0-benzotriazolylphenol, 0-benzotriazolyl-p- Chlorophenol, O-penzotriazolyl, dibutylphenol, O-benzotriazolyl-
Examples include p-10 lophenol. Among these, benzotriazole phenol derivatives are particularly preferred.

These materials are also detailed in the patents mentioned above.

These are dispersed and applied in a binder.

Water-soluble binders are generally used, such as polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, epichlorohydrin-modified polyamide, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, isobutylene-maleic anhydride. Examples include copolymers, polyacrylic acid, polyacrylic acid amide, methylol-modified polyacrylamide, starch derivatives, casein, and gelatin. In addition, in order to impart water resistance to these 2-inders, water-resisting agents (gelling agents, cross-meriting agents) are added, and emulsions of hydrophobic polymers, specifically styrene-butadiene rubber latex, acrylic @ It is also possible to add H emulsion or the like. The coating liquid is applied to base paper, high-quality paper, attached paper, plastic sheet, or neutral paper for a distance of about 2 to 1097 m.

Further, on the surface of the coating layer, a water-soluble or water-dispersible polymer such as polyvinyl alcohol, hydroxyethyl starch, or Evochishi-modified polyacrylamide and a crosslinking agent are added. It is also possible to provide a 2μ barrier layer to improve resistance.

When used for thermal paper (Nimata 0LS2221'Jr1
No. λ/101r! It incorporates various aspects described in Japanese special issues such as No. Alternatively, operations such as preheating, humidity control, or abrasion of the coated paper may be added prior to recording.

4-electric thermal paper is manufactured by the method described in, for example, Japanese Patent Application Laid-Open No. 31114, TO-T, Tryso, etc. The basic dye mainly consisting of the fluoran derivative of the present invention and the electron-accepting compound dispersed together with a binder are coated on a support such as paper, or conductive material is coated on the support to make it conductive. form a layer,
The electrothermal sensitive material A of the present invention is produced by coating thereon a coating liquid in which a colorless dye, a Naruko-receptive material string, and a binder are dispersed. Note that the above-mentioned thermofusible substance can also be used in combination to achieve the same rt.

For example, the light-sensitive and pressure-sensitive paper is disclosed in Japanese Patent Application Laid-Open No. 7-7913.
It is produced by the method described in Japanese Patent No. 7353. In general, a photopolymerization initiator such as silver iodobromide, silver bromide, silver behenate, Michler's ketone, benzoin 84, benzophenone derivative, etc. and a polyfunctional monomer such as polyallyl, poly(meth)acrylate, divinylbenzene, poly(meth)acrylamide A crosslinking agent, such as, is encapsulated in a synthetic resin wall capsule such as polyether urethane, polyurea, etc. together with a colorless dye and optionally a solution 41. After imagewise exposure, the colorless dye in the unexposed area is brought into contact with a color developer to display the color.

The initiator and the mode of use for this method are detailed in Japanese Patent Application Laid-open No. 6 No. 1983.

-3μ - The electron-donating colorless dye according to the present invention is synthesized by the following method. For example, a corresponding substituted benzoylbenzoic acid or fiL benzoylpyridinecarboxylic acid and an indole, or a corresponding carboxybenzoylindole or carboxypyridinecarbonylindole and an aniline derivative in the presence of a condensing agent such as acetic anhydride or phosphorus oxychloride, If necessary, use a volatile inert solvent such as chloroform, benzene, benzene chloride, or ethyl acetate.
! After the reaction is carried out for 70 to 10 minutes at a temperature of O to lg o 'C, the reactants are placed in ice water to hydrolyze the condensing agent, the above volatile inert solvent is added, and an inorganic base such as aqueous ammonia is added. The mixture is made alkaline with an aqueous sodium hydroxide solution, the solvent layer is separated, and the solvent is distilled off under reduced pressure or by steam distillation. Preferably, m
- A method of reacting a dialkylaminophenol derivative with carboxybenzoylindole or carboxypyridinecarbonylindole.

For the reaction method, known methods can be applied, for example, JP-A-47-
/4. The reaction conditions are also disclosed in No. r444L or No. t/-/rij/44 (No.

(Examples of the Invention) Examples are shown below, but the present invention is not limited to these examples.

Examples 1 to 4 ■ Preparation of color developer sheet Table 1 shows fl:,'#! 1. Child-accepting compound 1O part/-isopropylphenyl-λ-phenylethane 20
Add to volume and dissolve next. This is a polyvinyl alcohol aqueous solution! Part O, and 0.7 part of a 70% aqueous solution of triethanolamine salt of dodecylbenzenesulfonic acid were mixed and emulsified so that the average particle size was 3 μm.

Next, a dispersion consisting of 10 parts of calcium carbonate, 20 parts of oxidized lead, 7 parts of sodium hexametaphosphate, and 200 parts of water was mixed with the above emulsion, and 100 parts of 70% PVA aqueous solution M was added as a binder. and carboki 7 modified 8B
I (Latin 2 Fufu 0 part (as solid content)) was added and water was added so that the solid content concentration became 0% to obtain a coating liquid (A).

Next, a dispersion consisting of 10 parts of the color developer, 0 parts of Jilton clay, to parts of calcium carbonate, 20 parts of zinc oxide, 200 parts of sodium hexametaphosphate, and 200 parts of water was ground to an average particle size of 3 μm using a sand grinder. dispersed into

lt parts of 10*PVA aqueous solution and 10 IPVA in the Kono dispersion.
Add 1 DO part of aqueous solution and IO part of carboxy-modified SBB latex (as solids) to achieve a solids concentration of 20%.
Water was added to obtain a coating liquid (B).

Mix the coating liquid (A) and the coating liquid (B) at 7 pairs per color developer, and! 09/m2 base paper! , of/m'' of solid content was coated using an air knife coater and dried to obtain a color developer sheet.

■ Preparation of capsule sheet containing coloring agent Partial sodium salt of polyvinylbenzenesulfonic acid (National Starch Co., Ltd. H1VER8A, T Lzoo
) Part Z with hot water P! After dissolving in a portion, cool it.

Add an aqueous sodium hydroxide solution to this to give a pH of 4t.

It was set as O. On the other hand, the coloring agent shown in Table 7 was added to 3. ! Dissolve 100 parts of diisopropylnaphthalene into some of the sodium salt of polyvinylbenzenesulfonic acid! Aqueous solution 1
Emulsified and dispersed in 00 parts to have a diameter μ.

An emulsion with a particle size of 0μ was obtained. Separately, melamine part, 37 parts by weight formaldehyde aqueous solution/1 part, water 3 parts.
After 30 minutes, a transparent aqueous solution of melamine, formaldehyde and melamine-formaldehyde initial condensate was obtained.

This aqueous solution was mixed with the above emulsion. While stirring, the pH was adjusted to O with an aqueous phosphoric acid solution, the temperature of the solution was raised to 4j'C, and stirring was continued for 4 hours. This capsule solution was cooled to room temperature, pHed with an aqueous sodium hydroxide solution, and combined with O.

To this dispersion, 200 parts of a 10% polyvinyl alcohol aqueous solution and 10 parts of starch particles were added, and water was added to adjust the solid concentration of the microcapsule dispersion and a 20% coating solution.

This coating liquid! Of/? zt7 on the Fl base paper
Air knife coater 3 so that the solid content of m” is coated.
It was coated and dried at r- to obtain a color former-containing capsule sheet.

When the thus prepared color forming agent and the color developer sheet were brought into contact with each other and pressure or impact was applied, an impression of evening color was instantaneously obtained. The results of the light fastness test of this image are shown in Table 1.

Comparative Examples 1 and 2 The electron-donating colorless dye and the electron-accepting compound in Example 1 were changed to the compounds shown in Table 1, and the color was developed and the light resistance test was conducted in the same manner as in Example 1.

The results are shown in Table 1.

[Colored body lightfastness test]

The colored body was irradiated with light of 32,000 lux for 70 hours, and the color density before and after irradiation was compared to determine the residual rate.

-3ter- Example 5 30% o-(p) for the electron-donating colorless dye of Example 1
-Chlorobenzotriazole), λ,≠-dibutylphenol was added to develop a color in the same manner and a light fastness test was conducted, and the residual rate of the color former was over t00 parts.

Example 6 3-(≠-diethylamino-coethoxyphenyl)-
3-(/-ethyl-2-methylindol-3-yl)
20 parts of phthalide, 70 parts of 3-(dardiethylamino-coethoxyphenyl)-J-(/-n-octyl-2-methylindol-3-yl)-μ- or -7-azaphthalide, and 70% polyvinyl of ljO parts. A dispersion liquid was prepared by grinding an aqueous alcohol solution and 70 parts of water in a ball mill for 1 hour. The particle size after milling was approximately 1.1 microns. (Component A) IO tipolyvinyl alcohol aqueous solution of 30 parts of zinc-β-(p-methoxyphenoxy)ethoxysalicylate, 30 parts of cobenzyloxynaphthalene ItO, on the other hand;
Mix and grind the mixture with 33 parts of water using a sand mill to prepare a dispersion. The particle size of the insoluble material after pulverization was approximately 2 microns. (Component B) Next, 3 parts of Component A and 3 parts of Component B were mixed, applied to paper, and dried to obtain thermal paper.

This thermal paper turns blue when heated with a heat pen, etc. The resulting nine-color image was very stable against light, and even when the image was irradiated with an ultraviolet lamp for 7 hours, there was almost no change in hue or density.

Claims (1)

[Claims] In recording materials that utilize color development through contact between an electron-donating colorless dye and an electron-accepting compound, p-substituted aminophenylindolyl phthalide derivatives and p-substituted aminophenylindolyl phthalide derivatives are used as the colorless dye.
A recording material characterized in that it uses a substituted aminophenylindolyl azaphthalide derivative.