JPS63158287A - Recording material - Google Patents

Abstract

PURPOSE:To improve color development, preservability and stability of color- developed images and also give liquid preparation aptitude by using a specific phthalide compound as an electron donor colorless dye. CONSTITUTION:For instance, a compound is such as shown by the formula I. Five g of electron donor colorless dye dispersed solution containing 80% of 3-(4-diethylamino-2-3', 6'-dioxaoctyloxyphenyl)-3-(1-ethyl-2-methylindol-3-il) phthalide, 10g of electron receptor compound dispersed solution, 5g of thermally soluble material dispersed solution and 229 of baked kaolin and zinc oxide dispersed solution are mixed. In addition, 4g of zinc stearate emulsion and 55g of aqueous 2% (2-ethylehexyl) sodium sulfosuccinate solution are added to prepare a coating solution. If the color of the coated solution-applied paper is developed using a facsimile, a black image is obtained which is of high density and highly light-fast and heat-resistant. Further, this image absorbs light in a near infrared area. In the formula (I), R1 represents the polyoxialkylene group, R2-R10 hydrogen atoms, halogen atoms, the alkyl groups, alkoxy group, substituted amino group or aryl group, and R7, R8 and R9, R10 may form a ring by coupling each other.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of the Invention) The present invention relates to recording materials, and in particular to an electron-donating colorless dye that has improved color development, raw storage stability, and stability of colored images, and has also been imparted with liquid preparation suitability. and recording materials using electron-accepting compounds.

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

For example, British Patent No. 1ltAou9r, U.S. Patent No. 1suori No. 2, U.S. Patent No.
．． ? JJ issue, JP-A-Shoj7-/79. f36, same 40-
/23. jJ', No. 1.0-/23.557, etc. for details.

The performance that a recording material should have is (I) 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)
It has a high S/N ratio, (6) the color former has sufficient chemical resistance, and (7) it is easily soluble in organic solvents with a certain percentage, but currently there is no product that satisfies these requirements. Not yet.

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.

(Object of the Invention) Therefore, the object of the present invention is to provide a recording material using a material that has good color development properties, good shelf life, and stability of colored images, and has good suitability for liquid preparation, and also satisfies other necessary conditions. The goal is to provide the following.

(Structure of the Invention) The object of the present invention is to produce an electron-donating colorless dye of the following general formula (
This was achieved by a recording material characterized by using the compound shown in I).

In the above formula, R is a polyoxyalkylene group, R2 to RIO are hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups,
In the substituted amine group or aryl group, R7 and R8 and Ro and RIG may be bonded to each other to form a ring.

In addition, 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 norogen atom, a nitro group,
It may have a substituent such as a cyano group, a substituted carbamoyl group, a substituted sulfamoyl group, a substituted amine group, a substituted oxycarbonyl group, a substituted oxysulfonyl group, or an aryl group.

Further, the alkyl group represents a saturated or unsaturated alkyl group or 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.

In the above formula, R1 is a polyoxyalkylene group such as Ra
Ra represents the group shown.

Ra1Rb represents an alkyl or aryl group, and n represents an integer of λ to t.

Among the substituents represented by R2, R3, and R4, hydrogen atoms,
Alkyl groups, acyl groups or aryl groups having 1 to 1 carbon atoms are preferred, and these are substituted with halogen atoms, alkoxy groups, aryl groups, aryloxy groups, acyl groups, cyano groups, pyridyl groups, furfuryl groups, etc. Good too.

R3 and R2 are bonded to each other to form a yellow to t-membered ring, such as piperidi/, morpholine, pyrrolidine, piperazine,
A ring such as hexamethyleneimine or caprolactam indole may be formed.

no group, morpholino group, N-phenylpiperidino group, N-
Ethylpiperidino group, diethylamino group, dipropylamine group, dibutylamine group, N-ethyl-N-inbutylamino group, N-ethyl-N-inamylamino group, N
-Ethyl-N-cyclohexylamino group, cyamylamino group, diethylamino group, dioctylamino group, N-ethyl-N-tetrahydrofurfurylamino group, and the like.

Among the substituents represented by R5 and R6, hydrogen atoms, alkoxy groups having 1 to 3 carbon atoms, aryl groups having 6 to 10 carbon atoms, aryloxy groups, chlorine atoms and fluorine atoms, number of carbon atoms /, /, The alkyl group and substituted amino group of 2 are preferred.

R5 is particularly preferably a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

R and R8, Ro and RIO may be bonded to each other to form a ring, in which case the heteroatom is an oxygen atom,
An aromatic ring which may contain one or more nitrogen atoms or sulfur atoms is preferred. The aromatic ring may have a substituent as mentioned above for R or R2, an N-substituted carbamoyl group, an alkoxycarbonyl group, etc.

Particularly preferred are optionally substituted benzene rings, pyridine rings and piperazine rings.

The general formula of a preferred compound is as follows.

R1-2 and R13 are hydrogen atom, halogen atom, alkyl group, alkoxy group, aryl group, aryloxy group, carbamoyl group, substituted amino group, acyl group, alkanesulfonyl group, alkoxycarbonyl group, nitro group, cyano group, dialkyl group A substituent selected from amino groups etc.,
, Y is preferably a carbon atom at the meta position.

The electron-donating colorless dye according to the present invention has the advantage of being colorless to light-colored crystals, having high solubility in organic solvents (and rapidly developing color when it comes into contact with an electron-accepting substance).

The developed dye is significantly more stable than dyes produced from existing color formers, and hardly changes color or fades even when exposed to light, heat, or humidification over long periods of time, making it particularly advantageous in terms of long-term preservation of records. . In addition, the coloring agent has excellent stability and does not change in quality or color even after long-term storage, and has sufficient coloring ability, which is close to the ideal performance as a coloring agent for recording materials such as pressure-sensitive paper and thermal paper. has.

Representative examples of the electron-donating colorless dye according to the present invention include:
The following compounds are mentioned.

j-(4C-diethylamino!'-phenoxy-
3'-oxapentyloxyphenyl)-j-(/-ethyl-comethylindol-3-yl)phthalide, j
-(4L-diethyl-cott'-benzyloxy-3'
-oxapentyloxyphenyl)-J-(/-ethyl-2-methylindol-3-yl)phthalide, J-(
4! -diethylamino-2-31, A/ -dioxyoctyloxyphenyl)-J-(/-ethyl-2-methylindol-3-yl)phthalide, 3-(l-diethylamino-2-2/, 11-dimethyl -t'-phenoxy-3'-oxapentyloxyphenyl)-3-(
/-n-octyl-comethylindol-3-yl)
Phthalide, 3-(≠-dibutylamino, 2-j',
A'-dioxadecyloxyphenyl>-3-<t-
phenyl-comethylindol-3-yl)phthalide, j-(4(-diethylamino-2-r'-p-ethylphenoxy-31,41-dioxaoctyloxyphenyl)-J-(/-butyl-2- phenylindol-3-yl)phthalide, J-(4cm diethylamino-
2-11,tAl-dimethyl-t'-p-nonylphenoxy-3'-oxaintyloxyphenyl)-3-(
/-fi-propyl-2-methylindol-3-yl)-≠- or -7-azaphthalide, J-(4(-diethylaminocor!'-cumylphenoxy-3'-oxapentyloxyphenyl)-j -(/-benzyl-2-
methylindol-3-yl)-ψ,7-diazaphthalide, J-(u-diethylaminol-31,41,ri'
-trioxadecyloxyphenyl)-3-(/-ethyl-comethylindol-3-yl)phthalide, and the like.

In addition, these colorless dyes are already well-known triphenylmethane phthalide compounds, fluoran compounds,
When recording materials are used in combination with various compounds such as phenothiazine compounds, intriazal 7-thallide noncompounds, leucoauramine compounds, rhodamine lactam compounds, triphenylmethane compounds, triazene compounds, spiropyran compounds, and fluorene compounds, It can also be created.

In this case, it is preferable to use the above colorless dye in an amount of 20% or more from the viewpoint of improving properties.

Regarding these various existing colorless dyes, for example, specific examples of phthalides are U.S. Reissue Patent λ3.
Same 3. ψrii, tt(, issue, same 3, !Ori, 77μ issue,
Specific examples of fluoranes include U.S. Patent No. 3.62μ, No. 107, U.S. Pat.
Same 3. ≠≦, No. 2,121, same j, tri, Jri No. 0,
Same 3 degrees λ0. ! r10, same 3. Rijri, No. 371,
Specific examples of spirodipyrans are given in U.S. Patent 3. ri7/.

Rot No., pyridine-based and pyrazine-based compounds are approved in the United States *77r, u, zu, 3. l
r! J.

R6R, U.S. Patent μ, 2μ&, JIr, etc. Some examples of these include triarylmethane compounds such as 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-bis(
p-dimethylaminophenyl) phthalide, j-(p-dimethylaminophenyl)-J-(/, J-dimethylindol-3-yl) phthalide, 3-(p-dimethylaminophenyl)-J-(2-methyl indol-3-yl) phthalide, etc., and diphenylmethane compounds include μ,4L'-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl-leucoolamine, N-2,μ,j-tri There are chlorophenyl leuco auramines, etc., and xanthine compounds include rhodamine-B-anilinolactam, 3-diethylamino-
7, 1-benzofluorane, rhodamine (p-nitroanilino)lactam, rhodamine B (p-chloroanilino)lactam, 2-dibenzylamino-t-diethylaminofluorane, co-anili/-A-diethylaminofluorane, co-anilino 3-methyl -6-Dinithylaminofluorane, Coa-2IJ/+, 3-methyl-4-N-cyclohexyl N-methylaminofluorane, 2-〇-dichloroanilino-6-dinithylaminofluorane λ-m − Chloroanilino-6-diethylaminofluorane, 2-(3,ψ-dichloroanilino)-4
-diethylaminofluorane, co-octylaminot
-diethylaminofluorane, 2-dihexylamino-
6-diethylaminofluoran, λ-m-trifluoromethylanilino-t-diethylaminofluoran, coptylamino-3-chloro-6-diethylaminofluoran, coethoxyethylamino-3-chloro-6-diethylaminofluoran , λ-p-chloroanilino 3-
Methyl-6-sibutylaminofluorane, λ-anilino-3-methyl-4-dioctylaminofluorane, no-anilino-3-chloro-6-dinithylaminofluorane, -1-diphenylamino-6-dinithylaminofluoran/ , λ-anilino 3-methyl-AB-diphenylaminoethylaminofluorane, λ-phenyl-6-dinithylaminofluorane, λ-anilino 3-methyl-6
-N-ethyl-N-isoamylaminofluorane, λ-
Anilino 3-methyl-1chloro-6-dinithylaminofluorane, co-anilino 3-methyl-4-diethylamine-7-methylfluorane, co-anilino 3-
Methoxy-6-cyptylaminofluorane, co-0-chloroanilino-6-cyptylaminofluorane, λ-p
-chloroanilino 3- is phtadecyl-4-N-ethyl-N-isoamylaminofluorane, 2-〇-chloroanilino+-p-butylanilinofluoran, co-anilino 3-pentadecyl-6-diethylaminofluorane, 2-anilino-3-ethyl-6-sibutylaminofluorane, λ-anilino 3-methyl μ',! '-Dichlorofluoran, etc., and indolyl phthalide compounds include 3.3-bis(l-ethyl-λ-methylindol-3-yl)phthalide, 3.3-bis(l-octyl-λ- Methylindol-3-yl) phthalide, J-(
2-Ethoxy-μm diethylaminophenyl)-J-(
/-Ethyl-cotatylindol-3-yl)phthalide, 3-(2-nitoxy-μm dibutylaminophenyl)-! -(/-Ethyl-1-methylindol-3-yl)phthalide, 3-(coamyloxidadethylaminophenyl)-3-(l-ethyl-λ-methylindol-3-yl)phthalide, J- (2-ethoxy-4
-diethylaminophenyl)-J-(/-octyl-2
-methylindol-3-yl)phthalide, etc., and pyridine compounds include 3-(2-nitoxy-4C-
diethylaminophenyl)-j-(/-octyl-nomethylindol-3-yl)-μ or 7-azaphthalide, J-(J-ethoxy-buddha-diethylaminophenyl)-j-(/-ethyl-nomethylindole- 3-yl)-buddha or 7-azaphthalide, J-(J-hexyloxy-≠-diethylaminophenyl)-J-(/-ethyl-comethylindol-3-yl)-4' or cuaza7thalide, 3- (coethoxyq-diethylaminophenyl)-j-(/-ethyl-2-7eleindol-3-yl)-μ or 7-aza7talide, 3-(λ
-Butoxy≠-diethyl7/phenyl)-J-
(/-ethyl-λ-phenylindole-3-yl)-
μ or 7-azaphthalide, J-(J-ethoxyderjethylaminophenyl)-3-(/-octyl-cophenyly/dol-3-yl)-ly or 7-azaphthalide, etc., and as fluorene compounds. is 3'.

t'-bisdiethylamino-! -diethylaminospiro(isobenzofuran-l,ri'-fluorene)-3-one, 3/,4/-bisdimethylamino-! -dibutylaminospiro(isobenzofuran-7,ri'-fluorene)-3-one, 3'.

6'-bisdibutylamino-! -diethylaminospiro(isobenzofuran-1,ri'-fluorene]-3-one, 3',A'-bis-N-ethyl-N-yneamylaminospiro(isobenzofuran-/, ta'-diphenoxyethylamino) -!-fluorene)-3-one, etc., azine compounds include benzoylleucomethylene blue, p-nitrobenzoylleucomethylene blue, etc., and spiro compounds include 3-methyl-spiro-dinaphthopyran, 3-ethyl -spiro-dinaphthopyran, J,j'-cyclospirodinaphthopyran, 3-benzylspiro-dinaphthopyran, 3-methyl-naphtho-(3-methoxy-benzo)spirothiapyran, 3-propyl-spiro-dibenzobilane, etc. .

Electron-accepting compounds that provide color upon contact with colorless dyes include inorganic and organic Lewis and Brønsted acids. Typical examples include phenol derivatives, salicylic acid derivatives, metal salts of aromatic carboxylic acids, acid clay, and bentonite. Specifically, novolak resin,
Metal-treated novolac resin, Hiro-tertiary butylphenol, μm phenylphenol, q-hydroxydiphenoxide, α-naphthol, β-naphthol, hexyl-μm hydroxybenzoate, '+ 2'-dihydroxybiphenyl, 2,2-bis( μm hydroxyphenyl) furonon, 2-) thyl-4c, l-inpentylidene bisphenol, 'tI-bis(3-chloro-μm hydroxyphenyl)cyclohexane, /,
/-bis(3-chloro-μmhydroxyphenyl)-λ
-ethylbutane, da, μ'-secondary octylidene diphenol, 4c, μ'-dihydroxy-3,3
'-Diallyldiphenyl sulfone, 4c, 4'-5ec
-butylidene diphenol, 4(-p-ethylphenylphenol, μ, 2/-le% 1'-methylcyclohexylene diphenol,
μg/-dihydroxydiphenyl sulfite,/
, 4! -bis-(J'-hydroxycumyl)benzene,
i, 3-bis-(l'-hydroxycumyl)benzene,
≠ 4c/-thiobis(A-tert-butyl-3-
Methylphenol), Mu'-dihydroxydiphenyl sulfone, hydroquinone monobenzyl ether, 4
C-hi)”.

xybenzophenone, 2.4C-dihydroxybenzophenone, polyvinylbenzyloxycarbonylphenol, co, French, ≠′-trihydroxybenzophenone,
2.2', ≠, μ'-tetrahydroxybenzophenone, ≠-dimethyl hydroxyphthalate, ≠-methyl hydroxybenzoate, co.

4C,4C'-)IJ hydroxydiphenyl sulfone,
l,! -bis-p-hydroxyphenylpentane, /,
4-bis-p-hydroxyphenoxyhexane, ≠-tolyl hydroxybenzoate, μm hydroxybenzoic acid α-
Phenylbenzyl ester, phenylpropyl hydroxybenzoate, μm phenethyl hydroxybenzoate,
μm hydroxybenzoic acid-p-chlorobenzyl, μm hydroxybenzoic acid-p-methoxybenzyl, ψ-hydroxybenzoic acid benzyl ester, μm hydroxybenzoic acid-m-chlorobenzyl ester, l-hydroxybenzoic acid! ! 1β-phenethyl ester, μm hydroxy-2
Z4L/-dimethyl diphenyl sulfone, β-phenethylorselinate, cinnamyl oliselinate, orserinic acid-〇-chlorophenoxyethyl ester, 0-ethylphenoxyethyl orselinate, O-phenylphenoxyethyl orselinate, m- Phenylphenoxyethyl orseinate %'l''-dihydroxybenzoic acid-β-3'-1-butyl-μ'-hydroxyphenoxyethyl ester, /-j-butyl-μmp-hydroxyphenylsulfonyloxybenzene, μmN-benzyl sulfate Famoylphenol %'l''-dihydroxybenzoic acid-p-methylbenzyl ester, co-, hiro-dihydroxyan, 1L fragrant acid-β-phenoxyethyl ester,
2. Dartz hydroxy-6-methylbenzoic acid benzyl ester, bis-μm methyl hydroxyphenylacetate, ditolylthiourea, μ, Hiro'-diacetyldiphenylthiourea,! -α-ethylbenzylsalicylic acid, 3-phenylsalicylic acid, 3-cyclohexylsalicylic acid, 3
．． j-di-tert-butylsalicylic acid, 3. Taj-
Dodecylsalicylic acid, 3-methyl-benzylsalicylic acid, 3-phenyl-! -(α,α-dimethylbenzyl)salicylic acid, 3. ! -di(α-methylbenzyl)salicylic acid, λ-hydroxy-1-benzyl-3-naphthoic acid,! -hexadecylsalicylic acid,! -Octadecylsalicylic acid,! -α-(p-methylbenzylphenyl)
Ethylsalicylic acid, φ-dodecyloxysalicylic acid, ≠
-tetradecyloxysalicylic acid, μm hexadecyloxysalicylic acid, μm β-phenoxyethoxysalicylic acid, terβ-p-tolyloxyethoxysalicylic acid, co-β-p-ethylphenoxyethoxysalicylic acid, child-
β-p-methoxyphenoxyethoxysalicylic acid, terβ-p-ethoxyphenoxyethoxysalicylic acid, ψ-
β-m-tolyloxyethoxysalicylic acid, μmβ-0
-tolyloxyethoxysalicylic acid, μm (r-phenoxyoctyloxy)salicylic acid, cocarboxylic acid-β-phenoxyethoxy-1-naphthol, 3. ! −
Dicyclopentagenyl salicylic acid! -α-methyl-
Salicylic acid and salicylic acid derivatives such as (p-α-methylbenzyl)benzyl salicylic acid are preferably compounds having a total number of carbon atoms/4C or more from the viewpoint of water insolubility, particularly 16
The above is preferable.

Phenylphenol-salicylic acid-phor-q +) y
Organic color developers such as phenolic resins such as novolac, para-phenylphenol-formalin resin, and phenylphenol-acetylene resin, and also these organic color developers such as zinc, magnesium, aluminum, calcium, titanium, manganese, and tin. , salts with polyvalent metals such as nickel, and hydrohalic acids such as hydrogen chloride, hydrogen bromide, hydrogen iodide, boric acid, silicic acid, phosphoric acid, sulfuric acid,
Inorganic acids such as nitric acid, perchloric acid, halides such as aluminum, zinc, nickel, tin, titanium, and boron, acid clay, activated clay, athanol guide, bentonite,
Colloidal silica, aluminum silicate, magnesium silicate, zinc silicate, tin silicate, rhodan zinc, rhodan zinc-antipyrine complex salt, rhodan zinc-1-phenyl-coptyl-3-methyl-3-pyrazoline-! -one complex salts, zinc chloride, iron stearate, cobalt naphthenate, nickel oxide, inorganic color developers such as ammonium nitrate, aliphatic carboxylic acids such as oxalic acid, maleic acid, tartaric acid, citric acid, succinic acid, stearic acid, Benzoic acid 1. e. One or more of butylbenzoic acid, phthalic acid, gallic acid, etc. is used.

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

For use with pressure sensitive paper, U.S. Patent No. λ, 30, u7
No. 0, same co., jOj, lA7/no., same co.

rot, AT number, same λ, jμt, stt number, same 2.7
/2,107 issue, 2.7 JO, 4c14 issue 2,73
0.4'j7, JIOJuOu, J, it/r
, AjO issue, same uO100J! It can take various forms as described in prior patents such as No. Most commonly they consist of at least one pair of sheets containing separately an electron-donating colorless dye and an electron-accepting compound.

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

No. 100.457, No. 2.1100. A method using coacervation of a hydrophilic colloid sol described in No. 1, British Patent No. 1JL, No. 7,727, 70. $#
J No. 19, 24'1, l'i'iJ/10ri/
, 071. Examples include the interfacial polymerization method described in US Patent No. 3103≠op.

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 cotton oil and castor oil; Animal oils; Mineral oils and mixtures thereof)
After dissolving K and incorporating it into microcapsules,
A color forming agent sheet is obtained by coating it on a support such as paper, high quality paper, plastic sheet, resin coated paper, etc.

Neutral paper is particularly preferred as the support.

In addition, the electron-accepting compounds 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 to produce paper, plastic sheets, and resin-coated paper. A developer sheet is obtained by coating a support such as the following.

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 used in a dispersion medium at a concentration of /θμ or less, preferably 3
It is used after being crushed and dispersed to a particle size of μ or less. As a dispersion medium, generally 0. jt or i.

An aqueous solution of a water-soluble polymer having a concentration of about 10% is used, and dispersion is carried out using a ball mill, a sand mill, a horizontal sand mill, an attritor, a colloid mill, etc.

The ratio by weight of the electron-donating colorless dye to the electron-accepting compound used is preferably between 1:10 and 1:l, and particularly preferably between 1:j and 2:3. In this case, nitrogen-containing organic compounds such as fatty acid amide, stearamide, acetoacetanilide, diphenylamine, penzamide, carbazole, etc. or λ,3-di-m-)lylbutane, 0-fluorobenzoyldurene, l-hydroxy-2- Phenyl naphthoate, chlorobenzoylmesitylene, ≠, 4c'-dimethylpiphenyl, or carboxylic acid esters such as dimethyl isophthalate, diphenyl phthalate, dimethyl terephthalate, methacryloxybiphenyl, etc., or ether compounds such as di-m-)lyloxyethane. , β-naphthol benzyl ether, β-phenoxyethyl tosylate, β
-Phenoxyethoxyanisole, l-7 dinoxy J
-p-ethylphenoxyethane, bis-β-(p-methoxyphenoxy)ethoxymethane /-J/-methylphenoxycoμ'-ethylphenoxy: rJ17, /
-tolyloxy-col-methylphenoxyethane, l
, 2-diphenoxyethane, l.

≠-diphenoxybutane, bis-β-(p-ethoxyphenoxy)ethyl ether, l-7 di-noxy 2-p-
Chlorophenoxyethane, /-2'-methylphenoxy-2-4c"-ethyloxyphenoxyethane, /-4
It is preferable to use a compound having a 1-methylphenoxy-λ-μ"-fluorophenoxyethane with an M point of 7j'c-/JO'C.These are finely dispersed simultaneously with a colorless dye or an electron-accepting compound. It is particularly preferable to disperse it simultaneously with a colorless dye from the viewpoint of preventing fogging.The amount used is 20% of the electron-accepting compound.
It is added at a weight ratio of at least 300%, especially at a weight ratio of at least UO%! It is preferably 0% or less.

Additives are further added to the coating liquid thus obtained in order to meet various requirements.

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, and also to improve releasability from the head. For this purpose, fatty acids, metal soaps, etc. are added. 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 such as kaolin, calcined kaolin, talc, zinc oxide, diatomaceous earth, calcium carbonate, aluminum hydroxide, magnesium oxide, calcined gypsum, silica, magnesium carbonate, titanium oxide, alumina, barium carbonate, barium sulfate , mica, microballoon, urea-formalin filler, polyethylene particles, cellulose filler, etc. particle size 0. / or l! Selected from μ. Examples of waxes include Nor-R rough-in wax, carboxy-modified paraffin wax, carnauba 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.

As a hindered phenol, a small amount (Tomoko or 6
Phenol derivatives in which one or more of the positions are substituted with a branched alkyl group are preferred.

For example, /, /-bis(-2-methyl-Hiro-hydroxy-z-t-butylphenyl)butane% /1/, J
-) Lis(3-methyl-l-hydroxy-z-t-butylphenyl)butane, bis(2-hydroxy-3-t
-1 chill-! -methylphenyl)methane, bis(2-methyl-μmhydroxy-j-heavy-butylphenyl) sulfide, etc.

Examples of ultraviolet absorbers include cinnamic acid derivatives, benzophenone derivatives, benzotriazolylphenol derivatives, etc. For example, α-cyano-β-phenylbutyl cinnamate, 0-benzotriazolylphenol, o-benzotriazolyl-p- Chlorophenol, 0-benzotriazolyl-!
, 4C-dibutylphenol, 0-benzotriazolyl-p-chlorophenol, and the like.

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, shrimp chlorhydride/modified polyamide, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, and imbutylene. -Maleic anhydride copolymers, polyacrylic acid, polyacrylic acid amide, methylol-modified polyacrylamide, starch derivatives, casein, gelatin and the like. In addition, in order to impart water resistance to these binders, water-resistant agents (gelling agents, cross-linking agents) are added, or emulsions of hydrophobic polymers, specifically styrene-butadiene rubber latex, acrylic resin emulsions, etc. You can also add

The coating liquid is applied onto base paper, high-quality paper, synthetic paper, plastic sheet, or neutral paper at a thickness of about 2 to 10 9 /m 2 .

Furthermore, a protective layer of about 0.2 to 2 μm consisting of a water-soluble or water-dispersible polymer compound such as polyvinyl alcohol, hydroxyethyl starch, or epoxy-modified polyacrylamide and a crosslinking agent is provided on the surface of the coating layer to improve resistance. You can also do it.

When used for thermal paper, additionally 0LS22 t, trI
No. 211OIrtA, % Koshota No. 2-201μλ, and the like. Alternatively, operations such as preheating, humidity control, or stretching of coated paper may be added prior to recording.

Current-carrying thermal paper is, for example, published by Japanese Patent Publication No. 2003-100012.
- Manufactured by the method described in μr No. 230 and the like.

In general, a coating liquid in which a conductive substance, a basic dye mainly containing the fluoran derivative of the present invention, and an electron-accepting compound are dispersed together with a binder is applied to a support such as paper, or a conductive substance is coated on the support to conduct electricity. The electrically conductive thermal paper of the present invention is produced by forming a layer and applying thereon a coating liquid in which a colorless dye, an electron-accepting substance, and a binder are dispersed. Note that the sensitivity can also be improved by using the thermofusible substance described above in combination.

Examples of photosensitive and pressure-sensitive paper include JP-A No. 7-/7-rJt and JP-A-Sho! It is manufactured by the method described in Tarrli No. 13!3. In general, photopolymerization initiators such as silver iodobromide, silver bromide, silver behenate, Michler's ketone, benzoin derivatives, and benzophenone derivatives and polyfunctional Kitakami polymers such as polyallyl, poly(meth)acrylate, divinylbenzene, poly(meth) A crosslinking agent such as acrylamide is encapsulated in a synthetic resin walled capsule such as polyether urethane, voricrea, etc. along with a colorless dye and optionally a solvent. After imagewise exposure, the colorless dye in the unexposed area is brought into contact with a color developer and colored.
I am also familiar with issue 91.

The electron-donating colorless dye according to the present invention is synthesized by the following method. For example, a corresponding substituted benzoylbenzoic acid or substituted 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.
O~l≠0 (After reacting for 10~lJO at the temperature of IC, 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, water It can be obtained by making it alkaline with an aqueous sodium oxide solution, separating the solvent layer, and distilling the solvent under reduced pressure or by steam distillation.Preferably, l-
This is a method of reacting dialkylamino-3-polyoxyalkyleneoxybenzene with carboxybenzoylindole or carboxypyridinecarbonylindole.

For the reaction method, known methods can be applied, for example, JP-A-4/-
Reaction conditions are also disclosed in No. 74Ir6A4 and Ruiha Ti-Tyr/J44.

Synthesis example/j-(IA-diethylamino-2-3', z'-
Dioxaoctyloxyphenyl)-3-C/-ethyl-λ-methylindol-3-yl)phthalide m-diethylaminophenol 0.7 mol, 3.6-dioxaoctyl tosylate 001 mol, potassium carbonate Q, 1 Weigh the moles into a flask equipped with a stirrer and add sulfolane zO.
ml and stir while heating.

When poured into water/-diethylamino-! -3',tr'-dioxaoctyloxybenzene is obtained as a liquid. 0.0 part mole of this aniline derivative and /-X thyl-2-
3-0-carboxy/silyl-l-ethyl-comethylindole Q obtained by reacting methylindole with phthalic anhydride.

Weigh out 0 part mole in a flask, add acetic anhydride and heat. The reaction proceeds immediately and the system becomes blue-purple.

After pouring the reaction product into water, it is separated by column chromatography using chloroform-ethyl acetate as a solvent. The desired product is obtained as white crystals, melting point 1~7°C.

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

Examples and Comparative Examples ■ Preparation of color developer sheet 3! -Bis-α-methylbenzylsalicylic acid zinc salt I
Part Q was added to 20 parts of l-isopropylphenyl-λ-phenylethane and dissolved. This was mixed with j0 parts of λ% polyvinyl alcohol water bath solution and 0.7 parts of 10% dodecylbenzenesulfonic acid triethanolamine salt aqueous solution, and emulsified so that the average particle size was 3 μm.

Next, a dispersion consisting of 70 parts of calcium carbonate, 20 parts of zinc oxide, 1 part of sodium hexametaphosphate, and 200 parts of water was mixed with the above emulsion, followed by adding 100 parts of a 10% PVA aqueous solution and carboxylic acid as a binder. Modified SBR
10 parts of latex (as solid content) was added and water was added so that the solid content concentration was 20% to obtain a coating liquid (A).

Next, a dispersion consisting of io parts of the color developer, 20 parts of Jilton clay, 40 parts of calcium carbonate, 20 parts of zinc oxide, 1 part of sodium hexametaphosphate, and 200 parts of water was ground in a sand grinder to an average particle size of 3 μm. Dispersed.

To this dispersion, 10% PVA aqueous solution/Part A, 10% PVA
Add 100 parts of aqueous solution and 70 parts of carboxy-modified SBR latex (as solid content), and
% to obtain a coating liquid (B).

Coating liquid (A) and coating liquid (B) were mixed at a ratio of 1:1 in terms of color developer, and coated with an air knife coater so that a base paper YCR of r011/m2 and a solid content of OP7m2 were coated.
It was dried to obtain a color developer sheet.

(2) Preparation of Capsule Sheet Containing Color Former 1 part of a partial sodium salt of polyvinylbenzenesulfonic acid (VER8ASTL100, manufactured by National Starch Co., Ltd.) is dissolved in 1 part of hot water and then cooled.

An aqueous sodium hydroxide solution was added to this to adjust the pH to μ-〇. On the other hand, 7100 parts of diisopropyl naphthalene in which 3.3% of the coloring agent shown below was dissolved was emulsified and dispersed in 100 parts of a j% aqueous solution of a partial sodium salt of the polyvinylbenzenesulfonic acid to form particles with diameters μ and θμ. An emulsion was obtained. Separately, 6 parts of melamine, 3.7 parts by weight of formaldehyde aqueous solution, and 30 parts of water were heated and stirred for 1.06 CK, and 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 1.0 with an aqueous phosphoric acid solution, the liquid temperature was raised to 6!0C, and stirring was continued for 6 hours. This capsule liquid was cooled to room temperature, and the pH was adjusted to O with an aqueous sodium hydroxide solution.

To this dispersion, 200 parts of a 10% by weight polyvinyl alcohol aqueous solution and 50 parts of starch particles were added, and water was added to prepare a coating solution of a microcapsule dispersion with a solid content concentration of 20%.

This coating liquid! 117 on the original paper of Oi / m
The mixture was coated using an air knife coater so that a solid content of m 2 was coated, and dried to obtain a color former-containing capsule sheet.

When a pressure-sensitive recording sheet was prepared by combining the color developer sheet obtained as described above and a color former-containing capsule sheet and was colored, extremely clear images with good light resistance were obtained. In addition, 3-(≠-diethylamino-2
-ethoxyphenyl)-J-(/-ethyl-comethylindol-3-yl)phthalide to obtain an emulsion with a particle size of μ, Oμ.
~ // 3 hours is enough.

The coloring agent used is as follows.

Example 1 3-(4A-diethylamino-2-3',4/-dioxaoctyloxyphenyl)-J-(/-ethyl-comethylindol-3-yl)phthalide Example 1 Phthalide and crystal violet lactone in a 7/3 (weight ratio) mixture Example 3 3-(≠-diethylamino-2-t'-7 enoxy 3
'-oxapentyloxyphenyl)-3-(l-ethyl-λ-methylindol-3-yl)phthalide and 3-
(l-jethylaminocoethoxyphenoxy) -
J-(/-ethyl-comethylindol-3-yl)
/ / / (weight ratio) mixture of phthalides Example μ Phthalide of Example 1 and 3-(≠-jethylamino-coethoxyphenyl)-3-(t-n-octyl-2-methylindol-3-yl ) -4- or -7-azaphthalide r/2 (weight ratio) mixture examples! Compounds ltg and 3 of Example 1 as electron-donating colorless dyes
1.1/-bisdiethylamino-terdiethylaminospiro(inbenzofuran-l,ri'-fluorene)-3
- Ong, electron-accepting compound μ-β-p-methoxyphenoxyethoxyethoxysalicylic acid zinc 209 and thermofusible material λ-benzyloxynaphthalene 2077 were each mixed in a ball mill for a day and night with 100 g of a 1% aqueous polyvinyl alcohol solution. The particles were dispersed to have a volume average particle size of 3μ. On the other hand, calcined kaolin top and zinc oxide 2077 were added to 0.0% of sodium hexametaphosphate. t% solution it.

It was dispersed with I using a homogenizer.

Each of the dispersions dispersed as described above is defined as the electron-donating colorless dye dispersion ri, 'the bone-tolerant compound dispersion log, and the thermofusible substance dispersion! I. Calcined kaolin and zinc oxide dispersion 2
The mixture was mixed in a ratio of 21/21, and then a coating solution was obtained by adding Emulsion Hiroshi 9 of zinc stearate and Bathing Solution I of 2% sodium (coethylhexyl)sulfosuccinate. This coating liquid was dried on a neutral high-quality paper with a basis weight r O and St/m2, and applied with a wire bar so that the coating amount was t17m2, dried in a RO'C oven for 5 minutes, and calendered. Coated paper was obtained.

When color was developed using Fujitsu High Speed Facsimile PP-2000, a black printed image was obtained. This image had a high density (excellent light resistance and heat resistance).The image also had light absorption in the near-infrared region.

On the other hand, when 3-(μm diethylamino-2-ethoxyphenyl)-3-(/-ethyl-comethylindol-3-yl)7thallide is used as a colorless dye, a particle size of 3 μm is obtained, which is approximately three times as large. time is required.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendments Imported) 1, 77th day of the month of Showa T-2, 1, Showa T-2 Patent Application No. 3 ojrrJ
No. 2, Title of the invention Recording material 3, Relationship with the case of the person making the amendment Patent applicant 4, Subject of the amendment Column 5 of "Detailed explanation of the invention" of the specification, Details of the amendment as follows: to correct.

1) Page 1, line λ "-J-(/, J-dimethylindole") r-3-(i,2-dimethylindole").

2) Turn page 3 to line 3. "Inbenzofuran" "isobenzofuran" and correct it.

Claims (1)

[Scope of Claims] A recording material that utilizes color development due to contact between an electron-donating colorless dye and an electron-accepting compound, characterized in that a compound represented by the following general formula (I) is used as the colorless dye. material. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) In the general formula (I), R_1 is a polyoxyalkylene group, and R_2 to R_1_0 are hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, substituted amino groups, or aryl groups. and R_7 and R_8 and R_9 and R_1_0 may be combined with each other to form a ring.