JPS6378790A - Recording material - Google Patents

Abstract

PURPOSE:To enhance preservability, a color forming property and the stability of a developed color image, by using a specific compound as an electron donating leuco dye. CONSTITUTION:In recording material utilizing color development utilizing the contact of an electron donating leuco dye and an electron acceptive compound, a compound represented by general formula (I) (wherein R1-R10 are a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a substituted amino group or an aryl group, and R7 and R8 and R9 and R10 may bond to each other to form a ring. R is a group having a 1-12C addition polymerizable group) is used as the leuco dye. The electron donating leuco dye is a colorless-light-colored crystal and has high solubility to an org. solvent and rapidly forms a blue color upon the contact with the electron acceptive compound. The developed color dye is extremely stable and generates almost no discoloration and fading by long-time light irradiation, heating and humidification and, therefore, extremely advantageous from the viewpoint of long-term preservation of recording. Further, the stability of the color forming agent is also excellent and, further, by polymerizing said compound if necessary, new function can be imparted. Therefore, said compound has a capacity near to an ideal one as the color forming agent of a recording material such as pressure-sensitive paper, thermal paper or photosensitive pressure-sensitive paper.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of the Invention) The present invention relates to recording materials, and in particular to recording materials using colorless dyes having addition-polymerizable groups as substituents and having improved storage stability, coloring properties, and stability of colored images. Regarding materials. (Prior Art) Recording materials using electron-donating colorless dyes and electron-accepting compounds are already well known as pressure-sensitive paper, heat-sensitive paper, photosensitive pressure-sensitive paper, electrically conductive heat-sensitive recording paper, and the like.

For example, British patent co1po4A≠ri, U.S. patent μ≠10
0 octopus, same 1 hiro 36 octopus O1 special public show to-23, ri λ2
, Tokukai Akira! 7-/7ri, 136, same 40-/koJ,! j
I am familiar with 40-/ko J, Jj7, 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)
The S/N ratio is high, (6) the color former has sufficient chemical resistance, and it is easily soluble in organic solvents, but currently there is no product that completely satisfies these requirements. .

Especially in recent years, as recording systems have become faster and demands have become more diverse,
Research is being carried out to improve these characteristics.

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

For example, 3. ! -Bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (i.e., crystal violet lactone) develops quickly and exhibits a deep blue color, but the light resistance of the colored image is extremely poor. Also, 3,7-bis(dimethylamino), which is a leucomethylene blue compound
Although 10-benzoylphenothiazine (i.e., benzoyl leucomethylene blue) has extremely excellent light fastness in its color images, it has drawbacks such as very slow color development and very poor color development with organic color developers.

The present inventors investigated the oil solubility, water solubility, partition coefficient, p K 2 , polarity of substituent, position of substituent, polymerizability, crystallization, and the like for each of the electron-donating colorless dye and the electron-accepting compound. Focusing on characteristics such as changes in properties and solubility,
We have pursued the development of good materials for recording materials and recording materials.

(Object of the Invention) Therefore, the object of the present invention is to provide a recording material using a material that has improved storage stability, color development properties, and stability of color images, and satisfies other necessary conditions.

(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 using a recording material having the ff characteristic by using the compound shown in 1).

In the above formula, R1 to RIO represent a hydrogen atom, a hydrogen atom, an alkyl group, an alkoxy group, a substituted amine group, or an aryl group, and R7 and R8 and R9 and RIO represent groups that may be combined with each other to form a ring. , R represents a group having an addition-polymerizable group of /j to /j carbon atoms.

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 amino group, a substituted oxycarbonyl group, or a substituted oxysulfonyl group. Further, the alkyl group represents a saturated 211I or unsaturated alkyl group or a cycloalkyl group, and these include an aryl group,
It may have a substituent such as an alkoxy group, an aryloxy group, a norogen atom, or a cyano group.

Among the substituents represented by R1, R3, and R4 in the above formula, a hydrogen atom, an alkyl group having 1 to 1 carbon atoms, or an aryl group are preferable, and these include a hydrogen atom, an alkoxy group, an aryl group, an aryloxy It may be substituted with a group, an acyl group, a 77 group, a pyridyl group, a furfuryl group, etc.

Among the substituents represented by R2 and R5, hydrogen atoms, alkoxy groups with a carbon number of 1 to 2, aryl groups with 6 to 10 carbon atoms, aryloxy groups, fluorine atoms and fluorine atoms, and carbon atoms of 1 to 1 The alkyl group and substituted amine group of No. 2 are preferred.

R2 is particularly preferably a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

R7 and R8, R9 and RIO may be bonded to each other to form a ring, in which case an aromatic ring which may contain one or more heteroatoms, such as an enzyme atom, a nitrogen atom, or a sulfur atom, is used. preferable. The aromatic ring may have the fF1 group mentioned above for R1 or R2, an N-substituted rubamoyl group, an alkoxycarbonyl group, or the like.

Particularly preferred are optionally substituted benzene rings and pyridine rings.

Among the substituents represented by R, those having an unsaturated double bond, particularly a vinyl group or a vinylidene group, are preferred. As long as it has one or more addition-polymerizable groups, the mode of substitution does not matter. For example, a preferred example is when a portion of RO is derived from an acid halide, ester, halide, incyanate or epoxy compound having an addition polymerizable group.

Preferred compounds have the following general formula.

R12 and R13 represent the substituents described for R5, and X represents a carbon atom or a nitrogen atom.

Preferred specific examples of RO- are as follows. Acryloxy, methacryloxy, vinylbenzoyloxy, vinylphenoxyacetoxy, methacryloxyethoxy, acryloxyethoxy, vinylbenzenesulfonyloxy, allyloxy, vinyloxyethoxy, vinylanilinocarbonyloxy, β-methacryloxypropoxy, β-acryloxypropoxy, vinyl Benzyloxy, β-methacryloylaminoethoxy, β-acryloylaminoethoxy, β-p-vinylbenzoyloxyethoxy, γ-vinylphenoxy β-hydroxypropoxy, β, γ-dimethacrylokydipropoxy, glycidyloxy, β-vinyl Examples include phenoxyethoxy.

The electron-donating colorless dye according to the present invention has the advantage that it is a colorless or light-colored crystal, has high solubility in organic solvents, and quickly develops color on the back metal 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 stability of the coloring agent is excellent, and if necessary, it can be further polymerized to provide new functions.

Therefore, it has near-ideal performance as a coloring agent for recording materials such as pressure-sensitive paper, thermal paper, and photosensitive pressure-sensitive paper.

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

1) j-(≠-diethylamino-2-methacryloxyphenyl)-j-(/-ethyl-2-methylindol-3-yl)7talido J) J-(u-diethylamino-λ-p-vinylbenzyloxy phenyl]-3-<t-ethyl-comethylindol-3-yl)phthalide J)! -(4C-diethylamino-2-(Hiro-vinylbenzoyloxy)phenyl)-J-(t-ethyl-methylindole-3-
yl) phthalide p) j-(≠-diethylamino-co(vinyloxyethyloxy) phenyl)-J-(/-ethyl-2-methyl-indol-3-yl) phthalide g 3-(g-diethylamino-co(vinyloxyethyloxy) phenyl) β-acryloxyethoxy)phenyl]-J-(/-ethyl-2-methylindol-3-yl)7thallide 4) J-(≠-dibutylaminocor β-acrylamidoethoxyphenyl)-J-(/- Ether-comethylindol-3-yl)phthalide 7) J-(4(-diethylamine-2-vinylbenzyloxyphenyl)-3-(/,-1dimethylindol-3-yl)phthalide r)3-(p -diethylaminocor β, γ-dimethacryoxypropoxyphenyl)-J-(/-ethyl-2
-Phenylindol-3-yl)phthalidota)j-(Hiro-diethylaminoco(β-acryloxypropyloxy)phenyl)-3-(/-ethercomethylindol-3-yl)4A-azaphthalideto) 3 -(44-diethylamino-covinylbenzenesulfonyloxy)phenyl)-4-(/-ethyl-comethylindol-3-yl)-μm azaphthalide/1)J-(≠-diethylamino)-2-(β- vinylphenoxy)phenyl]-s-<i-ether-λ-1s
o-Pentylindol-3-yl)-guazaphthalide These colorless dyes are also well-known triphenylmethane phthalide compounds, fluoran compounds,
Recording materials can also be assembled in combination with various compounds such as phenothiazine compounds, intriazalphthalide compounds, leucoauramine compounds, rhodamine lactam compounds, triphenylmethane compounds, triazene compounds, and spiropyran compounds. can.

In this case, it is preferable to use the above-mentioned colorless dye in an amount of Ao% or more in order to improve the properties. Some examples of such colorless dyes used in combination include triarylmethane compounds such as 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalito (crystal violet lactone), 3 ,3-bis(
p-dimethylaminophenyl) phthalide, J-(p-dimethylaminophenyl)-j-(/,j-dimethylindol-3-yl)phthalide, 3-(p-dimethylaminophenyl)-j-(j-methyl Indol-3-yl) phthalide, etc., and diphenylmethane compounds include ≠, Hiro'-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl (1:17.t
-Lami7, N-2゜≠, J-t') Chlorophenylleucoauramine, etc., xanthine compounds include:
Rhodamine-B-anilinolactam, rhodamine (p-
nitroanilino)lactam, rhodamine B (p-chloroanilino)lactam, colabenzylamino-6-diethylaminofluorane, 2-anilino-6-diethylaminofluorane, coanilino-3-methyl-t-diethylaminofluorane, 2-anilino-3-methyl -6
-cyclohexylmethylaminofluorane, J-o-chloroanilino-4-diethylaminofluorane, 2-m
-chloroanilino-6-diethylaminofluorane, 2
-(j,≠-dichloroanilino)-1-diethylaminofluorane, λ-octylamino-6-dinithylaminofluorane, colohexylamino-2-diethylaminofluorane, 2-m-)rifuromethylanilino -t
-diethylaminofluorane, coptylamino-3-
Chloro-6-diethylaminofluorane, co-ethoxyethylamino-3-chloro-t-diethylaminofluoran, 2-p-chloroanilino-3-methyl-6-dibutylaminofluorane, co-anilino-3-methyl-6
-Shioctylaminofluorane, Noanilino-3-chloro-t-diethylaminofluorane, Colaphenylamino-6-diethylaminofluorane, Noanilino-3-methyl-6-siphenylaminofluorane, λ-
Phenyl-A-diethylaminofluorane, λ-anilino-3-methyl-4-N-ethyl-N-isoamylaminofluorane, no-anilino-3-methyl-chloro-6-dinithylaminofluorane, 2-anilino-3-
Methyl-6-diethylamino-twomethylfluorane,
--anilino-3-methoxy-6-dibutylaminofluorane, 2-o-chloroanilino-4-dibutylaminofluoran, col-chloroanilino-3-ethoxy-A-N-ethyl-N-isoamylaminofluorane, cor 0-chloroanilino t-p-butylanilinofluorane, noanilino-3-pentadecyl-6-diethylaminofluorane, λ-anilino 3-ethyl-6
-Cyptylaminofluorane, noanilino-3-methyl-p/, 3/-dichlorofluorane, λ-
o-toluidino 3-methyl-ot-diinpropylamino-p/, z/-dimethylaminofluorane, co-anilino 3-ethyl-A-N-ethyl-N-
Isoamylaminofluoran, λ-anilino-3-methyl-A-N-ethyl-N-η-methoxypropylaminofluoran, co-anilino-3-chloro-a-N-ethyl-N-isoamylaminofluoran, etc. as dithiazine-based compounds. Examples of spiro compounds include benzoylleucomethylene blue, p-nitrobenzoyl leucomethylene blue, etc., and spiro compounds include 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, and J.
,! '-Cyclolosespiro-dinaphthopyran, 3-benzylspiro-dinaphthopyran, 3-methylna7)-(
J-Methoxy-benz)spiropyran, 3-propyl-
Examples include spiro-dibenzopyran. Or other addition-polymerizable color formers or addition-polymerizable monomers such as λ-p-vinylbenzoylamino-6-dietheraminofluorane,
2-p-(4A/-vinylbenzoylamino)anilino-3-methyl-4-dibutylaminofluorane, Cop
(μ'-vinylbenzylamino)anilino-3-chloro-a -N-ethyl-N-ynamylaminofluorane, -monovinylbenzylideneamino-t-diethylaminofluorane, co-β-(p-vinylbenzoylamino)
ethylamino-3-chloro-&-') ethylaminofluorane, co-β-(p-vinylbenzoylaminoethylamino) ethylamino-6-diethylaminofluorane, co-vinylbenzenesulfonylamino-3-isoamyl-t- Diethylaminofluorane, 2-anilino-3-methyl-6-N-ethyl-N-β-p-vinylbenzoylaminoethylamino-fluoran, (p-vinylbenzoylamino)benzoylleucomethylene blue, '-N-2f h
-N-vinylbenzylaminophenyl phthalide, cole-vinylbenzoyloxy-hiro-diethylaminophenyl-co/p-vinylbenzyloxy-methyl-j'-anilinophenyl phthalide, cole-vinylphenylureido t- Diethylaminofluorane, co-vinylanilino-3-methyl-t-diethylaminofluorane, co-anilino-γ-p-vinylbenzoylaminobutyl-t-diethylaminofluorane, co-β-hydroxy-γ-p-vinylphenoxy-propylamino -6-diethylaminofluorane, chloromethylstyrene, acrylamide, cellosolve acrylate, styrene, methyl methacrylate, acrylonitrile,
Vinyl carbazole, octyl acrylate, sodium acrylamideprononesulfonate, butyl methacrylate.

Examples include ethyl acrylate, divinylbenzene, vinyl dioxolane, epichlorohydrin, allyl methacrylate, cinnamoyloxyethyl methacrylate, vinylbenzophenone, ethylene glycol diacrylate, and diethylene glycol diacrylate.

When the color former of the present invention is used in combination with other color formers or monomers, the color former of the present invention preferably contains 20% by weight or more.
It is desirable to use it so that it exceeds Ow t%.

Electron-accepting compounds that provide color upon contact with colorless dyes include inorganic and organic Lewis and Brønsted acids. Phenol derivatives, salicylic acid derivatives, metal salts of aromatic carboxylic acids, acid clay, bentonite, novolac resins, metal-treated novolac resins, Hiro-tertiary butylphenol, Hiro-phenylphenol, hydroxydiphenoxide, α-naphthol, β- Naphthol, hexyl-≠-hydroxybenzoate, co,co'-dihydroxybiphenyl, λ,-2-bis(4c
m-hydroxyphenyl)propane (bisphenol A)
, 4't4''-inpropylidene bis(comethylphenol), /, /-bis-(J-/RORO-Hirohiro-hydroxyphenyl)cyclohexane, /',/-bis(3-chloro-μmhydroxyphenyl)- Coethylbutane,
≠, 4! I-Septadaryisooctylidene diphenol, ≠-tert-octylphenol, μlμ′-8
ec-butylidene diphenol, e-p-methylphenylphenol, μ'-impentylidene diphenol, 4C,l-methylcyclohexylitine diphenol, 4C, l-dihydroxydiphenylsulfide)e,
/ , Hiro-bisu Hiro'-hydroxycumylbenzene,
l,3-bis-j'-hydroxycumylbenzene, ≠a
ll'-f obis(A-tert-butyl-3-methylphenol), p, μ'-dihydroxydiphenyl sulfone, hydroquinone monobenzyl ether, ≠-hydroxybenzophenone, co, 1LL-dihydroxybenzophenone, polyvinylbenzyloxycarbonylphenol, Co, ≠, 3'-trihydroxybenzophenone, 2,2', ≠, μ'-tetrahydroxybenzophenone, ≠-dimethyl hydroxy heptatalate, ≠-methyl hydroxybenzoate, 2, l, ≠'-trihydroxydiphenyl Sulfone 1. j-bis-p-hydroxyphenyl ester, l, A-bis-p-hydroxyphenoxyhexane, ≠-tolyl hydroxybenzoate, ≠-hydroxy anchorage, α-phenylbenzyl folic acid ester, ≠-phenylpropylene hydroxybenzoate phenethyl hydroxybenzoate, p-chlorobenzyl hydroxybenzoate, p-methoxybenzyl hydroxybenzoate, benzyl t-hydroxybenzoate, m-chlorobenzyl hydroxybenzoate, phenethyl hydroxybenzoate , Hiro-hydroxybenzoic acid β-phenethyl ester, ≠
-Hydroxy-2', μ'-dimethyl diphenyl sulfone, β-7enetelorthe IJ nate, cinnamyl orseinate, orselic acid-〇-chlorophenoxyethyl ester, 0-ethylphenoxyethyl orseinate, 0-phenylphenoxyethyl orselate Selinate, m
-Phenylphenoxyethyl orcelinate, λ, 4L
-dihydroxybenzoic acid-β-J'-t-ethyl-μ'
-Hydroxyphenoxyethyl ester, /-t-ethyl-≠-p-hydroxyphenylnulfonyloxybenzene, u-N-benzylsulfamoylphenol,
Ko, Hiro-dihydroxybenzoic acid-p-methylbenzyl ester, u, 4! -dihydroxybenzoic acid-β-phenoxyethyl ester, co.

≠-dihydroxy-6-methylbenzoic acid benzyl ester, bis-φ-methyl hydroxyphenylacetate, ditolylthiourea, ≠, ≠'-diacetyldiphenylthiourea, 3-phenylsalicylic acid, 3-cyclohexylsalicylic acid, J, r-di-tersha butylsalicylic acid, 3. j-di-dodecylsalicylic acid, 3-methyl-y-benzylsalicylic acid, 3-phenyl-t-(α, α-
dimethylbenzyl) salicylic acid, J,! −')−(
α-Methylbenzyl)salicylic acid, co-hydroxy-7
- aromatic carboxylic acids such as indi-3-naphthoic acid,
3. j-dicyclopentadienylsalicylic acid, para-
Organic color developers such as phenolic resins such as phenylphenol-formalin resin and para-butylphenol-acetylene resin, and these organic color developers and polyhydric compounds such as zinc magnesium, aluminum L, calcium, titanium, manganese, tin, and nickel. salts with metals, and rhodanic acids such as hydrogen chloride, hydrogen bromide, hydrogen iodide,
Inorganic acids such as boric acid, silicic acid, phosphoric acid, sulfuric acid, nitric acid, perchloric acid, halides such as aluminum, zinc, nickel, tin, titanium, boron, acid clay, activated clay, atta, oluguide, bentonite, Inorganic color developers such as colloidal silica, aluminum silicate, magnesium silicate, zinc silicate, tin silicate, zinc rhodan, zinc chloride, iron stearate, cobalt naphthenate, nickel peroxide, ammonium nitrate, oxalic acid, maleic acid, tartaric acid, citric acid One or more types of acids, aliphatic carboxylic acids such as conolilic acid and stearic acid, benzoic acid, latt-butylbenzoic acid, phthalic acid, and gallic acid are 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.

When used with pressure sensitive paper, U.S. Patent No. 10, Ko 7
No. 0, same λ, 606, ≠ No. 71, same co.

jOJr, μl number, same number, same number, Jtt number, same number 2.
7/2, No. 307, No. 2,730, 1ljt, No. 730. ≠! No. 7, No. 3103 Hiro θμ, No. i,
Air, No. 210, 4LO10031, and other prior patents may take various forms.

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 of manufacturing capsules is described in a US patent.

Too, Hiromu! A method using coacervation of a hydrophilic colloid sol described in No. 7, Ibid., No. 2, Too, Ttzr, British Patent No. 147,777, Ibid.! O,
Da Hong No. 3, same one, 244! No., same/.

Examples include the interfacial polymerization method described in U.S. Pat.

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 it in microcapsules,
A color former sheet is obtained by coating on a support such as paper, high quality paper, plastic sheet, resin coated sheet, 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 have a particle size of 70 μm or less, preferably 3 μm, in the dispersion medium.
It is used after being crushed and dispersed to a particle size of μ or less. As a dispersion medium, a water-soluble polymer aqueous solution with a concentration of about 0.1 to 10 parts is generally used, and dispersion is carried out using a ball mill, sand mill,
This is done using a horizontal sand mill, attritor, colloid mill, etc.

The ratio of the electron-donating colorless dye used to the electron-accepting compound is preferably between /:10 and l:l, and even l:!, in terms of weight ratio. A ratio between 2:3 and 2:3 is particularly preferred. that time,
Nitrogen-containing organic compounds or compounds such as fatty acid amides, acetoacetanilide, diphenylamine, penzamide, carbazole, etc.

j-Z-m-t9luputan, 0-fluoropenzoyldurene, chlorobenzoylmesitylene, ≠.

μ'-dimethylbiphenyl, or carboxylic acid esters such as dimethyl isophthalate, diphenyl phthalate, dimethyl terephthalate, methacryloxybiphenyl, etc., or polyether compounds such as di-m
-) Ryloxyethane, β-phenoxyethoxyanisole, l-phenoxy-Jp-ethylphenoxyethane, bis-β-(p-methoxyphenoxy)ethoxymethane, /-λ'-methylphenoxycoμ'- Etherphenoxyethane, /-) Zyloxy-2-p-methylphenoxyethane, /, J-diphenoxyethane, /,
#-Diphenoxybutane, bis-β-(p-ethoxyphenoxy)ethyl ether, l-phenoxy-2-p-
Chlorophenoxyethane, l-co'-methylphenoxy-111μ"-ethyloxyphenoxyethane, l-μ'
It is preferable to use a compound with a melting point of 71'C-/30'C, such as -methylphenoxy2-μ"-fluorophenoxyethane.These are used in finely dispersed form at the same time as a colorless dye or at the same time as an electron-accepting compound. In particular, it is preferable to disperse the colorless dye at the same time from the viewpoint of preventing fogging.
Yes. The amount of these used is 2 for the electron-accepting compound.
It is added at a weight ratio of 0% or more and 300% or less, especially aO%
It is preferable that the amount is more than or equal to izo%.

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, waxite, diatomaceous earth, luciram carbonate, aluminum hydroxide, magnesium hydroxide, calcined gypsum, silica, magnesium carbonate, titanium oxide, alumina, barium carbonate, Barium sulfate, mica, microballoon, urea-formalin filler, IJ ethylene ξ-ticle, cellulose filler, etc. Particle size o, i or /! lt
selected from. Examples of waxes include paraffin wax, carboxy-modified paraffin wax, cownaparow wax, microcrystalline wax, polyethylene wax, and higher fatty acid esters.

Examples of the metal soap include polyvalent metal salts of higher fatty acids, such as zinc stearate, aluminum stearate, calcium stearate, and zinc oleate.

These are dispersed and applied in a binder.

Water-soluble binders are common 1. Polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, epichlorohydrin-modified polyamide, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, imbutylene-maleic anhydride. Examples include acid copolymers, polyacrylic acid, polyacrylic acid amide, methylol-modified polyacrylamide, starch carriers, casein, and gelatin. In addition, for the purpose of imparting water resistance to these binders, water resistant agents (gelling agents, crosslinking agents) are added, or emulsions of hydrophobic polymers, specifically styrene-butadiene rubber latex,
Acrylic resin emulsion etc. can also be added. The coating liquid is applied onto base paper, high-quality paper, plastic sheet, synthetic paper, or neutral paper in an amount of about λ to lQP/rIL2.

Furthermore, a protective layer of about 1 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, QI, S, 212J'6
No. 11, same 2//Dr! II, Tokko Akira! 2-201≠2
Various embodiments described in, for example, can be used. Alternatively, operations such as preheating, humidity control, or stretching of coated paper may be added prior to recording.

For example, the electrically conductive thermal paper is published in Japanese Patent Application Publication No. Sho≠Tar//J≠Hiroshi, same JO.
-≠Manufactured by the method described in No. t230.

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.

The photosensitive and pressure sensitive paper is manufactured, for example, by the method described in JP-A-57-/7-1, R36. In general, photopolymerization initiators such as silver iodobromide, silver bromide, silver behenate, Michler's ketone, benzoin derivatives, and benzophenone derivatives and crosslinking agents such as polyfunctional monomers such as polyallyls, poly(meth)acrylates, and poly(meth)acrylamides A synthetic resin wall such as polyether urethane, polyurea, etc. is encapsulated in the capsule 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 to be colored.

The electron-donating colorless dye according to the present invention is synthesized by a known method. For example, the corresponding benzoylbenzoic acid or benzoylpyridinecarboxylic acid and indole, or the corresponding carboxybenzoylindole or carboxypyridinecarbonylindole and an aniline derivative are combined in the presence of a condensing agent such as acetic anhydride or phosphorus oxychloride to form the necessary Using volatile organic inert solvents such as chloroform, benzene, and benzene chloride! 0-/≠O0C
After reacting for 70 to 20 minutes at a temperature corresponding to It is obtained by fractionating and distilling off the solvent under reduced pressure. A preferred method is to first obtain an aminophenol derivative having an addition polymerizable group using m-substituted aminophenol or m-substituted aminophenoxyethanol as a starting material, and then react it with carboxybenzoylindole or carboxypyridinecarbonylindole.

For the reaction method, known techniques can be applied, for example, JP-A-Sho A/-
/4rj4≠ also discloses reaction conditions.

Synthesis Example 1 Synthesis of 3-(≠-diethylamino-2-β-methacryloxyethoxyphenyl)-3-(/-ethyl-cophenylindol-3-yl)phthalide m-diethylaminophenoxyethyl methacrylate o
, and 0.01 mole of 3-〇-carboxybenzoyl-1-ethyl-comethylindole obtained by reacting 7-ethyl-2-methylindole with 7-talic anhydride in a flask. Add acetic acid and heat.

The reaction proceeds immediately and the system becomes blue-purple. The reaction mixture was poured into water and then separated by column chromatography using chloroform-ethyl acetate as a solvent. The desired product is obtained as white crystals. Melting point/73-μ0C Synthesis example 3-[≠-diethylaminocovinylbenzyloxy)phenyl: 1-J-(t-ethyl-2-methylindol-3-yl)phthalide Synthesis example/m-diethylaminophenoxyethyl The reaction was carried out in the same manner except that m-diethylaminophenoxymethylstyrene was used instead of methacrylate.

The crude product was an oil with a bright blue-purple color on silica gel.

m −') ethylaminophenoxymethylstyrene is m
-diethylaminophenol and chloromethylstyrene (
mixture) in the presence of potassium carbonate.

(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, zinc j-bis-α-methylbenzylsalicylate 70
Part + 5-/-isopropylphenyl-λ-phenylethane was added to JO part and heated and dissolved at 0'C. This was added to 20 parts of a flat polyvinyl alcohol (PVA-1/7 manufactured by Kuraray) aqueous solution, and 0.1 part of a 10% dodecylbenzenesulfonic acid triethanolamine salt aqueous solution was added as a surfactant, and an emulsion was prepared using a homogenizer. An emulsion was prepared so that the average particle size was 3μ.

Next, a dispersion of 10 parts of calcium carbonate, 20 parts of zinc oxide, 1 part of sodium hexametaphosphate, and 200 parts of water was prepared using a Keddy mill, and after mixing the above emulsion, 70% PVA- / /7 Add 10 parts (as solid content) of water-soluble W and loo parts (manufactured by Kura V) and carboxy-modified SBR latex (SN-307, manufactured by Sumitomo Naugatux) so that the solid content concentration becomes 0%. Water was added and adjusted to obtain a coating liquid (A).

Next, using 10 parts of the color developer, 20 parts of Jilton clay, 60 parts of calcium carbonate, 20 parts of zinc oxide, 1 part of sodium hexametaphosphate, and 200 parts of water, they were uniformly dispersed with a sand grinder to an average particle size of 3 μm. did.

First, 4 parts of 10% PVA-103 (manufactured by Kuraray) aqueous solution was added to the obtained dispersion, and then 10% PVA-/7
700 parts of aqueous solution (manufactured by Kura V) and io parts (as solid content) of carboxy-modified SDR latex (SN-so7 manufactured by Sumitomo Naugatux) were added, water was adjusted so that the solid content concentration became io parts, and coating liquid (B ) was obtained.

Coating liquid (A) and coating liquid (B) in terms of developer: A/B = z
o / z o and coated on a jOy/rrL2 base paper using an air knife coater so that the solid content of z, op/ln2 was coated, and dried to obtain a color developer sheet.

■ Preparation of capsule sheet containing color former ■ Melamine/formaldehyde resin capsule Partial sodium salt of polyvinylbenzenesulfonic acid (manufactured by National Starch Co., Ltd., VER8A, TL100, average molecular weight z
oo, ooo)s parts were added to 3 parts of hot water at about rO0C with stirring and dissolved. After dissolving for about 30 minutes, it is cooled. The pH of the aqueous solution was λ~3, and a 20 M aqueous sodium thihydroxide solution was added thereto to obtain pHILL. On the other hand, 100 parts of diimpropylnaphthalene in which 3.5% of the coloring agent shown in Table 1 is dissolved is emulsified and dispersed in 100 parts of a multi-aqueous solution of a partial sodium salt of the polyvinylbenzenesulfonic acid to form particles with an average diameter≠, jμ. An emulsion with a certain size was obtained. Separately, 6 parts of melamine, 37 parts by weight of an aqueous formaldehyde solution, and 30 parts of water were heated and stirred to 0C, and after 30 minutes, a transparent mixed aqueous solution of melamine, formaldehyde, and melamine-formaldehyde initial condensate was obtained.

The pH of this mixed aqueous solution was 6-r. Hereinafter, this mixed aqueous solution of melamine, formaldehyde, and melamine-formaldehyde initial condensate will be referred to as an initial condensate solution. Add and mix the initial condensate solution obtained by the above method to the emulsion, stir, and then adjust the pH to t, o with a phosphoric acid solution of A weight ratio, and adjust the liquid temperature to l, j 0c. Up to 31
, continued stirring for 0 minutes. This capsule liquid was cooled to room temperature, and the pH was adjusted to 0 with 20% by weight sodium hydroxide.

To this capsule dispersion, 200 parts of a 70% by weight polyvinyl alcohol aqueous solution and IO parts of starch particles were added, and water was added to adjust the solid content concentration to 20% to prepare a coating liquid of the microcapsule dispersion.

This coating liquid! Coat with an air knife coater so that the solid content of jy/m2 is applied to the base paper of Oori/m2,
After drying, a capsule sheet containing a coloring agent used in the present invention was obtained.

A pressure-sensitive recording sheet was prepared by combining the color developer sheet and color former-containing capsule sheet obtained as described above, and the performance of each combination was evaluated. In all cases, the colored images were clear and had good light fastness.

The coloring agent (mixture) used was as follows.

Example 1 3-(≠-diethylamino-co-β-methacryloxyethoxyphenyl)-3-(/-ethyl-comethylindol-3-yl)phthalideExample 2 Phthalide of Example 1 and crystal violet lactone 7/3 (Weight ratio) Mixture Example 3 3-(≠-diethylamino-vinylbenzyloxyphenyl)-j-(i-ethyl-λ-methylindol-3-yl)phthalide and 3-(≠-diethylaminocor) ethyloxyphenyl)-3-(i-octyl-λ-
3/2// (weight ratio) mixture of methylindol-3-yl)-7-aza7thalide and divinylbenzene Example 4 3-(≠-diethylamino-λ-vinylbenzyloxyphenyl)-J-(i- A dispersion was prepared by mixing and pulverizing 30 parts of ethyl-λ-methylindol-3-yl)phthalide with 0 parts of a 70% polyvinyl alcohol aqueous solution and 70 parts of water using a ball mill for 12 hours. The particle size after crushing is approximately l.

It was 5 microns. (Component A) On the other hand, 30 parts of ≠-β-(p-methoxyphenoxy)ethoxysalicylic acid zinc oxide≠θ parts, 30 parts of λ-benzyloxynaphthalene/60 parts of IO polyvinyl alcohol aqueous solution, and 55 parts of water. The mixture was mixed and ground using a sand mill to prepare a dispersion liquid. The particle size of the insoluble material after pulverization is approximately 2
It was a micron. (Component B) Next, 3 parts of component A and ≠0 parts of component B were mixed, applied to paper, and dried to obtain thermal paper.

When this thermal paper was heated with a thermal pen, it turned blue. The color image obtained 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 zero degree.

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. Materials▲Mathematical formulas, chemical formulas, tables, etc.▼(I) In the above formula, R_1 to R_1_0 are hydrogen atoms, halogen atoms,
It represents an alkyl group, an alkoxy group, a substituted amino group, or an aryl group, and R_7 and R_8 and R_9 and R_1_0 may be bonded to each other to form a ring. R has 1 carbon atom
Represents a group having from 1 to 12 addition polymerizable groups.