JPH0257380A - Recording material - Google Patents

Abstract

PURPOSE:To improve durability by bringing specific alkylene or arylene bis- compound into contact with electron accepting compound, thereby introducing functional group which is not conventionally discussed at all. CONSTITUTION:In a recording material in which coloring reaction due to contact of electron donating colorless dye with electron accepting compound is utilized, alkylene or arylene bis-compound of fluorane derivative having anilino group at its second position is employed as colorless dye. The electron accepting compound for coloring in contact with the colorless dye includes, for example, normal compound such as phenol derivatives, salicylic acid derivatives, metal salt of aromatic carboxylic acid novolac, acid clay, etc. The ratio of the used electron donating colorless dye to the electron accepting compound is by weight 1:20 to 1:1, and more desirably 1:10 to 2:3. The obtained recording material has no fog during preservation, and excellent aging stability. The obtained colored image is of fresh dark black, and exhibits satisfactory durability against chemical, sunshine.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a recording material, and particularly to a recording material with improved image durability.

In particular, the present invention relates to recording materials that are effective for various uses such as pressure-sensitive recording, heat-sensitive recording, light-sensitive pressure-sensitive recording, electrically conductive heat-sensitive recording, and electrolytic recording.

(Prior art) As electron-donating colorless dyes that color when they come into contact with electron-accepting compounds, triphenylmethane phthalide compounds, fluoran compounds, phenothiazine compounds, indolyl phthalide compounds, leucoauramine compounds, and rhodamine are used. Application of various compounds such as lactam compounds, triphenylmethane compounds, and triazene compounds to recording materials has been investigated. When these materials are used as recording materials, there are various recording systems as described above, but there are common characteristics required for the materials.

One of these is physical properties such as low water solubility and lipophilicity. These are associated with properties such as low fog and high color density when used in recording materials.

Furthermore, although this has not been studied to date, there has been a strong desire to improve the durability of images, such as the chemical resistance and weather resistance of recording materials.

On the other hand, high-speed suitability of recording materials is also required, and it is difficult but important to improve these properties in a well-balanced manner.

As an attempt to improve the durability of images, Japanese Patent Publication No. 49-21609 (1982) attempted to convert a fluoran coloring agent into a bis, but this method had the disadvantage that it was not possible to obtain a black color, which is important for recording materials. Was.

The present inventor has investigated various ways to overcome the shortcomings of these conventional techniques, and as one solution, we have developed a recording material using an electron-donating colorless dye into which a functional group has been introduced, which has never been considered before. We have developed this technology and achieved the present invention.

(Objects of the Invention) The first object of the invention is to provide a recording material with improved durability. Second, the present invention provides a recording material using a fluoran derivative substituted with an arylenebisamino group substituted at the 2-position.

(Structure of the Invention) The above-mentioned object of the present invention is to provide an alkylene or arylene fluorane derivative having an anilino group at the 2-position in a recording material that utilizes a color-forming reaction caused by contact between an electron-donating colorless dye and an electron-accepting compound. This was achieved by developing a recording material characterized by the use of bis compounds.

In the present invention, fluoran derivatives having an anilino group at the 2-position include an anilino group at the 2-position (an arylamino group whose p-position is a hydrogen atom, such as anilino, 0-toluidino, m-anisidine, mI-luidino, (including 2,5-xylidino, 2,5-dume-1-xyanilino, etc.)
It is important to have the following.

Further, the nitrogen atom of the anilino group may be monosubstituted with an acyl group, an alkyl group, an aralkyl group, an aryl group, or the like.

The fluoran derivative has an alkyl group, an aryl group at the 3-position,
It may be substituted with a halogen atom.

The 6th position is preferably an alkylamine residue.

Preferably, the fluoran derivative of the present invention is a phthalide. However, the aromatic ring of the phthalide moiety may be a heteroartic ring or a fused ring with a pyridine ring, an indole ring, a pyrazine ring, a benzofuran ring, a naphthalene ring, etc.

-For boat fishing, the fluoran derivative having an anilino group at the 2-position of the present invention is represented by formula (1).

In the general formula (1), R represents a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group, an aryl group, or a substituted amino group, and R1, R3, and R2 represent a hydrogen atom, an alkyl group,
Acyl group, aryl group, R4 is alkyl group, halogen atom, R6 is hydrogen atom, halogen atom, hydroxy group, alkoxy group, aryoloxy group, acyl group, carbamoyl group, substituted amino group, ureido group, cyano group. group, alkyl group or aryl group, where aryl group represents phenyl group, naphthyl group or heteroaromatic ring group, these include alkyl group, alkoxy group, aryloxy group, halogen atom, nitro group, cyano group, It may have a substituent such as a substituted carbamoyl group, a substituted sulfamoyl group, a substituted amino group, a substituted oxycarbonyl group, or a substituted oxysulfonyl group. In addition, the alkyl group represents a saturated or unsaturated alkyl group or a cycloalkyl group, and these include an aryl group, an alkoxy group, an aryloxy group,
It may have a halogen atom, a cyan group, an acyl group, a tetrahydrofurfuryl group, or the like.

In the above formula, among the substituents represented by R1, hydrogen atom, bromine atom, chlorine atom, alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, aryl having 6 to 12 carbon atoms A mono- or dialkylamino group having 1 to 12 carbon atoms and a monoacylamino group having 1 to 12 carbon atoms are preferred.

In the above formula, among the substituents represented by Rz, Rx, or R1, hydrogen atoms, alkyl groups having 1 to 18 carbon atoms, and aryl groups having 6 to 12 carbon atoms are preferred, and these include halogen atoms, alkoxy groups, Aryl group, alkyl group,
It may be substituted with an acyl group, cyano group, hydroxy group, tetrahydrofurfuryl group, etc.

R, Rs or R3 is a hydrogen atom, carbon number 2 to 1
An alkyl group of 2 and an alkyl group having 6 to 12 carbon atoms are more preferred.

R2 and R4 are bonded to each other to form a 5- to 8-membered ring, such as piperidine, morpholine, pyrrolidine, piperazine,
A ring such as hexamethyleneimine, caprolactam, or indole may be formed.

Preferred substituents for Rz, R3 and R3 include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group,
Isobutyl group, amyl group, isoamyl group, hexyl group,
Cyclohexyl group, 3.3-dimethylhexyl group, 3.
3-dimethylbutyl group, 2-ethylhexyl group, octyl group, dodecyl group, cetyl group, octadecyl group, isoprenyl group, cyclopentagenyl group, cyclohexenyl group, dodecenyl group, benzyl group, phenethyl group, isopropylbenzyl group, Ethoxyphenethyl group, phenylpropyl 1,2-13- or 4-phenylbutyl group, or phenoxybutyl group, or lower alkyl group, alkoxy group, fluorine atom, chlorine atom, acylamino group, alkylamino group, carbamoyl group, as described above, Represents a phenyl group, naphthyl group or quinolyl group which may be substituted with a sulfamoyl group.

In particular, R1 is preferably a hydrogen atom in order to obtain black coloring.

Among the substituents represented by R4, an alkyl group having 1 to 12 carbon atoms, a chlorine atom, or a bromine atom is preferable in order to obtain a black color.

Preferred examples of R4 include methyl group, ethyl group, propyl group, butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, octyl group, dodecyl group, octadecyl group, chlorine atom, and bromine atom.

Among the substituents represented by R4, hydrogen atom, bromine atom, chlorine atom, hydroxy group, alkyl group having 1 to 12 carbon atoms, alkoxy group, acyl group, carbamoyl group, mono- or dialkylamino group, acylamino group, ureido group ,
An aryl group, aryloxy group or cyano group having 6 to 12 carbon atoms is preferred.

Alkylene or arylene bis compounds are easily obtained by reaction with biscarbinol compounds or their halides.

Biscarbinol as used in the present invention has 6 or more carbon atoms and 50 or more carbon atoms.
Those having at least one of the following aromatic rings are preferred. The carbinol is preferably secondary or tertiary, and hensyl alcohol derivatives are particularly preferred.

Biscarbinol compounds can be easily obtained, for example, by reducing a ketone having two carbonyl groups sandwiched between two aromatic rings. Bishalides can be synthesized from this according to conventional methods.

In general formulas, it can be represented by formulas (■) and (III).

R4゜ R8 R1@ R1+ A r+c-R+z-C-A r=
(III)0HOH In the formula (■), ([11), A' l and A r3 are aromatic rings, and r2 is an aromatic ring or a group containing an aromatic ring, R16, R11, R1! represents a hydrogen atom, an alkyl group, an aryl group, or a group thereof which may be substituted, and R1□ is a carbon atom number of 1 to 18 which may contain an ether bond, phenylene, ethylene, thioether, etc. -a or more represents a divalent group of

A''+, Ar3 may be a heterocyclic ring.

A specific example of Ar+, , Ars is shown in (IV).

A specific example of Art is indicated by (V).

When R9 OHOH R2° and R8 are aromatic rings, they can have a skeleton represented by (rV).

Specific examples of fluoran derivatives used in the present invention are as follows.

For example, 2-anilino-6-diethylaminofluorane, 2-anilino-3-methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6-N-cyclohexyl-N-methylaminofluorane, 2-anilino-3-methyl-6-diethylaminofluorane, o-Methoxyanilino-6-diethylaminofluorane, 2-(2
-Methylanilino)-3-methyl-6-diethylaminofluorane, 2-anilino-3-ethyl-6-sibutylaminofluorane, 2-anilino-3-methyl6-sioctylaminofluorane, 2-anilino3- Chloro-6
-diethylaminofluorane, 2-anilino-3-methyl-6-N-ethyl-N-isoamylaminofluorane, 2-anilino3-methyl-5-chloro-6-diethylaminofluorane, 2-anilino-3-methyl -6-dinithylamino-7-methylfluorane, 2-anilino-
3-methoxy-6-sibutylaminofluorane, 2-0
-chloroanilino-6-sibutylaminofluorane, 2
-0-chloroanilino-3-ethoxy-6-N-ethyl-N-isoamylaminofluorane, 2-0-chloroanilino-11i-p butylanilinofluorane, 2-anilino-3-pentadecyl-6-diethylaminofluorane , 2-anilino-3-ethyl-6-sibutylaminofluorane, 2-anilino-3-methyl-6-N-furfuryl-N-ethylaminofluorane, and the like can be used.

By changing the number of carbon atoms, substituents, skeleton, etc. of the carbinol used, there is an advantage that the properties of the product can be changed widely.

In the present invention, it is desirable to react the above-mentioned fluoran compound and carbinol compound in the presence of an acid catalyst. In particular, it is preferable to carry out in the presence of a scratching solvent.

For example, 0.3 to 0.6 equivalents, preferably 0.45 to 0.51 equivalents, of a carbinol compound are added to 1 molar equivalent of the above-mentioned fluoran in acetonitrile, using iron chloride, mercaptoglycolic acid, etc. as a cocatalyst, and hydrochloric acid or chloride is added. A method of treatment with hydrogen gas is an example of a preferred method.

Examples of the cicarbinol compound include xylylene glycol, 2,6-bishydroxymethylalkylanisole, 4,4'-bishydroxymethylbiphenyl, 4.
4'-bishydroxymethyldiphenylmethane, 1,4
-bis-α-hydroxybenzylbiphenyl, 4.4'
-bis-α-hydroxybenzyldiphenylmethane, 4
．． Examples include 4'-bis-α-hydroxybisisopropylbenzene and α,α-dimethyl-m-xylylene glycol.

Among them, those having one or more aromatic rings are preferred from the viewpoint of reactivity and handling.

Cicarbinol can be easily obtained, for example, by diacylating benzene, alkylbenzene, diarylalkane, biphenyl, alkylbiphenyl, alkylnaphthalene, etc. and then reducing the resultant.

Alternatively, a carbinol diether having an aromatic hydroxyl group such as 4-hydroxyphenylphenyl carbinol can be used as the starting material.

(Synthesis Example 1) 1,4-bis cp, pα hydroxyhensyl phenyl ether) was used as biscarbinol.

In a flask equipped with a stirrer, 0.10 mole of 2-anilino-3-methyl-6-diethylaminofluorane and 0.05 mole of the above-mentioned biscarbinol were weighed out in acetonitrile. A small amount of iron chloride and mercaptoglycolic acid were added to this, and nitrogen gas and hydrogen chloride gas were passed through the mixture while stirring.

After 12 hours of reaction, the reaction mixture was poured into water and the product was isolated as a viscous oil.

This compound showed a black color upon contact with bisphenol A, and the yield was good.

(Synthesis Examples 2 to 6) Bis-forms were obtained in the same manner as in Synthesis Example 1, except that the following compounds were used in place of 2-anilino-3-methyl-6-diethylaminofluorane.

2-anilino-3-methyl-6-N-methyl-N-cyclohexylaminofluorane (synthesis example 2), 2-anilino-3-methyl-6-N-ethyl-Nisoamylaminofluorane (synthesis example 3) , 2anilino-3-methyl-6
-sibutylaminofluorane (synthesis example 4), 2-N-methylanilino-3-methyl-6-diethylaminofluorane (synthesis example 5), 2-anilino-6-diethylaminofluorane (synthesis example 6) In any case Also, the compounds of Synthesis Examples 1 to 4, which gave products in relatively good yields, exhibited a black phase upon contact with bisphenol 8.

In addition, the colorless dye of the present invention may be a well-known triphenylmethane phthalide compound, a fluoran compound,
Phenothiazine compounds, indolyl (aza, diaza)
Phthalide compounds, leucoauramine compounds, rhodamine lactam compounds, triphenylmethane compounds,
It is also possible to assemble recording materials by using it in combination with various compounds such as diphenylmethane compounds, triazene compounds, spiropyran compounds, and fluorene compounds.

In this case, it is preferable to use the colorless dye described above in an amount of 40% or more in order to improve the properties.

Regarding these, for example, specific examples of phthalides are U.S. Reissue Patent No. 23024, U.S. Patent No. 3491111, and U.S. Patent No. 34
91112, 3491116, 3509174, and specific examples of fluorans are U.S. Pat.
27787, 3641011, 346282B, 3681390, 3920510, 3959571
, specific examples of fluorenes are disclosed in Japanese Patent Application No. 61-240989, and specific examples of spirodipyrans are disclosed in U.S. Patent No. 3,971,808.
, pyridine-based and pyrazine-based compounds are disclosed in U.S. Patent No. 37
No. 75424, No. 3853869, No. 4246318, etc.

Some examples of colorless dyes include crystal violet lactone and 3,3-bis(p-dimethylaminophenyl).
Phthalide, 3-(p-diethylamino-2-ethoxyphenyl)-3-(1-n octyl-2-methylindol-3-yl)phthalide, 3-(p-diethylamino-
2-butoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3-(4-diethylamino-2-ethoxyphenyl)-1-(n-octyl-2-methylindole-3 -il) = 4- or -7
-Azaphthalide, rhodamine-B anilinolactam, 4
．． 4'-bis-dimethylaminobenzhydrin benzyl ether, N-herophenyl leukoolamine, N-
There are 2,4,5-trichlorophenyl leukoolamine, etc., and xanthine compounds include rhodamine-B anilinolactam, rhodamine (p-nitroanilino)lactam, rhodamine-B-(p-chloroanilino)lactam, and 2-di Benzylamino-6 diethylaminofluorane, 2-anilino-6 diethylaminofluorane, 2-
Anilino-3methyl-6-diethylaminofluorane,
2-anilino-3-methyl-6-cyclohexyl-N-methylaminofluorane, 2-0-chloroanilino-6-diethylaminofluorane, 2-(24-dimethylanilino)-3-methyl-6-diethylaminofluorane ,2
-octylidenebisamino-6-diethylaminofluorane, 2-dihexylamino-3-ethyl-6-diethylaminofluorane, 2-m-trifluoromethylanilino-6-dinithylaminofluorane, 2-p-butylanilino -3-chloro-6-diethylaminofluorane,
2-Ethoxyethylamino-3-chloro-6-diethylaminofluorane, 2-p-lyroanilino-3-methyl-6-cyptylaminofluorane, 2-anilino-3
-Methyl-6-sioctylaminofluorane, 2-anilino-3chloro-6-diethylaminofluorane, 3.
6bisdiphenylaminofluorane, 2-anilino-3
-Methyl-6-siphenylaminofluorane, 2-phenyl-6-diethylaminofluorane, 2-anilino-
3-Methyl-6-N-ethyl N-isoamylaminofluorane, 2-anilino-3-methyl-5-chloro-6-
Diethylaminofluorane, 2-anilino-3-methyl-6-diethylamino-7-methylfluorane, 2-anilino-3-methoxy-6-sibutylaminofluorane, 2-o-chloroanilino-6-sibutylaminofluorane, 2 -p-chloroanilino-3-ethoxy6-N
-Ethyl-N-isoamylaminofluorane, 2-0-
Chloroanilino-Gp-butylanilinofluorane, 2
-anilino-3-pentadecyl-6-diethylaminofluorane, 2-anilino-3-ethyl-6-sibutylaminofluorane, 2-anilino-3-methyl-6methyl-xy-4',5'-dichlor Fluoran, 2-O'-) luidino 3-methyl-6-diitubrobylamino 4'5'-dimethylaminofluoran, 2-anilino-3
-Methyl-6-N-ethyl-N-γ-butoxypropylaminofluorane, 2-anilino-3-chloro-6-N
-ethyl N--isoamylaminofluorane, etc. Thiazine compounds include henzoyl]icomethylene flu, p-nitrobenzoylleucomethylene blue, etc. Spiro compounds include 3-methyl-spiro-dinaphthopyran, 3-ethyl spiro - dinaphthopyran, 3
．． 3'-dichlorospiro-dinaphthopyran, 3-penzylspi[''dinaphthothiapyran, 3-methyl-naphtho~
Examples include (3-methoxy-benzo)spiropyran, 3-probyl-spicodihenzobilane, trisdimethylaminofluorene, and trisdibutylaminofluorene.

Examples of the electron-accepting metal compound that imparts coloration upon contact with a colorless dye include conventional compounds such as phenol derivatives, salicylic acid derivatives, metal salts of aromatic carboxylic acid novolacs, and acid clay.

Among these, combinations of phenol derivatives having 12 or more carbon atoms, salicylic acid derivatives having 15 or more carbon atoms, and metal salts thereof, and the coloring agent represented by formula (1) are preferred from the viewpoint of coloring properties and durability of colored images. preferable. Salicylic acid derivatives are particularly preferably di-substituted, and examples of the substituent include an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and a cycloalkyl group having 1 to 8 carbon atoms. Examples include an alkoxy group which may have ~8 positions, an aryl group having 6 to 12 carbon atoms, an arylsulfonyl group, and a halogen atom.

Some examples of phenol derivatives include hexyl-4-
Hydroxybenzoate, 2.2'-dihydroxybiphenyl, 2.2-bis(4-hydroxyphenyl)propane (bisphenol A), 4.4'-isopylidene bis(l-methylphenol), 1.1-bis-(4-
hydroxyphenyl)cyclohexane, 1. 1-bis(3-chloro4-hydroxyphenyl)-2-ethylbutane, 4.4'-5ee-isooctylidene diphenol, 4 tert-octylphenol, 4.4'
-5ec butylidene diphenol, 4-p-butylphenylphenol, 4,4'-isopentylidene diphenol
Nor, 4,4'-methylcyclohequinylidene diphenol, 4,4'-dihydroxydiphenyl sulfide, 1,4-bis-(4'-hydroxycumyl)benzene, 1,3-bis-(4'-hydroxycumyl) mil)benzene, 4,4'-thiobis(6-butyl-3-methylphenol), 4°4'-dihydroxydiphenylsulfone, 4°4'-dihydroxydiphenylsulfone monoisopropyl ether, bis(3-allyl-4- hydroxyphenyl) sulfone, bis(3-methyl-4-hydroxyphenyl) sulfone, 34-dihydroxydiphenyl sulfone, 4-hydroxybenzophenone, 2.
4-dihydroxyhensibuenone, polyvinylbenzyloxycarbonylphenol, 2,4,4'-trihydroxyhensiphenone, 2,2',4,4'-tetrahydroxybenzophenone, dimethyl 4-hydroxyphthalate, 4- Methyl hydroxybenzoate, 2°4.4'-
Trihydroxydiphenylsulfone, 1.5-bis-p
-Hydroxyphenylpentane, 1.5-bis-m-hydroxyphenoxypentane, tolyl 4-hydroxybenzoate, 4-hydroxybenzoic acid α-phenylbenzyl ester, 4-hydroxybenzoic acid M phenylpropyl, 4
-Phenethyl hydroxybenzoate, 4-hydroxybenzoic acid M p-chlorobenzyl, 4-hydroxybenzoic acid M
-p-methoxybenzyl, 4-hydroxybenzoic acid henzyl ester, 4-hydroxybenzoic acid-m-chlorobenzyl ester, 4-hydroxybenzoic acid β-phenethyl ester, 4-hydroxy-2', 4'-dimethyldiphenyl Sulfone, β-phenethyl orcellinate, cinnamyl orcellinate, orcellic acid-〇-chlorophenoxyethyl ester, 0-ethylphenoxyethyl orcellinate, 0-phenylphenoxyethyl orcellinate, m-phenylphenoxyethyl orcellinate 2,4-dihydroxybenzoic acid-β-3'-1-butyl-4'-hydroxyphenoxyethyl ester, 1
-t-butyl-4p-hydroxyphenylsulfonyloxybenzene, 4-N-hensylsulfamoylphenol, 2,4-dihydroxybenzoic acid-p-methylhensyl ester, 2,4-dihydroxybenzoic acid-β-phenoxyethyl Ester, 2,4-dihydroxydi-6-
Benzyl methylbenzoate, methyl bis-4-hydroxyphenylacetate, ditolylthiourea, 4.4'
, diacetyldiphenylthiourea, etc. Some examples of phenol resins include p-substituted phenol formaldehyde resin, p-substituted phenol acetylene resin, and the like. Some examples of salicylic acid derivatives include:
3-phenylsalicylic acid, 3-cyclohexylsalicylic acid, 3.5-di-tert-butylsalicylic acid, 3.5
-di-dodecylsalicylic acid, 3-methyl-5-benzylsalicylic acid, 3-phenyl-5-(α,α-dimethylbenzyl)salicylic acid/IJ! , 3. 5-bis-(α-methylbenzyl)salicylic acid, 3,5-dicyclohexylsalicylic acid, 5-phenyl-3-(α,α-dimethylbenzyl)salicylic acid, 5-t-octylsalicylic acid, 3chloro-5-salicylic acid Myrsalicylic acid, 3-methyl-5t-octylsalicylic acid, 3-methyl-5-cumylsalicylic acid,
3.5-di[-amylsalicylic acid, 3-phenyl-5
-Benzylsalicylic acid, 3-phenyl-5-t-octylsalicylic acid, 3-phenyl-5-α-methylbenzylsalicylic acid, 3.5-di-t-octylsalicylic acid, 3,
5 dicumylsalicylic acid, 5-triphenylmethylsalicylic acid, 5-diphenylmethylsalicylic acid, 4ntadecylsalicylic acid, 5-(1,3 diphenylbutyl)
Salicylic acid, 5-n-octadecylsalicylic acid, 5-dodecylsulfonyl 4J lycylic acid, 3-t-phthyl-5
-α-methylbenzylsalicylic acid, 3-t-butyl-5
-α, α-dimethylhensylsalicylic acid, 5-α-methyl (α phenylethyl) benzyl salicylic fl, 4-β
Examples include (4-methoxyphenoxy)ethoxysalicylic acid, a carboxy-modified product of a terpene phenol resin consisting of gum turpentine and phenol, and a carboxy-modified product of a terpene phenol resin consisting of a diterpene and phenol.

Some examples of aromatic carboxylic acid derivatives include 2-hydroxy-1-benzyl-3-naphthoic acid, pentachlorobenzoic acid, pentafluorobenzoic acid, 3-nitrobenzoic acid, 4-nitrobenzoic acid, and 2β-hydroxy. Examples include ethoxycarbonyltetrachlorobenzoic acid, benzoic acid, pt-butylbenzoic acid, phthalic acid, and gallic acid.

Some examples of aliphatic carboxylic acid derivatives include oxalic acid, maleic acid, tartaric acid, citric acid, succinic acid, and stearic acid.

Furthermore, these organic color developers and polyvalent metal salts such as zinc, magnesium, aluminum, calcium, tin, and nickel, inorganic acids, acid clay, activated clay, attapulgide, bentonite, colloidal silica, aluminum silicate, magnesium silicate, zinc silicate, Examples include tin silicate, zinc rhodan, complexes thereof, chlorinated iron, iron stearate, cobalt naphthenate, ammonium nitrate, and other non-alpha color developers, and one or more of these may be used. Among the metal salts, zinc salts are preferred from the viewpoint of light resistance of colored images.When these colorless dyes and electron-accepting compounds are used in recording materials, they are used in the form of fine dispersions or fine droplets.

For use with pressure sensitive paper, U.S. Patent No. 2,505.47
No. 0, No. 2,505.471, No. 2゜505.489
No. 2,548.366, No. 2,712,507, No. 2,730,456, No. 2,730.457, No. 3. 103. No. 404, No. 3,418.25
It can take various forms as described in prior patents such as No. 0 and No. 4,010°038. Most commonly they consist of at least one pair of sheets containing separately an electron-donating colorless dye and an electron-accepting compound.

For a method of manufacturing capsules, see U.S. Patent No. 2800.4.
57, a method using coacervage gin of a hydrophilic colloid sol described in British Patent No. 867.797, British Patent No. 950,443, British Patent No. 989.
, No. 264, No. 1091.076, and the method described in US Pat. No. 3,103,404.

The capsule wall material is preferably a synthetic resin-based wall material, for example, a polyurethane and/or polyurea-based material, or a melamine resin-based material.

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; Cotton oil; Vegetable oils such as castor oil; Animal oils; Mineral oils or mixtures thereof, etc.)
After dissolving it in 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.

The combination of electron-donating colorless dyes of the present invention has good solubility in synthetic oils such as alkylated naphthalene, alkylated diphenyl, and alkylated diphenylalkanes, so it has the advantage that it can be used in combination with low-solubility paraffinic oils, etc. be.

In addition to the electron-donating colorless dye, ultraviolet absorbers, antioxidants, and the like may be added as additives to the microcapsules. In particular, from the viewpoint of improving the stability of the electron-donating colorless dye in the capsule before use and the coloring of the capsule, benzotriazole-based ultraviolet absorbers, hindered amine-based antioxidants, hindered phenol-based antioxidants,
It is preferable to add an aniline antioxidant, a quinoline antioxidant, or the like.

Electron-accepting compounds, alone or in combination or with other electron-accepting compounds, include styrene-butadiene latex,
A color developer sheet is obtained by dispersing it in a binder such as polyvinyl alcohol and applying it to a support such as paper, plastic sheet, or resin-coated paper together with a pigment described below.

The amount of the electron-donating colorless dye and the electron-accepting compound to be used depends on the desired coating thickness, the form of the pressure-sensitive copying paper, the capsule manufacturing method, and other conditions, and can be appropriately selected according to the conditions. It is the container that determines the amount used.

When used in thermal paper, the electron-donating colorless dye r) and the electron-accepting compound are ground and dispersed in a dispersion medium to a particle size of 10 μm or less, preferably 3 μm or less. A water-soluble polymer aqueous solution having a concentration of about 0.5 to 10% is generally used as the dispersion medium, 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 by weight of the electron-donating colorless dye to the electron-accepting compound used is preferably between 1:20 and I:I, particularly preferably between 1:10 and 2:3; Aromatic ether compounds such as aromatic alkyl or substituted alkyl ethers and/or amides having long-chain alkyl groups disclosed in JP-A-58-57989 and JP-A-58-87094 are used as thermofusible substances. Examples of such ether compounds include phenoxyethyl biphenyl ether, phenethyl biphenyl, bis-β-(2-naphthyloxy)ethyl ether, β-benzyloxynaphthalene, benzylbiphenyl,
-) lyloxyethane, β-phenoxyethoxyanisole, 1-phenoxy-2-p-ethylphenoxyethane or bis-β-(p-methoxyphenoxy)ethquinmethane, l-2'-methylphenoxy-2-41ethylphenoxy siethane, 1-tolyloxy2-p-methylphenoxyethane, l,2-diphenoxyethane, 1
．． 4-diphenoxybutane, bis-β-(p-methoxyphenoxy)ethyl ether, l-phenoxy-2-p
-chlorophenoxyethane, 1-2'-methylphenoxy-241-ethyloxyphenoxyethane, 1-4'
Ethers such as methylphenoxy-2-45-fluorophenoxyethane or 1-phenoxy-2-p-methoxyphenylthioethane, 1,2bis-p-methoxyphenylthioethane, i-tolyloxy-2-p-methoxyphenylthioethane Alternatively, it is preferable to use compounds such as stearamide, methylene bisstearamide, stearanilide, and stearyl urea in combination.

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.

The amount used is 300% for the electron-accepting compound.
It is added in the following weight ratio, particularly preferably 10% or more and 150% 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, pigments, waxes, antistatic agents, ultraviolet absorbers, hindered phenols, antifoaming agents, conductive agents, fluorescent dyes, and surfactants are generally used. Additives such as these are applied to the support to form a recording material.

Specifically, pigments such as kaolin, calcined kaolin, talc, zinc oxide, diatomaceous earth, calcium carbonate, aluminum hydroxide, magnum hydroxide, calcined gypsum, silica, magnesium carbonate, titanium oxide, alumina, and barium carbonate. , sulfuric acid/N-lium, mica, microballoon,
The filler is selected from urea-formalin filler, polyethylene particles, cellulose filler, etc. having a particle size of 0.1 to 15 μm.

Examples of waxes include paraffin wax, carboxy-modified paraffin wax, cowna wax, microcrystalline wax, polyethylene wax, and higher fatty acid esters.

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

Examples of hindered phenols include those having a branched alkyl group adjacent to a phenolic hydroxyl group;
1. l 3-Tris-4-hydroxy-5-t-butyl-2-methylphenylbutane, tetra-t-butylbisphenol A, and the like are used.

Examples of ultraviolet absorbers include cinnamic acid derivatives, benzphenone derivatives, hensitriazolylphenol derivatives, such as α-cyano-β-phenylbutyl cinnamate, 0-hensitriaprilphenol, O-benzotriazolyl-p- Chlorophenol, 0-benzotriazolyl-2
, 4-dibutylphenol, 0-benzotriazolyl-
Examples include p-chlorophenol.

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- Examples include maleic anhydride copolymer, polyacrylic acid, polyacrylic acid amide, methylol-modified polyacrylamide, starch derivatives, casein, and gelatin. In addition, in order to impart water resistance to these binders, water-resisting 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

Furthermore, for the purpose of imparting chemical resistance to the surface of the coating layer, a gelatinizer (hardening agent) consisting of a water-soluble polymer compound such as polyvinyl alcohol, hydroxyethyl starch or Evoquin-modified polyacrylamide and a gelling agent (hardening agent) is added. A layer of about 2μ can also be provided.

The coating fluid is most commonly applied to base paper, wood-free paper or synthetic paper, preferably neutral paper.

Generally, the coating amount is about 2 to Log/rrl based on the solid content.

In addition, when used for thermal paper, OL, S 22285
Various types B described in Japanese Patent Publication No. 81, No. 2110854, and Japanese Patent Publication No. 52-20142 may be used. Alternatively, operations such as preheating, humidity control, or stretching of coated paper may be added prior to recording.

Electric thermal paper is disclosed in, for example, JP-A-41-11344 and JP-A-41-11344;
It is manufactured by the method described in eg No. 148930.

Generally, a coating liquid in which a conductive substance, a basic dye mainly composed of the compound of 2(1) 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. The electrically conductive thermal paper of the present invention is manufactured by coating the conductive layer to form a conductive layer, and then applying 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 pressure sensitive paper is manufactured by the method described in, for example, Japanese Patent Application Laid-open No. 57-179836. In general, photopolymerization initiators such as silver iodobromide, silver bromide, silver hehesate, Michler's ketone, benzoin derivatives, hensifenone derivatives, and polyfunctional heptamers such as polyallyls, poly(meth)acrylates, poly(meth)acrylamides, etc. The crosslinking agent is encapsulated in a synthetic resin wall capsule such as polyether urethane, polyurea, etc. together 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, and was developed by the present inventors.

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

Example 1 ■ 3.5-bis-α-methylbenzylsalicylic acid zinc salt 1 manufactured by J of color developer sheet
0 parts to 1-isopropylphenyl-2 phenyletaph 2
0 parts and dissolved. This was mixed with 50 parts of a 2% polyvinyl alcohol aqueous solution, and l.

% dodecylbenzenesulfonic acid triethanolamine salt aqueous solution and emulsified to have an average particle size of 3 tt.

Next, a dispersion consisting of 80 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, and then, as a binder, 100 parts of a 10% PVA aqueous solution and carboxy-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 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 was dispersed with a sand grinder so that the average particle size was 3 μm. did.

Add 16 parts of 10% PVA aqueous solution to this dispersion, add 10% PVA
Add 100 parts of aqueous solution and 10 parts of carboxy-modified SBR latex (as solid content) to achieve a solid content concentration of 20%.
Water was added to obtain coating/& (B).

Coating liquid (A) and coating liquid (B) were mixed at a ratio of 1:1 in terms of developer, and an air knife coater was used to coat the solid content of 5.0 g/rd onto 50 g/cd base paper. A developer sheet was obtained by coating and drying.

■ Preparation of capsule sheet containing coloring agent Partial sodium salt of polyvinylbenzenesulfonic acid (VER3A, Tl2O3, manufactured by Nassinal Starch) 5
1 part is dissolved in 95 parts of hot water and then cooled. An aqueous sodium hydroxide solution was added to this to adjust the pH to 4.0. On the other hand, 100 parts of diisopropylnaphthalene in which 3.5% of the coloring agent of Synthesis Example 10 was dissolved was emulsified and dispersed in 100 parts of a 5% aqueous solution of a partial sodium salt of the polyvinylbenzenesulfonic acid to form particles with a diameter of 4.0μ. An emulsion was obtained. Separately,
6 parts of melamine, 11 parts of 37% by weight formaldehyde aqueous solution
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 6.0 with a 2M phosphoric acid solution, the temperature of the solution was raised to 65°C, and stirring was continued for 6 hours. This capsule liquid was cooled to room temperature and adjusted to pH 9.0 with an aqueous sodium hydroxide solution.

200 parts of a 10ffi 1% polyvinyl alcohol aqueous solution and 50 parts of starch particles were added to this dispersion,
Water was added to prepare a coating solution containing a microcapsule dispersion with a solid content concentration of 20%.

Apply this coating liquid to 50 g/= base paper at a rate of 5 g/rrr.
The mixture was coated using an air knife coater so that the solid content 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 and color former-containing capsule sheet obtained as described above and color was developed, an extremely clear black image was obtained. Furthermore, even when this colored image was held in a transparent polyvinyl chloride file and further irradiated with light, there was almost no blurring or decrease in density of the image.

Example 2 4 g of the coloring agent shown in Synthesis Example (2) was dispersed with 25 g of a 3.5% polyvinyl alcohol (fineness: 99%, degree of polymerization: 1000) aqueous solution using a sand mill to give an average particle size of 2 μm.

On the other hand, 2-anilino-3-methyl-6-N-methyl-N
- 4g of cyclohexylaminofluorane in 3.5% polyvinyl alcohol (gen fineness 99%, degree of polymerization 1000)
Using a sand mill with 25g of an aqueous solution, the average particle size is 2μ.
dispersed into

10 g of bisphenol A and 8 g of 2-Hensyl 4-sinaphthalene were dispersed in a ball mill overnight with 50 g of a 3% polyvinyl alcohol aqueous solution.

Further, 8 g of β-p-methoxyphenoxyethyloxysalicylic acid and 10 g of zinc oxide were dispersed in a ball mill overnight with 50 g of a 3% polyvinyl alcohol aqueous solution. Furthermore, 1,1. f-) 0.2 g of lis-2'methyl-4'-hydroxy-5'-t-butylphenylbutane is dispersed overnight with 15 g of a 5% polyvinyl alcohol aqueous solution.

After mixing this thoroughly, add 15g of Zidjiakaolin, 1
6 g of particulate silica was added and well dispersed, and 4 g of a 50% dispersion of paraffin wax emulsion 3 (Middle East Oil Cellosol 6428) was added to prepare a coating liquid.

The coating liquid has a basis weight of 45 g/m and is SBI so that the fine lucium carbonate is 2 g/l. The solids coating amount was 5.6 g/
It was applied so that it became ffl. After drying at 60° C. for 1 minute, a super calender was applied at a linear pressure of 50 kirW/cm to obtain a coated paper.

Coated paper is heated by facsimile with energy of 35 m
J/am'' to determine the color density, which was found to be 0.92 using a Maches reflection densitometer.

The obtained recording material was free from fog during raw storage and had excellent stability over time.

On the other hand, the obtained colored images were clear black and showed good resistance to chemicals, water, sunlight, etc.

Claims (1)

[Claims] A recording material that utilizes a coloring reaction caused by contact between an electron-donating colorless dye and an electron-accepting compound, characterized in that it uses an alkylene or arylene bis compound of a fluoran derivative having an anilino group at the 2-position.