JPS59162086A - Recording material using spiro compound - Google Patents

Abstract

PURPOSE:To reduce ground fogging of a recording material and markedly reduce fogging generated during preservation and a lowering of a color development performance with time, by using a specified spiro compound excellent as a coloring matter precursor. CONSTITUTION:A spiro compound of formula I is used in a recording material which provides a colored body on contact with an acid. The spiro compound can be synthesized by a method wherein a compound of formula II is treated with a chlorinating reagent such as phosphorus pentachloride, phosphorus oxychloride or thionyl chloride, and the resultant compound is brought into reaction with a bezoic acid having an amine residue at the meta-position or a derivative thereof. The spiro compound is a colorless or light-colored crystal, has a high solubility to organic solvents, and speedily develops a color when being brought into contact with an electron-acceptive substance. Thus developed coloring matter is extremely stable as compared with a coloring matter formed from a color former, and it hardly undergoes discoloration or decoloration even when being irradiated with light for a long period of time or being subjected to heat or moisture. In the formulas, each of R1 and R2 is H, halogen, alkyl, alkoxy, nitro or the like, R3 is an amine residue, and Y is a group required for forming a 6-membered ring consisting of non-metallic atoms.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a recording material using a spiro compound, and more particularly to a recording material that gives a colored body upon contact with an acid.

The compound according to the present invention is particularly useful as a dye precursor for various printing recording materials such as pressure-sensitive paper, thermal paper, and electrically conductive thermal paper. It is also a compound that can be applied to photosensitive recording sheets, ultrasonic recording sheets, electron beam recording sheets, electrostatic recording sheets, ballpoint pen inks, crayons, etc.

The use of various lactone ring-containing compounds as dye precursors for pressure-sensitive or thermal papers is already well known. 2nd degree, 2t2. /, Specification No. 27, Patent j/-j Zakogu! It is disclosed in Book a. However, the compounds used in these methods have drawbacks such as being unstable in the atmosphere, and the dyes produced by them having poor resistance to light, moisture, etc.

Therefore, an object of the present invention is to provide a durable recording material using a new spiro compound which is particularly excellent as a color patch precursor for a recording material.

The object of the present invention has been achieved by a recording material characterized by using a compound represented by the following general formula (I).

In the above formula, R1 and R2 are hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, nitro groups, amine residues, carbamoyl groups, sulfamoyl groups, acyl groups, cyano groups, and trifluoromethyl groups. R3
represents an amine residue, and Y represents a group necessary to form a t-membered ring consisting of a nonmetallic atom.

In particular, the heat-sensitive recording material containing the spiro compound according to the present invention exhibits excellent performance, with little discoloration of the background and very little deterioration in coloring performance due to aging during storage.

The spiro compound according to the present invention is obtained by treating a compound represented by the following general formula (II) with a chlorinating reagent such as phosphorus pentachloride, phosphorus oxychloride, or thionyl chloride, and then forming an amino acid at the m-position.
It is synthesized by reacting with benzoic acid having a residue or a derivative thereof.

In the above formula, %R1 and R2 are a group selected from a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a nitro group, an amine residue, a carbamoyl group, a sulfamoyl group, an acyl group, a cyano group, and a trifluoromethyl group, Y represents a group necessary to form a ring consisting of nonmetallic atoms.

In particular, it is important that the above formula (IIN-ary1) has a partial skeleton, and (2) it has an amine residue at the m-position of benzoic acid.

(1) Having the N-ary1 partial skeleton (a)
The stability of the compound is increased, and when used as a recording material, the background pg before color development, light fastness after color development, and color erasure are improved. ←) Improves solubility in aromatic solvents. (c) It has good crystallinity, is easy to handle, and is easy to synthesize. (b) It is possible to introduce various substituents such as those mentioned above, and the hue can be controlled over a wide range.

There are 10 points such as　　　　　　　.

(2) By having an amine residue at the m-position of benzoic acid ((a) when the lactone ring opens, this amine residue contributes to the resonance stabilization and conversion of the opened ring). (B) The absorption wavelength can be shifted to the longer wavelength side.

It has the following advantages. Therefore, it is important that the amine residue is at the m-position of benzoic acid, and its electron donating property is 1.
It is mourning.

Preferably, the amine residue is a secondary amine residue having a total number of carbon atoms of lt or less, such as dioctylamino, diallylamino, methyltoluidino, methylcyclohexylamino, piperidino, dipronolylamino, dibenzylamino, diallylamino, piperazino, dibutylamino. , diethylamino, dimethylamino, etc., and dialkylamino, particularly diethylamino, dimethylamino, etc., are convenient from the viewpoint of industrial availability. The same applies to the amine residue of R□%R2, but in this case, primary amine residues such as acylamino, sul-7-amoylamino, ureido, etc. may be used as they have a low contribution to the hue.

As the halogen atom for R□ and R2, a fluorine atom, a chlorine atom, a bromine atom, etc. are convenient, but an iodine atom is not preferred from the viewpoint of stability of the compound.

The 4-alkyl group and alkoxy group may further have a substituent, and examples of the substituent include an aryl group, a halogen atom, alkoxy, aryloxy, and a carbamoyl group. The total number of carbon atoms is preferably about 0.2 or less; if it is too large, it will exhibit unfavorable properties for recording materials, such as decreased solubility and decreased color density.

Y is preferably one that forms an aromatic acid such as a benzene ring or a naphthalene ring, and may be substituted with the above-mentioned R1% R2. The most preferred group is a group forming a substituted or unsubstituted benzene ring.

The spiro compounds according to the present invention are all novel compounds, and have the advantage of being colorless or light-colored crystals, having high solubility in organic solvents, and rapidly developing color when they come into contact with electron-accepting substances. Compared to pigments produced from existing color formers, the nine-color complex is extremely stable and hardly changes color or fades even after long periods of light irradiation, heating, or humidification, making it especially advantageous in terms of long-term preservation of records. It is. In addition, the coloring agent has excellent stability, does not deteriorate or discolor even after long-term storage, and has sufficient coloring ability, making it an excellent coloring agent for recording materials such as pressure-sensitive paper and thermal paper. have.

Examples of preferred compounds of the present invention include the following compounds.

(1) Spiro [acridineta (10H) 1. /'
(j'H)-isobenzofuran)10-phenyl-! ′
-(dimethylamino)-3'-one (2) Spiro[acridineta (lOH), l'(
j'H)-isobenzofuran] lo-(4'-chlorophenyl)-j'-C dimethylamino)-nomethoxy-3'-one (3) spiro[acridineta(/OH
), l'(J'H)-inbenzofuran] IO-phenyl-, t'-C dimethylamino)-nomethoxy-3
'-on (4) spiro [acridinta Cl0H), /'(J'
H)-isobenzofuran] to-(≠-inbutylphenyl) s/-(diethylamino)-3'-one (5) Spiro[acridineta(/OH), 7'
(j'H)-isobenzofuranzlo-phenyl-21
(dimethylamino)-2-n-butoxy-37-one (6n spiro[acridine-ta(10H), l/(J
'H)-isobenzofuran"JIO-(4t-methoxyphenyl)-j'-(dimethylamino)-J-t-octylamino-3'-one (caspiro[acridineta(/OH),/l(J
'H)-isobenzofuran) t, o-(≠-chlorophenyl)-j'-(dimethylamino)-2-isopropylamino-3'-one (8) Spiro[acridineta (10H), l'(j'
H)-isobenzofuran]l0-(≠-dimethylaminophenyl)-yo'-(dimethylamino)-λ-dimethylamin-3'-one 2- (9) Spiro[acridineta(/OH),/'(J
')I)-isobenzofuran)to-(Hiro-methoxyphenyl)-1'-(dimethylamino)-nodimethylamino-3'-one Synthesis Example 1 Spiro[acridine-taCl0H), / / (37H
)-isobenzofuran]10-phenyl-! Synthesis of '-(dimethylamino)-3'-one Attach a stirrer to 7C.
Weigh out the phenylacridone (a, iy), and the phosphorus oxychloride (is, sy) into a three-necked flask of /θOml, and hold at 1000C for 1 hour and 30 minutes while stirring. Run a water pump to reduce the pressure and evaporate to dryness. Then t゛,♂
1 of methyl m-dimethylaminobenzoate was gradually added,
After holding it for 5 hours, pour it into a caustic soda water bath solution・1.toal.・
Extract with ethyl acetate and benzene and dry with anhydrous sodium sulfate. The solvent was distilled off under reduced pressure and purified by column chromatography using silica gel as a carrier and ethyl chloroform-acetate-io'-ate as the developing solvent. A component exhibiting a black color was obtained. This material can be recrystallized from benzene, the elemental analysis values are as follows, and the molecular weight is Hirot r (
MS).

CHN calculated value is 10.3! , 2% iA Tachi actual measurement value
7ri, Ko 21 L3jlt t, Ko 31 Synthesis example λ Spiro [acridineta (/ 01-1 ), /' (j
Synthesis of 'H)-isobenzofuran]10-(≠-chlorophenyl)zl (dimethylamino)-3'-one In place of phenylacridone in Synthesis Example 1, ≠.

The same operation was carried out except that p-chlorophenylacridone of ty was used, and j% caustic soda aqueous solution l! Pour into θme.

Using chloroform-ethyl acetate as a developing solvent, 2ff of a component showing a purple-black color on a silica plate was obtained. The molecular weight was ≠33 cMs).

Next, a specific method for producing a recording material using the spiro compound according to the present invention will be described.

Pressure-sensitive paper using spiro compounds of the present invention is disclosed in U.S. Pat.
．． rot, ≠ No. 70, same, rot, No. 777, same J
,, toj, t, try issue, same 2, j'i#.

,? A6, same, 7/2, 307, 4, 73o,
4A, rt issue, same number λ, 730, g! No. 7, No. 3,
It can take various forms as described in ≠/I, Ko J-0, etc. That is, the above spiro compounds alone or in combination, or together with other dye precursors, solvents (alkylated naphthalene, alkylated diphenyl, styrene timer, diphenylalkane, alkylated terphenyl, chlorinated) R rough in, dibutyl maleate. , synthetic oils such as dimethyl phosphate and dibutyl malonate; vegetable oils such as soybean oil and castor oil; natural oils; mineral oils or mixtures thereof) and dispersed in a binder; It can be obtained by incorporating it into microcapsules and then coating it on a support such as paper, plastic sheet, or resin-coated paper. The spiro compound of the present invention particularly has the advantage of being soluble in the above-mentioned solvents at high concentrations.

The amount of spiro compound used depends on the desired coating thickness, the form of the pressure-sensitive paper,
It varies depending on the capsule manufacturing method and other conditions, so it may be selected appropriately depending on the conditions. When encapsulating a dye precursor in a capsule, a method using coacervation of a hydrophilic colloid sol described in U.S. Pat. No. 2.100.1117 and No. 1rt7.727 Specification, 210. The interfacial polymerization method described in Kou No. 3 Specification, Kou No. 1, OP/, No. 074 No. 8A Specification, etc. can be used.

Next, a general method for producing thermal paper using the spiro compound of the present invention will be described.

A spiro compound, an electron-accepting substance, and a thermofusible substance are sufficiently finely ground and mixed with a liquid in which the binder is dissolved or dispersed in a solvent or dispersion medium, and the mixture is coated on a support such as paper, plastic sheet, resin-coated paper, etc., and dried. By doing so, you can get more. When preparing a liquid mixture, all the components may be mixed at the same time and pulverized, or they may be combined in appropriate combinations, pulverized and dispersed separately, and then mixed.

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

Furthermore, an opacifying agent may be added and mixed during mixing.

The amounts of each component constituting the thermal paper are: 1-2 parts by weight of a spiro compound, 1-4 parts by weight of an electron-accepting substance, and 0 to 10 parts by weight of a thermofusible substance.
30 parts by weight, pigment θ~/! Part by weight, binder/-11
parts by weight and 20 to 300 parts by weight of the dispersion medium (solvent).

As the dye precursor, one or a mixture of spiro compounds of the present invention may be used, or compounds known as coloring agents for pressure-sensitive papers such as crystal violet lactone, benzoyl leucomethylene blue, and fluoran derivatives may be used as the dye precursor. It may be used in combination with a spiro compound. The electron acceptor acid will be described later. Water is most desirable as the dispersion medium (solvent).

Next, all examples of binders used in the present invention are shown -/! - and styrene-butadiene copolymers, alkyd resins, acrylamide copolymers, vinyl chloride-vinyl acetate copolymers, styrene-maleic anhydride copolymers, synthetic rubbers, gum arabic, polyvinyl alcohol,
Examples include hydroxyethylcellulose.

In particular, water-soluble binders such as gum arabic, polyvinyl alcohol, hydroxymethylcellulose, and carboxydimethylcellulose are desirable in relation to the dispersion medium (solvent).

Thermofusible substances include stearamide, erucamide, oleic acid amide, stearanilide, ethylene bisstearamide, benzoin, α-naphthol benzoate, β-naphthol p-methylbenzoate, Varar t-butylphenol. Phenoquizoacedate, rose-phenylphenol p-chlorophenoxyacetate, 4', Hiro'-cyclohexylitine diphenol diacetate, Hiro, 4t'-isopropylidene diphenol, β-phenylethyl-p-enylphenol ether , phthalic anhydride, maleic anhydride, stearic acid, erucic acid, nomilmitic acid, para-hydroxybenzoic acid methyl ester, phthalic acid sheephenyl ester, triphenyl phosphate, hala-hydroxydiphenyl ether, 2,2-bis(4'- It is possible to use one or more of (β-hydroxyethoxy)phenyl)bronoξ, /ξmirabisβ-hydroxyjethoxy)benzene, hydroquinone diacetate, and the like.

These substances are colorless solids at room temperature and have a sharp melting point at a temperature suitable for heating for copying, that is, around 70 to 100C.

These are substances that dissolve at least one, preferably both, of the color patch precursor and the electron-accepting substance in a molten state.

In addition, examples of electron-accepting compounds include acid clay, phenolic compounds, organic acids or their metal salts, oxybenzoic acid esters, etc. In particular, phenolic compounds and salicylic acid derivative metal salts require only a small amount. , is preferably used, for example US time f (3,4t/1,210.
! , 1732, 3.17.3.911, 121, 3. ri93.13/, j.

Tata t, lit, J, Tata t, +tos, ≠, 000
．． 017, Tokko Akira≠j-/G032, Tokko Akira! l-λ
It is described in detail in the rJo issue and others.

Specifically, ≠-tertiary butylphenol, ≠-
phenylphenol, ≠-hydroxydiphenonoxide, α-naphthol, β-naphthol, methyl-≠-hydroxybenzony), 2. ．． 2'-dihydroxybiphenyl, λ, -monobis(≠-hydroxyphenyl)pronozone (bisphenol A), 4't≠'-isopropylidene bis(comethylphenol), 1ll-
Bis-(!J-chloro-hydroxyphenyl)cyclohexane%/11-bis-(3-chloro-≠-hydroxyphenyl)-λ-ethylbutane, +, 4I-'-
Secondary imbutylidene diphenol, g-hydroxybenzoic acid benzyl ester, g-hydroxybenzoic acid-m-chlorobenzyl ester, l-hydroxybenzoic acid β-phenethyl ester, J, J-l 7-zinc di-t-butylsalicylate, 3. j-di-α-methylbenzylsalicylic acid zinc, rhodan zinc, 3°! -Zinc also includes zinc monooctylsalicylate.

In order to produce an electrically conductive thermal paper using the spiro compound of the present invention, JP-A Akihirota//J≠l, JP-A-Koji O-4
The method disclosed in 0 is helpful.

That is, a conductive substance, a spiro compound, and an electron-accepting substance are placed on a support such as paper, together with a binder, in a dispersion medium such as water.
A conductive layer is formed by applying a liquid containing a hot or dispersed substance, or by coating the entire conductive substance on the support, and then coating the entire liquid dispersed in water or the like together with a spiro compound and an electron-accepting substance lavinder. obtained by. Note that the temperature at which both the spiro compound and the electron-accepting substance are preferred (generally 70 to 1
If the material does not melt at 300 C2), a thermofusible material that melts at a preferred temperature and dissolves at least one of the spiro compound or the electron-accepting material can be added. By doing this, the sensitivity to Joule heat caused by energization'
fr: Can be prepared.

-/1- As the electron-accepting substance and the thermofusible substance, the same substances as those described in the method for producing thermosensitive recording paper can be used.

In order to produce a recording sheet using the spiro compound of the present invention, it is necessary to
, Tokko Sho 4Ar-/3.2jl, Tokko Sho ≠ Turco O Hiro,
Patent Akiko Tarco 6 col λ, Patent Koko Sho μ Turco r4tp2, Published Patent Publication No. 77-3/Bu II, Published Patent Application No. 441-32132, Published Patent Publication No. 441-32132, Published Patent Publication No. 449-/3j417,
Lactone compounds, lactam compounds, spiropyran compounds, which are used in JP-A-10-17317, JP-A-17317, JP-A-1999-1, etc., weighed to one λl,
It is produced by using the spiro compound of the present invention in place of or together with a dye precursor such as a carhinol compound, an ethylene compound, a leucoauramine compound, or an oxazine compound.

Other recording materials can also be produced by using the spiro compounds of the present invention in place of conventional dye precursors.

Example/ One part (by weight, the same shall apply hereinafter) of the spiro compound of the present invention (compound 1) was converted into alkylated naphthalene 1. It was dissolved in 73 parts and 2 parts of siftyl maleate.

This solution was added to 50 parts of water in which 1 part of gelatin and 1 part of gum arabic had been dissolved, with vigorous stirring, and emulsified.
After forming oil droplets of 6 μm in size, 20 parts of water was added. Acetic acid was added little by little to bring the pH to approximately ≠ to cause coacervation, and a wall of gelatin and gum arabic was formed around the oil droplets.Formalin was added, and then the pH was raised to harden the wall.

The microcapsule dispersion thus obtained was applied to paper and dried. This paper is treated with acidic organic matter, phenolic resin, ≠
, San'-inpropylidenediphenol, 31! -ji(
When in contact with paper coated with zinc α-methylbenzyl) salicylate, benzyl p-hydroxybenzoic acid ester, zinc nomiladolenesulfonate, alone or in mixtures, etc. When pressure was applied, a black image was instantly obtained. This image had high density and excellent light and heat resistance.

Example! A microcapsule-coated paper was prepared in the same manner as in Example 1 except that the compound in Example 1 was replaced with the compound in Example 1 as a coloring agent, and ditolylethane and dimethyl succinate were incorporated in the solvent. A pressure-sensitive paper was obtained that developed color quickly and with high density, and the colored characters had extremely excellent light resistance and heat resistance.

Example 3 20 parts of the spiro compound of the present invention (compound 3), noanilino-3-methyl-6-cyptylaminofluoro2
The dispersion was prepared by mixing and grinding 10 parts of a 10% aqueous solution of polyvinyl alcohol and 70 parts of water using a sand mill. The particle size after milling was approximately 2.5 microns. (Component A) stearyl urea, on the other hand 30 parts of bisphenol As''m stearyl urea, isom 70%
A dispersion was prepared by mixing and grinding an aqueous polyvinyl alcohol solution and 55 parts of water using a sand mill. The particle size after crushing was approximately 2 microns. (Component B) Next, 1 part of Component A and 30 parts of Component Bt were mixed, applied to paper, and dried to obtain thermal paper. □ This thermal paper turns black when heated with a hot blower. Also, when this thermal paper was overlapped with the original image and heated in a thermal copying machine, a black copy image was obtained.The color image obtained was very stable against light, and the image was irradiated with an ultraviolet lamp for 7 hours. However, there was almost no change in hue or density.

Patent applicant: Fuji Photo Film Co., Ltd. -, 2! −

Claims (1)

[Scope of Claims] A recording material characterized by using a compound represented by the following general formula (I), where R□ and R2 are a hydrogen atom, a hydrogen atom,
Alkyl group, alkoxy group, nitro group, amiyfi group,
A group selected from a carbamoyl group, a sulfazoyl group, an acyl group, a cyano group, and a trifluoromethyl group, R3 represents an amine residue, and a group necessary to form a t-membered ring consisting of a YFi nonmetal atom.