JPS5911286A - Pressure-sensing or thermo-sensitive recording material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a pressure-sensitive or heat-sensitive recording material containing at least one metal complex compound represented by formula (1) as a color developer.

(R) ye (An) n/r
(1)-n In the formula, (7) Me is a zero-valent metal ion, and R is a colorless organic monodentate or monodentate ligand that forms a complex with the metal ion via a heteroatom. An is an r-valent anion, k is the coordination number of the metal ion and is 4 or 6 depending on the type of metal, n is 1, 2, 3 or 4, and r is 1 or 2.

The metal complex compound used in the present invention has an atomic weight of 24 to 210
, preferably 40 to 140, most preferably 50
It is advantageously derived from 120 to 120 divalent, trivalent or tetravalent metals. Examples of such metals include aluminum, barium, lead, cadmium, calcium, chromium, iron, gallium, cobalt, copper, magnesium, manganese, molybdenum, nickel, mercury, silver, strontium, tantalum, titanium, vanadium, Tungste (8
), zinc, tin, and zirconium. Preferred metals are barium, cadmium, calcium, mankanium, strontium, titanium, vanadium, and tin, and a particularly preferred metal is zinc.

The colorless organic ligand of the metal complex compound of the present invention includes R and (
k-n) can be combined with the metal ion Me via 1, 2 or 3 heteroatoms to form a complex. Suitable heteroatoms include, for example, nitrogen, oxygen, sulfur, selenium, and phosphorus, of which nitrogen is preferred.

In the metal complex compound of formula (1) used as a color developer, the (k−n) ligands R may be the same or different, but they are the same monodentate ligands. It is preferable to have one.

The value of (k−n) cannot be 0. Preferably, k is 4 and n is 2. r is usually 1.

The colorless ligand of the metal complex compound of the present invention is monodentate, bidentate,
or a nitrogen atom in a tridentate molecule, such as a nitrogen atom found in a primary, secondary, or tertiary amino group, a substituted or unsubstituted imino group, a nitro group, an oximino group, a hydrazino group, or a hydrazino group. It is preferable that the metal ion is bonded to the metal ion via elementary atoms (plural atoms) to form a complex.

Monodentate (monofunctional) ligands containing nitrogen include, for example, nitrogen-containing secondary or tertiary saturated or unsaturated heterocyclic ring systems in which one or more nitrogen atoms In addition to those contained as ring members, aliphatic,
Cycloaliphatic, aromatic, aryl substituted aliphatic (aral
iphatic) or heterocyclic amines.

Representative aliphatic, cycloaliphatic, and aryl-substituted aliphatic nitrogen-containing ligands include, for example, methylamine, ethylamine, n-probylamine, isoprobylamine, n-
C□-C1g alkylamines such as butylamine, n-hexylamine, n-octylamine, isooctylamine, n-decylamine, n-dodecylamine, and ophtaterylamine (stearylamine); such as cyclopentylamine and cyclohexylamine. Cycloaliphatic amines; examples include benzylamine, 4-methylbenzylamine, and α- or β-phenyl-ethylamine. Particularly preferred is α-phenylethylamine.

Examples of secondary heterocyclic ligands containing nitrogen as a heteroatom include pyrrolidine, piperidine, pipecoline,
Morpholine, thiomorpholine, imidacilline, indoline, benzomorpholine, benzomorpholine, tetrahydroquinoline, and 2,2,4-)lyntyltetrahydroquinoline are suitable.

The colorless organic ligand of the metal complex compound used in the present invention is preferably a monodentate aromatic amine, particularly an aromatic nitrogen-containing heterocyclic ring system.

Examples of aromatic amines include aniline; (11) Nuclear substituted anilines such as luaniline, methoxyaniline, and dichloroaniline; N-methylaniline, N-ethylaniline, N,N-dimethylaniline, N,N-diethyl N-alkyl- or N,N-dialkyl- such as aniline
Anilines; furthermore, diphenylamine, 4゜4'-diaminodiphenyl ether; 4,4'-diaminodiphenyl sulfide; 4,4'-diaminodiphenylsulfone;4,4'-diaminodiphenylmethane and 4,4'-diaminodiphenylethane; Like 4,
4'-diaminodiphenylalkane;4,4'-
Diaminoazobenzene is suitable.

Particularly suitable organic ligands are 5- or 6-membered aromatic heterocycles containing nitrogen as a heteroatom, wherein the heterocycle is an auto-C18 alkyl group, more preferably an auto-C4 alkyl group, Self-C4 alkoxy group, cyano group, hydroxyl group, vinyl group, phenyl group, ClC4 acyl group, or amino (1
2) It may be substituted with a group and/or it may form a condensed ring with a benzene nucleus, and this benzene nucleus is substituted with, for example, a halogen atom, a C1-C4 alkyl group, or an auto-C4 alkoxy group. You can leave it there.

Specific examples of such ligands include pyrrole, 2,4
-dimethylpyrrole, pyrrolidone, imidazole, 1-
Methylimidazole, 2-methylimidazole, 1-vinylimidazole, 2-phenylimidazole, pyrazole, 3,4-dimethyl-5-pyrazolone, triazole, pyridine, α-1β-1 or γ-picoline, lutidine, collidines, parvoline , conilines, methoxypyridines, aminopyridines (e.g. 3-aminopyridine, 2,3-diaminopyridine, 2,6-diaminopyridine), 4-formylpyridine, 4-cyanopyridine, pyrimidine, pyrazines, triazine , melamine, guanamines, amerine, quinoline, 2-ethylquinoline, isoquinoline, quinaldine, quinazoline, quinoxaline, phthalazine, dinoline, indolizine, indoles (e.g. 2-methylindole, 2-phenylindole), benzimidazole, 2- Methylbenzimidazole, 1,2-dimethylbenzimidazole, 2-stearylbenzimidazole, 2-aminobenzimidazole, benzoxazole, benzothiazole, 2-
Thiobenzothiazole, 2-aminobenzothiazole,
Examples include benzotriazole, carbazole, acridine, phenazine, antipyrine, diguanamine, guanidine, bipyridyl, 2 + 6- (di-2-pyridyl)-pyridine (terpyridyl), phenanthroline, phenanthroline, and dipyridyl ketone.

Particularly preferred metal complex compounds include pyridines, picolines, imidazoles, benzimidazoles, benzothiazoles, and quinolines as the colorless heterocyclic ligand R.

R can also be a nitrogen-containing ligand with bidentate (bifunctional) or higher functionality.

In this case, the plurality of nitrogen atoms bonded to the metal in the ligand are carbon atoms or saturated or unsaturated two- or three-membered chain bonds consisting of carbon atoms and nitrogen atoms. It is highly preferable that they be connected to each other via. Specific examples of such ligands are alkylene diamines such as ethylene diamine and propylene diamine, phenylene diamine chains, dialkylene triamines, and triaminoalkanes. Dialkylene triamines are, for example, diethylene triamine, monoethylene-monopropylene triamine, dipropylene triamine, and N-alkyl derivatives thereof, and triaminoalkanes are, for example, α, β, γ-triaminopropane, α ,β
.

δ-triaminobutane, and α,γ-diamino-β-
(aminoethyl)propane.

(15) A plurality of nitrogen atoms bonded to a metal and a plurality of carbon atoms bonded to them can also form one heterocycle or one heterocyclic ring system. Representative examples of such bidentate nitrogen-containing ligands are piperazine, imidacilline, and diazobicyclo[2,2,2]-octane.

Other compounds suitable as nitrogen-containing ligands are hydrazines such as hydrazine, C1-C5 alkyl-hydrazine, arylhydrazine (Phenylhydrazinhiko); hydrazones such as acetone hydrazone, acetophenone hydrazone; acetadratide, benzadratide hydratides such as hydroxylamine; amidines such as formamidine; amides such as formamide, dimethylformamide, tetramethylurea, acetamide, benzamide; and oximes such as acetaldoxime and acetoxime.

The ligand R in the metal complex compound of the present invention can also be coordinated via an acid (16) atom, a sulfur atom, or a phosphorus atom.

Examples of organic ligands that coordinate via an oxygen atom or a sulfur atom include carbonyl compounds such as benzophenone and pyrone, amine oxides, phosphine oxides such as triphenylphosphine oxide, urea, thiourea, etc. Thiocarbonyl compounds and their substituted products include 4,4'-bis(dimethylamino)benzophenone (
Michler's ketone) is suitable. moreover,
Examples of the ligand containing a sulfur atom include mercaptans such as 2-mercaptobenzthiazole, and thiones such as 3-dimethylimidacylin-2-thione. Examples of organic ligands that bond to metals via phosphorus atoms include phosphines such as triphenylphosphine.

Suitable anionic groups An are found in inorganic as well as organic ions. Depending on the value of r, this anion may be monovalent or divalent.

Inorganic anions include halide ions such as chloride, bromide, fluoride, and iodide; residues of sulfur-containing acids such as hydrozine sulfate, sulfates, binary acids, and amino sulfuric acids; cibide rosin phosphate,
Residues of phosphorous oxyacids such as hydrosine phosphate, phosphate, metaphosphate; residues of nitrogen-containing oxyacids such as nitrate ions; carbonate ions such as bicarbonate, carbonic acid; anions of other oxyacids and complex acids; for example,
Methosulfate, ethosulfate, hexafluorosilicate, cyanate, thiocyanate, hexacyanophelate (■), hexacyanophelate (I),
Trichlorozinc acid, tetrachlorozinc acid, tribromozinc acid, tetrabromozinc acid, stannic acid, boric acid, divanadic acid, tetravanadic acid, molybdic acid, tungstic acid, chromic acid, dichromic acid, tetrafluoroboric acid, boric acid Examples include borate ester anions such as glycerin ester anions, and phosphate ester anions such as methyl phosphate anions.

Organic anions include saturated or unsaturated aliphatic, cycloaliphatic, aromatic, aryl-substituted aliphatic, and heterocyclic carboxylic or sulfonic acid anions.

Suitable aliphatic anions are, for example, acetic acid, halogenacetic acid, aminoacetic acid, cyanoacetic acid, thioacetic acid, propionic acid, hydroxypropionic acid, butyric acid, halogenbutyric acid, thioglycolic acid, glyceric acid, phosphoric acid, valeric acid. , caproic acid, lauric acid, palmitic acid, stearic acid, oleic acid, ricinoleic acid, coconut oil acid, acrylic acid, methacrylic acid, crotonic acid, propalkyl acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, Pimelic acid, superric acid, azelaic acid, sebacic acid, tartaric acid, citric acid, fumaric acid, male (19) inic acid, itaconic acid, aminoethylsulfonic acid, nitrilosulfonic acid, methanesulfonic acid, ethanesulfonic acid,
It is an anion such as paraffin sulfonic acid (mersolate).

Suitable alicyclic anions are, for example, anions such as cyclohexanoic acid and 3-cyclohexenoic acid.

Suitable aromatic anions are, for example, benzoic acid, methylenebenzoic acid, tert-butylbenzoic acid, chlorobenzoic acid, nitrobenzoic acid, hydroxybenzoic acid, methoxybenzoic acid, aminobenzoic acid, phthalic acid, halogens. These are anions such as phthalic acid, isophthalic acid, sulfobenzoic acid, benzenetetracarboxylic acid, abietic acid, hydroxynaphthoic acid, diphenylcarboxylic acid, naphthalenetetracarboxylic acid, benzenedicarboxylic acid, toluenesulfonic acid, and naphtholsulfonic acid.

Suitable aryl-substituted aliphatic anions are those such as phenylacetic acid, methylphenylacetic acid (20) and mandelic acid.

Suitable heterocyclic anions are, for example, pyromucic acid, dehydromucic acid, indolyl-3-acetic acid, 5-
It is an anion such as quinoline nonaphonate.

Preferred anions as An include halide ions such as chloride, bromide, and iodide, pseudohalide ions such as thiocyanate, other inorganic acid ions such as nitrate, sulfate, phosphate, and borate, and furthermore, formic acid, acetic acid, and propion. acid, an organic acid ion such as citric acid, stearic acid, benzoic acid, oxalic acid, phthalic acid, etc., and the most preferred anion An is thiocyanate ion.

An interesting color developer is one of formula (2).

In the formula, M e 1 is a monovalent metal ion with an atomic weight of 40 to 140; R1 and R2 each independently represent a monodentate 5- to 6-membered aromatic N-heterocyclic ring system, which is It forms a complex with the metal ion via a nitrogen atom, and this heterocycle has one or two cyano groups, vinyl groups, formyl groups, phenyl groups, or c, C1g alkyl groups, preferably methoxy or may contain a fused benzene ring. The valence n of the metal ion is preferably 2.3 or 4.

In formula (2), Mel is particularly preferably a cadmium ion, most preferably a zinc ion. Preferably, R1 and R2 are the same and each is a pyridine, quinoline, imidazole, or benzimidazole ligand, and this ligand forms a complex with a metal ion via its nitrogen atom. N-heterocycle is methyl,
Substituted or unsubstituted with methoxy, cyano, vinyl, formyl, phenyl, or amino. Particularly preferred ligands R, and Rzld pyridine, picoline, 2
-methoxypyridine, quinoline, imidazole and penzimidazole, most preferred are benzothiazole, 1-methylimidazole and 2-methylimidazole.

Although some of the compounds of formulas (1) and (2) used in the present invention are known compounds, they constitute a new group of color developers, ie, electron acceptors, for color formers. These are obtained by methods known per se. For example, although it differs depending on the type of ligand, one metal atom is n /
Reacting 1 mole of an inorganic or organic salt of a metal (e.g. zinc thiocyanate or zinc acetate) containing r moles of inorganic or organic moieties with (k−n) moles of the corresponding monodentate or polydentate ligand. obtained by letting This reaction is conveniently carried out in a polar solvent. A small amount of catalyst may or may not be added.

(23) Water or water-miscible organic solvents are suitable as this solution.

Water-miscible solvents include aliphatic C solvents such as methanol, ethanol, propatool, and isobutanol.
, -C, alcohol; alkylene glycols such as ethylene glycol and propylene glycol; monoalkyl ethers of glycols such as ethylene glycol monoethyl ether, monoethyl ether, monobutyl ether, diethylene glycol monomethyl ether and monoethyl ether; acetone; Ketones such as methyl ethyl ketone, cyclohexanone, and diacetone alcohol; ethers or acetals such as diisopropyl ether, diphenyl oxide, dioxane, and tetrahydrofuran, as well as tetrahydrofurfuryl alcohol, pyridine, acetonitrile, γ-butyrolactone, N,N-dimethylformamide , N,N-dimethylacetamide, tetramethylurea, tetramethylenesulf(24)phone, etc. are used.

The reaction can usually be carried out at room temperature (20-25°C), but sometimes higher temperatures are required, such as 40-150°C.
It may be preferable to use a temperature range of . It is also possible to react the reactants in the molten state. Examples of melting aids in this case include lower fatty acid salts such as sodium acetate, lower fatty acid amides such as acetamide, urea, thiourea, N-
Substituted substances etc. are suitable.

The metal thiocyanate complex is prepared by mixing a metal donor with a solution of an alkali thiocyanate, ammonium thiocyanate, or preferably potassium thiocyanate in one of the above polar solvents, and then combining this mixture with the desired coordination. It is suitably obtained by reacting with a child.

Preferred metal donors are metal salts of strong mineral or organic acids, especially sulfates, halides, nitrates, formates, acetates.

Known metal complex compounds of formulas (1) and (2) and their production methods are described, for example, in the Gmelins Handbuch Derano Chemistry Handbook.
(Zinc), Volume 32, Page 271 (Zinc), and the same supplement (Supplement).
(1956)
"Zinc", pp986-987, and I Nis Ahuja (I.

S, AHυJA) and Ní Garda (A, Gar
g), J, inorg, nucl, Chem,
34.1929-1935 (1972).

The compound of formula (1) is substantially colorless and odorless, and is highly reactive with conventionally used coloring agents.
Natural, stable, non-fading reproducible.

Color formers suitable for use in the recording or copying materials of the invention are known colorless or slightly colored chromogens of the formula (1
) becomes colored or changes color when brought into contact with metal complex compounds.

For example, azomethines, fluorans, benzofluoranes, phthalides, spiropyrans, spiropyrans, leuphoramines, triarylmethaneleucodyes, rubazolylmethanes, chromenoindoles,
Color formers belonging to chromenopyrazoles, phenoxazines, phenothiazines, etc., or mixtures thereof, and chromeno or chromano color formers can be used.

Specific examples suitable as such color formers are as follows. Crystal Violet Lactone (registered trademark), 3.3-bis(aminophenyl)-phthalide,
3.3-bis(substituted indolyl) phthalide, 3-aminophenyl-3-indolyl phthalide, 6-dialkylamino-2-n-octylaminofluorane, 6-
dialkylamino-2-arylaminofluorane, 6
-Dialkylamino-3-methyl-2-arylaminofluorane, 6-dialkylamino-2- or -3-lower alkylfluorane, 6-dialkylamino-2-dibenzylaminofluorane, 6-pyrrolidino-2-aryl -aminofluorane, bis(aminophenyl)fur(27) furyl-1-phenyl-1 or -carbazolylmethane,
3'-phenyl-7-dialkylamino-2,2'-spirodibenzopyran, bis(dialkylamino)benzhyttrol-alkyl- or -aryl sulfinates, benzoyl dialkylphenothiazines, and benzoyl dialkylaminophenoxazines.

The compound of formula (1) is suitable for use as a color developer in pressure-sensitive or heat-sensitive recording materials. This recording material can also be used as a copying material.

The pressure-sensitive material includes, for example, at least one pair of sheets each containing at least one color former dissolved in an organic solvent and a color developer represented by formula (1).

The color developer is preferably applied in a layered form to the front surface of the transfer sheet.

The color developers of formula (1) can be used in combination with each other or with other known color developers. Typical examples of known color developers are attapulgite, acid clay, (28) active materials such as bentonite, montmorillonite, acid-treated activated clays such as bentonite or montmorillonite; Also, zeolite, halloysite, silica, alumina, aluminum sulfate, aluminum phosphate, zinc chloride, zinc nitrate, kaolin, or various clays; furthermore, for example, unsubstituted phenols, nuclear substituted phenols, salicylic acid, salicylic acid esters, metal salts thereof, etc. acidic organic compounds; e.g.
These are acidic polymers such as carbolic acid polymers, alkylphenol acetylene resins, maleic acid-rosin resins, partial or complete hydrolysates of copolymers of maleic acid and styrene, ethylene, or vinyl methyl ether, and carboxypolymethylene.

Color developers can also be combined with other fundamentally inert or nearly inert pigments, as well as auxiliaries such as silica gel, UV absorbers such as 2-(2-hydroxyphenyl)penztriazole and its derivatives, etc. They can also be used together. Examples of pigments include clays such as talc, titanium dioxide, zinc oxide, chalk, and kaolin, and urea/formalin condensates [BET method, specific surface area 2-75].
m'/g), and organic pigments such as melami condensed water and luminaldehyde condensates.

The color former produces a colored mark where it comes into contact with the developer. In order to prevent the color forming agent contained in the pressure-sensitive recording material from developing color before use, the color forming agent is usually separated from the groove coloring agent. For this purpose, it is convenient to incorporate the color former into a foam-like, sponge-like or honeycomb-like structure. A preferred method is to encapsulate the color former in microcapsules; these microcapsules are generally rupturable under pressure.

When the microcapsules are ruptured with pressure, for example a pen pressure, and the color former solution is thus transferred to an adjacent sheet coated with the developer of formula (1), a colored area is created. The color is due to the dye produced, which absorbs in the visible portion of the electromagnetic spectrum.

It is preferable to encapsulate the coloring agent in a state in which it is dissolved in an organic solvent. Suitable solvents are preferably non-volatile, such as polyhalogenated paraffins such as chlorinated paraffins; polyhalogenated diphenyls such as monochlorodiphenyl, trichlorodiphenyl; tricresyl phosphate and di-n-butyl phthalates; aromatic ethers such as benzyl phenyl ether; hydrocarbon oils such as paraffin and kerosene; alkylated (e.g. isopropylated or isobutylated) diphenyl derivatives; also diphenylalkanes, naphthalene, triphenyl, dibenzyltoluene, terphenyls, etc. Partially hydrogenated terphenyl, benzylated xylene, other hydrogenated or hydrogenated or condensed aromatic hydrocarbons, etc. are used.

Mixtures of different solvents are often used to obtain optimal solubility for color development, rapid and intense coloration, and favorable viscosities for microencapsulation (31).

A uniform capsule shell wall can be generated around the droplet of color former solution by coacervasion. The encapsulant may also consist of gelatin and gum arabic, as described, for example, in US Pat. No. 2,800,457. However, British Patent Specification No. 98
As described in No. 9264, No. 1156725, No. 1301052, and No. 1355127,
It can also be suitably made from amino resins or modified amino resins by polycondensation. By interfacial polymerization, e.g. polyester, polycarbonate, polysulfonamide,
Alternatively, microcapsules made from polysulfonates, especially polyamides or polyurethanes, are also suitable.

The microcapsules containing color formers, in combination with the present color developer, are used in the production of a wide variety of known types of pressure sensitive copying materials. Various types of reproduction systems differ substantially in the arrangement of microcapsules, (32) coloring reactant or developer, and support. Among these, preferred is one in which the microencapsulated color former is arranged in a layer on the back side of the transfer sheet, and the color developer is arranged in a layer on the front side of the transfer sheet.

Another different arrangement is that the microcapsules containing the color former and the color developer form one or more layers each in or on the same sheet, or they are present in the paper pulp. It is something to do.

Preferably, the microcapsules are fixed to the support by a suitable adhesive. The preferred support is paper, and these adhesives are primarily paper coatings such as gum arabic, polyvinyl alcohol, hydroxymethylcellulose, casein, methylcellulose, dextrin, starch, polymer latex, and the like.

As this latex, for example, butadiene/styrene copolymer, acrylic homopolymer, or copolymer latex is used.

The paper used is not only a conventional paper made from cellulose fibers, but also one in which the cellulose fibers have been partially or completely replaced by synthetic polymers.

The metal complex compound of formula (1) can also be used particularly in heat-reactive recording materials.
Used as a color developer. This recording material usually consists of at least one
It includes a species carrier, a color former, and an electron acceptor, and optionally a binder and/or wax.

Thermoresponsive recording systems include, for example, thermosensitive recording materials, copying materials and paper. These systems record information,
For example, electronic computers, teleprinters or telewriters,
It is also used in recording and measuring instruments such as electrocardiographs. In this case, the image (symbol) can be created manually using a heated pen, or a thermal indicator mark can be created using a laser beam. In a heat-reactive recording material, a color former is dispersed or dissolved in one binder layer, and a color developer is in a second layer.
can be made to be dissolved or dispersed in a layer of binder. It is also possible to disperse the color former and the color developer in one layer. The heat softens the binder in certain areas, the color former comes into contact with the developer at the point where the heat is applied, and the desired color immediately appears. The color developer of formula (1) can be used alone, or in combination of two or more types, and further mixed with other known color developers for use in heat-sensitive recording materials.

For this purpose, in addition to the known color developers as for pressure-sensitive recording papers, for example 4-tert-butylphenol, 4-phenylphenol, 4-hydroxydiphenyl ether, α-naphthol, β-naphthol can be used. , 4-
Hydroxybenzoate-methyl, -ethyl, -n-butyl, -benzyl, 4-hydroxyacetophenone, 2,
2'-dihydroxydiphenyl, 4,4'-isopropylidene diphenol, 4'-4'-isopropylidene-bis(2-methylphenol), 4,4'-bis(hydroxyphenyl)valeric acid, hydroquinone, pyrocaloe (
35) Phenolic compounds such as 1, phloroglucin, p+, m-1 and 0-hydroxybenzoic acid, gallic acid, 1-hydroxy-2-naphthoic acid; and boric acid; organic dibasic carboxylic acids, preferably fats. Group dibasic carboxylic acids such as tartaric acid, oxalic acid, maleic acid, citric acid, citraconic acid, succinic acid, etc. are used.

For the production of heat-reactive recording materials, it is preferable to use a binder that is meltable and has film-forming ability. Such binders are usually water soluble, whereas color formers and developers are water insoluble. The binder must be capable of dispersing and fixing the color former and developer at room temperature.

The binder is softened or melted by heating, the color forming agent comes into contact with the color developer, and a color is formed.

Specific examples of binders that are soluble or at least swell in water include polyvinyl alcohol, polyacrylic acid, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, polyacrylamide, polyvinylpyrrolidone, gelatin, starch, and etherification. Hydrophilic polymers such as cornstarch.

If the color former and developer are present in two separate layers, a water-insoluble binder, i.e. a non-polar or slightly polar solvent-soluble binder, such as natural rubber, synthetic rubber, Binders such as chlorinated rubber, alkyd resin, polystyrene, styrene/butadiene copolymer, polymethyl acrylate, ethyl cellulose, nitrocellulose, polyvinyl carbazole, and the like can be used. However, it is preferable to contain the color former and the color developer in a single layer in the water-soluble binder.

The heat-reactive coating film can further contain other components. To improve the white skin, to make it easier to print on paper, or to prevent hot pens from sticking, white clay such as talc, TiO2, ZnO, CaCO3 (e.g. chalk), kaolin, etc. can be added to this coating. Furthermore, organic pigments,
For example, urea/formaldehyde polymers or melamine/formaldehyde polymers can be included.

In order to cause the color formation to occur only within a certain limited temperature range, the following substances can also be added: These include urea, thiourea, diphenylthiourea, acetamide, acetanilide, stearylamide, phthalic anhydride, metal chlorides, metal stearates such as zinc stearate, phthalonitrile, or color formers and developers. Other fusible substances suitable for simultaneous melting can be added. Further, it is preferable that the heat-sensitive recording material contains a wax such as carnauba wax, montan wax, paraffin wax, or polyethylene wax, or a condensate of higher fatty acid amide and formaldehyde, or a condensate of higher fatty acid and ethylenediamine. .

The invention is further illustrated by the following examples. In the examples, "parts" and "percentages" are by weight unless otherwise specified.

Example 1 Heat-sensitive recording system Two dispersions A and B were first prepared.

Dispersion A was prepared by milling the following mixture in a ball mill for 3-6 hours to a particle size of 2-4 microns.

Imidazole complex of zinc thiocyanate 8g polyvinyl alcohol (25/140) 32.9 part 1
0 彊 aqueous solution water 2
0.9 Dispersion B was prepared by milling the following mixture in a ball mill to a particle size of 2-4 microns.

Crystal violet lactone 1g water
2 g of these two dispersions were mixed.

Using a doctor blade, mix this colorless mixture with a basis weight of 5.
(Coated on Jjj/lr? paper. Coating amount (39) is 3 g/??+! (dry weight). The recording paper obtained in this way is normally colorless, but at 125°0 It quickly turned blue and the color reached saturation at 220°C.

The imidazole complex of zinc thiocyanate used in this example was synthesized as follows.

Dissolve 14.4 g of zinc sulfate (ZnSO4.7H20) and 29.2 g of potassium thiocyanate in 2507 g of water. A solution of 6.89 f imidazole in 200 ml of water is added to the above solution under stirring and a white precipitate forms immediately. This precipitate is separated from each other, washed with water, and then dried at 60°C. The reaction product thus obtained has a melting point of 143°-
It showed 145°C.

Example 2 A heat-sensitive recording material was produced by the method described in Example 1. However, in the preparation of Dispersion A, picoline lead body 8.1 of zinc thiocyanate was used instead of the imidazole complex.

This recording paper is also originally colorless, but at 125℃ (40℃) The color quickly turns blue and reaches saturation at 220°C.

The picoline complex of zinc thiocyanate of this example was synthesized as follows.

Dissolve 14.4 g of zinc sulfate (ZnSO4.7H20) and 29.2.9 g of potassium thiocyanate in 500 rnl of water. A solution of 9.3 I of 2-picoline in 150 ml of ethanol is added to the above solution with stirring, immediately resulting in the formation of a white crystalline precipitate of the reaction product. This precipitate is washed with water and dried at 50°C. The melting point of the obtained picoline-metal complex was 148°-152°C.

Example 3 A heat-sensitive memory material was produced by the method described in Example 1. However, in the preparation of Dispersion A, 8 g of a pyridine complex of cadmium thiocyanate was used in place of the imidazole complex. This recording paper was also originally colorless, but quickly turned blue at 125°C.

The pyridine complex of zinc thiocyanate of this example was synthesized as follows.

Cadmium chloride (CdCIV2 ・H2'O) 10 g
and 29.2 g of potassium thiocyanate are dissolved in 500 g of water. A solution of 7.9 I of pyridine in 50 ml of ethanol is added to the above solution under stirring, and a white crystalline precipitate of the reaction product immediately forms.

This precipitate is separated from each other, washed with water, and then dried at 70°C. The melting point of the obtained pyridine-cadmium complex is 208-210°
It was C.

Example 4-40 Metal complexes of the following formula (3) shown in the following table were produced by the method described in Example 1-3 using the corresponding starting materials and under the reaction conditions shown in the following table. did.

Using each of the metal complex compounds prepared in Example 4-40 as a color developer, a heat-sensitive recording material was prepared in the same manner as described in Example 1-3, and the light resistance was good and stable, good to excellent. The color has been changed.

Example 41 Pressure Sensitive Recording System The following mixture was milled in a ball mill with a knife to a particle size of 2-4 microns.

China clay 30
Part styrene/butadiene (son) copolymer 10
Department water
Using a doctor blade, 70 parts of the obtained dispersion was added.
The amount of C coated on the base paper with a basis weight of 48 fi/ml was 6 ji/m").

The entire coated paper is used as a transfer sheet, and is superimposed on a commercially available carbon paper [donor sheet (CB receipt, one containing a coloring agent, such as a solution of crystal violet rough (45) ton in microcapsules)], and a pen or tie plate is used. - As a result of recording, a dark blue copy was obtained.

Example 42 Pressure Sensitive Recording System The following mixture was milled in a ball mill to a particle size of 2-4 microns.

Methoxypyridine complex of zinc thiocyanate 10 parts (prepared in Example 6) China clay 40
Part naphthalenesulfonic acid/formaldehyde 1
Partial condensate polyvinyl alcohol 8 parts water
Using a doctor blade, 12 parts of the obtained dispersion were used, and the basis weight was 4B9/rr? (coating amount 6.9/silence).

This transfer sheet is superimposed on a commercially available carbon paper [donor sheet (containing a color former, for example, a crystal violet lactone solution in microcapsules)].
When recorded with a pen or (46) typewriter, a dark blue copy was produced.

Example 43 Pressure Sensitive Recording System The mixture was milled in a ball mill with a trench to a particle size of 2-4 microns.

china clay 2
0.7 parts styrene/butadiene (sol) copolymer 1 part water
8 parts of the obtained dispersion was applied to a base paper with a basis weight of 48.9/ff1'' using a doctor blade (coating amount: 3 g/
rr? ).

When this transfer sheet was overlaid with a commercially available carbon paper [donor sheet (containing a coloring agent, such as a crystal violet lactone solution, in microcapsules)] and recorded with a pen or typewriter, the result was a dark The blue copy was changed.

Example 44 Pressure-sensitive recording system benzothiazole complex of zinc thiocyanate (Example 12)
(prepared in ) was dissolved in 60 parts of acetone and mixed with 5 parts of Chagonaclay for 30 minutes with stirring, and then the acetone was removed by evaporation.

Remaining mixture 8 parts styrene/butadiene (5oqIr) copolymer 1.2 parts water
12
A portion was milled in a ball mill to a particle size of 2 to 4 microns.

Using a doctor blade, the obtained dispersion was adjusted to a basis weight of 4B.
Coated on base paper of g/- (coating amount 6.5g/?71″)
.

This transfer sheet is superimposed on a commercially available carbon paper [donor sheet (containing a coloring agent, for example, a crystal violet lactone solution in microcapsules)].
When recorded with a pen or typewriter, a dark blue copy was obtained.

Example 45 Pressure Sensitive Recording System The following mixture was milled in a ball mill in a trench to a particle size of 2-4 microns.

China clay 10 parts styrene/butadiene (50elI) copolymer 20
Department water 3
00 parts of the obtained dispersion was applied to a base paper with a basis weight of 48 ji/rn' using a doctor blade (coating amount 69/rn').
rr? ).

This transfer sheet is superimposed on commercially available carphone paper [donor sheet (coloring agent, such as that contained in the crystal violet lactone solution microcapsules)].
When recorded with a pen or typewriter, a dark blue copy was obtained.

(49) =464-

Claims (1)

[Scope of Claims] 1. A pressure-sensitive or heat-sensitive recording material ( R) M e (A n ) n /r
m-n In the formula, Me represents an n-valent metal ion, and R represents a monodentate or polydentate colorless organic ligand that binds to the metal ion via a heteroatom to form a complex. , An represents an r-valent anion, k is the coordination number of all the class ions and represents 4 or 6 depending on the type of metal, and n represents 1, 2, 3, or 4. , r indicates l or 2). 2. In the color developer represented by formula (1), Me has an atomic weight of 24 to 210, preferably 40 to 140.
2. The recording material according to claim 1, wherein the recording material is a valent, trivalent, or tetravalent metal ion. 3. A patent characterized in that, in the color developer represented by formula (1), R is a monodentate or polydentate ligand that binds to a metal ion via a nitrogen atom to form a complex. Recording material according to claims 1 and 2. 4. In the color developer represented by formula (1), R has a 5- or 6-membered aromatic heterocycle having a nitrogen atom as a petro atom, and the heterocycle has a When combined with a metal ion to form a complex, the heterocycle may contain a hydroxyl group, a cyano group, a Cl-C4 alkyl group, a Cl-C
4 alkoxy group, vinyl group, phenyl group, cl-C4 acyl group or amino group, and/
The recording material according to claim 3, wherein the recording material may form a condensed ring with an unsubstituted or substituted benzene nucleus. 5. In the color developer represented by formula (1), An is halogen, thiocyanic acid, nitric acid, sulfuric acid, phosphoric acid, boric acid, formic acid, acetic acid, propionic acid, stearic acid, benzoic acid, oxalic acid, citric acid, or 5. The recording material according to claim 1, wherein the recording material is a phthalate anion. 6. The recording material according to claim 5, wherein in the color developer represented by formula (1), An is a thiocyanate anion. 7. Recording material C according to claim 1, wherein the color developer is a metal complex compound represented by formula (2), where M e 1 is a divalent compound having an atomic weight of 40 to 140; Valence, (3
) or a tetravalent metal ion, R1 and R2 each independently represent a 5- or 6-membered aromatic heterocycle having a nitrogen atom as a heteroatom. However, the heterocycle forms a complex with the metal ion via the nitrogen atom, and a methoxy group, Cl-C4 as a substituent.
(It may have one or more alkyl groups, cyano groups, vinyl groups, formyl groups, phenyl groups, or amine groups, and may form a condensed ring with a benzene ring). 8. In the color developer represented by formula (2), Mel is 2
a valent zinc ion or a cadmium ion, R1 and R2 are respectively pyridine, imidazole, quinoline, benzothiazole, or benzimidazole ligands forming a complex via their nitrogen atoms; Claim 7, characterized in that the heterocycle having a heteroatom is unsubstituted or substituted with methyl, methoxy, cyano, vinyl, formyl, phenyl, or amino. Recording materials. 9. In the color developer represented by formula (2), Mel is 2
The valent zinc ions, R1 and R2 each form a complex via their nitrogen atoms. 8. The recording material according to claim 7, which is a pyridine, 2-methoxypyridine, picoline, imidazole, benzthiazole, quinoline, or benzimidazole ligand. 10. M e 1 in the color developer represented by formula (2)
is a divalent zinc ion, R1 and R2 are respectively,
8. The recording material according to claim 7, which is a 1-methylimidazole or 2-methylimidazole ligand that forms a complex via its nitrogen atom. 11. M e 1 in the color developer represented by formula (2)
is a divalent zinc ion, Rx and R2 are each
8. The recording material according to claim 7, which is a benzthiazole ligand that forms a complex via its nitrogen atom. 12. The recording material according to claims 1 to 11, which is heat-sensitive. 13. At least one layer contains at least one color former and at least one color developer described in claims 1 to 10, and in some cases at least one color developer. 13. The heat-sensitive recording material according to claim 12, which may contain a binder and/or a wax. 14. The recording material according to claims 1 to 11, which is pressure sensitive. 15. The pressure-sensitive recording material according to claim 14, which contains a coloring agent dissolved in an organic solvent. 16. The pressure-sensitive recording material according to claims 14 and 15, wherein the coloring agent is encapsulated in microcapsules. 17. Claims characterized in that the coloring agent encapsulated in capsules exists in a layered form on the back side of the transfer sheet, and the color developer of formula (1) exists in a layered form on the surface side of the transfer sheet. 17. Pressure-sensitive recording material according to item 16. 18. Claims 1 to 11, characterized in that the compound of formula (1) coexists with one or more other color developers
Pressure-sensitive or heat-sensitive recording materials described in Section 1. Use of metal complex compounds of the formulas described in claims 1 to 11 as color developers for pressure-sensitive or heat-sensitive recording materials.