JPH047314B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD The present invention relates to a pressure- or heat-sensitive recording material containing at least one metal complex compound represented by formula (1) as a color developer for coloring a color former in its coloring reaction system. . (R) _ko Me(SCN) _o (1) where Me is an n-valent metal ion, and R is a monodentate or polydentate colorless organic moiety that forms a complex with the metal ion via a heteroatom. k is the coordination number of the metal ion, which is 4 or 6 depending on the type of metal, n is 1, 2, 3, or 4, and the difference between k−n is zero. isn't it. The metal complex compound used in the present invention has an atomic weight of 40 to
140, most preferably 50 to 120, divalent, trivalent,
or advantageously derived from a tetravalent metal. 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, tungsten, zinc, tin, and zirconium. Preferred metals are zinc, cadmium and cobalt, and a particularly preferred metal is zinc. The colorless organic ligand of the metal complex compound of the present invention is R
and (k−n) can be combined with the metal ion Me via 1, 2, or 3 heteroatoms to form a complex. As this heteroatom, nitrogen is preferred. In the metal complex compound of formula (1) used as a color developer, (k−n) ligands R may be the same or different, but monodentate ligands are the same. It is preferable that 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 a nitrogen atom in a monodentate, bidentate, or tridentate molecule,
For example, primary, secondary, or tertiary amino groups, substituted or unsubstituted imino groups, nitro groups, oximino groups,
Preferably, the metal ion is bonded to the metal ion to form a complex via a hydrazino group or a plurality of nitrogen atoms found in the hydrazino group. Examples of monodentate (monofunctional) ligands containing nitrogen include, for example, nitrogen-containing secondary or tertiary saturated or unsaturated heterocyclic ring systems in which the nitrogen atoms are 1
Also suitable are aliphatic, cycloaliphatic, aromatic, aryl-substituted aliphatic, or heterocyclic amines, which are included as members of one or more rings. Representative aliphatic, cycloaliphatic, and aryl-substituted aliphatic nitrogen-containing ligands include, for example, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, n-hexylamine, n-octylamine. , isooctylamine, n-decylamine, n-dodecylamine,
and octadecylamine (stearylamine)
_{cycloaliphatic} amines such as cyclopentylamine and cyclohexylamine; 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,
imidazoline, indoline, benzomorpholine,
Benzimidazoline, tetrahydroquinoline and 2,2,4-trimethyltetrahydroquinoline 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; 2
Nucleically substituted anilines such as -, 3-, or 4-methylaniline, chloroaniline, methoxyaniline, dichloroaniline; N-methylaniline, N-ethylaniline, N,N-dimethylaniline, N,
N-alkyl- or N,N-dialkyl-anilines such as N-diethylaniline; further diphenylamine, 4,4'-diaminodiphenyl ether; 4,4'-diaminodiphenyl sulfide;
4,4'-diaminodiphenyl sulfone; 4,4'-
4,4'-diaminodiphenyl alkanes such as diaminodiphenylmethane and 4,4'-diaminodiphenylethane;4,4'-diaminoazobenzene are suitable. A particularly suitable organic ligand is a 5- or 6-membered aromatic heterocycle containing nitrogen as a heteroatom, and the heterocycle is a C ₁ -C ₁₈ alkyl group, more preferably a C ₁ -C ₄ alkyl group. Alkyl group, _C1 - _C4 alkoxy group,
Cyano group, hydroxyl group, vinyl group, phenyl group, C ₁ ,
It may be substituted with a C ₄ acyl group or an amino group, and may form a condensed ring with a benzene nucleus, such as a halogen atom,
It may be substituted with a _C1 - _C4 alkyl group or a _C1 - _C4 alkoxy group. 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-, β-, 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, shinoline, indolizine, indoles (e.g. 2-methylindole, 2-phenylindole), benzimidazole, 2-Methylbenzimidazole, 1,2-dimethylbenzimidazole, 2-stearylbenzimidazole, 2-aminobenzimidazole, benzoxazole, benzothiazole, 2-thiobenzothiazole, 2-aminobenzothiazole, benzotriazole, carbazole, acridine , phenazine, antipyrine, diguanamine, guanidine, bipyridyl, 2,6-(di-2-pyridyl)-
Pyridine (terpyridyl), phenanthridine,
Examples include phenanthroline and dipyridyl ketone. Particularly preferred metal complex compounds are those containing 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. The fact that they are connected to each other through
More preferred. Specific examples of such ligands are alkylene diamines such as ethylene diamine and propylene diamine, phenylene diamines, dialkylene triamines, and triamino alkanes. Dialkylene triamines are, for example, diethylene triamine, monoethylene-monopropylene triamine, dipropylene triamine, and N-alkyl derivatives thereof,
Triaminoalkanes are, for example, α,β,γ-triaminopropane, α,β,δ-triaminobutane, and α,γ-diamino-β-(aminoethyl)propane. The plurality of nitrogen atoms bonded to the metal and the 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, imidazoline, and diazobicyclo[2,2,2]-octane. Other compounds suitable as nitrogen-containing ligands are hydrazine, _C1 - _C5 alkyl-hydrazine,
Arylhydrazine (such as phenylhydrazine)
hydrazines such as; hydrazones such as acetone hydrazone and acetophenone hydrazone; hydratides such as acetohydratide and benzhydratide;
Hydroxylamine; amidines such as formamidine; formamide, dimethylformamide,
Amides such as tetramethylurea, acetamide, and benzamide; and oximes such as acetaldoxime and acetoxime. An interesting color developer is one represented by formula (2). In the formula, Me ₁ is an n-valent metal ion with an atomic weight of 40 to 140; R ₁ and R ₂ are each independently a monodentate 5 to 6
Indicates a membered aromatic N-heterocyclic ring system that forms a complex with the metal ion via a nitrogen atom, and this heterocyclic ring contains one or two cyano groups, vinyl groups, etc. , formyl group, phenyl group, or
_C1 - _C18 alkyl group, preferably methoxy group, _C1
It may be substituted with a _-C4 alkyl group or an amino group, or may contain a fused benzene ring. The valence n of the metal ion is preferably 2, 3 or 4. In formula (2), Me ₁ is particularly preferably a cadmium ion, most preferably a zinc ion. R ₁ and R ₂ are the same, respectively pyridine,
Preferably, it is a quinoline, imidazole or benzimidazole ligand, which is complexed with the metal ion via its nitrogen atom, and the N-heterocycle is methyl, methoxy, cyano. , vinyl, formyl, phenyl, or amino substituted or unsubstituted. Particularly preferred ligands R ₁ and R ₂ are pyridine, picoline, 2
-methoxypyridine, quinoline, imidazole and benzimidazole, 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,
It constitutes a novel color developer, ie an electron acceptor, of the group. These are obtained by methods known per se. For example, it may contain n/r moles of inorganic or organic moiety per metal atom, depending on the type of ligand. It is obtained by reacting 1 mole of an inorganic or organic salt of a metal (for example zinc thiocyanate or zinc acetate) with (kn) moles of the corresponding monodentate or polydentate ligand. This reaction is conveniently carried out in a polar solvent. A small amount of catalyst may or may not be added. Water or water-miscible organic solvents are suitable as this solution. Water-miscible solvents include, for example, aliphatic _C1 - _C4 alcohols such as methanol, ethanol, propanol, and isobutanol; alkylene glycols such as ethylene glycol, propylene glycol; ethylene glycol monoethyl ether, monoethyl ether, Monoalkyl ethers of glycols such as monobutyl ether, diethylene glycol monomethyl ether, and monoethyl ether; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and diacetone alcohol; ethers or acetals such as diisopropyl ether, diphenyl oxide, dioxane, and tetrahydrofuran and others, tetrahydrofurfuryl alcohol, pyridine, acetonitrile, γ-butyrolactone, N,N-dimethylformamide, N,N-
Dimethylacetamide, tetramethylurea, tetramethylene sulfone, etc. are used. The reaction can usually be carried out at room temperature (20-25°C), but sometimes much higher temperatures are required;
A temperature range of 0.degree. C. may be preferred. It is also possible to react the reactants in the molten state. Suitable melting aids in this case include, for example, lower fatty acid salts such as sodium acetate, lower fatty acid amides such as acetamide, urea, thiourea, N-substituted products, and the like. The metal thiocyanate complex is prepared by mixing a metal donor and a solution of alkali thiocyanate or ammonium thiocyanate, preferably potassium thiocyanate, in one of the above polar solvents, and then combining this mixture with the desired coordination. It can be suitably obtained by reacting with a child. Preferred metal donors are metal salts of strong mineral or organic acids, especially sulfates, halides, nitrates,
Formate and acetate. Known metal complex compounds of formulas (1) and (2) and their preparation methods are described, for example, in the Gmelins Handbuch.
deranorganishen Chemie), Volume 32, Page 271 (Zinc), and Supplementary
Volume) (1956) “Zinc”, pp986-987, further I. S. AHUJA and A. Garg, J. inorg nucl.
Chem. 34 , 1929-1935 (1972). The compound of formula (1) is substantially colorless and odorless and highly reactive with conventionally used color formers, resulting in natural, stable, and non-fading reproductions. Color formers suitable for use in the recording or copying materials of the invention are known colorless or slightly colored chromogens which become colored or colored when brought into contact with the metal complex compound of formula (1). is subject to change. For example, azomethines, fluorans, benzofluoranes, phthalides, spiropyrans, spirodipyrans, lyuco-olamines, triarylmethane lyuco-dyes, carbazolylmethanes, chromenoindoles, chromenopyrazoles , color formers belonging to phenoxazines, phenothiazines, etc.
or mixtures thereof as well as chromenow 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-sialkylamino-
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)furfuryl-, -phenyl-, or -carbazolylmethane, 3'-phenyl-7-dialkylamino-2,2'-spirodibenzopyran, bis (Dialkylamino)benzhydrol-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 active materials such as attapulgite, acid clay, bentonite, montmorillonite, acid-treated activated clays such as bentonite or montmorillonite; also zeolites. , halloysite, silica,
Alumina, aluminum sulfate, aluminum phosphate, zinc chloride,
Zinc nitrate, kaolin or various clays; Furthermore, acidic organic compounds such as unsubstituted phenols, nuclear substituted phenols, salicylic acid, salicylic acid esters, and metal salts thereof; for example, carbolic acid polymers,
These are acidic polymers such as alkylphenol acetylene resins, maleic acid-rosin resins, partial or complete hydrolysates of copolymers of maleic acid with styrene, ethylene, or vinyl methyl ether, and carboxypolymethylene. Color developers can also include other fundamentally inert or nearly inert pigments, as well as auxiliaries such as silica gel, UV absorbers such as 2-(2-hydroxyphenyl)benztriazole and its derivatives, etc. It can also be used in combination with Examples of pigments include clays such as talc, titanium dioxide, zinc oxide, thioyoke, and kaolin, as well as urea/formalin condensates [BET method, specific surface area 2-75
m ² /g] and organic pigments such as melamine/formaldehyde 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 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 designed to break down under pressure. Break the microcapsules with pressure, such as pressure from a pen,
When the color former solution is thus transferred to an adjacent sheet coated with the color developer of formula (1), a colored area is generated. The color is due to the dye produced, which absorbs in the visible portion of the electromagnetic spectrum. The encapsulation of the color former is preferably carried out in a state dissolved in an organic solvent. A suitable solvent for this is
Preferably non-volatile, such as polyhalogenated paraffins such as chlorinated paraffins; polyhalogenated diphenyls such as monochlorodiphenyl and trichlorodiphenyl; tricresyl phosphate and di-n-butyl phthalate; Aromatic ethers such as enyl ether; hydrocarbon oils such as paraffin and kerosene; alkylated (e.g. isopropylated or isobutylated) diphenyl derivatives; also diphenyl alkanes, naphthalene, triphenyl, dibenzyltoluene, terphenyl, especially partially hydrogenated terphenyl. , benzylated xylene, and other chlorinated or hydrogenated or condensed aromatic hydrocarbons. Mixtures of different solvents are often used to obtain optimal solubility for color development, rapid and intense coloration, and favorable viscosities for microencapsulation. A uniform capsule shell wall can be generated around the droplet of color former solution by coacelvation. The encapsulant is described, for example, in U.S. Pat.
It can also be made of gelatin and gum arabic, as described in No. 2800457.
However, British Patent Specifications Nos. 989264 and 1156725
It can also be suitably made from amino resins or modified amino resins by polycondensation, as described in US Pat. Microcapsules made by interfacial polymerization, for example from polyesters, polycarbonates, polysulfonamides or polysulfonates, especially from 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, coloring reactants or developers, and supports. Among these, 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 is preferable. 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, hydroxymethyl cellulose, casein, methyl cellulose, dextrin, starch, polymer latex, and the like. As this latex,
For example, latexes such as butadiene/styrene copolymers, acrylic homopolymers, and copolymers are used. The paper used may not only be a conventional paper made from cellulose fibers, but also one in which the cellulose fibers are partially or completely replaced by synthetic polymers. The metal complex compound of formula (1) is also used as a color developer, especially in heat-reactive recording materials. The recording material usually contains at least one carrier, one color former, and one electron acceptor, and optionally a binder and/or wax. Thermoresponsive recording systems include, for example, thermosensitive recording materials, copying materials and paper. These systems are used for information recording, such as electronic computers, teleprinters or telewriters, and 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. A heat-reactive recording material can be made such that the color former is dispersed or dissolved in one binder layer and the color developer is dissolved or dispersed in the binder of a second layer. 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 contacts 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 paper, for example 4-tert-butylphenol, 4-phenylphenol, 4-hydroxydiphenyl ether, α-naphthol ,
β-naphthol, methyl 4-hydroxybenzoate, -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, pyrogallol, phloroglucin, p-, m-, and o-hydroxybenzoic acid, gallic acid , 1-hydroxy-
Phenol compounds such as 2-naphthoic acid; and boric acid; organic dibasic carboxylic acids, preferably aliphatic dibasic carboxylic acids, such as tartaric acid, oxalic acid, maleic acid, citric acid, citraconic acid, succinic acid, etc. are used. In producing the heat-reactive recording material, 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 dissolve or at least swell in water include:
Hydrophilic polymers such as polyvinyl alcohol, polyacrylic acid, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, polyacrylamide, polyvinylpyrrolidone, gelatin, starch, and etherified cornstarch. If the color former and color 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. For example, talc, TiO ₂ ,
Clays such as ZnO, CaCO ₃ (for example Chiyoke), kaolin, and also organic pigments such as 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: Namely, urea, thiourea, diphenylthiourea,
Acetamide, acetanilide, stearylamide, phthalic anhydride, metal chlorides, metal stearates such as zinc stearate, phthalonitrile,
Alternatively, other fusible substances suitable for simultaneously melting the color former and color developer can be added. Further, heat-sensitive recording materials include, for example, carnauba wax, montan wax, paraffin wax,
Wax such as polyethylene wax, or condensate of higher fatty acid amide and formaldehyde,
It is preferable to contain a condensate of higher fatty acid and ethylenediamine. The invention is further illustrated by the following examples. In the examples, unless otherwise specified, "parts" and "percentages" are based on weight. Example 1 Thermal 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 10% aqueous solution of polyvinyl alcohol (25/140) 32g Water 20g For dispersion B, mix the following mixture in a ball mill for 2 to 4 hours.
It was prepared by grinding to a micron particle size. Crystal Violet Lactone 1g 10% aqueous solution of polyvinyl alcohol (25/140) 4g Water 2g These two dispersions were mixed. This colorless liquid mixture was applied to paper having a basis weight of 50 g/m ² using a doctor blade. Coating amount is 3
g/m ² (dry weight). The recording paper obtained in this way was normally colorless, but quickly turned blue at 125°C, 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 (ZnSO ₄ 7H ₂ O) and 29.2 g of potassium thiocyanate in 250 ml of water. A solution of 6.8 g of imidazole in 200 ml of water is added to the above solution under stirring, and a white precipitate immediately forms. This precipitate is separated, washed with water, and dried at 60°C. The reaction product thus obtained has a melting point of
It showed 143°-145°C. Example 2 A heat-sensitive recording material was manufactured by the method described in Example 1. However, in the preparation of Dispersion A, 8 g of picoline complex of zinc thiocyanate was used instead of the imidazole complex. Although this recording paper was originally colorless, it quickly turned blue at 125°C, and the color reached saturation at 220°C. The picoline complex of zinc thiocyanate of this example was synthesized as follows. Dissolve 14.4 g of zinc sulfate (ZnSO ₄ 7H ₂ O) and 29.2 g of potassium thiocyanate in 500 ml of water. A solution of 9.3 g of 2-picoline in 150 ml of ethanol is added to the above solution under stirring, immediately resulting in the formation of a white crystalline precipitate of the reaction product. This precipitate is separated, washed with water, and dried at 50°C. The melting point of the picoline-metal complex obtained was 148°-152°C. Example 3 A heat-sensitive recording 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 instead of the imidazole complex. This recording paper was originally colorless, but it rapidly turned blue at 125°C. The pyridine complex of zinc thiocyanate of this example was synthesized as follows. When 10 g of cadmium chloride (CdCl ₂ H ₂ O) and 29.2 g of potassium thiocyanate are dissolved in 500 ml of water, and a solution of 7.9 g of pyridine dissolved in 50 ml of ethanol is added to the above solution under stirring, the reaction product, white crystals, is immediately formed. A sexual precipitate forms. This precipitate is separated, washed with water, and dried at 70°C. The melting point of the obtained pyridine-cadmium complex was 208-210°C. Example 4-40 The metal complexes of the following formula (3) shown in the following table were prepared by the method described in Example 1-3 using the corresponding starting materials and under the reaction conditions shown in the following table. It was manufactured using

【table】

[Table] Using each of the metal complex compounds prepared in Example 4-40 as a color developer, a heat-sensitive recording material was prepared according to the same procedure as described in Example 1-3. Good to excellent coloring was obtained. Example 41 Pressure Sensitive Recording System The following mixture was milled in a ball mill to a particle size of 2-4 microns. Benzimidazole complex of zinc thiocyanate (prepared in Example 22) 10 parts china clay 30 parts naphthalene sulfonic acid/formaldehyde condensate 1 part styrene/butadiene (50%) copolymer 10 parts water 70 parts The resulting dispersion was doctored. using a blade,
It was applied to a base paper with a basis weight of 48 g/ml (the coating amount was 6 g/ml).
^m2 ). This coated paper was used as a transfer sheet, and it was superimposed on a commercially available carbon paper [donor sheet (CB sheet), one containing a coloring agent such as crystal violet lactone solution in microcapsules], and a pen or type plater was used. The recording resulted in a dark blue copy. 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 (prepared in Example 6) 10 parts china clay 40 parts naphthalene sulfonic acid/formaldehyde condensate 1 part polyvinyl alcohol 8 parts water 12 parts The obtained dispersion was mixed using a doctor blade.
Coated on base paper with a basis weight of 48 g/ ^m2 (coating amount: 6 g/m2)
^m2 ). When this transfer sheet was superimposed on a commercially available carbon paper [donor sheet (containing a color former, e.g., crystal violet lactone solution in microcapsules)] and recorded with a pen or typewriter, the result was a deep blue color. I received a copy of Example 43 Pressure Sensitive Recording System The following mixture was milled in a ball mill to a particle size of 2-4 microns. α-phenylethylamine complex of zinc thiocyanate (prepared in Example 37) 1 part china clay 2 parts naphthalene sulfonic acid/formaldehyde condensate 0.1 part styrene/butadiene (50%) copolymer 0.7 parts water 18 parts Resulting dispersion Remove the liquid using a doctor blade.
Coated on a base paper with a basis weight of 48 g/ ^m2 (coating amount: 3 g/m2)
^m2 ). When this transfer sheet was overlapped with a commercially available carbon paper [donor sheet (containing a color former, e.g., crystal violet lactone solution and microcapsules)] and recorded with a pen or typewriter, the result was a deep blue color. I received a copy of Example 44 Pressure Sensitive Recording System 1 part of the benzothiazole complex of zinc thiocyanate (prepared in Example 12) was dissolved in 60 parts of acetone, mixed with 5 parts of China clay under stirring for 30 minutes, and then the acetone was removed by evaporation. The remaining mixture: 8 parts naphthalene sulfonic acid/formaldehyde condensate 0.8 parts styrene/butadiene (50%) copolymer 1.2 parts polyvinyl alcohol [e.g. Polyviol VO3/140] and 3 parts water 12 parts were milled into granules in a ball mill. It was ground to a diameter of 2-4 microns. The obtained dispersion was mixed using a doctor blade.
Coated on a base paper with a basis weight of 48 g/ ^m2 (coating amount: 6.5 g/m2)
^m2 ). When this transfer sheet was superimposed on a commercially available carbon paper [donor sheet (containing a color former, e.g., crystal violet lactone solution in microcapsules)] and recorded with a pen or typewriter, a deep blue color was obtained. I received a copy of Example 45 Pressure Sensitive Recording System The following mixture was milled in a ball mill to a particle size of 2-4 microns. Picoline complex of zinc thiocyanate (prepared in Example 2) 10 parts china clay 10 parts naphthalene sulfonic acid/formaldehyde condensate 5 parts styrene/butadiene (50%) copolymer 20 parts water 300 parts The resulting dispersion was doctor-bladed. Using,
Coated on base paper with a basis weight of 48 g/ ^m2 (coating amount: 6 g/m2)
^m2 ). When this transfer sheet was superimposed on a commercially available carbon paper [donor sheet (containing a color former, e.g., crystal violet lactone solution in microcapsules)] and recorded with a pen or typewriter, a deep blue color was obtained. I received a copy of

Claims (1)

[Scope of Claims] 1. A pressure-sensitive or heat-sensitive recording material characterized by containing at least one metal complex compound of formula (1) as a color developer for a color former in its coloring reaction system ( R) _ko Me(SCN) _o (1) (where Me is an n-valent metal ion, and R is a monodentate or polydentate colorless organic moiety that forms a complex with the metal ion via a heteroatom. k is the coordination number of the metal ion, which is 4 or 6 depending on the type of metal, n is 1, 2, 3, or 4, and the difference between k−n is zero. isn't it). 2. The recording material according to claim 1, which contains a color developer of formula (1), where Me is Zn, Cd or Co. 3. The recording material according to claim 2, which contains a color developer of formula (1), wherein the metal is zinc. 4. The color developer according to claim 1, wherein R is a monodentate or polydentate ligand forming a complex with the metal ion via a nitrogen atom. Recording materials. 5 R is a 5- or 6-membered aromatic N-heterocycle, which forms a complex with a metal ion via the nitrogen atom, and is unsubstituted or has a hydroxyl group, a cyano group, a C Benzene ring substituted with ₁ - _C4 alkyl group, _C1 - _C4 alkoxy group, vinyl group, phenyl group, _C1 - _C4 acyl group or amino group, and unsubstituted or substituted 5. A recording material according to claim 4, which can be condensed with. 6 Claim 1 containing the color developer of formula (2)
Recording materials listed in section. (In the formula, Me ₁ is a divalent, trivalent, or tetravalent metal ion with an atomic weight of 40 to 140, and R ₁ and R ₂ are each independently a 5- or 6-membered aromatic is an N-heterocycle which forms a complex with the metal ion via the nitrogen atom and is unsubstituted or a methoxy group, a C ₁ -C ₄ alkyl group, a cyano group,
a benzene ring which is substituted with one or more of the same or different substituents selected from a vinyl group, a formyl group, a phenyl group, and an amino group, and which is unsubstituted or substituted; (can be condensed). 7 In the color developer of formula (2), Me ₁ is a divalent zinc ion or cadmium ion, and R ₁ and
R ₂ is a pyridine, imidazole, quinoline, benzothiazole, or benzimidazole ligand forming a complex through its nitrogen atom, respectively, and the N-heterocycle is unsubstituted or methyl, methoxy 7. A recording material according to claim 6, wherein the recording material is substituted by , cyano, vinyl, formyl, phenyl or amino. 8 In the color developer of formula (2), Me ₁ is a divalent zinc ion, and R ₁ and R ₂ are pyridine, 2-methoxypyridine, picoline, which form a complex via their nitrogen atoms, respectively. 7. The recording material according to claim 6, which is an imidazole, benzthiazole, quinoline, or benzimidazole ligand. 9 In the color developer of formula (2), Me ₁ is a divalent zinc ion, and R ₁ and R ₂ are 1-methylimidazole or 2-methyl that form a complex via their nitrogen atoms, respectively. The recording material according to claim 6, which is an imidazole ligand. 10 In the color developer of formula (2), Me ₁ is a divalent zinc ion, and R ₁ and R ₂ are each a benzthiazole ligand that forms a complex via its nitrogen atom. Recording material according to claim 6. 11 In the color developer of formula (1), Me ₁ is a divalent zinc ion, and R is an antipyrine ligand that forms a complex via its nitrogen atom, according to claim 1 recording materials. 12 At least one layer contains at least one color former and at least one color developer [formula (1)] according to claim 1, or in addition thereto, a binder and a wax. The heat-sensitive recording material according to claim 1, containing at least one of the following. 13. The pressure-sensitive recording material according to claim 1, which contains a coloring agent dissolved in an organic solvent. 14. The pressure-sensitive recording material according to claim 13, wherein the coloring agent is encapsulated in microcapsules. 15 A color developer encapsulated in a capsule is present in a layer on the back side of the transfer sheet, and a color developer of formula (1) or (2) is present in a layer on the surface side of the transfer sheet, A pressure-sensitive recording material according to claim 14.