JPS643674B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a recording material that obtains a colored image through the formation of a complex between a metal compound and a ligand compound, and more particularly to a recording material that has very little coloring itself and has excellent initial color development. In recent years, recording materials have been developed using electron-donating coloring agents such as crystal violet lactone and benzoyl leucomethylene blue, and electron-accepting substances such as activated clay, phenol resin, polyvalent metal salts of aromatic carboxylic acids, and bisphenol A. Various types of recording media such as pressure-sensitive copying paper, thermal recording paper, and current-carrying recording paper are in widespread use, and these recording media can produce clear colored images on relatively white substrates. However, the color image has poor light resistance, the color tone changes economically, and furthermore, the color image fades or disappears due to the use of line markers, cellophane tape, etc., and has serious defects. It could not be used for important documents. On the other hand, chelate-based recording materials that utilize a color reaction caused by complex formation between a ligand compound and a metal compound are published in Japanese Patent Publications No. 43-23709, No. 43-23710, and No. 44-14382.
No. 44-16137, No. 45-4700, No. 45-5617
No. 45-5618, No. 45-38206, No. 45-41212
No. 46-9287, No. 46-9288, No. 46-9289
No. 49-27133, No. 49-32966, No. 49-
Many of them are known from publications such as No. 43566 and No. 53-31405. Recording materials that utilize these complex formations have excellent light resistance, and there is almost no change in color tone over time, and the color images do not fade or disappear even when line markers, cellophane tape, etc. are used. However, on the other hand, there are many systems in which high color density cannot be obtained, and even in systems where relatively high color density can be obtained, either the ligand compound or the metal compound is significantly colored. There are many things that are. For example, 3
All of the iron compounds in this method are colored dark brown, and when trying to obtain a clear colored image, the recording sheet itself becomes darkly colored, resulting in the disadvantage that only products with low commercial value can be obtained. As mentioned above, each of the conventional recording materials has advantages and disadvantages, and a recording material that combines the advantages of both is desired. As a result of intensive research into recording materials that utilize complex formation, the present inventors have developed an organic phosphorous iron compound having a P-O ^- ...Fe ³⁺ or P-S ^- ...Fe ³⁺ bond as a metal compound. It was discovered that when used, clear recorded images could be obtained with almost no unnecessary coloration, and an application was filed earlier as Japanese Patent Application No. 137291-1983.
However, subsequent detailed studies revealed that although such recording materials can provide clear recorded images, they are somewhat inferior in initial color development. However, as a result of further research, it was discovered that by further incorporating an organic base into the recording material, the above-mentioned advantages were maintained, and the initial color development and even the final color development were significantly improved. The invention was completed. The present invention consists of an organophosphorous iron compound having a P-O ^- ...Fe ³⁺ or P-S ^- ...Fe ³⁺ bond, and a ligand compound that forms a complex with the iron compound to develop color. This recording material is characterized in that it further contains an organic base. Examples of organic phosphorus compounds having P-O ^- ...Fe ³⁺ or P-S ^- ...Fe ³⁺ bonds used in the present invention include, for example, organic phosphorus compounds represented by the following general formulas () to (). Examples include salts in which hydrogen in the -H or PS-H bond is replaced with Fe ³⁺ . In the formula, X ₁ , X ₂ , X ₃ , X ₄ and X ₅ each represent an oxygen atom or a sulfur atom, and R ₁ , R ₂ , R ₃ ...R ₂₅ , R ₂₆ and R ₂₇ represent an alkyl group or an aryl group. represents. The alkyl group represented by R ₁ to _{R 27} includes saturated and unsaturated substituted and unsubstituted alkyl groups, and may be any of a linear alkyl group, a branched alkyl group, and a cycloalkyl group. These alkyl groups preferably have 1 to about 20 carbon atoms, excluding carbon atoms in substituent moieties. Specific examples of these alkyl groups include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-amyl group, and i-amyl group. group, n-hexyl group, t-octyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-heptadecyl group, n-octadecyl group, decenyl group, dodecenyl group, tetradecenyl group, heptadecenyl group,
Examples include octadecenyl group, decynyl group, octadecynyl group, and cyclohexyl group. Furthermore, the aryl group represented by R ₁ to R ₂₇ includes
Both unsubstituted aryl groups and substituted aryl groups are included, and those having 6 to 14 carbon atoms excluding the carbon atoms in the substituent part are preferred, and specific examples thereof include phenyl group, naphthyl group, anthryl group, etc. I can give an example. Furthermore, R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ , R ₁₁ and R ₁₂ ,
Alkyl or aryl groups attached to the same phosphorus atom directly or via an oxygen or sulfur atom, such as R ₁₃ and R ₁₄ , R ₁₅ and R ₁₆ , and R ₁₇ and R ₁₈ , are bonded to each other to form a 5- or 6-membered ring. It may form a ring, and
When the group is an aryl group, they may be bonded at different positions of the same aromatic ring to form a 5- or 6-membered ring. Specific examples of such structures include (a) below, where two alkyl groups are bonded to form a ring, and (b), where two aryl groups are bonded to form a ring. ), the following is a case where an alkyl group and an aryl group combine to form a ring.
(c), cases in which rings are formed by bonding at different positions of the same aromatic ring include the following (d) and (e).

【formula】

【formula】

【formula】

【formula】

[Formula] Alkyl group represented by R ₁ to R ₂₇ as above,
Examples of substituents for the aryl group and the alkyl group and aryl group when forming a 5- or 6-membered ring include the following. Halogen atoms such as chlorine, bromine, fluorine, cyano group, hydroxyl group, amino group, carboxyl group, sulfonic acid group, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-
Butyl group, n-hexyl group, t-octyl group, n
-decyl group, n-dodecyl group, n-tetradecyl group, n-heptadecyl group, n-octadecyl group,
A saturated or unsaturated substituted or unsubstituted straight-chain or branched alkyl group having 1 to 20 carbon atoms, such as a vinyl group, decenyl group, cyclohexyl group, methoxyethoxyethyl group, benzyl group, anisyl group, α-methylbenzyl group, Substituted or unsubstituted aryl groups such as phenyl group, naphthyl group, hydroxyphenyl group, methoxy group, ethoxy group,
Substituted or unsubstituted alkoxy groups such as propoxy, butoxy, and methoxyethoxy groups; substituted or unsubstituted aryloxy groups such as phenoxy, triloxy, naphthoxy, and methoxyphenoxy groups; methoxycarbonyl and butoxycarbonyl groups; , substituted or unsubstituted alkoxycarbonyl groups such as phenoxymethoxycarbonyl groups, substituted or unsubstituted aryloxycarbonyl groups such as phenoxycarbonyl groups, triloxycarbonyl groups, methoxyphenoxycarbonyl groups, formyl groups, acetyl groups, etc. substituted or unsubstituted acyl groups such as valeryl group, stearoyl group, benzoyl group, trioyl group, naphthoyl group, p-methoxybenzoyl group, substituted or unsubstituted acylamino group such as acetamido group, benzoylamino group, methoxyacetamido group group, substituted or unsubstituted carbamoyl group such as N-butylcarbamoyl group, N,N-diethylcarbamoyl group, N-(4-methoxy-n-butyl)carbamoyl group, N-butylsulfamoyl group, N,N −
Diethylsulfamoyl group, N-dodecylsulfamoyl group, N-(4-methoxy-n-butyl)
Substituted or unsubstituted sulfamoyl groups such as sulfamoyl groups, substituted or unsubstituted sulfonylamino groups such as methylsulfonylamino groups, phenylsulfonylamino groups, methoxymethylsulfonylamino groups, mesyl groups, tosyl groups, methoxymethanesulfonyl groups, etc. Substituted or unsubstituted sulfonyl group, etc. In addition, as the organic phosphorus compound in the present invention, a homopolymer consisting of a monomer having at least one P-SH or P-OH bond, such as p-vinylphenylphosphonic acid or p-vinylphenyl phosphate, may also be used. Examples include copolymers with other monomers and oligomers thereof. In the present invention, among such organophosphorus iron compounds, one or more of the above-mentioned organophosphorus compounds and one or more of carboxylic acids, thio acids, and dithio acids represented by the following general formula () are used.
It has also become clear that when a complex iron salt with Fe ³⁺ (hereinafter referred to as a binary double salt) is used, a recording material particularly excellent in color development, particularly in initial color development, can be obtained. In the formula, R is an alkyl group or an aryl group,
X and Y represent oxygen atoms or sulfur atoms. Examples of the alkyl group or aryl group represented by R include saturated and unsaturated substituted and unsubstituted alkyl groups and substituted and unsubstituted aryl groups as exemplified for R ₁ to R ₂₇ of the organic phosphorus compound. It will be done. Furthermore, the examples given for the organic phosphorus compounds are also applicable to the substituents for these alkyl groups and aryl groups. In addition, as the carboxylic acid in the present invention, P-
Homopolymers made of monomers having a carboxyl group such as vinylbenzoic acid, copolymers with other monomers, or oligomers thereof can also be effectively used. The molar ratio of carboxylic acid, thioic acid and dithioic acid to the organic phosphorus compound in the binary double salt is not particularly limited, but if it is too high, it will not be possible to obtain a recording material with high whiteness, which is the object of the present invention. Therefore, it is desirable that the molar ratio of carboxylic acid, etc. is 250 mol or less, more preferably in the range of 30 to 200 mol, per 100 mol of the organic phosphorus compound. According to the study results of the present inventors, an iron compound can be obtained by using in combination one or more compounds selected from the group of sulfonic acids, sulfinic acids, and sulfuric esters during the production of the above-mentioned binary double salt. It is also clear that when a complex iron salt (hereinafter referred to as a ternary double salt) is used, a recording material with higher whiteness can be obtained while retaining the excellent coloring properties of a binary double salt. Summer. Specifically, the sulfonic acids, sulfinic acids and sulfuric esters used here include benzenesulfonic acid, alkylbenzenesulfonic acids, naphthalenesulfonic acids, alkylnaphthalenesulfonic acids, polystyrenesulfonic acids, dialkylsulfosuccinic acids, alkylbenzenesulfinic acids, Examples include alkyl sulfates, and the alkyl is preferably a C ₁ to C ₂₀ unsubstituted, saturated straight chain one. The molar ratio of such sulfonic acid, sulfinic acid and sulfuric acid ester is in the range of 2 to 100 mol (more preferably 5 to 100 mol) per 100 mol of the organic phosphorus compound.
30 moles) is preferred. The method for preparing the iron compound used in the present invention is not particularly limited, but examples include P-O ^-... Na ⁺ and/or P-S ^-...
There is a method in which an aqueous solution of ferric chloride or ferric sulfate is added to an aqueous solution of an organic phosphorus compound having a Na ⁺ bond to precipitate the iron salt of the organic phosphorus compound. In the case of binary or ternary double salts, P−O ⁻ …Na ⁺ and/or P−S ⁻ …Na ⁺
Second chloride is added to an aqueous solution containing an organic phosphorus compound having a bond of An aqueous solution of iron or ferric sulfate can be added to precipitate the iron double salt, respectively. In addition, during preparation, for the purpose of further lightening the color of the iron compound or changing the tone of the colored image, etc.
It is also possible to contain other metal ions in addition to Fe ³⁺ ions, such as Ca ²⁺ , Mg ²⁺ ,
Al ³⁺ , Zn ²⁺ , Cd ²⁺ , Cu ²⁺ , Ti ⁴⁺ , Sr ²⁺ , Ba ²⁺ ,
Examples include Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Mn ²⁺ , Pb ⁴⁺ , etc.
Two or more of these metal ions can also be used in combination. In addition, the obtained single salt, binary salt, or ternary salt of Fe ³⁺ and an organic phosphorus compound is
These iron compounds can be used alone or in combination. The ligand compound that forms a complex with the iron compound and provides a colored image is not particularly limited, and examples thereof include various ligand compounds and chelate compounds that can be easily ion-exchanged with Fe ³⁺ . A specific example is shown below. Di-n-butylammonium di-n-butyldithiocarbamate, t-octylammonium t
-Octyl dithiocarbamate, stearyltrimethylammonium ethylene bisdithiocarbamate, dibenzothiazyl disulfide, toluene-3,4-dithiot, benzoylacetone,
Dibenzoylacetone, salicylic acid, 3,5-di(α-methylbenzyl)salicylic acid, hydroxynaphthoic acid, naphthoic acid hydroxyethylamide, naphthoic acid anilide, 2-hydroxy-1
- Naphthaldehyde, tropolone, hinokitiol, methoxyhydroxyacetophenone, resorcinol, t-butylcatechol, dihydroxybenzenesulfonic acid, gallic acid, ethyl gallate, propyl gallate, isoamyl gallate, octyl gallate, lauryl gallate, gallic acid benzyl acid, tannic acid, pyrogallol tannin, protocatechuic acid, ethyl protocatechuate, pyrogallol-4-carboxylic acid, alizarin, N-nitrosonaphthylhydroxyamine ammonium salt, diphenylcarbazide, 8-hydroxyquinoline,
Dichloro-8-hydroxyquinoline, dibrome-
8-hydroxyquinoline, chlorobromo-8-hydroxyquinoline, methyl-8-hydroxyquinoline, butyl-8-hydroxyquinoline, lauryl-8-hydroxyquinoline, methylenebis(8
-hydroxyquinoline), N-benzoyl-N-
Phenylhydroxylamine, salicylaldoxime, anthranilic acid, quinolinecarboxylic acid,
Nitrosonaphthol, 2-mercaptoimidazoline, diphenylthiocarbazone, 6-ethoxy-
2,2,4-trimethyl-1,2-dihydroquinoline, 6-phenyl-2,2,4-trimethyl-
1,2-dihydroquinoline, 6-decyl-2,
2,4-trimethyl-1,2-dihydroquinoline, 2-imidazoline, phenyl-α-naphthylamine, phenyl-β-naphthylamine, zinc butylxanthate, zinc salicylate, 3,5-di(α-methylbenzyl)zinc salicylate Such. Among these ligand compounds, gallic acid, ethyl gallate, propyl gallate, isoamyl gallate, octyl gallate, lauryl gallate, benzyl gallate, tannic acid, protocatechuic acid,
Ethyl protocatechuate and the like are particularly preferably used because they are easily available and are hardly colored themselves. The organic base used in the present invention includes:
Examples include various aliphatic amines, aromatic amines, alicyclic amines, amidines, guanidines, nitrogen-containing heterocyclic compounds, and heterocyclic amines. Specific examples are shown below, but the invention is not limited to these. Tripropylamine, tri(n-octyl)
Amine, tribenzylamine, N-dimethylbenzylamine, N-methyldibenzylamine, N-
Ethyldibenzylamine, dibenzyl-β-aminoethanol, di(2-ethylhexyl)amine, didodecylamine, dioctadecylamine,
Dibenzylamine, dodecylamine, hexadecylamine, octadecylamine, N-dibutylphenylamine, N-diethyl-p-tolylamine, N-dibenzylphenylamine, N-ethyl-N-benzylphenylamine, N- diphenylmethylamine, ethylanilinoethanol, N-
Dodecyl phenylamine, diphenylamine, N
-naphthylphenylamine, N-(p-octylphenyl)phenylamine, mecidine, dicyclohexylamine, N,N'-diphenylformamidine, 1,3-diphenylguanidine, 1,
1,3,3-tetraphenylguanidine, pyridine, quinoline, morpholine, 1,2,3,4-tetrahydroquinoline,

【formula】

【formula】

[Formula] etc. The amount of organic base to be used varies depending on its type and the intended recording material, and cannot be determined unconditionally, but it is generally 0.01 to 300% of the iron compound.
A weight percent range is preferred. In the present invention, such an organic base is used in combination with a specific organophosphorous iron compound and a ligand compound, but some organic bases color the iron compound, and the iron compound itself is not colored. In order to suppress this as much as possible, it is desirable that such an organic base be contained in the recording material without coming into contact with the iron compound. Therefore, for example, a method in which a binder or the like is interposed between the two substances, a method in which microcapsules are formed, a method in which the two substances are formed as different layers, etc. are preferably used. Specifically, the recording material of the present invention includes pressure-sensitive copying paper,
Although it can be used as heat-sensitive recording paper, current-carrying recording paper, etc., pressure-sensitive copying paper, which is a typical embodiment, will be described below. Pressure-sensitive copying paper is a recording material that generally develops color by the reaction of an electron-donating coloring agent such as crystal violet lactone or benzoyl leucomethylene blue with an electron-accepting coloring agent such as activated clay. Upper paper (CB) in which microcapsules containing a coloring agent made by separation method, interfacial polymerization method, in-situ method, etc. are coated on one side of the support, and lower paper in which coloring agent is coated on one side of the support. (CF), microcapsules containing a coloring agent used when multiple copies are desired, and inner paper (CFB) in which the coloring agent is coated on different sides of the same support.
In addition, there is also a so-called single pressure-sensitive copying sheet which is made by coating microcapsules containing a color former and a color former on the same side of a support in a laminated or mixed layer. In addition, when applying the recording material of the present invention to pressure-sensitive copying paper, it is preferable to use at least one in the molecule, especially among those listed above, because it has good solubility in organic solvents during microencapsulation. Organic bases containing aromatic hydrocarbons are more preferably used. When a ligand compound, an iron compound, or an organic base is microencapsulated individually or as a mixture, they are contained in an organic solvent as necessary. The organic solvent used in this case is desirably one that has a high solubility and is nonvolatile or low volatile. Specific examples are listed below, but the invention is not limited to these, and these may be used alone or in combination. Vegetable oils such as cottonseed oil, mineral oils such as kerosene, paraffin, naphthenic oil, and chlorinated paraffin, aromatic carbonization such as alkylated biphenyl, alkylated terphenyl, alkylated naphthalene, diarylethane, triarylmethane, and diphenylalkane. Hydrogens, alcohols such as oleyl alcohol, tridecyl alcohol, benzyl alcohol, 1-phenylethyl alcohol, glycerin,
Organic acids such as oleic acid, esters such as dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, dioctyl phthalate, diethyl adipate, propyl adipate, di-n-butyl adipate, dioctyl adipate,
Organic phosphorus compounds such as tricresyl phosphate, tributyl phosphate, tributyl phosphite, tributyl phosphine oxide, ethers such as phenyl cellosolve, benzyl carbitol, polypropylene glycol, propylene glycol monophenyl ether, N,N-dimethyl Amides such as lauramide, N,N-dimethylstearamide and N,N-dihexyl octylamide, ketones such as diisobutyl ketone and methylhexyl ketone, alkylene carbonates such as ethylene carbonate and propylene carbonate, and the like. Encapsulation methods include conventionally known coacervation methods, interfacial polymerization methods, and in-situ methods.
Any method can be used, such as the Japanese Patent Publication No. 54-16949, Japanese Patent Publication No. 16949, and Japanese Patent Publication No.
It is particularly preferable to use the urea formaldehyde resin encapsulation method and the melamine formaldehyde resin encapsulation method disclosed in Publication No. 53-84881 because capsules with better performance can be obtained. Furthermore, when an organic base is encapsulated, the aminoaldehyde resin encapsulation method described in Japanese Patent Application No. 174815/1988 is particularly preferably used. Incidentally, these microcapsules can also contain an antioxidant and an ultraviolet absorber, if necessary. The microcapsules obtained in this way can be treated with water-soluble or latex binders, capsule protectants, and furthermore dispersants, antifoaming agents, preservatives, and fluorescent materials used in the field of pressure-sensitive copying paper, as required. Photobrightener, colored dye, PH
Adjustment agents and the like are added as appropriate to prepare a microcapsule coating liquid. Examples of water-soluble binders include proteins such as gelatin, albumin, and casein, starches such as grain starch, pregelatinized starch, oxidized starch, etherified starch, and esterified starch, cellulose such as carboxymethyl cellulose and hydroxyteethyl cellulose, agar, and alginic acid. There are water-soluble natural polymer compounds such as sutucarose such as soda and gum arabic, and water-soluble synthetic polymer compounds such as polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, polyacrylamide, and maleic acid copolymers. Examples include styrene-butadiene latex, acrylonitrile-butadiene latex, acrylic acid ester latex, vinyl acetate latex, methyl methacrylate-butadiene latex, and carboxy-modified (for example, acrylic acid) latexes thereof. In addition, cellulose powder, starch particles, talc,
Examples include calcined kaolin and calcium carbonate. Note that the amounts used of these binders, capsule protectants, etc. are not particularly limited. On the other hand, when used without encapsulation, the powder is pulverized using a ball mill, attritor, sand mill, etc. as necessary, and then the commonly used white pigments, binders, dispersants, colored dyes, fluorescent materials, etc. Brightener, ultraviolet absorber, antioxidant,
It is prepared as a coating liquid with various auxiliary agents such as stabilizers such as acids. It should be noted that wet pulverization using water as a medium is preferable for such pulverization treatment, and the dispersants used at that time and the dispersants used as auxiliary agents when preparing the coating solution include the following examples of low molecular or polymeric dispersants. Dispersants and surfactants are used. Anionic active agents such as sodium alkyl sulfate, sodium alkylbenzene sulfonate, sodium alkylnaphthalene sulfonate, sodium polystyrene sulfonate, sodium oleamide sulfonate, sodium dialkyl sulfosuccinate, and sulfated castor oil; trimethylaminoethyl alkyl halides Cationic activators such as amides, alkylpyridinium sulfates, alkyltrimethylammonium halides; polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene alkyl phenyl ethers, polyhydric alcohol fatty acid esters, polyoxyethylene polyhydric Nonionic surfactants such as alcohol fatty acid esters and sucrose fatty acid esters; surfactants such as amphoteric surfactants such as alkyltrimethylaminoacetic acid and alkyldiethylenetriaminoacetic acid, starch, phosphorylated starch, polyvinyl alcohol, carboxymethylcellulose, sodium alginate, sodium polyacrylate,
Water-soluble polymer compounds such as sodium salt of vinyl acetate-maleic anhydride copolymer, ammonium salt of styrene-maleic anhydride copolymer, and sodium salt of butadiene-methacrylic acid copolymer. In addition, white pigments include aluminum, zinc,
Oxides, hydroxides, carbonates, sulfates, halogen compounds, and acid clay, activated clay, attapulgite, etc. of magnesium, calcium, titanium, etc.
Examples include clays such as zeolite, bentonite, kaolin, and calcined kaolin. Further, the binder can be appropriately selected from binders similar to those used in the microcapsule coating liquid and used alone or in combination. When the recording material of the present invention is applied to heat-sensitive recording paper or electrically conductive recording paper, conventional color formers and coloring agents are replaced with the ligand compound and iron compound of the present invention, and an organic base is added by the method described above. Coating liquids can be prepared by conventional techniques together with auxiliary materials known in the respective fields. The recording material coating liquid obtained as described above can be applied alone or in combination using various known coating methods such as an air knife coater, roll coater, blade coater, size press coater, curtain coater, bill blade coater, short dwell coater, etc. The composition is coated on a suitable base material such as paper, synthetic fiber paper, or synthetic resin film, and used as a pressure-sensitive recording material, a heat-sensitive recording material, or a current-carrying recording material, respectively. In addition to the above-mentioned coating method, it is also possible to apply the ligand compound and/or iron compound to water-based or solvent-based flexo ink, letterpress and lithographic ink, UV cure ink, EB cure ink, etc. using a printing method. It may be formed on a material, or it may be formed together with paper stock. Furthermore, the recording material of the present invention can also be used in combination with other chelate-based and leuco dye-based recording materials in order to further increase the color density. The coating amount of the recording material varies depending on the type and amount of the ligand compound or iron compound used, and the intended recording material, but cannot be determined unconditionally. Or as an iron compound
It may be formed on the base material in an amount of about 0.2 to 10 g/m ² , preferably 0.2 to 6 g/m ² . Examples and comparative examples are listed below in order to make the effects of the present invention even clearer, but the present invention is not limited to these examples.
In addition, unless otherwise specified, parts and % in the examples represent parts by weight and % by weight, respectively. Example 1 Preparation of top paper Ethylene was placed in a stirring mixing container equipped with a heating device.
150 parts of a 3.3% aqueous solution of maleic anhydride copolymer (trade name: EMA-31, manufactured by Monsanto) was added, and a 20% aqueous solution of caustic soda was added to adjust the pH to 4.0 to prepare an aqueous medium for capsule production. Separately, 15 parts of lauryl gallate and 3 parts of dibenzylamine were dissolved in a mixed solvent of 70 parts of di-n-butyl adipate and 30 parts of diethyl adipate to prepare a capsule core material. This core material was placed in the above aqueous medium with an average particle size of 5.0μ.
After emulsifying and dispersing the mixture, the temperature of the system was raised to 60°C. Separately, 10 parts of melamine was added to 30 parts of a 37% formaldehyde aqueous solution and reacted at 60°C for 15 minutes to prepare a prepolymer aqueous solution. This aqueous prepolymer solution was dropped into the emulsion, heated to 70° C. with gentle stirring, kept warm for 3 hours, and then allowed to cool to obtain a milky white capsule dispersion. Wheat starch powder 20% into the resulting capsule dispersion
1 part and 10 parts of pulp powder are added and mixed until the solid content concentration is
Add water to 25% to make a capsule coating liquid, and make 40%
g/ ^m2 paper with an air knife coater to reduce the solid content to 5.
The upper paper was obtained by smearing at a concentration of g/m ² . Creation of the bottom sheet Stir an aqueous solution prepared by adding 250 parts of diphenyl phosphate to 800 parts of a 5% aqueous solution of caustic soda, and an aqueous solution of 90 parts of ferric chloride (FeCl ₃ 6H ₂ O) dissolved in 500 parts of water. The iron salt of diphenyl phosphate was added as a precipitate, which was filtered, washed and dried to obtain a pale yellow fine powder. Next, 1 part of sodium polystyrene sulfonate and 1 part of polyvinyl alcohol as a dispersant were dissolved in 250 parts of water, and 20 parts of the above fine powder and 30 parts of zinc oxide were dissolved therein.
After adding 50 parts of aluminum hydroxide to the dispersion and treating it with a sand grinder, 15 parts of styrene-butadiene copolymer latex (50% concentration) was added to the dispersion to obtain a coating liquid. The coating solution thus obtained was applied to a 40 g/m ² paper using a blade coater to give a dry weight of 5 g/m ² to obtain a base paper with almost no coloring. The whiteness of this bottom paper was measured with a reflectance photometer (ELREPHO, manufactured by Carl Zeiss, using a No. 8 filter) and found to be 78%. The obtained upper paper and lower paper were placed one on top of the other so that the coated surfaces faced each other, and color printing was performed using a typewriter. Then, the color densities 10 seconds and 1 hour after printing were measured using a Macbeth densitometer (model RD-100R, manufactured by Macbeth Co., Ltd., using an amber filter), and the initial and final color densities were determined as the initial and final color densities, respectively. Shown in the table. Comparative Example 1 Preparation of top paper A top paper was obtained in exactly the same manner as in Example 1 except that dibenzylamine was not used. The obtained upper paper was placed on the lower paper obtained in the same manner as in Example 1, and the initial color density and final color density were measured in the same manner as in Example 1, and the results are listed in Table 1. Example 2 Preparation of top paper Ethylene was placed in a stirring mixing container equipped with a heating device.
30 parts of a 3.3% aqueous solution of maleic anhydride copolymer (trade name: EMA-31, manufactured by Monsanto) was added, and a 20% aqueous solution of caustic soda was added to adjust the pH to 4.0 to prepare an aqueous medium for capsule production. Separately, 1.8 parts of dibenzylamine was dissolved in a mixed solvent of 14 parts of di-n-butyl adipate and 6 parts of diethyl adipate to prepare a capsule core material. This core substance was placed in the above aqueous medium with an average particle size of 7.0μ.
After emulsifying and dispersing the mixture, the temperature of this system was raised to 60°C. Separately, 2 parts of melamine was added to 6 parts of a 37% formaldehyde aqueous solution and reacted at 60°C for 15 minutes to prepare a prepolymer aqueous solution. This aqueous prepolymer solution was dropped into the emulsion, heated to 70° C. with gentle stirring, kept warm for 3 hours, and then allowed to cool to obtain a milky white capsule dispersion. To a capsule dispersion obtained by mixing the dibenzylamine-containing microcapsule dispersion thus obtained and a lauryl gallate-containing microcapsule dispersion obtained in exactly the same manner as in Comparative Example 1, 22 parts of wheat starch powder, Add and mix 11 parts of pulp powder, add water to make a solid content concentration of 25% to make a capsule coating liquid, and smear it on 40 g/m ² paper using an air knife coater to make a solid content of 6 g/m ² . and obtained the upper paper. Preparation of the bottom sheet To an aqueous solution prepared by adding 188 parts of diphenyl phosphate and 134 parts of 4-tert-butylbenzoic acid to 1200 parts of a 5% aqueous solution of caustic soda, add ferric chloride to 1000 parts of water.
An aqueous solution containing 135 parts of phosphate was added under stirring to form a precipitate, a two-component double salt of diphenyl phosphate and 4-tert-butylbenzoic acid, which was filtered, washed, and dried to give a pale yellow, finely divided salt. A powder was obtained. Next, 1 part of sodium alkylnaphthalene sulfonate and 1 part of polyvinyl alcohol were dissolved in 250 parts of water, and 20 parts of the above fine powder, 30 parts of zinc oxide, and 50 parts of aluminum hydroxide were added thereto, and this was treated with a sand grinder. Then, add styrene to the dispersion.
15% butadiene copolymer latex (50% concentration)
A coating solution was obtained. The coating liquid thus obtained was applied to a 40 g/m ² paper using an air knife coater to give a dry weight of 5 g/m ² to obtain a base paper with a whiteness of 75. The obtained upper paper and lower paper were combined, Example 1
The initial color density and final color density were measured in the same manner as above, and the results are shown in Table 1. Example 3 Preparation of top paper Microcapsule dispersion containing both lauryl gallate and dibenzylamine prepared in exactly the same manner as in Example 1, and dibenzylamine-containing microcapsules prepared in exactly the same manner as in Example 2. The capsule dispersion obtained by mixing with the capsule dispersion,
Add and mix 22 parts of wheat starch powder and 11 parts of pulp powder, add water to make a solid content concentration of 25% to make a capsule coating liquid, and apply it to 40 g/m ² paper with an air knife coater to make a solid content of 6 g/m2. The upper paper was obtained by smearing it so that it became ² . The obtained upper paper was placed on the lower paper obtained in the same manner as in Example 2, and the initial color density and final color density were measured in the same manner as in Example 2.
Shown in the table. Example 4 Upper paper obtained in the same manner as Example 1 and Example 2
and the lower paper obtained in the same manner as above, and the initial color density and final color density were measured in the same manner as in Example 2, and the results are listed in Table 1. Comparative Example 2 In Example 2, the color density was measured in exactly the same manner as in Example 2, except that the upper paper obtained in the same manner as in Comparative Example 1 was used as the upper paper, and the results are also listed in Table 1. did. Examples 5 to 8 In Example 2, 3 parts of mecidine (Example 5), 5 parts of tribenzylamine (Example 6), 5 parts of N,N-dimethylbenzylamine (Example 6), and 1.8 parts of dibenzylamine were used instead of 1.8 parts of dibenzylamine. Example 7), and 1, 2,
5 parts of 3,4-tetrahydroquinoline (Example 8)
Performed in exactly the same way except using 4.
Got the above paper of a kind. The obtained four types of upper paper were each used in Example 2.
In combination with the lower paper obtained in the same manner as above, the sample was evaluated in the same manner as in Example 2, and the results are shown in Table 1. Example 9 Preparation of top paper Ethylene was placed in a stirring mixing container equipped with a heating device.
Add 15 parts of a 3.3% aqueous solution of maleic anhydride copolymer (trade name EMA-31, manufactured by Monsanto) and add
A 20% caustic soda aqueous solution was added to adjust the pH to 4.0 to obtain an aqueous medium for capsule production. Tri-n-octylamine 5 in the above aqueous medium
After emulsifying and dispersing the sample so that the average particle size was 7.0μ, the system was heated to 60°C. Separately, 0.5 parts of melamine was added to 1.5 parts of a 37% formaldehyde aqueous solution, and the mixture was reacted at 60° C. for 15 minutes to prepare a prepolymer aqueous solution. This aqueous prepolymer solution was dropped into the emulsion, heated to 70° C. with gentle stirring, kept warm for 3 hours, and then allowed to cool to obtain a milky white capsule dispersion. A top paper was prepared in exactly the same manner as in Example 2, except that the thus obtained tri-n-octylamine-containing microcapsule dispersion was used instead of the dibenzylamine-containing microcapsule dispersion. The obtained upper paper was combined with the lower paper obtained in the same manner as in Example 2, and evaluated in the same manner as in Example 2. The results are also listed in Table 1. Example 10 Preparation of bottom paper 500 parts of water was added to an aqueous solution prepared by adding 89 parts of 4-tert-butylbenzoic acid, 125 parts of diphenyl phosphate, and 70 parts of sodium laurylbenzenesulfonate to 800 parts of a 5% aqueous solution of caustic soda. An aqueous solution containing 108 parts of ferric chloride dissolved in the solution was added under strong stirring to form a pale yellow fine particulate ternary double salt, which was then filtered and washed to obtain a slurry. Next, add 1 part of sodium polyacrylate to 200 parts of water.
Dissolve 1 part of hydroxyethylcellulose, add 20 parts of the above slurry in solids, and 40 parts of titanium oxide.
After adding 40 parts of calcium carbonate and strongly dispersing, the dispersion was mixed with carboxy-modified styrene-butadiene copolymer latex (solid content concentration 50 parts).
%) was added to obtain a coating liquid. The resulting coating liquid was applied to 40g/ ^m2 paper at a dry weight of 5.
g/m ² using a rod blade coater to obtain a base paper with a whiteness of 77%. The upper paper obtained in the same manner as in Example 1 was placed on the lower paper and evaluated in the same manner as in Example 1. The results are shown in Table 1. Example 11 Preparation of bottom paper To an aqueous solution prepared by adding 89 parts of 4-tert-butylbenzoic acid, 125 parts of diphenyl phosphate, and 70 parts of sodium laurylbenzenesulfonate to 800 parts of a 5% aqueous solution of caustic soda, add 500 parts of water. An aqueous solution in which 108 parts of ferric chloride was dissolved was added under strong stirring to form a pale yellow fine particulate ternary double salt, and then 20% sodium 4-t-butylbenzoate was added to the dispersion. 500 parts of an aqueous solution of was added thereto, and then 25 parts of TiCl ₄ were gradually added to this dispersion under strong stirring to obtain a pale yellow fine particle dispersion, which was filtered and washed to obtain a slurry. Next, add 1 part of sodium polyacrylate to 200 parts of water.
Dissolve 1 part of hydroxyethylcellulose, add 20 parts of the above slurry in solids, and 40 parts of titanium oxide.
After adding 40 parts of calcium carbonate and strongly dispersing, the dispersion was mixed with carboxy-modified styrene-butadiene copolymer latex (solid content concentration 50 parts).
%) was added to obtain a coating liquid. The resulting coating liquid was applied to 40g/ ^m2 paper at a dry weight of 5.
g/m ² using a rod blade coater to obtain a base paper with a whiteness of 80%. The color density was measured in exactly the same manner as in Example 10 except that this lower paper was used, and the results are also listed in Table 1. Example 12 Preparation of bottom paper An iron compound-containing coating liquid prepared in exactly the same manner as in the production of the bottom paper in Example 2, and dibenzylamine prepared in the same manner as in the production of the top paper in Example 2. The mixed solution with the containing microcapsule dispersion was used as a coating liquid, and the dry weight was 5.8 g/m2 on 40 g/ ^m2 paper.
A base paper with a whiteness of 76% was obtained by applying it with an air knife coater so that it had a thickness of m ² . The upper paper obtained in the same manner as in Comparative Example 1 was superimposed on the lower paper, and the color density was measured in the same manner as in Example 1. The results are shown in Table 1. Example 13 Preparation of upper paper After dissolving 26.6 parts of di(2,4-di-α-methylbenzylphenyl) phosphate and 7.1 parts of 4-tert-butylbenzoic acid in 200 parts of methanol, 4.5 parts of potash was dissolved. 90 parts of di-n-butyl adipate and 10 parts of diisopropylnaphthalene were added thereto.
Separately, add ferric chloride ( _FeCl3 .
A solution containing 7.2 parts of 6H ₂ O) was prepared, and this solution was added to the above-mentioned solution while stirring to form a binary double salt. Next, 30 parts of Glauber's salt was added to this liquid, and after 1 hour, it was filtered and methanol was distilled off to obtain a yellow internal phase liquid. Separately, place ethylene/maleic anhydride copolymer (trade name: EMA-) in a stirring mixing vessel equipped with a heating device.
31, manufactured by Monsanto) 150 parts of a 3.3% aqueous solution was added,
Add 20% caustic soda aqueous solution to this to adjust the pH to 4.0.
It was adjusted to be an aqueous medium for capsule production. After emulsifying and dispersing 100 parts of the above internal phase liquid in this aqueous medium so that the average particle size was 6.0μ, this system was
The temperature was raised to ℃. Separately, 10 parts of melamine was added to 30 parts of a 37% formaldehyde aqueous solution and reacted at 60°C for 15 minutes to prepare a prepolymer aqueous solution. This aqueous prepolymer solution was dropped into the emulsion, heated to 70° C. with gentle stirring, kept warm for 3 hours, and then cooled to obtain a pale yellow capsule dispersion. 20 parts of wheat starch powder and 10 parts of pulp powder were added to a mixture of the iron compound-containing microcapsule dispersion obtained as described above and the dibenzylamine-containing microcapsule dispersion prepared in exactly the same manner as in Example 2. Add and mix and add water to make the solid content concentration 25% to make capsule coating liquid, 40g/m ²
The above paper was coated with an air knife coater to a solid content of 6 g/m ² to obtain a top paper. Preparation of the bottom paper Dissolve 1 part of sodium polystyrene sulfonate, 1 part of polyvinyl alcohol, and 1 part of citric acid as dispersants in 250 parts of water, and add 30 parts of lauryl gallate, 30 parts of zinc oxide, and 40 parts of aluminum hydroxide. was added and treated with a sand grinder, and then 15 parts of styrene-butadiene copolymer latex (concentration of 50 parts) was added to this dispersion to obtain a coating liquid. The coating liquid thus obtained was applied to a 40 g/m ² paper using a blade coater to give a dry weight of 5 g/m ² to obtain a base paper. The upper paper and lower paper obtained as described above were combined, and the color density was measured in the same manner as in Example 1. The results are shown in Table 1. Comparative Example 3 A capsule coating liquid was obtained in the same manner as in Example 13, except that the dibenzylamine-containing microcapsule dispersion was not added and mixed in the preparation of the top paper of Example 13, and applied to 40 g/m ² paper. A top paper was obtained by coating with an air knife coater so that the solid content was 5 g/m ² . The color density was measured in the same manner as in Example 13, except that the obtained upper paper was used, and the results are also listed in Table 1.

[Table] As is clear from the results in Table 1, all pressure-sensitive copying papers using the recording material of the present invention exhibit excellent pressure-sensitive copying with markedly improved initial color development and even final color development. It was warm with paper. Example 14 A dibenzylamine-containing microcapsule dispersion prepared in the same manner as in the preparation of the upper paper in Example 2, and a two-component double salt-containing coating liquid prepared in the same manner as in the production of the lower paper. A uniform coating liquid was prepared by mixing the following. Separately, on the coated surface of capsule-coated paper prepared in the same manner as the upper paper of Comparative Example 1, the above coating liquid was smeared with an air knife coater to a solid content of 6 g/m ² to form a single pressure-sensitive copying paper. I got it. A piece of high-quality paper was placed on top of the coated surface of the obtained single-piece pressure-sensitive copying paper, and a typewriter was used to develop color prints. Then, the color density was measured 10 seconds and 1 hour after printing using a Macbeth densitometer (model RD-100R, manufactured by Macbeth, using an amber filter).
The initial color density and final color density are listed in Table 2, respectively. Example 15 A two-component double salt-containing coating liquid prepared in exactly the same manner as in the preparation of the lower paper of Example 2 was applied onto the coated surface of capsule coated paper prepared in the same manner as the upper paper of Example 1. Solid content 6g/m ² with air knife coater
A single pressure-sensitive copying paper was obtained by smearing it so as to give the following effect. The obtained single pressure-sensitive copying paper was evaluated for printing in the same manner as in Example 14, and the results are shown in Table 2. Comparative Example 4 A two-component double salt-containing coating liquid prepared in exactly the same manner as in the preparation of the lower paper of Example 2 was applied onto the coated surface of capsule coated paper prepared in the same manner as the upper paper of Comparative Example 1. Solid content 5g/m ² with air knife coater
A single pressure-sensitive copying paper was obtained by smearing it so as to give the following effect. The obtained single pressure-sensitive copying paper was evaluated for printing in the same manner as in Example 14, and the results are shown in Table 2. Example 16 A dibenzylamine-containing microcapsule dispersion prepared in the same manner as in the preparation of the upper paper in Example 2, a two-component double salt-containing coating liquid prepared in the same manner as in the production of the lower paper, Further, a dispersion of microcapsules containing a ligand compound prepared in the same manner as in the case of making the upper paper of Comparative Example 1 was mixed to make a uniform coating liquid, and the mixture was solidified on a 40 g/m ² paper using an air knife coater. A single pressure-sensitive copying paper was obtained by smearing at a concentration of 10 g/m ² . Using this single pressure-sensitive copying paper, the color density was measured in the same manner as in Example 14, and the results are shown in Table 2. Comparative Example 5 A single pressure-sensitive copying paper was obtained in exactly the same manner as in Example 16, except that the dibenzylamine-containing microcapsule dispersion was not mixed. This single pressure-sensitive copying paper was printed and evaluated in the same manner as in Example 14, and the results are also listed in Table 2.

[Table] As is clear from the results in Table 2, all of the stand-alone pressure-sensitive copying papers using the recording material of the present invention have excellent stand-alone impression with markedly improved initial color development and even final color development. It was made of pressure copy paper. Example 17 To an aqueous solution obtained by adding 603 parts of distearyl phosphate to 1600 parts of a 2.5% caustic soda aqueous solution at 60°C,
An aqueous solution of 100 parts of ferric chloride (FeCl ₃ .6H ₂ O) dissolved in 1000 parts of water was added under stirring to form an iron salt, which was then filtered and washed to obtain a pale yellow slurry. Separately, 30 parts of distearylamine in a molten state at 80°C was added to 120 parts of a 3% polyvinyl alcohol aqueous solution at 80°C, and the mixture was emulsified with a homomixer to give an average particle size of 5μ. The mixture was cooled to room temperature with stirring to obtain a distearylamine dispersion. Next, 30 parts of lauryl gallate was dispersed in 120 parts of a 3% polyvinyl alcohol aqueous solution, and then treated with a sand grinder. To the resulting dispersion, 30 parts of colloidal silica, 5 parts of ethylenediaminetetraacetic acid,
1 part of citric acid, 30 parts of the above iron salt in solid content, 100 parts of the above distearylamine dispersion, and styrene-butadiene copolymer latex (solid content
50%) was added to prepare a coating liquid for thermal recording paper. The resulting coating liquid was applied to 40 g/ ^m2 paper with a dry weight of 10
A heat-sensitive recording paper was obtained by coating with an air knife coater so as to give a coating density of g/m ² . When this thermosensitive recording paper was used to develop color with a thermal pen, a clear colored image was obtained.

Claims (1)

[Claims] 1. An organophosphorus iron compound having a P-O ^- ...Fe ³⁺ or P-S ^- ...Fe ³⁺ bond, and a ligand compound that forms a complex with the iron compound to develop color. 1. A recording material comprising: further comprising an organic base. 2. The iron compound is a double salt of one or more organic phosphorus compounds having a P-OH or P-SH bond and one or more carboxylic acids, thio acids, and dithio acids represented by the following general formula (). A recording material according to claim 1. (In the formula, R represents an alkyl group or an aryl group,
Y represents an oxygen atom or a sulfur atom. ) 3 The iron compound is one or more organic phosphorus compounds having a P-OH or P-SH bond, one of the compounds selected from the group of carboxylic acids, thio acids and dithio acids represented by the above general formula (). 3. The recording material according to claim 2, which is a double salt with at least one compound selected from the group consisting of sulfonic acids, sulfinic acids and sulfuric esters. 4 The organic base is an aliphatic amine, aromatic amine, alicyclic amine, amidine, guanidine,
Claims 1 and 2 are at least one selected from nitrogen-containing heterocyclic compounds and heterocyclic amines.
Or the recording material described in Section 3.