JPH01145189A - Color developer for pressure-sensitive recording paper, aqueous dispersant of the same, and preparation thereof - Google Patents

Abstract

PURPOSE:To contrive higher instantaneous color forming characteristics and higher developed color density by incorporating as a main constituent at least one multivalent metal salt of a specified nuclear-substd. salicylic acid in a color developer for a pressure-sensitive recording paper and in an aqueous dispersant of the color developer. CONSTITUTION:A color developer for a pressure-sensitive recording paper and an aqueous dispersant of the color developer each comprise at least one multivalent metal salt of a nuclear-substd. salicylic acid of the formula as a main constituent. In the formula, R1 is a 1-12C alkyl, R2 is hydrogen or a 1-12C alkyl, M is a multivalent metal atom., and m is the valence of M. At least one of R1 and R2 is sec-butyl, sec-hexyl, isohexyl, isononyl or isododecyl, and the total number of carbon atoms. of R1 and R2 is 8-18. A preferable nuclear- substd. salicylic acid is 3-methyl-5-isononylsalicylic acid or the like. A preferable multivalent metal for forming the multivalent metal salt of the nuclear-substd. salicylic acid is magnesium, aluminum or the like, in which zinc is most preferable.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a color developer for pressure-sensitive recording paper, an aqueous dispersion thereof, and a method for producing the same.

[Conventional technology]

Pressure-sensitive recording paper is disclosed in U.S. Patent Nos. 2,712,507 and 280.
No. 0457 and No. 3418250, etc., a solution of an electron-donating colorless dye (hereinafter referred to as "dye") and an electron-accepting compound (hereinafter referred to as "color developer") encapsulated in microcapsules. ), and when the microcapsules are destroyed by pressure, the dye solution and color developer come into contact and react to produce color, and is generally called carbonless paper. It has become popular.

Color developers for pressure-sensitive recording paper include inorganic compounds such as activated clay, formaldehyde polycondensates of substituted phenols, and metal salts of nuclear-substituted salicylic acids (JP-A-51-25
No. 174, No. 62-19486, No. 62-176'8
No. 75, No. 62-178387 and No. 62-1783
Organic compounds such as No. 88) have been put into practical use, and the present invention relates to metal salts of this nuclear-substituted salicylic acid.

Many of the polyvalent metal salts of nuclear-substituted salicylic acid are water-insoluble, and as a color developer, they are particularly superior to other color developers in terms of high color density and stability of color images. It has been widely put into practical use. Generally, it is a resinous substance with a high softening point. - Prepare the paint by finely pulverizing and dispersing it in water using a pulverizing media such as Lumil, Atroughter, and Sand Grinder, then adding inorganic pigments, clay pickles, adhesives, dispersants, antifoaming agents, etc., and apply it on the substrate. It is often applied and fixed. Therefore, polyvalent metal salts of nuclear-substituted salicylic acids are amorphous compounds with relatively high softening points that are suitable for pulverization and dispersion and have been put into practical use as color developers. However, such high softening point color developers have the following two drawbacks.

(1) The organic color developer with a high softening point dissolves in the dye solution encapsulated in microcapsules, reacts with the dye, and develops color at a slow rate, so the microcapsules are destroyed and the dye solution and color developer come into contact. After that, it takes a long time for the density or tone of the colored image to become constant. This tendency becomes more pronounced as the temperature decreases, and the gradual change in color density over time is related to instantaneous color development characteristics, and the change in color tone over time is especially noticeable in black colors made of multiple mixed dyes. It is seen as a problem.

(2) A color developer with a high softening point or a high melting point will not soften or melt at the drying temperature of the dye on the substrate and will not adhere, so a slightly narrow adhesive is used to fix the color developer to the substrate. is necessary. This tendency becomes more pronounced as developer particles are made finer for the purpose of improving color density or instantaneous color development, and this goal is often not achieved due to the color development inhibiting effect of the adhesive.

The softening point of polyvalent metal salts of nuclear-substituted salicylic acids is closely related to the structure of the substituents. When a substituent contains a ring structure, its softening point is generally high. However, just because the substituent does not contain a ring structure does not necessarily mean that a polyvalent metal salt of a nuclear-substituted salicylic acid having a low softening point and a low melting point can be obtained. Already, anacardic acid, 5-tertiary octylsalicylic acid, 3-
Methyl-5-tertiaryoctylsalicylic acid, 3,5-
Nuclear-substituted salicylic acids that do not contain a ring structure in their substituents, such as ditanyaritylsalicylic acid, 3,5-diteramylsalicylic acid, 3-tertiaryoctyl-5-methylsalicylic acid, or 3-tertiaryoctyl-5-ethylsalicylic acid, Although valent metal salts have been proposed, these are all compounds with high melting points, cannot be dissolved in the dye solution, and do not produce a sufficiently high color density.

[Problem that the invention seeks to solve]

The object of the present invention is to provide high color density and excellent instantaneous color development characteristics; 1. It is an object of the present invention to provide a color developer for pressure-sensitive recording paper, an aqueous dispersion for cutting, and a method for producing a cutting, the main component being a polyvalent metal salt of nuclear-substituted salicylic acid having a low softening point and a low melting point.

[Means for solving problems]

According to the present invention, in the general formula CI) R2 (in the general formula [1), R1 is an alkyl group having 1 to 12 carbon atoms, R2 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and M is a polyvalent metal atom. m indicates the valence of M. Also, at least one of R4 and R2 is a secondary butyl group, a secondary hexyl group, an inhexyl group, an isononyl group, or an isododecyl group, and the total number of carbon atoms of R4 and 82 is 8 to 18. ) A color developer for pressure-sensitive recording paper containing as a main component one or more polyvalent metal salts of nuclear-substituted salicylic acids and an aqueous dispersion thereof are provided. Further, according to the present invention, according to the general formula [■] (in the general formula [■], R1 is an alkyl group having 1 to 12 carbon atoms, R2 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and N is an alkali metal atom). and at least one of R1 and R2 is a secondary butyl group, a secondary hexyl group, an isohexyl group, an innonyl group, or an indodecyl group, and the total number of carbon atoms of R1 and R2 is 8 to 18.) An aqueous solution of an alkali metal salt of a nuclear-substituted salicylic acid represented by
Provided is a method for producing a color developer for pressure-sensitive recording paper, which is characterized by causing double decomposition in the presence of an organic solvent at 80°C.

Generally, when the melting point and softening point of a color developer are low, the color developer has a high dissolution rate in a dye solution, a quick color reaction, good instantaneous color development characteristics, and a small temporal change in color tone. Furthermore, if the softening point is low enough to soften and fuse at the drying temperature of the dye on the substrate, the color developer will have self-adhesive properties, so the amount of adhesive used in the paint can be reduced, and the color development of the adhesive will be reduced. The inhibitory effect can be kept to a minimum.

As already explained, the softening point of polyvalent metal salts of nuclear-substituted salicylic acid is closely related to the structure of its substituents, but in order to further reduce its crystallinity and obtain a sufficiently low melting point, specific The selection of substituents is necessary. A polyvalent metal salt of salicylic acid in which at least one nucleus is substituted with a secondary butyl group, a secondary hexyl group, an isohexyl group, an innonyl group or an indodecyl group, more preferably an isononyl group or an indodecyl group, has a low softening point and a low melting point. . Here, the secondary hexyl group refers to 1-hexene to salicylic acid,
The isohexyl group, innonyl a and isododecyl groups are groups produced by adding globylene dimer, prohyne trifiltrate, propylene tetramer or 1-butene trimer to salicylic acid, respectively. None of these groups is a single group, but a mixed group such as optical isomerism or geometric isomerism, and the polyvalent metal salt of substituted salicylic acid containing these groups also forms a mixture of many isomers. It is presumed that the reason why compounds containing these substituents have a low melting point is that the isomers interact with each other to lower the melting point.

In fact, when two or more polyvalent metal salts of nuclear-substituted salicylic acid according to the present invention are further mixed, the melting point inevitably decreases.

One object of the present invention is to provide a color developer with excellent instantaneous color-forming properties, which is mainly composed of a polyvalent metal salt of nuclear-substituted salicylic acid with a low softening point and a low melting point. In order to function satisfactorily as a coloring agent, some other structural characteristics are required.

R1 in general formula [I] is an alkyl group having 1 to 12 carbon atoms. If the R4 position is hydrogen, for some reason the color density is lower and the water resistance of the recorded image is poorer than when it is an alkyl group. This is thought to be caused by the shielding effect of the alkyl group on the hydroxyl group, and it is more preferable that R1 is an alkyl group having 3 to 12 carbon atoms. This can be estimated from the following test results.

(1) Zinc 3-isononylsalicylate>5~Zinc isononylsalicylate (2) Zinc 3-innonyl-5-methylsalicylate>3
-Methyl-5-isononylsalicylate zinc (3) 3
-innonyl-5-isopropylsalicyl rlN zinc=
Zinc 3-innorovir-5-isononylsalicylate (This is a comparison of the color-forming ability of each zinc salt with respect to crystal violet lactone. Two inequality signs represent a large difference in color-forming ability, and a minus sign represents a large difference in color-forming ability. (The equal sign indicates that there is no difference in coloring ability.) Specific examples of R1 include methyl group, isononyl group, sec-butyl group, tert-butyl group, tert-aryamyl group. group, secondary hexyl group, isohexyl group, isononyl group, or isododecyl group. Further preferred specific examples of R1 include isopropyl group, sec-butyl group, tert-butyl group, tert-aryamyl group, sec-hexyl group, isohexyl group, isononyl group and indodecyl group.

R2 in the general formula CD is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and this has less direct influence on coloring ability than R1. However, when R2 is a hydrogen atom, the color developer tends to turn slightly brown in an atmosphere of concentrated nitrogen oxides, so if you are concerned about this tendency, R4 is an alkyl group having 1 to 12 carbon atoms. is preferable, and specific examples include methyl group, ethyl group,
Examples include isopropyl group, sec-butyl group, tertiary-butyl group, tertiary-amyl group, secondary hexyl group, isohexyl group, isononyl group, and indodecyl group.

The total number of carbon atoms in R1 and R2 has an important effect on the hydrophilicity and lipophilicity of the polyvalent metal salt of nuclear-substituted salicylic acid. If the color developer is hydrophilic, the colored image will not be sufficiently stable against water or humidity, and furthermore, it will generally be poor in lipophilicity and will not be sufficiently soluble in the dye solution. When the total number of carbon atoms of R1 and R2 is small, the hydrophilicity is high, and as the total number of carbon atoms increases, the base oil property increases. Based on this knowledge, in the present invention, R4
Compounds in which the total number of carbon atoms of R2 and R2 are 7 or less are excluded.

On the other hand, as the total number of carbon atoms in R4 and 82 increases, the molecular weight of the nuclear-substituted salicylic acid also increases, and the color-forming ability is diluted by the size of the substituent. Requires agent. In the present invention, the total number of carbon atoms of R4 and R2 is limited to 18 or less, and it cannot be said that even if the color developer exceeds this limit, its drawbacks are serious. . In the present invention, the total number of carbon atoms in R4 and R2 ranges from 8 to 18, but is preferably from 10 to 13. Preferred nuclear substituted salicylic acids for the purposes of the present invention include 3-methyl-
5-isononylsalicylic acid, 3-methyl-5-indodecylsalicylic acid, 3-isoprobyl-5-innonylsalicylic acid, 3.5-disendiliptylsalicylic acid, 3
-sec-butyl-5-isohexylsalicylic acid, 3
-Secondarybutyl-5-isononylsalicylic acid, 3-
Tert-butyl-5-isohexylsalicylic acid, 3-
Tert-butyl-5-isononylsalicylic acid, 3-tert-butyl-5-isohexylsalicylic acid, 3-tert-butyl-5-isononylsalicylic acid, 3-sec-hexyl-5-sec-butylsalicylic acid, 3
-Secondarybutyl-5-tert-butylsalicylic acid, 3.5-・zosecondaryhexylsalicylic acid, 3-secondaryhexyl-5-isohexylsalicylic acid, 3-
Isohexyl-5-tajarizotylsalicylic acid, 3-
Isohexyl-5-secondary hexylsalicylic acid, 3
, 5-diisohexylsalicylic acid, 3-isononylsalicylic acid, 3-innonyl-5-methylsalicylic acid, 3-
Isononyl-5-ethylsalicylic acid, 3-isononyl-
5-tert-butylsalicylic acid, 3,5-diisononylsalicylic acid, 3-indodecylsalicylic acid, 3-indodecyl-5-methylsalicylic acid, 3-indodecyl-
Examples include 5-ethylsalicylic acid and 3-isododecyl-5-isopropylsalicylic acid. More preferred are 3-isopropyl-5-ynonylsalicylic acid, 3-ternyabutyl-5-isononylsalicylic acid, 3-isononyl-5-methylsalicylic acid, 3-ynonyl-5-
Examples include tert-butylsalicylic acid, 3-indodecylsalicylic acid, and 3-indodecyl-5-methylsalicylic acid.

Preferred polyvalent metals for converting nuclear-substituted salicylic acid into a polyvalent metal salt for use as a color developer include magnesium, aluminum, calcium, cobalt, nickel, strontium, and tin, and the most preferred is zinc. be.

Although most of the nuclear-substituted salicylic acids related to the present invention are new compounds, they can be produced from industrially easily available raw materials by several already known methods.

Its main raw materials include pheno-/l/, f-IJ thylic acid, sorafresolic acid, ortho-creso-A/, and 4-
1 Ethylphenol, armpit.

Pyrphenol, Noya secondary butylphenol,
Nora tertiary butylphenol, tertiary amylphenol, propylene, propylene trimer, propylene trimer, propylene tetramer, 1-butene, 1-butene trimer, imbutylene, isoamylene (impentene), 1- Examples include hexene, alkali hydroxide, and carbon dioxide gas.

A polyvalent metal salt of a nuclear-substituted salicylic acid can be obtained as a water-insoluble salt by a metathesis reaction between an aqueous solution of an alkali metal salt of a corresponding nuclear-substituted salicylic acid and an aqueous solution of a water-soluble polyvalent metal salt. These are usually resinous substances with a low softening point but extremely high viscosity near room temperature, and are extremely difficult to handle as they are. It becomes more fluid when heated in water, so heating it or adding an organic solvent will lower the viscosity and make it easier to handle. Further, preferably, if an organic solvent is coexisting in advance during the metathesis reaction, the polyvalent metal salt of the nuclear-substituted salicylic acid produced by the reaction is immediately dissolved in the organic solvent and the viscosity is lowered, so that the reaction can be carried out smoothly even at low temperatures. be. Since the target product after metathesis must be separated from the aqueous layer as an oil layer, it is preferable that the organic solvent has a low solubility in water, and an organic solvent having a solubility in water of 10% by weight or less is used. Since the used organic solvent must be removed eventually, those having a high boiling point are not preferred, and those having a boiling point in the range of 60°C to 180°C are used. Preferred specific examples thereof include benzene, toluene, xylene, ethylbenzene, chloroform, carbon tetrachloride, ethylene chloride, vinylidene chloride,
Examples include 1,2-dichloroethylene, butanol, amyl alcohol, isoglobil ether, butyl ether, methyl ethyl ketone, methyl ethyl ketone, methyl isodity ketone, and ethyl acetate. And usually
0.0 per part by weight of polyvalent metal salt of nuclear-substituted salicylic acid
5 parts by weight to 5 parts by weight are used.

Since the polyvalent metal salt of the nuclear-substituted salicylic acid according to the present invention is slightly hydrated in water and its softening point is lowered by 50°C to 80°C, it is usually carried out with other organic color developers.
It is not very suitable for fine pulverization and dispersion in water. If you choose to use such a method, ■ Pulverize and disperse at a very low temperature. ■ Mix it with a resinous substance that has a high softening point; ■ Add an inorganic substance with a large surface area as a grinding aid. Measures such as these must be taken. In order to finely disperse the polyvalent metal salt of nuclear-substituted salicylic acid according to the present invention, it is preferable to liquefy it by heating or adding an organic solvent to emulsify and disperse it in water containing a dispersant. This organic solvent can be exactly the same as that used in the metathesis reaction, and if the metathesis product contains a solvent, the dispersion process can be carried out as it is without adding a new solvent. The organic solvent can be removed azeotropically with water after emulsification and dispersion, if necessary. As the emulsification dispersion media used here, an ultrasonic homogenizer, a high-pressure homogenizer, a homomixer, a sand glider, etc. are preferable. Dispersants used include sodium alkyl sulfate, sodium alkyl sulfonate, sodium alkylaryl sulfonate, sodium salt of sulfoconophosphate, sodium prearylpolysulfonate, sodium I-lyacrylate, sodium polymethacrylate, and maleic acid. Sodium salt of acid copolymer, polyvinyl alcohol, polyacrylamide,
Examples include acrylamide copolymer or hydroxyethyl cellulose.

Polyvalent metal salts of nuclear-substituted salicylic acid may be added with dispersants or metal oxides, metal hydroxides, metal carbonates, polymer compounds, softeners, and antioxidants after dispersion to increase their value as color developers. , an ultraviolet absorber or other color developer can be mixed.

When using a polyvalent metal salt of nuclear-substituted salicylic acid as a color developer for pressure-sensitive recording paper, a paint is prepared by dissolving it in an organic solvent or dispersing it in water, and the paint is applied and fixed on the substrate. It is normal to do so. Depending on the purpose, the paint may further contain inorganic pigments, clay pickles, dispersants, adhesives, thickeners, antifoaming agents, antioxidants, external radiation absorbers, softeners, lubricants, or organic solvents. Can be done.

Next, in order to further clarify the present invention, specific examples will be given and explained.〇Example 1 Internal volume with stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen gas inlet Phenol 2.63 in a 5,000ml hard glass five-loaf flask
Charge 2 grams (28 moles) and 15 grams of small-grain aluminum, heat the flask while slowly bubbling nitrogen gas, and begin stirring when the temperature of the contents reaches 50°C. When the temperature of the contents is further increased to 150° C., aluminum is dissolved while generating hydrogen gas. Once the aluminum is dissolved, the heating is adjusted to such an extent that the liquid is refluxed little by little from the reflux condenser, and 882 g (7.0 mol) of isononene (propylene 31) is added dropwise from the dropping funnel over 10 hours. If the reaction is continued for another 40 hours after the dropwise addition is completed, the added isononene will be almost completely gone, so the flask is cooled to bring the temperature of the contents to 90°C. Add 700 milliliters of 3N hydrochloric acid and 500 grams of toluene and stir vigorously for 30 minutes while heating the flask again. If the contents are transferred to a separating funnel with an internal volume of s and ooo milliliter and left to stand, it will separate into two layers, so remove the lower aqueous layer. Add another 700 ml of boiling water at 70°C, shake the separatory funnel, let it stand, and perform two washing operations such as separating the liquids. The oil layer is transferred to a vacuum distillation apparatus made of hard glass having an internal volume of 5,000 ml, and low-boiling fractions are removed under a vacuum of 25 Torr until the temperature of the kettle reaches 150°C.

The contents remaining in the pot are transferred to a hard glass vacuum distillation apparatus with an internal volume of 2,000 milliliters, and the fraction whose temperature at the top of the distillation column ranges from 105°C to 110°C is collected under a vacuum of 1.2 Torr. , 280 grams of a clear colorless liquid are obtained.

This has a hydroxyl number of 253.2 (theoretical value; 254.
6) According to the Sumika analysis (Figure 1), the peak pattern of benzene nuclear hydrogen around 7 ppm coincides with 2-substituted phenol, the hydrogen of the hydroxyl group around 5 ppm, and the hydrogen of the hydroxyl group around 7 ppm. 0 hen 4a nuclear hydrogen and 1 pp
The ratio of each absorption value of alkyl group hydrogen near m is 1:4:19
It is confirmed that it is 2-innonylphenol.

Example 1-2 The mixture obtained in Example 1 was placed in a hard glass three-necked flask with an internal volume of 1,000 ml, equipped with a stirrer, a thermometer, and a device capable of azeotropically separating and removing water.
440 grams (2 moles) of isononylphenol, 250 grams of toluene, 250 grams of diethylene glycol dimethyl ether and 157 grams (1,96 moles) of 50-cent sodium hydroxide are charged. Heat the flask while stirring to remove water azeotropically. After confirming that water has been completely removed, transfer the entire contents to a stainless steel autoclave with an internal volume of 1,000 ml. Add carbon dioxide gas to the autoclave at a pressure of 1
Blow in at 5 kg/1 m2 and react at 170°C until carbon dioxide gas is no longer absorbed. The reaction is completed in about 1 hour. After lowering the temperature of the contents to 60℃, add water, oool!
Inject into J.

The previous aqueous solution and 1,000 grams of toluene were placed in a 10,000 milliliter hard glass back-door flask equipped with a stirrer, thermometer, reflux condenser, and reserve port, and the flask was heated while stirring. Bring the contents to a slight boil. Stop heating and stirring, leave the flask still, and remove the upper toluene layer from the preliminary port. Add 500 durams of toluene again, stir for 10 minutes, leave the flask still, and remove the top toluene layer. Repeat this washing operation five times. After switching the reflux condenser to the distillation port, the 7/F Sco is heated to remove toluene that has been azeotropically solubilized with water. A dropping funnel is installed in the preliminary spout, and 600 grams of 20 nof-cent dilute sulfuric acid is added dropwise while stirring the contents vigorously. 2 more after dripping
If the mixture is stirred vigorously for 0 minutes and then allowed to stand still, a pale brown viscous liquid will be released.

After removing the aqueous layer, add 1,000 milliliters of water, heat the flask while stirring vigorously to bring the contents to a slight boil, let stand, and then remove the aqueous layer.

Repeat this washing operation three times. The light brown viscous liquid is transferred to a vacuum distillation apparatus made of hard glass with an internal volume of 1,000 ml, and continuous components are removed under a vacuum of 1.2 Torr until the temperature of the kettle reaches 120°C. After dehydration, 482 grams of the product was a viscous, pale brown transparent liquid with an acid value of 211 (theoretical value: 212.2), and a benzene concentration of around 7 ppm according to trace analysis (Figure 2). The hydrogen peak pattern is consistent with 3-substituted salicylic acid, and the infrared absorption spectrum (Figure 3) shows an absorption of strongly hydrogen-bonded carbnyl group at 1.665CWr', which is 3-substituted salicylic acid.
-Confirmed to be isononylsalicylic acid.

Example 1-3 2.000 g of water containing 60 g of sodium hydroxide in a hard glass beaker with an internal volume of 3,000 ml.
Example 1-2 while stirring the contents.
Gradually add the 3-isononylsalicylic acid obtained in .

It takes 398 grams of 3-nonylsalicylic acid to reach a voice of 7. It is clear that this solution is an aqueous sodium 3-isononylsalicylate solution, and analysis by liquid chromatography shows a complete single peak. 1,800 grams of an aqueous solution containing 200 grams of zinc sulfate was placed in a 5,000 ml hard glass flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel, and the flask was heated while stirring. Bring the contents to a slight boil. While maintaining this state)
Add all of the IJum salt aqueous solution dropwise. Immediately after dropping, stop heating the flask and continue stirring for an additional 30 minutes. When the flask is allowed to stand still, a light brown viscous resinous substance is liberated. After removing the aqueous layer, add 1,000 ml of water, stir while heating the flask, and once it boils, let it stand and remove the aqueous layer. This cleaning operation does not require a double layer of gold.

The resulting resinous material contains about 8 percent water. A portion of this was removed in a vacuum dryer under a vacuum of 5 Torr.
Dry at 100°C for 1 hour to prepare an analysis sample. This has a zinc content of 10.8/! It is clearly a light brown transparent resinous substance with a softening point of 97 DEG C. at -cent (theoretical value; IL, 0.4 percent), and is clearly zinc 3-innonylsalicylate.

Example 1-4 300 grams of toluene is added to 400 grams of the water-containing zinc 3-isononylsalicylate obtained in Example 1-3 and dissolved. This was placed in a hard glass beaker with an internal volume of 3,000 ml +) liters, and 3 g of sodium dodecylbenzenesulfonate and K 98 ``''-
1,2 cents of water containing 8 grams of polyvinyl alcohol
00 grams and stirred at 10,000 revolutions per minute using a homomixer (manufactured by #Shuukikakogyo Co., Ltd.: TK-M type).
Emulsify and disperse for 5 minutes.

Transfer this emulsion to a hard glass three-bottle flask with an internal volume of 3,000 ml, equipped with a stirrer, thermometer, and distillation port, and heat the bottom of the flask while stirring to azeotrope the toluene with water. Distilled into. The liquid after toluene distillation is milky white, and the average particle size of the dispersion is 0.
．． Chill at 6 microns.

Drying for 1 hour at 100 DEG C. under a 20 torr vacuum gives a volatile residue of 34.5 percent, which is an aqueous dispersion of zinc 3-isononylsalicylate.

Example 2 A five-loop flask with an internal volume of s and ooo milliliters is charged with 2,632 grams (28 moles) of 7 enol and 20 grams of small-grain aluminum. The flask is heated while blowing nitrogen gas, and aluminum is dissolved in the same manner as in Example 1. 941 grams (5.6 moles) of indodecene (7″ tetrapropylene) was added dropwise over 15 hours while heating the solution little by little to reflux from a reflux condenser.After the dropwise addition was completed, the reaction was continued for an additional 30 hours. Since the added isododecene is almost gone, cool the flask and bring the temperature of the contents to 90°C.Here, add 800 mIJ I of 3N hydrochloric acid.
Add 400 g of toluene and stir for 1 hour while heating. This was transferred to a separating funnel with an internal volume of 5,000 ml, the aqueous layer was removed, and the mixture was washed in two layers with 70° C. water in the same manner as in Example 1. The internal volume of the oil layer is 5.0
Transfer to a vacuum distillation apparatus of 00 mi IJ IJ liter, and
Low-boiling components are removed under Torr vacuum until the kettle temperature reaches 150°C. The contents of the pot are measured by the internal volume 2. 2. Transfer to an OOO milliliter vacuum distiller and collect the fraction whose temperature at the top of the distillation column ranges from 130°C to 138°C under a vacuum of 2.1.2 torr.
1,120 grams are obtained. This has a hydroxyl value of 215.0 (theoretical value; 213.8), and according to NMR analysis (Figure 4), it coincides with a phenol substituted at the 2-position, similar to the peak pattern of benzene nuclear hydrogen around 7 ppm y511X1. It was confirmed that it was 2-indodecyl quenol.

Example 2-2 472 g (1.8 mol) of 2-indodecylphenol obtained in Example 2, 300 g of xylene, and 50 no.-cent sodium hydroxide aqueous solution 140 g were placed in a three-bottle flask with an internal volume of 1,000 ml. grams (1,7
5 mol) was charged, and water was removed azeotropically with xylene in the same manner as in Example 1-2.

This was transferred to an autoclave with an internal volume of 1,000 mIJ IJ liter, and the carbon dioxide gas pressure was reduced to 9/crn2.170.
React at ℃. The reaction is completed in about one hour. 6.0 ml of water in a four-bottle flask with an internal volume of 10,000 ml
00 ml, xylene 500 g, and butanol 300 g were charged, and the contents of the autoclave cooled to 60° C. were poured into the autoclave while stirring.

Heat the flask until the contents boil, let it stand, and remove the upper layer. It is further washed five times with a mixture of 400 grams of toluene and 100 grams of butanol.

The reflux condenser is switched to the distillation port to remove the solvent azeotropically dissolved with water. Transfer 50 grams of it into an Erlenmeyer flask and use it as an analysis sample. While heating the Erlenmeyer flask, add 5 grams of diluted sulfuric acid of 20 or 1 cent, stir vigorously and leave to stand. A light brown liquid will be liberated, so discard the aqueous layer and wash it three times with 50 ml of 70°C water. If a light brown viscous liquid is dried at 100°C under a vacuum of 5 torr for one hour, the liquid becomes transparent. This is because the liquid chromatography peak is single and the acid value is 1s1.2.
(Theoretical value; 183.1). According to NMR analysis (
FIG. 5) As in FIG. 2, it is completely consistent with the 3-substituted salicylic acid, and it is confirmed that this is 3-indodecylsalicylic acid.

Example 2-3 16 grams of a 50 percent aqueous sodium hydroxide solution is added to the sodium 3-isododecylsalicylate aqueous bath solution obtained in Example 2-2. While heating this to 90℃,
1,200 grams of an aqueous solution containing 0.00 grams of zinc sulfate are added dropwise. After dropping, stir further for 30 minutes and then let stand. Remove the aqueous layer and wash 3 times by adding 1:0001'Jttle of boiling water.

Take about 10 grams of it and put it under a vacuum of 5 torr for 10 minutes.
Dry at 0°C for 1 hour to prepare an analysis sample. The sample was a light brown transparent resinous material with a softening point of 93°C and a zinc content of 11.
8% (theoretical value; 9.67%).

It is assumed that the deviation of the zinc content from the theoretical value is due to the inclusion of zinc hydroxide and zinc carbonate.

Example 2-4 200 grams of xylene was added to the resinous material obtained in Example 2-3, and further 3 grams of sodium dibutylnaphthalene sulfonate and saponification degree of 98.! - Cento? Add 1.200 ml of water containing 6 g of libinyl alcohol and mix with a homomixer at 10,000 revolutions per minute.
Emulsify and disperse for 0 minutes. This is transferred to a flask with an internal volume of 3,000 ml, and xylene is distilled off together with water. This is an aqueous dispersion of a color developer whose main component is zinc 3-indodecylsalicylate, with an average particle size of 0.4 microns and a non-volatile content of 37.2 cents/thousand. .

Example 3 2,700 grams (25 moles) of para-cresol and 14 grams of small particulate aluminum are charged into a four-loaf flask having an internal volume of 3,000 milliliters, and the aluminum is dissolved in substantially the same manner as in Example 1. Once the aluminum is melted, it is transferred to an autoclave with an internal volume of 5,000 milliliters. 756 grams (6 moles) of isononene are forced into the autoclave over a period of 5 hours while maintaining the temperature of the contents at 230°C. Thereafter, the reaction was continued for 10 hours, and the temperature of the contents was cooled to 90°C. This has an internal volume of 5,000
Transfer to a 0 ml four-bottle flask, and wash with dilute hydrochloric acid followed by hot water in the same manner as in Example 1. Vacuum distillation is carried out again in the same manner as in Example 1, and 1.026 g of a fraction whose temperature at the top of the distillation column ranges from 105° C. to 110° C. is collected under a vacuum of 1.0 Torr. This has a hydroxyl value of 238.8 (theoretical value;
239.4), and according to ■ analysis (Figure 6) 7
The heat and turn of benzene nuclear hydrogen around ppm is 2,
The 4-substituted phenol was confirmed to be 2-isononyl-4-methylphenol.

Example 3-2 An aqueous dispersion of zinc 3-isononyl-5-methylsalicylate is obtained according to the methods from Example 1-2 to Example 1-4.

Example 4 A five-loaf flask with an internal volume of 5,000 milliliters is charged with 2,700 grams (25 moles) of cresol and 80 grams of methanesulfonic acid. The temperature of the contents is 180
756 grams of isononene is added dropwise over 5 hours while maintaining the temperature. After the dropwise addition was completed, the reaction was continued for another 10 hours, and the temperature of the contents was cooled to 90°C. 7. Rinse 4 times with 7 liters of boiling water. This was vacuum distilled in the same manner as in Example 1, and 1,058 g of a fraction having a distillation column temperature of 113 DEG C. to 118 DEG C. was collected under a vacuum of 1.2) liters. This has a hydroxyl value of 237.2 (theoretical value; 2
39.4) The NMR analysis was exactly the same as in Figure 6, confirming that it was 2-isononyl-4-methylphenol.

Subsequently, an aqueous dispersion of zinc 3-isononyl-5-methylsalicylate is obtained according to the methods of Examples 1-2 to 1-4.

Example 5 Example 3 was prepared in exactly the same manner as Example 3 and Example 3-2 except that para-cresol in Example 3 was replaced with 2-ethylphenol.
An aqueous dispersion of zinc -innonyl-5-ethylsalicylate is obtained. However, the boiling point of the intermediate 2-isononyl-4-ethylphenol is 1.1 Torr and 109°C to 1
The temperature was 14°C, and the hydroxyl value was 223.1 (theoretical value;
225.9).

Example 6 2-isononyl-
5-Ingropylphenolka can be obtained. It has a boiling point of 1.2 torr, 132°C to 140°C, and a hydroxyl number of 211.9 (theoretical value; 213.8).

Subsequently, 3 was carried out in the same manner as in Example 2-2 to Example 2-4.
An aqueous dispersion of zinc -innonyl-5-isoglobilsalicylate is obtained.

Example 7 An aqueous dispersion of zinc 3-isononyl-5-tert-butylsalicylate was obtained in the same manner as in Example 6, except that the inglovirphenol in Example 6 was further replaced with the parent tertiary phenol. It will be done.

Example 8 2-Indodecyl-4-methylphenol is obtained by replacing isononene in Example 3 with isododecene (propylene tetramer). Subsequently, an aqueous dispersion of zinc 3-indodecyl-5-methylsalicylate is obtained in the same manner as in Examples 2-2 to 2-4.

Example 9 An aqueous dispersion of zinc 3-indodecyl-5-ethylsalicylate is obtained in the same manner as in Example 8 except that nocracresol in Example 8 is replaced with paraethylphenol.

Example 10 1,410 g (15 moles) of 7 enol and 70 g of activated clay were placed in a five-loaf flask with an internal volume of s and ooo milliliters.
Prepare grams. Heat the flask while slowly blowing nitrogen gas, and when the temperature of the contents reaches 50°C, start stirring and bring the temperature of the contents to 160°C. A mixture of 1,008 grams (12 moles) of 1-hexene and i,00 grams of hisohexene (propylene dimer) is added dropwise from the dropping funnel over 20 hours. After the dropwise addition, the reaction was continued for another 10 hours, and the temperature of the contents was cooled to 100°C. This was filtered by suction to remove activated clay, then transferred to a vacuum distiller, and distilled under a vacuum of 1.2 torr from 128°C to 142°C.
Collect 1,680 grams of fraction up to ℃. This has a hydroxyl value of 209.8 (theoretical value; 213.8),
According to gas chromatography analysis, they are divided into two groups that are close to each other, but each of them is composed of a complex group. These include 2,6-dise-ndahexylphenol, 2-hexyl-6-ithexylphenol, and 2,6-substituted group 7' (!: 2,4-disehexylphenol). It appears to be a 2,4-displaced group of phenol, 2-secondary hexyl-4-isohexylphenol, 2-isohexyl-4-secondaryhexylphenol and 2,4-diisohexylphenol.

Example 10-2 The mixture obtained in Example 10 was treated in the same manner as in Example 2-2 to Example 2-4, and 3,5=dis-sec-hexylzinc salicylate, 3-sec-hexyl-5-isohexyl An aqueous dispersion is obtained consisting of a mixture of zinc salicylate, zinc 3-isohexyl-5-secondaryhexylsalicylate and zinc 3,5-diisohexylsalicylate.

Example 11 Paratertiary butylphenol 3. Dissolve 27 grams of aluminum in ooo grams and transfer to an autoclave with an internal volume of 5,000 milliliters. 210 g (2.5 mol) of 1-hexene and 21 mol of hysohexene at 230°C
Inject 0 grams (2.5 mol) of the mixture. Thereafter, in the same manner as in Example 3, 938 grams of an equimolar mixture of 2-sec-hexyl-4-tert-butylphenol and 2-isohexyl-4-tert-butylphenol was obtained.

This has a hydroxyl number of 238.1 (theory (fi;
239.4) and sb, the boiling point at 1.2 torr is 112°C
to 119°C.

Example 11-2 In the same manner as in Examples 1-2 to 1-4, zinc 3-secondaryhexyl-5-ternarybutylsalicylate and 3-ynhexyl-5-
An aqueous dispersion of a mixture of zinc tanyabutylsalicylate is obtained.

Example 12 - 2,350 grams (25 moles) of phenol and 1 activated clay in a five-loaf flask with an internal volume of s and ooo milliliters
Charge 50 grams and raise the temperature while slowly blowing nitrogen gas to bring the temperature of the contents to 160°C. 1,512 grams (12 moles) of isononene are added dropwise over 20 hours, and the reaction is continued for an additional 10 hours. This is cooled to 100°C and filtered under suction to remove activated clay. This was transferred to a vacuum evaporator with an internal volume of 5,000 mm and a Raschig ring rectifier with a filling height of 750 mm, and heated from 115°C to 125°C under a vacuum of 1.2 Torr.
Collect 1.910 grams of fraction up to ℃. This has a hydroxyl value of 252.5 (theoretical value; 254.6),
From gas chromatography analysis, 2-isononylphenol of 2.8 g cents was found to be 97.2 g cents 1) 4
- It is confirmed that it is a mixture of isononylphenol.

Example 12-2 7 grams of aluminum is dissolved in 660 grams of the product obtained in Example 12 and transferred to an autoclave having an internal volume of 1,000 milliliters. While maintaining the temperature of the contents at 240°C, 63 grams of Gloref was press-fitted. Once the internal pressure of the autoclave has decreased, proceed in the same manner as in Example 1.
Obtain 5 grams of target. This has a hydroxyl value of 21
1.7 (theoretical value; 213.8), and the boiling point at 1.2 Torr is 128°C to 138°C. Also, according to gas chromatography, 4-isononylphenol of 0.3 to 1 cent, 2-1 soprobil-6-innonylphenol of 0.9 to 1 cent, and 2-impropylene of 96.8 to 1 cent. Bir-4-isononylphenol and H2.0/? -St 2,6-diisopropyl-4-
It is confirmed that it is a mixture of isononylphenol.

Example 12-3 The product of Example 12-2 was converted from Example 2-2 to Example 2-
Aqueous dispersion containing zinc 3-improbyl-5-innonylsalicylate as a main component can be obtained by carrying out the treatment in steps up to 4.

Example 13 The product obtained in Example 12 was treated in the same manner as in Example 12-2 and Example 12-3 except that propylene in Example 12-2 was replaced with 1-butene to obtain 3-sec-butyl-5. −
An aqueous dispersion containing zinc isononylsalicylate as a main component is obtained.

Example 14 The product obtained in Example 12 was treated in the same manner as in Example 12-2 and Example 12-3 except that propylene in Example 12-2 was replaced with isobutylene to obtain 3-turnyabutyl-5.
An aqueous dispersion containing zinc isononylsalicylate as a main component is obtained.

Example 15 The product obtained in Example 12 was treated as in Example 12-2 and Example 12-3 except that propylene in Example 12-2 was replaced with impentene to obtain 3-tertiaryamyl-5.
An aqueous dispersion containing zinc isononylsalicylate as a main component is obtained.

Example 16 Inononene in Example 12 was replaced with inhexene.

4-Isohexylphenol is obtained in the same manner as in Example 12. It has a hydroxyl number of 3-12.7 (theoretical value: 314.7) and a boiling point of 93 at 1.2 torr.
℃ to 97℃.

Example 16-2 The product obtained in Example 16 is treated in the same manner as in Example 12-2 to obtain 2-improvil-4-isohexylphenol. It has a hydroxyl number of 254.1 (theoretical value: 254.6) and a boiling point of 1.2)
03°C to 108°C.

Example 16-3 The product obtained in Example 16-2 was treated in the same manner as in Examples 1-2 to 1-4 to obtain 3-isopropyl-5-
An aqueous dispersion containing zinc isohexylsalicylate as a main component is obtained.

Example 17 The product obtained in Example 16 is treated in the same manner as in Example 13 to obtain an aqueous dispersion containing zinc 3-sec-butyl-5-isohexylsalicylate as a main component.

Example 18 The product obtained in Example 16 is treated in the same manner as in Example 14 to obtain an aqueous dispersion containing zinc 3-tert-butyl-5-isohexylsalicylate as a main component.

Example 19 The product obtained in Example 16 is treated in the same manner as in Example 15 to obtain an aqueous dispersion containing zinc 3-tertiaryamyl-5-isohexylsalicylate as a main component.

Example 20 /2,4-dise-sec-butylphenol was obtained from 4'-race-sec-butylphenol and 1-butene in the same manner as in Example 3, and then from Example 1-2 to Example 1-
In the same manner as in Step 4, an aqueous dispersion containing zinc 3,5-nectandaliptylsalicylate as the main component is obtained.

Example 21 An aqueous dispersion containing zinc 3-sec-hexyl-5-sec-butylsalicylate as a main component is obtained in the same manner as in Example 20, except that 1-hexene is substituted for 1-butylene in Example 20.

Example 22 2-Secondaryhexyl-4-tajarizotylphenol is obtained from paratertiary butylphenol and 1-hexene in the same manner as in Example 3, and then prepared from Example 1-
An aqueous dispersion containing zinc 3-secondaryhexyl-5-tert-butylsalicylate as a main component is obtained in the same manner as in Example 2 to Example 1-4.

Example 23 An aqueous dispersion containing zinc 3-isohexyl-5-tert-butylsalicylate as a main component is obtained in the same manner as in Example 22 except that 1-hexene in Example 22 is replaced with inhexene.

Example 24 2-Methyl-4-isononylphenol was obtained from orthocresol and isononene in the same manner as in Example 12, and then 3-methyl-4-isononylphenol was obtained in the same manner as in Example 1-2 to Example 1-4. An aqueous dispersion containing zinc 5-isononylsalicylate as a main component is obtained.

Example 25 Orthocresol and isododecene (propylene tetramer)
2-methyl-4-indodecylphenol was obtained in the same manner as in Example 12, and then zinc 3-methyl-5-indodecylsalicylate was obtained in the same manner as in Example 2-2 to Example 2-4. An aqueous dispersion containing 〇 as the main component is obtained.

Example 26 Indodecene (globylene tetramer) used in Example 2
2-Indodecylphenol is obtained in exactly the same manner as in Example 2 except that 1-butene trimer is substituted for 1-butene trimer. This is almost indistinguishable from the 2-indodecylphenol obtained in Example 2. Also, successively, Example 2-2 to Example 2
An aqueous dispersion of zinc 3-indodecylsalicylate is obtained according to the methods up to -4, but this is also completely indistinguishable from that obtained in Example 2-4.

Example 27 Example 2- was prepared from the sodium 3-indodecylsalicylate aqueous solution obtained in Example 2-2 and the cobalt chloride aqueous solution.
An aqueous dispersion containing cobalt 3-indodecylsalicylate as a main component is obtained in the same manner as in Example 3 and Example 2-4.

Example 28 Example 2- was prepared from the sodium 3-isododecylsalicylate aqueous solution obtained in Example 2-2 and the nickel sulfate aqueous solution.
An aqueous dispersion containing nickel 3-indodecylsalicylate as a main component is obtained in the same manner as in Example 3 and Example 2-4.

Example 29 2-Indodecylphenol 472 obtained in Example 2
g (1,8 mol), xylene 300 g and 50
An aqueous sodium hydroxide solution was treated in the same manner as in Example 2-2 to produce 3-isododecylsalicylic acid) IJ
An aqueous solution of umum is obtained. Add 300 grams of xylene to this, stir vigorously, and then dropwise dropwise add 17-cent zinc sulfate aqueous solution.

After the addition was completed, the mixture was stirred for another 30 minutes, and then transferred to a separatory funnel to remove the lower aqueous layer. Wash 3 times with i,oo ml of water, then mix with 1,200 ml of water containing 3 g of sodium dodecylbenzenesulfonate and 6 g of polyvinyl alcohol with a saponification degree of 98 or 1 cent, and mix with a homomixer at 10 min. ,000 rotations for 20 minutes, and xylene is distilled off together with water to obtain an aqueous dispersion containing zinc 3-indodecylsalicylate as a main component and having a non-volatile component of 36.2 cents.

Example 30 Paraisonorovirphenol 2. 20 grams (20 moles)
15 grams of aluminum was dissolved in the solution, and 1.176 grams (7 mol) of indodecene (globylene tetramer) was reacted in the same manner as in Example 2 to produce 1,608 grams of 2-indodecyl-4-isopropylphenol. obtain. This has a hydroxyl value of 184.0 (theoretical value: 184.3)
Ash, boiling point at 1.2 Torr is 152℃ to 160℃
It is ℃.

Example 30-2 456 grams (1,5 mol) of 2-indodecyl-4-improbylphenol obtained in Example 30, 300 grams of xylene and 120 grams (1,5 mol) of 50/4'-cent sodium hydroxide aqueous solution mol) in the same manner as in Example 2-2. This was transferred to an autoclave with an internal volume of 1.000 ml, and the carbon dioxide pressure was 20 kg/l.
J, React at 170°C. The contents of the autoclave were cooled to 80°C, poured into 3,000 ml of water, and 1,200 grams of 157 or 1 cent zinc sulfate aqueous solution was added dropwise while stirring vigorously. After the addition is complete, stir for another 30 minutes, then transfer to a separatory funnel, remove the lower aqueous layer, and wash three times with 1,000 milliliters of water. This is processed as shown in column 29 to give 3-indodecyl-5
- An aqueous dispersion containing zinc isopropyl salicylate as a main component is obtained.

Example 31 An aqueous dispersion containing zinc 3,5-diynnonylsalicylate as a main component is obtained from 4-isononylphenol and innonene obtained in Example 12 in the same manner as in Example 30 and Example 30-2.

Example 32 100 parts of finely powdered aluminosilicate, 10 parts of zinc oxide, 98.9-cent saponification degree? Divinyl alcohol 0
．． 5 parts, polyvalent metal salts of nuclear-substituted salicylic acids obtained in Examples to Example 31, or as reference examples, 3,5-dicyclohexylsalicylic acid lead (Reference example 1) and 3,5-di(α-methyl Add 10 parts of each solid content of zinc benzyl salicylate (Reference Example 2) and add water to make a total of 300 parts, and grind 2,000 times per minute in a pot-type sand grinder with an internal volume of 1,000 ml. Disperse for 10 minutes at a rotation speed of . To the obtained dispersion, 100 parts of a polyvinyl alcohol aqueous solution with a saponification degree of 98. Oxymodified styrene-butadiene latex 1
Add 0 parts (as solids) and further reduce the total solids to 20/4
'- Prepare the paint by adding water to make cents. If 1,000 meters of this paint is applied to 50 grams of base paper, the remaining dry amount will be 1.
It is coated with a bar coater to give a silogram per square meter and dried to obtain pressure-sensitive recording paper.

Next, in exactly the same manner as above, only the polyvalent metal salt of each nuclear-substituted salicylic acid was reduced to one-third to obtain a pressure-sensitive recording paper for comparison. Crystal iolet lactone in paint,
The top sheet of commercially available pressure-sensitive recording paper using diisopropylnaphthalene as the solvent was layered on each comparison pressure-sensitive recording paper, and printed using an electric typewriter. For comparison. The previously obtained pressure-sensitive recording paper was layered with a commercially available top-sheet paper, and printed using an electric typewriter in a room cooled to -10°C until the recorded density was the same for comparison and visual observation. The time (seconds) is measured and used as a guideline for instantaneous color development. Next, add 20 more
After 24 hours had elapsed after the samples were transferred to a room at ℃, the color density was compared and evaluated on a five-point scale. (5; most dense, 4
; Kana #) Thick, 3; Slightly thick, 2; About the same as normal commercially available products,
l; Slightly inferior) The results obtained are shown in Table 1. The table also shows the dry softening point of the polyvalent metal salt of nuclear-substituted salicylic acid obtained in each example and the average particle size (microns) of the emulsified dispersion used.

Table 1 Continued from Table 1 [Effects of the invention] As is clear from the above, the color developer according to the present invention has a low melting point,
It has a low softening point, and has particularly improved effects on instantaneous color development characteristics and color density of recorded images.

[Brief explanation of the drawing]

Figure 1 shows the NMR spectrum of 2-isononylphenol, Figure 2 shows the NMR spectrum of 3-innonylsalicylic acid,
Figure 3 is the infrared absorption spectrum of 3-isononylsalicylic acid, Figure 4 is the m spectrum of 2-indodecylphenol, and Figure 5 is the NMR spectrum of 3-indodecylsalicylic acid (
Figure 6 is a diagram showing the NMR spectrum of 2-isononyl-4-methylphenol. I 1-3-1 Kanzaki Paper Co., Ltd. Kami

Claims (1)

[Claims] 1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・[I
] (In the general formula [I], R_1 is an alkyl group having 1 to 12 carbon atoms, R_2 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, M is a polyvalent metal atom, and m is the valence of M. Furthermore, at least one of R_1 and R_2 is a secondary butyl group, a secondary hexyl group, an isohexyl group, an isononyl group, or an isododecyl group, and R_1
The total number of carbon atoms of and R_2 is 8 to 18. ) A color developer for pressure-sensitive recording paper, the main component of which is one or more polyvalent metal salts of nuclear-substituted salicylic acid. 2) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・[I
] (In the general formula [I], R_1 is an alkyl group having 1 to 12 carbon atoms, R_2 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, M is a polyvalent metal atom, and m is the valence of M. Furthermore, at least one of R_1 and R_ is a secondary butyl group, a secondary hexyl group, an isohexyl group, an isononyl group, or an isododecyl group, and the total number of carbon atoms of R_1 and R_2 is 8 to 18. An aqueous dispersion in which a color developer for pressure-sensitive recording paper whose main component is one or more polyvalent metal salts of nuclear-substituted salicylic acid is dispersed in water. 3) Nuclear substituted salicylic acid is 3-methyl-5-isononylsalicylic acid, 3-methyl-5-isododecylsalicylic acid,
3-isopropyl-5-isononylsalicylic acid, 3,5
-dise-sec-butylsalicylic acid, 3-sec-sec-butyl-5-isohexylsalicylic acid, 3-sec-sec-butyl-5-isononylsalicylic acid, 3-tert-butyl-5-isohexylsalicylic acid, 3-tert-butyl-5-isononyl Salicylic acid, 3-tertiaryamyl-
5-isohexylsalicylic acid, 3-tertiaryamyl-
5-Isononylsalicylic acid, 3-Secondaryhexyl-
5-Secondarybutylsalicylic acid, 3-secondaryhexyl-5-tert-butylsalicylic acid, 3,5-disendaryhexylsalicylic acid, 3-secondaryhexyl-5-isohexylsalicylic acid, 3-isohexyl-5
-tert-butylsalicylic acid, 3-isohexyl-5
-Secondaryhexylsalicylic acid, 3,5-diisohexylsalicylic acid, 3-isononylsalicylic acid, 3-isononyl-5-methylsalicylic acid, 3-isononyl-5-
Ethylsalicylic acid, 3-isononyl-5-tert-butylsalicylic acid, 3,5-diisononylsalicylic acid, 3
-isododecylsalicylic acid, 3-isododecyl-5-methylsalicylic acid, 3-isododecyl-5-ethylsalicylic acid or 3-isododecyl-5-isopropylsalicylic acid according to claim 1 or 2. Color developer for pressure-sensitive recording paper or its aqueous dispersion. 4) Polyvalent metal salts of nuclear-substituted salicylic acid include 3-isopropyl-5-isononylsalicylic acid and 3-tert-butyl-
A zinc salt of a nuclear substituted salicylic acid selected from 5-isononylsalicylic acid, 3-isononyl-5-methylsalicylic acid, 3-isononyl-5-tert-butylsalicylic acid, 3-isododecylsalicylic acid or 3-isododecyl-5-methylsalicylic acid. A color developer for pressure-sensitive recording paper or an aqueous dispersion thereof according to any one of claims 1 to 3. 5) General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・[II] (In the general formula [II], R_1 is an alkyl group having 1 to 12 carbon atoms, and R_2 is a hydrogen atom or carbon an alkyl group of numbers 1 to 12, N represents an alkali metal atom, R_1 and R_
At least one of 2 is a secondary butyl group, a secondary hexyl group, an isohexyl group, an isononyl group, or an isododecyl group, and the total number of carbon atoms of R_1 and R_2 is 8 to 18. ) An aqueous solution of an alkali metal salt of a nuclear-substituted salicylic acid represented by General formulas [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・〔I
] (In the general formula [I], R_1 is an alkyl group having 1 to 12 carbon atoms, R_2 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, M is a polyvalent metal atom, and m is the valence of M. , R_1 and R_2 are a secondary butyl group, a secondary hexyl group, an isohexyl group, an isononyl group, or an isododecyl group, and the total number of carbon atoms of R_1 and R_2 is 8 to 18.) A method for producing a color developer for pressure-sensitive recording paper, the main component of which is one or more polyvalent metal salts of nuclear-substituted salicylic acid.