JPH05270124A - Manufacture of color developer composition - Google Patents

Abstract

PURPOSE:To perform the manufacture of a color developer composition of 3,5-diisononylsalicylic acid polyvalent metal salt by adding water to 2,4- diisononylphenol alkali metal salt through Corbeschmit chemical reaction in a water-insoluble solvent, to remove carbonate alkali metal salts. CONSTITUTION:97mol% of 2,4-diisononylphenol and 3mol% of a material which has the same molecular weight as the former and does not react chemically to form salts with alkali hydroxide are blended, then xylene is added to the blend and it is thermally stirred, followed by the titration of an aqueous 50% potassium hydroxide solution. Next, the blend is allowed to chemically react in an autoclave and then is with a CO2 gas. After thermally stirring this reaction product, it is left still to separate the lower layer water containing potassium carbonate and hydrogen potassium carbonate. Thus the upper layer solution containing potassium 3,5-diisononylsalicylate and 2,4-diisononylphenol is extracted, then this extract is thermally stirred with the addition of an aqueous potassium sulfate solution, and is left still to separate and remove water.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a developer composition containing a polyvalent metal salt of 3,5-diisononylsalicylic acid as a main component.

[0002]

2. Description of the Related Art Polyvalent metal salts of nucleus-substituted salicylic acid have excellent properties as a color developing agent for pressure-sensitive recording sheets and have been widely put into practical use. Regarding the method for producing a polyvalent metal salt of a nucleus-substituted salicylic acid using the Kolbe-Schmidt reaction, JP-B-51-25174, JP-A-1-14
No. 5189, No. 2-85231, No. 2-122977
The description can be found in each of the publications, No. 2-142747 and No. 204472. However,
Almost no description can be found in the detailed method for producing the color developer containing a polyvalent metal salt of 3,5-diisononylsalicylic acid as a main component in the present invention.

[0003]

When an alkali metal salt of a nucleus-substituted salicylic acid is to be obtained by a reaction between an alkali metal salt of a nucleus-substituted phenol and carbon dioxide, a so-called Kolbe-Schmidt reaction, the reaction is Due to the equilibrium reaction, the unreacted alkali metal salt of the nuclear-substituted phenol and excess carbon dioxide are also present in the reaction mixture. If water is added to the reaction mixture in this state, the unreacted alkali metal salt of the nuclear-substituted phenol reacts with carbon dioxide gas to produce the nuclear metal and the alkali-metal salt of carbonic acid (alkali carbonate or alkali hydrogen carbonate). If a water-soluble salt of a polyvalent metal is applied to this for the purpose of inducing a developer composition, a metathesis reaction should occur, and a polyvalent metal salt of nucleus-substituted salicylic acid and a polyvalent metal salt of carbonic acid should be formed. is there. It is known that polyvalent metal salts of carbonic acid are generally insoluble in water and solvents. However, when the metathesis reaction as described above is carried out, in many cases of conventional types of polyvalent metal salts of nucleus-substituted salicylic acid, regardless of the presence or absence of a solvent, unless a large amount of carbonic acid is produced, a large amount of carbonic acid is produced. No valent metal salts are released. This is just a phenomenon that it can be seen that polyvalent metal salts of carbonic acid are dissolved in polyvalent metal salts of nuclear-substituted salicylic acid, and if the polyvalent metal content is actually measured, it is true that the theoretical value for nuclear-substituted salicylic acid is The above values are obtained. It is unlikely that they form a uniform composition as such a phenomenon, but anyway, this excess amount of polyvalent metal has a negative effect on the developing ability when the composition is used as a developer. It has been found to provide benefits such as increased or improved lightfastness. Therefore, the metathesis reaction is currently carried out under the condition that the conventional alkali metal salt of the nucleus-substituted salicylic acid does not prevent the formation of the polyvalent metal salt of carbonic acid.

However, in the alkali metal salt of 3,5-diisononylsalicylic acid, which is the object of the present invention, the polyvalent metal salt of carbonic acid becomes colloidal when the same metathesis operation as that of the conventional species is applied. Since it is released, no phenomenon that it seems to be dissolved in the polyvalent metal salt of 3,5-diisononylsalicylic acid is observed at all. Although this difference seems quite strange, as a practical matter, the polyvalent metal salts of free carbonic acid have no advantage in the property as a color developer, and the colloidal substance is produced by metathesis. Its presence is not preferred because it significantly interferes with the separation of the polyvalent metal salt of 5-diisononyl salicylic acid from water.

Therefore, the object of the present invention is to
(1) A process for avoiding the formation of polyvalent metal salts of carbonic acid at the time of metathesis or a treatment for removing the formed polyvalent metal salts of carbonic acid has been found to facilitate the production process, and if necessary, the above-mentioned (1) In addition to the treatment, (2) finding a treatment in which an excess amount of the polyvalent metal uniformly dissolved in the polyvalent metal salt of 3,5-diisononylsalicylic acid is found to realize higher properties as a developer. is there. That is, it is possible to smoothly produce a high-performance developer composition containing a polyvalent metal salt of 3,5-diisononylsalicylic acid as a main component by the treatment of the former alone or both treatments. Is the purpose.

[0006]

The first embodiment of the method for producing a color developer composition containing a polyvalent metal salt of 3,5-diisononylsalicylic acid as a main component of the present invention is (a) substantially water. The Kolbe-Schmidt reaction is carried out on an alkali metal salt of 2,4-diisononylphenol in an insoluble solvent,
(B) Water is added to the reaction mixture to remove by-produced alkali metal salts of carbonic acid together with (b-1) water, or (b-2) mineral acid is added to decompose, and then ( C)
It is characterized by metathesis by a water-soluble salt of a polyvalent metal in the presence of water.

The second aspect of the manufacturing method of the present invention is (a)
The Kolbe-Schmidt reaction is carried out with an alkali metal salt of 2,4-diisononylphenol in a substantially water-insoluble solvent, and (b) a water-soluble salt of a polyvalent metal is added to the reaction mixture to prepare water. In the presence of the above, the compound is characterized in that (c) the polyvalent metal salt of carbonic acid produced as a by-product is decomposed by removing (c-1) or (c-2) a mineral acid is decomposed. To do.

The third aspect of the manufacturing method of the present invention is (a)
A Kolbe-Schmidt reaction is carried out with an alkali metal salt of 2,4-diisononylphenol in a substantially water-insoluble solvent, and (b-1) water is added to the reaction mixture to produce a carbonic acid as a by-product. Alkali metal salts of 1) are separated and removed together with water and carbon dioxide gas remaining from the above step (a) in this step is removed by heating, or (b-2) water is added to the reaction mixture to produce a by-product. The alkali metal salt of carbonic acid is decomposed by adding a mineral acid, the generated carbon dioxide gas and the carbon dioxide gas remaining from the above step (a) are removed by heating, and then (c) water and a metal oxide or metal water. It is characterized by metathesis by a water-soluble salt of a polyvalent metal in the coexistence with an oxide.

The fourth aspect of the manufacturing method of the present invention is (a)
The Kolbe-Schmidt reaction is carried out with an alkali metal salt of 2,4-diisononylphenol in a substantially water-insoluble solvent, and (b) a water-soluble salt of a polyvalent metal is added to the reaction mixture to prepare water. And co-decomposition in the presence of a metal oxide or a metal hydroxide, and then (c) the by-produced polyvalent metal salt of carbonic acid is removed by filtration.

A fifth aspect of the production method of the present invention is characterized in that the composition obtained by the production method of each of the above aspects is further mixed with an oxide or hydroxide of a polyvalent metal.

The developer composition containing a polyvalent metal salt of 3,5-diisononylsalicylic acid as a main component, which is produced by the production method of each of these embodiments, has a light resistance when applied to a pressure-sensitive recording sheet. It is excellent in various properties such as water resistance, sharpness of recorded image, and color development speed of recording at low temperature, so that it can be clearly distinguished from the conventional type.

In the present specification, 2,4-diisononylphenol has a structure formed by adding one molecule of propylene trimer (isononene) to the 2-position and 4-position of phenol, 5-Diisononyl salicylic acid is defined as having a structure formed by carbonating 2,4-diisononylphenol. As already known, propylene trimer is a mixture of many isomers, and further, 2,4-diisononylphenol and 3,5-diisononylsalicylic acid derived therefrom are a collection of many isomers. All of them are non-crystalline. Therefore, the polyvalent metal salt of 3,5-diisononylsalicylic acid is also non-crystalline and very easily soluble in the solvent. This is one of the reasons why it is suitable as a color developer for pressure-sensitive recording sheets.

2,4-Diisononylphenol can form salts with alkali metals. The salt formation is the smoothest and most complete when the method of azeotropically removing water by mixing 2,4-diisononylphenol and an aqueous alkali hydroxide solution in a substantially water-insoluble solvent is used.
At this time, it is preferable that the amount of 2,4-diisononylphenol and the amount of alkali hydroxide are completely equimolar, and if an excessive amount of alkali hydroxide is used or water is present, Kolbe-Schmidt's Care must be taken as this will cause a decrease in the reaction yield. It should be noted that alkali carbonate may be used instead of alkali hydroxide.

In the present specification, the substantially water-insoluble solvent is an organic solvent having a solubility in water of 2% by weight or less at room temperature, and in the present invention, it is a hydrocarbon,
Halogenated hydrocarbons or ethers are preferred. In addition, since it is necessary to azeotropically remove water to form an alkali metal salt of 2,4-diisononylphenol and to remove the solvent in the step following the metathesis, their boiling points at atmospheric pressure are 60 ° C. As described above, the temperature is preferably 200 ° C. or lower. Specific examples thereof include n-hexane, n-heptane, n-octane, isooctane, n-decane, petroleum benzine, ligroin, petroleum spirit,
Petroleum naphtha, isononene, isododecene, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, p-cymene, naphthalene, tetralin, decalin, dipentene, turpentine oil, chlorobenzene, dichlorobenzene, chlorotoluene, isopropyl. Examples thereof include ether, n-butyl ether, diisoamyl ether, anisole and ethylphenyl ether.
Also, preferred alkali metals for forming a salt with 2,4-diisononylphenol are sodium and potassium, and potassium is more preferred.

As described above, the alkali metal salt of 2,4-diisononylphenol obtained by azeotropically removing water using the substantially water-insoluble solvent as a medium is used as it is or after adjusting the amount of the solvent to some extent. The Kolbe-Schmidt reaction can be carried out. The Kolbe-Schmidt reaction is carried out under a carbon dioxide gas pressure of 1 to 60 kgf / cm ² ,
The reaction temperature is preferably 80 to 180 ° C.

In the reaction mixture after completion of the Kolbe-Schmidt reaction, a substantially water-insoluble solvent is used as a medium.
It mainly contains an alkali metal salt of 5-diisononylsalicylic acid and an unreacted alkali metal salt of 2,4-diisononylphenol, and some carbon dioxide gas is dissolved therein. When water is added to this, the alkali metal salt of 2,4-diisononylphenol reacts with the dissolved carbon dioxide gas to become alkali metal salts of carbonic acid and 2,4-diisononylphenol. Here, the alkali metal salts of carbonic acid are water-soluble and dissolve in water to form an aqueous phase.
The alkali metal salts of diisononylphenol and 3,5-diisononylsalicylic acid are generally dissolved in a solvent to form a solvent phase, and when left to stand, they are separated into two layers. However, if the amount of the by-produced alkali metal salt of carbonic acid is small or the amount of water added is too large, a part of the alkali metal salt of 3,5-diisononylsalicylic acid is dissolved in the aqueous phase and the system becomes an emulsified state. .. If it is necessary to separate the aqueous phase and the solvent phase, the addition of an alkali metal salt of sulfuric acid, hydrochloric acid, phosphoric acid or carbonic acid will immediately destroy the emulsified state by the salting out effect, and the separation of both phases will be smooth. ..

Water is added to the reaction mixture formed by the Kolbe-Schmidt reaction and heated, if desired, to separate away the alkali metal carbonates of carbonic acid dissolved in the aqueous phase together with the water, after which the solvent phase is present in the presence of water. If metathesis is carried out with a water-soluble salt of a polyvalent metal under the conditions below, no insoluble polyvalent metal salt of carbonic acid will be generated, and therefore the separation of the aqueous phase and the solvent phase after the metathesis reaction will be smooth and unnecessary. Can be easily removed. The polyvalent metal salt of 3,5-diisononylsalicylic acid produced by the metathesis is completely dissolved in the solvent phase, and can be finished as a developer composition by a subsequent operation. The solvent phase before the metathesis can be washed with water again for the purpose of more completely removing the alkali metal salts of carbonic acid. However, in this case, if the alkali metal salt of sulfuric acid or hydrochloric acid is not present in the added water, the system will be in an emulsified state and the washing operation will be difficult. For the purpose of removing the alkali metal salts of carbonic acid in the reaction mixture containing water, instead of separating and removing the aqueous phase,
It is also possible to decompose (neutralize) the alkali metal salt of carbonic acid by adding a mineral acid such as sulfuric acid or hydrochloric acid. It is desirable that the carbon dioxide gas generated at that time be actively removed by heating or the like. If the decomposition (neutralization) is completed when the pH of the aqueous phase is 4 to 7 and then metathesis is carried out with a water-soluble salt of a polyvalent metal, the same treatment is performed thereafter.

If a water-soluble salt of a polyvalent metal is added directly to the reaction mixture produced by the Kolbe-Schmidt reaction to cause metathesis in the presence of water, the polyvalent value of 3,5-diisononylsalicylic acid dissolved in the solvent is increased. The metal salt and 2,4-diisononylphenol form a solvent phase, the water-soluble salt of an alkali metal and an excess amount of a water-soluble salt of a polyvalent metal dissolved in water form an aqueous phase, and the insoluble carbonic acid Polyvalent metal salts are produced. The polyvalent metal salts of carbonic acid are distributed in the system in the form of colloid, which significantly hinders the separation of the solvent phase and the aqueous phase and makes the subsequent operation impossible to proceed smoothly. At this time, if the mixture is filtered with a relatively fine filter paper or filter cloth to remove the polyvalent metal salts of carbonic acid, the solvent phase and the aqueous phase of the filtrate can be separated smoothly. Further, instead of removing the polyvalent metal salt of carbonic acid by filtration, a mineral acid such as sulfuric acid or hydrochloric acid may be added to decompose the polyvalent metal salt of carbonic acid. It is desirable that the carbon dioxide gas generated at that time be actively removed by heating or the like. The decomposition reaction is a heterogeneous reaction and takes a little time. The completion of the decomposition can be determined by the disappearance of the colloidal substance, but it is convenient to add the mineral acid based on the point that the pH of the aqueous phase becomes 4 to 5.5. The solvent phase obtained by removing the aqueous phase is similarly finished as a developer composition.

The solvent phase obtained by the above two operation methods contains a polyvalent metal salt of 3,5-diisononylsalicylic acid, and the amount of the polyvalent metal is approximately equivalent to 3,5-diisononylsalicylic acid. Is. The polyvalent metal salt of the nucleus-substituted salicylic acid used as the developer is equal to or more than the equivalence ratio of the polyvalent metal contained in the homogeneous phase of the nucleus-substituted salicylic acid, that is, the sharpness of the recorded image is equal to or more than the theoretical value. It has already been obtained that it is more excellent in various properties such as light resistance. The same applies to the polyvalent metal salt of 3,5-diisononylsalicylic acid. As already explained, in the conventional species of the polyvalent metal salt of the nucleus-substituted salicylic acid, the polyvalent metal salt of carbonic acid is dissolved in it, so that the reaction mixture formed by the Kolbe-Schmidt reaction in the presence of water is used. A homogeneous composition containing an excessive amount of polyvalent metal was spontaneously obtained only by metathesis by a water-soluble salt of polyvalent metal. However, the polyvalent metal salt of 3,5-diisononyl salicylic acid does not dissolve the polyvalent metal salt of carbonic acid at all, and therefore it is impossible to add an excessive amount of the polyvalent metal in the same manner. However, it has been found that the polyvalent metal salt of 3,5-diisononyl salicylic acid is relatively easily dissolved only in the oxide of the polyvalent metal or the hydroxide of the polyvalent metal, and this is the excess amount of the polyvalent metal. It was confirmed that it is an effective means for containing and that it is superior as a developer. In the present invention, the expression “dissolution” is used here again, but like the above, this is only observed as a phenomenon, and is distinguished from simple physical dissolution. It must be. It should be considered that the basic salt of polyvalent metal is partially formed. The preferred excess of these polyvalent metals is 5 to 50 percent of theory.

By adding water to the reaction mixture produced by the Kolbe-Schmidt reaction and heating, adding water while heating, or adding water after heating, the remaining free carbon dioxide gas is removed. Is released. If the aqueous phase is separated here, the alkali metal salts of carbonic acid dissolved in the aqueous phase are removed. Also in this operation, salting out can be carried out using salts as described above and further washing with water can be carried out. In this way, the solvent phase from which carbon dioxide gas and alkali metal salts of carbonic acid have been removed is subjected to metathesis with a water-soluble salt of a polyvalent metal in the presence of water and a metal oxide or a metal hydroxide to form a solvent phase. Contains a polyvalent metal salt of 3,5-diisononylsalicylic acid containing an excess amount of polyvalent metal and 2,4-diisononylphenol, and the solvent phase and the aqueous phase can be easily separated. Alternatively, the alkali metal salts of carbonic acid dissolved in the aqueous phase may be decomposed (neutralized) by a mineral acid instead of being separated and removed as described above, and the resulting carbon dioxide gas may be removed to cause double decomposition. The results obtained are comparable. However, in this case, unless the carbon dioxide gas generated by decomposition (neutralization) is completely removed by heating or the like, it reacts with the subsequently added metal oxide or metal hydroxide to regenerate carbonic acid salts. It is inconvenient. The solvent phase thus obtained is finished as a developer composition in the same manner as described above.

The reaction mixture formed by the Kolbe-Schmidt reaction is directly added with a water-soluble salt of a polyvalent metal to undergo metathesis in the presence of water and a metal oxide or a metal hydroxide, whereby the reaction mixture is formed. The solvent phase contains a polyvalent metal salt of 3,5-diisononylsalicylic acid containing an excess amount of polyvalent metal, and the water phase contains a water-soluble salt of an alkali metal and a water-soluble salt of a polyvalent metal. Excess is dissolved. Since the polyvalent metal salt of carbonic acid is insoluble in both phases, it is distributed in a colloidal form, which makes it difficult to separate the two phases. If the polyvalent metal salt of carbonic acid is filtered through a filter paper or filter cloth having a relatively fine mesh, the polyvalent metal salt of carbonic acid in a colloidal form is removed and the separation of both phases becomes smooth. However, if the remaining free carbon dioxide gas is not removed prior to this metathesis, it may form a salt with a metal oxide or metal hydroxide, which may reduce the utilization efficiency, so caution is required. is there.
Therefore, it is preferable to remove carbon dioxide gas by heating before the metathesis treatment. The solvent phase thus obtained is finished as a developer composition in the same manner as described above.

3,5 obtained by each of the above operating methods
-In the solvent phase containing the polyvalent metal salt of diisononyl salicylic acid, a polyvalent metal oxide or a polyvalent metal hydroxide is further mixed, if necessary, to increase the content of the uniformly dissolved polyvalent metal. And these are similarly finished as a developer composition.

Examples of the water-soluble salts of polyvalent metals used in the present invention include magnesium sulfate, magnesium chloride, calcium chloride, zinc sulfate, zinc chloride, aluminum sulfate, aluminum chloride, cobalt chloride or nickel sulfate. Preferred is zinc sulfate or zinc chloride.
The metal oxide or metal hydroxide used in the present invention includes lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium oxide, magnesium hydroxide, calcium hydroxide, zinc oxide, zinc hydroxide, and hydroxide. Aluminum, cobalt hydroxide, nickel hydroxide and the like can be mentioned, and zinc oxide, sodium hydroxide, potassium hydroxide or zinc hydroxide is most preferable. Examples of the polyvalent metal oxide or polyvalent metal hydroxide include magnesium oxide, magnesium hydroxide, calcium hydroxide, zinc oxide, zinc hydroxide, aluminum hydroxide, cobalt hydroxide or nickel hydroxide. And most preferably zinc oxide or zinc hydroxide.

3,5 obtained by the production method of the present invention
-A polyvalent metal salt of diisononyl salicylic acid, especially a developer composition for a pressure-sensitive recording sheet containing a zinc salt as a main component, has light resistance, water resistance, color development speed at low temperature, color density, and stability of recorded image. It has excellent properties that could not be obtained in the past in terms of the properties or the non-contamination property of the white paper portion by sunlight and nitrogen oxides. And further improve these various characteristics,
For the purpose of adjusting the quality as a developer composition, another developer is added to the developer composition obtained by the production method of the present invention,
Additives such as polymer compounds, ultraviolet absorbers, ultraviolet stabilizers, antioxidants, plasticizers or inorganic pigments can also be added.

The color developer for the pressure sensitive recording sheet is usually applied to the pressure sensitive recording sheet as fine particles having an average particle diameter of 0.5 to 5 μm. However, since the developer composition containing a polyvalent metal salt of 3,5-diisononylsalicylic acid as a main component has a relatively low softening point, it is possible to obtain a desired degree of fine particles by a conventional mechanical method. It is difficult to crush. Fortunately, according to the production method of the present invention, the developer composition can be obtained in a state of being dissolved in a substantially water-insoluble solvent, so that it is emulsified and dispersed in an aqueous solution containing a dispersant, and if necessary, To remove the solvent,
It can be finished to the desired particle size. Then, the developer composition is preferably supplied and used as an aqueous dispersion. Therefore, it is possible to adjust the amount of the solvent for the purpose of facilitating the emulsion dispersion. Also, it is most preferable that the substantially water-insoluble solvent is consistently operated in the same species, but if necessary, it is not limited to that. As the dispersant, an anionic surfactant, polyvinyl alcohol, acrylamide copolymer, or the like is used.

An inorganic pigment, a clay mineral, an adhesive, a dispersant and an antifoaming agent are added to an aqueous dispersion of the developer composition obtained by the production method of the present invention to prepare a paint, which is used as a substrate. The color development surface of the pressure sensitive recording sheet is finished by applying and fixing it on top.

As can be understood from the above description, the present invention consists of two technical ideas which are related to each other. One of them is to facilitate the production process, and is a method of removing alkali metal salts of carbonic acid by-produced by the Kolbe-Schmidt reaction or polyvalent metal salts of carbonic acid subsequently produced by metathesis. One of them is to improve the properties of a polyvalent metal salt of 3,5-diisononylsalicylic acid as a developer, and a method of containing an excessive amount of polyvalent metal uniformly dissolved therein.

[0028]

EXAMPLES In the following, specific examples will be described in order to facilitate understanding of the present invention. In each of the examples, the term "percent" means weight percent.

Example 1 2,4-Diisononylphenol 97 was placed in a 1,000 ml hard glass four-necked flask equipped with a stirrer, a thermometer, a reflux condenser capable of separating water, and a dropping funnel. Mole percent and unknown substances (2,
It has the same molecular weight as 4-diisononylphenol and does not undergo a salt-forming reaction with alkali hydroxide. ) Charge 232 grams of a 3 mole percent mixture and 180 grams of xylene and heat the flask with agitation to add 72.9 grams (0.65 moles) of a 50 percent aqueous potassium hydroxide solution when the contents begin to boil. It was dripped slowly. During that time, the water separated in the reflux condenser was removed in each case. The dehydration operation is completed when the addition of the aqueous potassium hydroxide solution is finished and water is no longer separated in the reflux condenser. The contents of the flask after the dehydration operation were transferred to a stainless steel autoclave having an internal volume of 500 ml, and the autoclave was sealed, and then 140 ° C. for 2 hours, 120 ° C. for 4 hours and 100 ° C.
The reaction temperature was programmed so as to reach 18 ° C. for 18 hours, and the reaction was carried out at a carbon dioxide gas pressure of 55 kgf / cm ² . The reaction mixture, that is, the reaction mixture produced by the Kolbe-Schmidt reaction, contained 9-potassium 3,5-diisononylsalicylate.
It contained 0.8 mole percent, 6.2 mole percent unreacted potassium salt of 2,4-diisononylphenol, and 3 mole percent unknown. The reaction mixture was transferred to a three-necked flask with an internal volume of 2,000 ml equipped with an agitator, a thermometer and a reflux condenser,
300 grams of water was added and the flask was heated with stirring to bring the temperature of the contents to 85 ° C. This is the internal volume 2,0
When transferred to a 00 ml separatory funnel and allowed to stand still, an aqueous phase containing potassium carbonate and potassium hydrogen carbonate in the lower layer, 3,5-diisononylsalicylate potassium in the upper layer,
A xylene phase containing 2,4-diisononylphenol and unknowns separated. The aqueous phase is removed and the separating funnel is charged with 9 grams of 300% 2% aqueous potassium sulfate solution.
The mixture was heated to 0 ° C., added, shaken well, and then allowed to stand again to remove the aqueous phase.

Example 1-2 (metathesis reaction) The xylene phase containing potassium 3,5-diisononylsalicylate obtained in Example 1 was mixed with an agitator, a thermometer, and a reflux condenser to have an internal volume of 1,000 ml. The mixture was transferred to a three-necked flask (3), 320 g of a 25% zinc sulfate aqueous solution was added thereto, and the flask was heated while stirring to bring the temperature of the contents to 80 ° C. After stirring at this temperature for 2 hours, the contents were transferred to a separating funnel and allowed to stand.
The separation of the aqueous phase and the xylene phase was smooth. The aqueous phase was removed. The non-volatile component of the xylene phase is 59.8%, and the non-volatile component is 92.0% zinc 3,5-diisononylsalicylate, 5.5% 2,4-diisononylphenol and 2.
It was 5 percent. Further, the zinc content in the non-volatile component was 7.2%, which was almost the theoretical value with respect to 3,5-diisononylsalicylic acid.

Example 1-3 (Preparation of Aqueous Dispersion) The whole volume of the xylene solution containing zinc 3,5-diisononylsalicylate obtained in Example 1-2 was 2,000.
Transferred to a milliliter beaker, to which was added 0.5 grams of sodium carbonate, 5 grams of polyvinyl alcohol with a saponification degree of 98 percent, and 400 grams of an aqueous solution containing 5 grams of a copolymer of butyl acrylate and acrylamide. This was emulsified and dispersed with a TK homomixer model M (made by Tokushu Kika Kogyo Co., Ltd.), and the average particle diameter of the dispersoid was 1.1.
It was adjusted to be 5 microns. Water 30 in this dispersion
After adding 0 gram, the mixture was transferred to a flask having an inner volume of 2,000 ml equipped with a stirrer, a thermometer and a distillation port, and the flask was heated with gentle stirring to azeotropically remove xylene and water. Finally, the water removal was adjusted so that the nonvolatile content of the water dispersion was 40%. The average particle size of the dispersoid in the obtained aqueous dispersion was 1.0 micron.

Example 2 232 grams of a mixture of 97 mole percent of 2,4-diisononylphenol and 3 mole percent of an unknown substance and 180 grams of toluene were added to a hard glass four-necked flask having an internal volume of 1,000 milliliters used in Example 1. The flask was heated with stirring, and when the contents began to boil, 68.4 g (0.61 mol) of a 50% aqueous potassium hydroxide solution and 3.2 g (0% of a 50% aqueous sodium hydroxide solution) were added. .0
4 mol) was gradually added dropwise. The dehydration operation was completed while removing the water separated by the reflux condenser. The flask contents were placed in the same autoclave as in Example 1, the reaction temperature was programmed to be 130 ° C. for 2 hours, 110 ° C. for 4 hours and 90 ° C. for 20 hours, and carbon dioxide gas pressure was 25 kg.
The reaction was carried out at f / cm ² . The reaction mixture contained 90% potassium and sodium 3,5-diisononylsalicylic acid.
It contained 8 mole percent, 6.2 mole percent 2,4-diisononylphenol salt and 3 mole percent unknown. Stirrer the reaction mixture,
Internal volume with thermometer, dropping funnel and reflux condenser 2,
Transfer to a 4,000 ml four-necked flask and add water 300
Add 1 gram and heat the flask with stirring to allow the contents to boil slowly.
The pH of the contents was adjusted to 5.7 by adding 0% diluted sulfuric acid dropwise.
I chose During this time, carbon dioxide gas was generated and removed.

Example 2-2 (metathesis reaction) Following Example 2, 320 g of a 25% zinc sulfate aqueous solution was added to the content of the flask whose pH was adjusted, and the mixture was stirred at 80 ° C. for 2 hours, and then the content was separated. It was transferred to a liquid funnel and allowed to stand. The separation of the water phase and the toluene phase was smooth. The aqueous phase was removed. The non-volatile component of the toluene phase is 6
0.1%, and the breakdown of non-volatile components is 3,5
-Zinc diisononyl salicylate 92.0-percent, 5.5% 2,4-diisononylphenol and 2.5% unknown. In addition, the zinc content in the non-volatile component was 7.1%, which almost coincided with the theoretical value.

Example 2-3 (Preparation of Aqueous Dispersion) The toluene phase obtained in Example 2-2 was treated in exactly the same manner as in Example 1-3, and the nonvolatile component was 40%.
An aqueous dispersion having an average particle size of the dispersoid of 1.0 micron was obtained.

Example 3 In exactly the same manner as in Example 1, 91.0 mol% of potassium 3,5-diisononylsalicylate and unreacted 2,4
A reaction mixture formed by the reaction of Kolbe-Schmidt containing 6.0 mol% of potassium salt of diisononylphenol and 3 mol% of unknown substance was obtained.

Example 3-2 (metathesis reaction) Internal volume 2, equipped with a stirrer, thermometer and reflux condenser
In a 000 ml three-necked flask, the whole reaction mixture obtained in Example 3, 50 g of xylene and 300 g of water.
Grams and 350 grams of a 25 percent aqueous zinc sulfate solution were charged and the flask was heated with stirring to bring the temperature of the contents to 80 ° C. Stir at this temperature for 2 hours. Two
Even after the stirring was stopped and the liquid was allowed to stand still after a lapse of time, the aqueous phase and the xylene phase were not separated smoothly. The entire contents of the flask were suction filtered with a No. 2 filter paper, the filtrate was transferred to a separating funnel and allowed to stand. The separation of the water phase and the xylene phase is smooth,
The aqueous phase was removed and the xylene phase was collected. Some xylene was distilled off under mild vacuum to adjust the non-volatile content of the xylene phase to 60 percent.

Example 3-3 (Preparation of Aqueous Dispersion) From the xylene phase obtained in Example 3-2, 40% of the non-volatile component and the average particle size of the dispersoid were obtained in the same manner as in Example 1-3. An aqueous dispersion with a diameter of 1.0 micron was obtained.

Example 4 Exactly the same reaction mixture was obtained as in Example 1.

Example 4-2 (metathesis reaction) All of the reaction mixture obtained in Example 4 was placed in a 2,000 ml four-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser. Then, 300 g of water and 320 g of a 25% zinc sulfate aqueous solution were charged, and the temperature of the flask was brought to 80 ° C. while stirring. 10% dilute sulfuric acid was added little by little from the attempted addition at this temperature. On the way, stirring was sometimes stopped and the contents were allowed to stand, and colloidal substances gathering near the boundary between the aqueous phase and the xylene phase were observed. Since the colloidal substance was almost gone, the dropping of dilute sulfuric acid was completed. At this time, the pH of the aqueous phase was 5.1. It took about 2 hours to operate during this period. When this was transferred to a separating funnel and allowed to stand still, the separation was smooth. The aqueous phase was removed and the xylene phase was collected. The xylene phase obtained was exactly the same as that obtained in Example 1-2.

Example 4-3 From the xylene phase obtained in Example 4-2, an identical aqueous dispersion was obtained in the same manner as in Example 1-3.

Example 5 In exactly the same manner as in Example 1, a reaction mixture formed by the Kolbe-Schmidt reaction was obtained. The whole reaction mixture and 300 g of water were charged and the flask was heated with stirring to boil the contents. After 30 minutes, the contents were transferred to a separating funnel and allowed to stand. The lower aqueous phase was removed and to the separatory funnel was added 300 grams of a 2 percent aqueous sodium sulfate solution at 90 ° C. The separating funnel was vigorously shaken and left to stand still again to remove the aqueous phase, and the xylene phase was collected.

Example 5-2 (metathesis reaction) All the xylene solution obtained in Example 5 was added to the three-necked flask having an internal volume of 2,000 ml used in Example 1-2, and a 25% potassium hydroxide aqueous solution. 29.2 g (0.133 mol) and 360 g of a 25% zinc sulfate aqueous solution were charged, and the contents were heated to 80 ° C. by heating the flask while stirring. After stirring at this temperature for 2 hours, the contents were transferred to a separating funnel and allowed to stand. The separation of the two phases was smooth. The aqueous phase was removed and the xylene phase was collected. The nonvolatile component of the xylene phase is 62.1
It was a percentage. The zinc content in the non-volatile component is 8.7%, which is about 22% of the theoretical value in excess of 3,5-diisononylsalicylic acid.

Example 5-3 (Preparation of Aqueous Dispersion) From the xylene phase obtained in Example 5-2, the non-volatile component was 40% and the average particle size of the dispersoid was the same as in Example 1-3. An aqueous dispersion with a diameter of 1.0 micron was obtained.

Example 6 A carbonate-free mixture was obtained in exactly the same manner as in Example 2.

Example 6-2 (metathesis reaction) Following Example 6, the pH adjusted flask contents were charged with 360 grams of 25 percent aqueous zinc sulfate solution and 25 grams.
29.2 g of a percent potassium hydroxide aqueous solution was added, and the mixture was stirred at 80 ° C. for 2 hours. When the contents were transferred to a separating funnel and allowed to stand still, the separation was smooth. The aqueous phase was removed and the toluene phase was collected. The nonvolatile component of the toluene phase is 60.
9% and the zinc content in the non-volatile components is 8.
6 percent. This is about 22 percent theoretical over 3,5-diisononyl salicylic acid.

Example 6-3 (Preparation of Aqueous Dispersion) From the toluene phase obtained in Example 6-2, the nonvolatile component was 40% and the average particle size of the dispersoid was the same as in Example 1-3. A 1.0 micron aqueous dispersion was obtained.

Example 7 In exactly the same manner as in Example 1, the same reaction mixture as in Example 1 produced by the Kolbe-Schmidt reaction was obtained.

Example 7-2 (metathesis reaction) The whole reaction mixture obtained in Example 7 and 300 g of water were charged into the three-necked flask having an inner volume of 2,000 ml used in Example 3-2. The contents of the flask were boiled by heating the flask while stirring. When it was boiled for 30 minutes, the dissolved carbon dioxide gas was completely removed. This was followed by 360 grams of 25 percent aqueous zinc sulfate solution followed by 20.8 percent 25 percent aqueous sodium hydroxide solution.
Added gram. After stirring at about 80 ° C. for 2 hours, the contents were filtered with a No. 2 filter paper. When the filtrate was transferred to a separating funnel and allowed to stand still, the liquid was smoothly separated, so the aqueous phase was removed and the xylene phase was collected. The nonvolatile component of the xylene phase was 61.1 percent and the zinc content in the nonvolatile component was 8.5 percent. This is an excess of about 20 percent with respect to 3,5-diisononylsalicylic acid.

Example 7-3 (Preparation of Aqueous Dispersion) From the xylene phase obtained in Example 7-2, in the same manner as in Example 1-3, the nonvolatile component was 40%, and the average particle size of the dispersoid. An aqueous dispersion with a diameter of 1.0 micron was obtained.

Example 8 Following Example 1, Example 1 was carried out in the same manner as Example 1-2.
A xylene solution exactly the same as that obtained in -2 was obtained.

Example 8-2 (mixing of polyvalent metal with oxide) Internal volume 1,0 equipped with stirrer, thermometer, reflux condenser
In a 00 ml three-necked flask all of the xylene solution obtained in Example 8, 1 gram of water and 5.3 zinc oxide.
Grams were charged, and the contents were heated to 80 ° C. by heating the flask while stirring. After about 10 hours, white turbidity due to zinc oxide almost disappeared. The nonvolatile component of the xylene phase was 61.3 percent and the zinc content in the nonvolatile component was 8.7 percent. This is a 23 percent excess over 3,5-diisononyl salicylic acid.

Example 8-3 In the same manner as in Example 1-3, the nonvolatile component was 40% from the xylene phase obtained in Example 8-2, and the average particle diameter of the dispersoid was 1.0 micron. An aqueous dispersion was obtained.

Example 9 Subsequent to Example 5, the same xylene solution as that obtained in Example 5-2 was obtained in the same manner as in Example 5-2.

Example 9-2 (mixing with hydroxide of polyvalent metal) The xylene solution obtained in Example 9 was placed in the three-necked flask having an internal volume of 1,000 ml used in Example 8-2. The whole and 3.2 g of zinc hydroxide were charged and the flask was heated with stirring to bring the temperature of the contents to 80 ° C.
When kept at this temperature for 3 hours, the cloudiness of zinc hydroxide disappeared. This xylene solution had a nonvolatile content of 62.6% and a zinc content in the nonvolatile content of 9.2%. This is a 33 percent excess over 3,5-diisononyl salicylic acid.

Example 9-3 (Preparation of Aqueous Dispersion) From the xylene solution obtained in Example 9-2, Example 1-3 was prepared.
In the same manner as above, an aqueous dispersion having a nonvolatile content of 40% and an average particle size of dispersoid of 1.0 micron was obtained.

Example 10 (Test as Pressure Sensitive Recording Sheet) Preparation of Developer Coating Liquid Example 1-3, Example 2-3, Example 3-3, Example 4
-3, Example 5-3, Example 6-3, Example 7-3, Example 8-3 and Example 9-3 using the 40% aqueous dispersion of the developer, Nine kinds of developer coating solutions were prepared by the formulation.

80 parts of calcium carbonate in 100 parts by weight of water,
25 parts by weight of 40% aqueous dispersion of the above color developer and zinc oxide 1
0 parts by weight are mixed and dispersed, and further 50 parts by weight of a 10% polyvinyl alcohol aqueous solution and 10 parts by weight of a carboxyl-modified SBR latex (trade name: SN-307, solid content: 50%, manufactured by Sumitomo Nogatac Co., Ltd.) are mixed as a binder. Dispersed to obtain a developer coating solution.

Production of color-developing paper for pressure-sensitive recording sheet The color-developing liquid coating solution obtained above was applied to one side of a base paper of 40 g / m ^{2 so} that the dry weight was 4 g / m ^2, and dried to obtain 9 types. A color-developing paper for pressure-sensitive recording sheet was obtained.

The nine types of color developing papers for pressure-sensitive recording sheets obtained as described above were subjected to a quality evaluation test according to the following method. The results are shown in Table 1.

Manufacture of Top Paper A microcapsule coating solution prepared by dissolving crystal violet lactone in alkylated naphthalene and microencapsulating this oily solution was applied to one side of a high quality paper so that the dry weight was 4 g / m ^2. Then, it was dried to obtain a top paper.

Low temperature color development test The color developing paper and the upper paper obtained as described above were left to stand in an atmosphere of 0 ° C. for 10 hours. After that, the coated surfaces of the color paper and the top paper are made to face each other, and color is developed by a drop-type color tester (weight: 150 g, height: 15 cm) in an atmosphere of 0 ° C., and then printed with a Macbeth reflection densitometer. The color density after 10 seconds of pressure was measured (the higher the value, the better).

Color density The color test sample developed as described above was allowed to stand at room temperature (25 ° C., 65% RH) for 2 days, and then the color density was measured again with a Macbeth reflection densitometer. Larger is better).

Light resistance test A sample colored as above was developed by a drop-type color tester (weight: 150 g, height: 15 cm) at room temperature with the coated surfaces of the color paper and the upper paper facing each other. , At room temperature 1
After leaving it for 2 hours or more and then exposing it to sunlight for 8 hours, the color density was measured again with a Macbeth reflection densitometer (the larger the value, the better).

Water resistance test A color image was formed in the same manner as in the above light resistance test, the sample left for 5 minutes was immersed in water at about 20 ° C. for 5 hours, and then the color density was measured again by a Macbeth reflection densitometer. It was measured (the larger the number, the better).

[0065]

[Table 1]

[0066]

The effect obtained by the production method of the present invention is 3,
A developer composition for a pressure-sensitive recording sheet containing a polyvalent metal salt of 5-diisononylsalicylic acid, particularly a zinc salt thereof, as a main component, has light resistance, water resistance, color development speed at low temperature, color density,
In terms of stability of recorded images and non-contamination of white paper by sunlight and nitrogen oxides, it has excellent properties that have not been obtained in the past.

Front page continuation (72) Eiji Kawabata Eiji Kawabata, 1-10-24, Itsukaichi, Ibaraki-shi, Osaka Inside Sanko Research Institute Inc. Company Kanzaki Mill (72) Inventor Toshio Kimura 4-3-1 Jōkoji, Amagasaki City, Hyogo Prefecture Kanzaki Paper Mill Kanzaki Mill

Claims (7)

[Claims] 1. (a) In a substantially water-insoluble solvent,
The Kolbe-Schmidt reaction is carried out with respect to the alkali metal salt of 4-diisononylphenol, and (b) water is added to the reaction mixture to form the by-produced alkali metal salt of carbonic acid together with (b-1) water. Separated or removed, or
2) Mineral acid is added and decomposed, and then (c) Main component is polyvalent metal salt of 3,5-diisononylsalicylic acid, which is characterized by metathesis by water-soluble salt of polyvalent metal in the presence of water. A method for producing a developer composition. 2. (a) In a substantially water-insoluble solvent,
A Kolbe-Schmidt reaction is carried out on an alkali metal salt of 4-diisononylphenol, (b) a water-soluble salt of a polyvalent metal is added to the reaction mixture to cause metathesis in the presence of water, and then (c) A polyvalent metal salt of 3,5-diisononylsalicylic acid, characterized in that the polyvalent metal salt of carbonic acid produced as a by-product is decomposed by (ha-1) filtration or (ha-2) addition of a mineral acid. A method for producing a developer composition containing salt as a main component. 3. (a) In a substantially water-insoluble solvent,
A Kolbe-Schmidt reaction is carried out on the alkali metal salt of 4-diisononylphenol, (b-1) water is added to the reaction mixture to separate and remove the by-produced alkali metal salt of carbonic acid together with water, and During this step, the carbon dioxide gas remaining from the above step (a) is removed by heating, or (b-2) water is added to the reaction mixture to remove by-produced alkali metal salts of carbonic acid and mineral acid. In addition, it decomposes and removes the generated carbon dioxide gas and the carbon dioxide gas remaining from the above step (a) by heating, and then (c) in the coexistence of water and a metal oxide or metal hydroxide, A method for producing a developer composition containing a polyvalent metal salt of 3,5-diisononylsalicylic acid as a main component, which is characterized in that metathesis is performed with a water-soluble salt. 4. (a) In a substantially water-insoluble solvent,
The Kolbe-Schmidt reaction is carried out on an alkali metal salt of 4-diisononylphenol, and (b) a water-soluble salt of a polyvalent metal is added to the reaction mixture to form water and a metal oxide or a metal hydroxide. A developer composition containing a polyvalent metal salt of 3,5-diisononylsalicylic acid as a main component, which is subjected to metathesis in the coexistence and then (c) the polyvalent metal salt of carbonic acid, which is a by-product, is removed by filtration. Manufacturing method. 5. The method for producing a color developer composition according to claim 1, wherein the water-soluble salt of a polyvalent metal is zinc sulfate or zinc chloride. 6. The method for producing a developer composition according to claim 3, wherein the metal oxide or metal hydroxide is one or more selected from zinc oxide, sodium hydroxide, potassium hydroxide and zinc hydroxide. Method. 7. The composition obtained by the method according to claim 1, 2, 3, 4, 5 or 6, further comprising a polyvalent metal oxide or hydroxide. , 5-
A method for producing a developer composition containing a polyvalent metal salt of diisononylsalicylic acid as a main component.