JPH1199743A - Developer composition for pressure-sensitive recording material, its water-dispersing liquid, and pressure-sensitive recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the storage stability of a recorded image by adding bring metal salt and polycyclic nuclear substitute salicylic polyvalent metal salt in a developer of a pressure-sensitive recording material utilizing the coloring reaction of a dye with the developer represented by specified formulas I and II. SOLUTION: Catalysts as a pressure-sensitive recording material, which is inferior heretofore, of a developer is improved perfectly when polycyclic nuclear substitute salicylic polyvalent metal salt is mixed with polyvalent metal salt such as 3-methyl-5 secondary decylsalicylic acid represented by formulas I and II (In the formulas, one of R1 and R2 represents methyl, (n) represents an integer of 1 to 5, and at least two kinds or more of values are provided and the total number of carbon is 12. M represents polyvalent metal atoms and (m) represents the atomic value of M.), or an organic polymer compound composed of hydrocarbon is added therein and used as a developer composition. Not only a simple mutual replacement relation but also the remarkable quality balance considered as the synergistic effect can be realized.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a developer composition for a pressure-sensitive recording material, an aqueous dispersion thereof, and a pressure-sensitive recording material using the same. Furthermore, in a pressure-sensitive recording material utilizing a color-forming reaction between an electron-donating colorless dye and an electron-accepting color developer, a developer composition with improved light resistance and plasticizer resistance, and The present invention relates to a pressure-sensitive recording material using the same.

[0002]

2. Description of the Related Art Electron-donating colorless dyes (hereinafter referred to as "dyes")
Called. ) Containing a microcapsule containing an organic solvent solution and an electron-accepting color developer (hereinafter, referred to as a "color developer"), and forming a recorded image by a color-forming reaction between the dye and the color developer. A recording material utilizing this process is generally called carbonless paper, pressure-sensitive copy paper, pressure-sensitive recording material, or the like, and has been known for a long time and widely used.

When a pressure-sensitive recording material is applied with pressure to break microcapsules containing a dye solution, the dye and the developer come into contact with and react with each other to form a recorded image corresponding to the pressure. This is based on the principle used. Generally, a dye layer in which microcapsules containing a dye solution are coated and fixed on the surface of a support and a developer layer containing a color developer are formed on the surface of a support different from the dye layer or on the same surface as the dye layer. A copying paper type pressure-sensitive recording material formed on the opposite surface of the support so that the dye layer and the color developer layer are in opposing contact, and microcapsules containing a dye solution on the same surface of the support. There is a so-called self-coloring type pressure-sensitive recording material provided with a self-coloring layer which simultaneously contains a color developing agent. Self-coloring type pressure-sensitive recording materials are also known as press-type paper, self-contained paper or cell-con paper.

In a copying paper type pressure-sensitive recording material, a dye layer is formed on one side (generally, the back side) of a support to form an upper sheet.
A medium layer is formed by forming a color developer layer on the surface of the support and a dye layer on the back surface of the support, and a lower paper is formed by forming the color developer layer on the surface of the support. Then, a necessary combination is made of the upper sheet, the middle sheet and the lower sheet, and pressure is applied so that the dye layer and the developer layer alternately face and contact with each other so that a recorded image is formed. When pressure is applied, the microcapsules are broken and the dye solution moves from face to face from the dye layer to the developer layer. The transferred dye and the developer contact and react on the developer layer to form a recorded image corresponding to the pressure.

In the self-coloring type pressure-sensitive recording material, when pressure is applied to the surface on which the self-coloring layer is provided, the microcapsules are destroyed. Then, a recorded image corresponding to the pressure is formed on the self-color-forming layer. Therefore, the self-coloring type pressure-sensitive recording material can be placed on a plain paper on the surface of the self-coloring layer, and the image of a character or the like can be copied and recorded with a writing instrument or a typewriter on the plain paper. Instead of using an ink ribbon, it is also possible to form a recorded image by directly performing pressure printing with a typewriter or a printer.

As a dye for a pressure-sensitive recording material, CVL is used.
(Crystal violet lactone) and other simple chemical structures were first used, but with the development of pressure-sensitive recording materials, their product lineup has progressed, and now the type of color, solubility in solvents, or recorded images The range of choice of dyes is remarkably widened due to the properties such as light resistance of the dyes.

The developer is a clay mineral such as activated clay (US Pat. Nos. 2,730,457 and 27,304).
No. 65 or 3,418,250), but for the purpose of improving the storage stability of the recorded image of the pressure-sensitive recording material, a phenolic resin developer is used followed by a nuclear-substituted salicylic acid. Of zinc salt (JP-B-51-251)
No. 74).

At present, among the developers used in pressure-sensitive recording materials, zinc salts of nucleus-substituted salicylic acid are said to have the best storage stability of blank paper and recorded images. Still, complaints that the light resistance of the recorded image of the pressure-sensitive recording material is inferior to other recording materials are still persistent.

On the other hand, as a recent general tendency, environmental pollution on a global scale by chemical substances has been regarded as a problem even if it is noisy. However, it is said that if a certain chemical substance is decomposed and digested by microorganisms, the problem of environmental pollution caused by the chemical substance is eliminated. Some of the nuclear-substituted salicylic acids as color developers have been found to be degradable by microorganisms.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a pressure-sensitive recording material utilizing a color-forming reaction between an electron-donating colorless dye and an electron-accepting developer, and particularly to the storage stability of a recorded image. An object of the present invention is to provide an improved developer composition having excellent properties.

[0011]

According to the present invention, there is provided a pressure-sensitive recording material utilizing a color development reaction between a dye and a developer, wherein the developer is 3-methyl-5-secondary dodecylsalicylic acid or 3-secondary dodecyl-5. -A developer composition for a pressure-sensitive recording material, characterized by containing a polyvalent metal salt of methyl salicylic acid and a polyvalent metal salt of polycyclic nucleus-substituted salicylic acid; Methyl-5-secondary dodecyl salicylic acid or 3-secondary dodecyl-5
A pressure-sensitive composition comprising a polyvalent metal salt of methyl salicylic acid, a polyvalent metal salt of polycyclic nucleus-substituted salicylic acid, and an organic polymer compound mainly composed of hydrocarbon and having a molecular weight of 300 to 50,000. The present invention relates to a developer composition for a recording material, an aqueous dispersion thereof, and a pressure-sensitive recording material using the same.

The usefulness of 3-methyl-5-secondary dodecylsalicylic acid or a polyvalent metal salt of 3-secondary dodecyl-5-methylsalicylic acid as a developer for pressure-sensitive recording materials is disclosed in JP-A-4-110186. Are already known.

However, the pressure-sensitive recording material having such excellent characteristics and using a color developer composed of a polyvalent metal salt thereof has a low coloring property at a low temperature and a light fastness of a white paper. And although the properties such as water resistance of the print (recorded image) are extremely excellent, only slightly inferior properties are found in the light resistance of the print and the plasticizer resistance of the print, and when viewed as a pressure-sensitive recording material, It is a pity that the balance of the characteristics is lacking, and it has not yet been put to practical use.

However, by mixing a polyvalent metal salt of polycyclic nucleus-substituted salicylic acid with these polyvalent metal salts or further adding an organic polymer compound mainly composed of hydrocarbons, a developer composition is obtained. When used, it was found that the properties as a pressure-sensitive recording material, which were inferior to that time, were completely improved. It is not only a mere complementarity relationship but also a stunning balance of quality that can be considered as a synergistic effect, and the discovery of such a developer composition was the beginning of the completion of the present invention. is there.

The properties of pressure-sensitive recording materials that are generally required and problematic include color development, low-temperature color development, light resistance of white paper, light resistance of printing, water resistance of white paper, water resistance of printing, Examples include the moisture resistance of blank paper, the moisture resistance of printing, the heat resistance of blank paper, and the plasticizer resistance of printing. In addition, self-coloring type pressure-sensitive recording materials also include background contamination due to water of white paper, background contamination due to humidity of white paper, background contamination due to heat of white paper, background contamination due to solvent of white paper or friction due to friction of white paper. is there. The quality of these properties of the pressure-sensitive recording material largely depends on the quality of the color developer, and the selection or development of a developer with excellent quality is extremely important for improving the properties of the pressure-sensitive recording material. I must say that it is an issue.

Next, the above-mentioned various characteristics and a test method thereof will be specifically described. (1) The color developing property is related to the color developing ability of a color developer, and is represented by the maximum density of color development of a pressure-sensitive recording material. After printing, the printed image is left at 25 ° C. for 24 hours, and then the density of the recorded image is measured. 2 The color development at low temperature is the color development of a pressure-sensitive recording material in extremely cold conditions, and printing is performed in an atmosphere at -20 ° C, and the ultimate density of a recorded image in a short time is measured. 3 The light fastness of the white paper is related to the light fastness of the color developer in the pressure-sensitive recording material.
The highest density of the recorded image is measured and compared with the unexposed one. At the same time, the degree of yellowing of the white paper due to sunlight exposure is visually determined. 4 The light fastness of the printed image is determined by comparing the density of a recorded image faded by exposing a recorded image of a pressure-sensitive recording material to sunlight and comparing it with an unexposed recorded image. 5 Water resistance of the white paper is measured by exposing the developed surface of the pressure-sensitive recording material to running water at 25 ° C. for 30 minutes, drying, printing, and measuring the density of the recorded image. 6 The water resistance of the print was determined by exposing the pressure-sensitive recording material immediately after printing to running water at 25 ° C. for 30 minutes, and visually determining the degree of fading of the recorded image or blurring of the print. 7 Moisture resistance of blank paper is measured at 40 ° C, 9
It is left to stand in 0% humidity for 24 hours, dried, and subjected to the same test as the color development described in the item 1 to make a judgment. 8 For the moisture resistance of the printed image, the printed lower paper was left at 40 ° C. and 90% humidity for 24 hours to determine the degree of fading of the recorded image. 9 The heat resistance of blank paper is as follows.
After leaving it for 4 hours, perform the same test as the color development of item 1.
Compare and judge. 10 The plasticizer resistance of printing is such that three commercial polyvinyl chloride wrap films containing a plasticizer are brought into contact with each other under pressure so as to be in close contact with the recorded image of the lower paper left for 24 hours after printing. After standing at room temperature of 25 ° C. for 7 days, the degree of fading or bleeding of the recorded image is visually determined.

All of the above properties are greatly affected by the quality of the developer used in the pressure-sensitive recording material, and which property is emphasized is determined by the manufacturer of the pressure-sensitive recording material. However, in general, a good balance of various characteristics is required.

In addition, the self-coloring type pressure-sensitive recording material also has other unique characteristics as described in the following specific description, which is problematic. 11 The background contamination of blank paper is determined by exposing a self-coloring type pressure-sensitive recording material to running water at 25 ° C. for 1 hour and then drying, and visually determining the degree of background contamination. 12 The background contamination due to the humidity of the white paper is determined by leaving the self-coloring type pressure-sensitive recording material at 40 ° C. and 90% humidity for 24 hours, and then visually determining the degree of the background contamination. 13. For background contamination due to the heat of blank paper, a self-coloring type pressure-sensitive recording material is left at 70 ° C. for 24 hours, and then the degree of the contamination is visually determined. 14 For background contamination due to the ink solvent on blank paper, a printing ink which is relatively easy to cause background contamination is selected and actually printed on a pressure-sensitive recording material, and the degree of background contamination is visually determined. 15. The background contamination due to the friction of the white paper is determined by visually rubbing the coloring surface of the pressure-sensitive recording material after rubbing it under certain conditions.

As described above, the characteristics unique to the self-coloring type pressure-sensitive recording material are not necessarily related only to the quality of the color developer, but the quality of the color developer depends largely on the quality of the color developer.
Is in question.

The polyvalent metal salts of 3-methyl-5-secondary dodecylsalicylic acid and 3-secondary dodecyl-5-methylsalicylic acid have similar properties as a color developing agent. And there may be no significant difference in quality between the two. And, as already described, the pressure-sensitive recording material using a developer containing only these polyvalent metal salts as a main component is one of the above-mentioned characteristics, that is, the coloring property, the coloring property under low temperature, the light resistance of blank paper, Extremely high levels of water resistance of white paper, water resistance of printing, moisture resistance of white paper, moisture resistance of printing, heat resistance of white paper, and self-coloring pressure-sensitive recording materials are exhibited. However, the light fastness of the print and the plasticizer resistance of the print are inferior to those of a developer which is already practically used and is mainly composed of a polyvalent metal salt of a polycyclic nucleus-substituted salicylic acid. It is a problem that the characteristics required for the recording material are lacking in balance.

However, as has been frequently described, if these polyvalent metal salts are mixed with a polyvalent metal salt of a polycyclic nucleus-substituted salicylic acid and used as a developer composition, the disadvantage of printing, which is a drawback, is obtained. It has been discovered that lightfastness and the plasticizer of the print are significantly improved. Now, it is difficult to explain the reason, but in terms of the light fastness of the print, a superior result is obtained as compared with the case where the mixed polyvalent metal salts of the nucleus-substituted salicylic acid are separately used as a developer. What was done is surprising.

3-Methyl-5-secondary dodecylsalicylic acid and 3-secondary dodecyl-5-methylsalicylic acid are monocyclic nuclear substituted salicylic acids. In addition to these, many monocyclic nuclear-substituted salicylic acids are known, and their polyvalent metal salts are converted to 3-methyl-5-secondary dodecylsalicylic acid or polyvalent metal salts of 3-secondary dodecyl-5-methylsalicylic acid. Many attempts have been made to mix and use as a developer composition, but for some reason no quality improvement effect was observed, and all attempts failed. Further, when the secondary dodecyl group in the general formula (1) is changed to another alkyl group, for example, when the octyl group or the decyl group is used, the water resistance of white paper and printing deteriorates, and when the octadecyl group is used, the same applies. The practicality as a pressure-sensitive recording material is generally reduced, such as deterioration of oil resistance (plasticizer resistance).

The polycyclic nucleus-substituted salicylic acid is a salicylic acid having two or more ring structures in one molecule, and includes 3-methyl-5- (α-methylbenzyl) salicylic acid and 3-isopropyl-5- (α- Methylbenzyl) salicylic acid, 3-
Secondary butyl-5- (α-methylbenzyl) salicylic acid, 3-secondaryhexyl-5- (α-methylbenzyl) salicylic acid, 3-cyclohexyl-5-methylsalicylic acid, 3-cyclohexyl-5-isopropylsalicylic acid, 3-cyclohexyl- 5-secondary butylsalicylic acid, 3-cyclohexyl-5- (α-methylbenzyl) salicylic acid, 3-phenyl-5- (α-methylbenzyl) salicylic acid, 3-benzylsalicylic acid, 5-benzylsalicylic acid, 3,5-dibenzyl Salicylic acid, 3
-(Α-methylbenzyl) salicylic acid, 5- (α-methylbenzyl) salicylic acid, 3- (α-methylbenzyl)
-5-methylsalicylic acid, 3- (α-methylbenzyl)
-5-isopropylsalicylic acid, 3- (α-methylbenzyl) -5-secondary butylsalicylic acid, 3,5-di (α-methylbenzyl) salicylic acid, a reaction product obtained by adding styrene to salicylic acid, salicylic acid and benzyl chloride and styrene And a copolycondensation reaction product of salicylic acids and phenols with formaldehyde. These polycyclic nucleus-substituted polyvalent metal salts of salicylic acid can be used for the purpose of the present invention alone or in combination of two or more.

Any of these polycyclic nucleus-substituted polyvalent metal salts of salicylic acid may be used as a mixture with a polyvalent metal salt of 3-methyl-5-secondary dodecylsalicylic acid or 3-secondary dodecyl-5-methylsalicylic acid. If so, the effect of improving the quality as a color developer is remarkable. In particular, 3-
(Α-methylbenzyl) salicylic acid, 5- (α-methylbenzyl) salicylic acid, 3,5-di (α-methylbenzyl) salicylic acid, a reaction product obtained by adding styrene to salicylic acid, reaction of salicylic acid with benzyl chloride and styrene More preferred results are obtained with polyvalent metal salts of polycyclic nucleus-substituted salicylic acids such as products or products of copolycondensation of salicylic acids and phenols with formaldehyde. Furthermore, a polyvalent metal salt of 3,5-di (α-methylbenzyl) salicylic acid gives the most favorable results. Furthermore, the selected polycyclic nucleus-substituted salicylic acid is also degradable by microorganisms at the same time, which is preferable for the purpose of the present invention.

10 to 90% by weight of polymethyl metal salt of 3-methyl-5-secondary dodecylsalicylic acid or 3-secondary dodecyl-5-methylsalicylic acid, so-called monocyclic nucleus-substituted salicylic acid, and polycyclic nucleus-substituted salicylic acid A developer composition containing 90 to 10% by weight of a polyvalent metal salt of the above is suitable for the purpose of the present invention. Furthermore, a polycyclic metal salt of a monocyclic nucleus-substituted salicylic acid is added at 20 to 70% by weight
And a developer composition containing 80 to 30% by weight of a polyvalent metal salt of a polycyclic nucleus-substituted salicylic acid,
30 to 60 monovalent nuclei-substituted polyvalent metal salts of salicylic acid
% By weight and a polyvalent metal salt of a polycyclic nucleus-substituted salicylic acid
Developer compositions containing 0 to 40% by weight are most preferred. It is desirable that these developer compositions are microscopically and uniformly mixed, but a mixture of the respective fine particles is also used for the purpose of the present invention.

3-Methyl-5-secondary dodecylsalicylic acid and 3-secondary dodecyl-5-methylsalicylic acid were prepared from a large number of monocyclic nucleus-substituted salicylic acids by ease of industrial production or as a developer composition. It was chosen for reasons such as high quality at times. In addition, 3-secondary dodecyl-5-methylsalicylic acid is most preferable from the viewpoint of easy industrial production.

The secondary dodecyl group of 3-methyl-5-secondary dodecylsalicylic acid and 3-secondary dodecyl-5-methylsalicylic acid means that a linear dodecyl group is located at the 2, 3, 4, 5 and 6-position nucleus of salicylic acid. It is a generic name of a bond, and when a phenol compound and normal dodecene are used as starting materials and an acid catalyst is used for production, almost any kind of normal dodecene can produce almost the same mixed secondary dodecyl group. As described above, although the polynuclear property of the accidentally obtained nuclear-substituted salicylic acid is preferable because it prevents crystallization of the polyvalent metal salt of the nuclear-substituted salicylic acid when applied as a color developer.

[0028] 3-Methyl-5-secondary dodecylsalicylic acid can be produced as follows. That is, orthocresol and normal dodecene are subjected to an addition reaction in the presence of an acidic catalyst, and a portion mainly composed of 2-methyl-4-secondary dodecylphenol is separated from the reaction product. The analysis results confirm that 2-methyl-4-secondary dodecylphenol is a mixture of secondary dodecyl groups bonded at the 2, 3, 4, 5, and 6 positions. When the sodium or potassium salt of the nuclear-substituted phenol is reacted with carbon dioxide, a sodium or potassium salt of the nuclear-substituted salicylic acid is obtained, and subsequently, the nuclear-substituted salicylic acid or a polyvalent metal salt thereof is obtained by a known method. Further, 3-secondary dodecyl-5-methylsalicylic acid is produced in the same manner.
Para-cresol and normal dodecene are subjected to an addition reaction in the presence of an acidic catalyst to isolate 2-secondary dodecyl-4-methylphenol from the reaction product. Analysis confirms that 2-secondary dodecyl-4-methylphenol is a mixture of secondary dodecyl groups linked at the 2, 3, 4, 5, or 6 positions. By reacting the sodium or potassium salt of the nuclear-substituted phenol with carbon dioxide, a sodium or potassium salt of the nuclear-substituted salicylic acid is obtained. This is treated in a conventional manner to obtain a nuclear-substituted salicylic acid or a polyvalent metal salt thereof.

A method for producing a polycyclic nucleus-substituted salicylic acid or a polyvalent metal salt thereof is described in JP-B-51-25174, JP-B-6-104786, and JP-A-63-18672.
No. 9 or JP-A-2-95885.

The polyvalent metal forming the salt of the nuclear-substituted salicylic acid used in the present invention refers to a metal having a valence of 2 or more, but actually, magnesium, aluminum, calcium, manganese, iron, cobalt, nickel , Copper, zinc or strontium. And, the most preferably used industrially is zinc. All of the nuclear substituted salicylic acids are capable of forming salts with these polyvalent metals. The polyvalent metal salt of the nuclear-substituted salicylic acid can be obtained as a water-insoluble salt by dissolving or dispersing the sodium or potassium salt of the nuclear-substituted salicylic acid in water and adding a water-soluble salt of the polyvalent metal to cause a metathesis reaction. At this time,
An organic solvent may coexist for the purpose of facilitating the metathesis reaction, or heating may be performed. Another method for producing a polyvalent metal salt of a nuclear-substituted salicylic acid is to mix a nuclear-substituted salicylic acid with a hydroxide, oxide or carbonate of a polyvalent metal to cause a neutralization reaction. Water or an organic solvent may be present for the purpose of smoothing the neutralization reaction, or heating may be performed for the purpose of promoting the neutralization reaction.

The organic high molecular weight compound having a molecular weight of 300 to 50,000, which is mainly composed of hydrocarbon and which can be contained in the color developer composition, is not used merely for the purpose of merely increasing the content of the color developer composition. . By using such an organic polymer compound as one component of the color developer composition, the necessary properties of the pressure-sensitive recording material, such as color development at low temperatures, light resistance of printing, water resistance of white paper, and moisture resistance of white paper All of the properties, heat resistance of printing, and other characteristics required for the self-coloring type pressure-sensitive recording material are improved. It should also be noted that the developer composition containing an organic polymer improves the storage stability of an aqueous suspension or dispersion.

When the molecular weight of the organic high molecular compound is less than 300, the effect of improving the light resistance of printing, the water resistance of printing or the contamination of self-coloring white paper is small. On the other hand, when the molecular weight is 50,0
If it is larger than 00, the coloring property and especially the coloring property at low temperature are adversely affected, which is not preferable.

The organic polymer compound mainly composed of hydrocarbon preferably has a molecular weight of 300 to 50,000, more preferably 300 to 20,000.
0. It is desirable that the polycyclic metal salt of the monocyclic nuclear substituted salicylic acid and the polyvalent metal salt of the polycyclic nuclear substituted salicylic acid are uniformly dissolved and mixed. Organic polymer compounds that meet these conditions include styrene polymers, vinyl toluene polymers, copolymers of styrene and some other monomers,
α-methylstyrene polymer, styrene / α-methylstyrene copolymer or petroleum resin can be mentioned. More preferably, it is selected from styrene polymers, α-methylstyrene polymers, styrene / α-methylstyrene copolymers, petroleum resins and the like. The organic polymer compound exists from a liquid state to a substance having a softening point exceeding 150 ° C. The preferred softening point of the organic polymer compound for the purpose of the present invention is 40 to 150 ° C. These may be used in combination of two or more.

The petroleum resin is obtained by polymerizing diolefins and monoolefins contained in a cracked oil fraction by-produced from a plant when producing ethylene or propylene by petroleum steam cracking.
It can be roughly divided into the following three types. Primarily carbon number of the cracked oil fraction of five unsaturated hydrocarbons, so-called aliphatic what the C ₅ fraction and the raw material system or C ₅ petroleum resin mainly unsaturated carbon atoms 9 The one using a hydrocarbon C ₉ fraction as a raw material is referred to as an aromatic petroleum resin, and the one using both as a raw material is referred to as a C ₅ / C ₉ copolymerized petroleum resin. Since all of them use a mixed fraction as a raw material, their chemical structures are generally difficult to determine. In addition, there are those in which the polymer of the cracked oil fraction is used as the basic skeleton and other modifiers are copolymerized depending on the application, and those in which the remaining unsaturated bonds are hydrogenated (hydrogenated). The varieties are quite diverse. In addition, some petroleum resins exhibit a relatively high softening point despite having a low molecular weight of about 300, which does not match the general concept of a polymer compound. Is difficult to distinguish from other high molecular compounds, and therefore, is defined as an organic high molecular compound.

These organic polymer compounds mainly composed of hydrocarbons are not degradable by microorganisms.
It is preferable because it has little toxicity to living organisms, has little problem with the gas generated by incineration, and has negligible effect on the environment.

The total of 20-95% by weight of the total of the polyvalent metal salt of 3-methyl-5-secondary dodecylsalicylic acid or 3-secondary dodecyl-5-methylsalicylic acid and the polycyclic nucleus-substituted salicylic acid is 20 to 95% by weight and mainly carbonized. A developer composition containing 80 to 5% by weight of an organic polymer compound consisting of hydrogen and having a molecular weight of 300 to 50,000 is preferred for the purpose of the present invention. 30 to 85% by weight of the total of the polyvalent metal salt of the nuclear substituted salicylic acid
And a developer composition containing the organic polymer compound in a ratio of 70 to 15% by weight is more preferable for the purpose of the present invention. Furthermore, the total amount of the polyvalent metal salt of the nuclear-substituted salicylic acid is 40 to 75% by weight and A developer composition containing an organic polymer compound in a proportion of 60 to 25% by weight is most preferred for the purpose of the present invention. However, the required characteristics are slightly different between the copy paper type pressure-sensitive recording material and the self-coloring type pressure-sensitive recording material, and the polyvalent metal of the nucleus-substituted salicylic acid constituting the developer composition to be used. The preferred content ratios of the salt and the organic polymer compound are different. Generally, the developer composition used for the self-coloring type pressure-sensitive recording material has a higher content ratio of the organic polymer compound.

The polycyclic metal salt of a monocyclic nucleus-substituted salicylic acid, the polyvalent metal salt of a polycyclic nucleus-substituted salicylic acid, and an organic high molecular compound are preferably mixed uniformly. An organic polymer compound is uniformly dissolved and mixed in one or both of a polyvalent metal salt of a substituted salicylic acid and a polycyclic metal salt of a polycyclic nucleus-substituted salicylic acid. It can serve the purpose of the present invention.

Further, the color developer composition of the present invention may include a material for improving color development at low temperature, such as esters, ethers, urethanes, carboxamides or sulfonamides, an ultraviolet absorber or an oxidizing agent. Materials for improving the storage stability of the pressure-sensitive recording material, such as a stabilizer, can be added as needed.

These developer compositions for pressure-sensitive recording materials are pulverized or dispersed to a particle size suitable for finishing the developer layer.

In order to obtain an aqueous suspension of finely divided fine particles of the developer composition, the composition which has been previously ground to an average particle diameter of 100 to 200 microns is prepared by adding a water suspension containing a wetting agent and a dispersing agent. And then pulverized by a pulverizing medium such as a ball mill, an attritor or a sand grinder until a desired average particle size is obtained. The average particle size of the aqueous suspension thus obtained is limited to about 1 micron and is adjusted to an average particle size of 1 to 5 microns.
In general, a water suspension has a disadvantage that it has a high viscosity even at a relatively low concentration, and is not suitable for transportation.

There is a method suitable for obtaining an aqueous dispersion having a high concentration of the developer composition and a small average particle diameter. First, the developer composition is dissolved in a virtually water-insoluble organic solvent. Next, this solution is emulsified and dispersed in water containing a dispersant using a dispersing medium such as a homomixer or a pressure shock type homogenizer. Finally, the dispersion is heated to distill off the organic solvent. The microparticles thus obtained are spherical and the dispersion has a low viscosity even at high concentrations and is suitable for transport or storage. The organic solvent practically insoluble in water used at this time is preferably selected from cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, chlorobenzene, isopropyl ether, normal butyl ether, isobutyl ether or methyl isobutyl ketone. .

Another method for obtaining an aqueous dispersion of a developer composition is a method using no organic solvent, and has a relatively low softening point and a low viscosity under heating. Applied to First, a developer composition pulverized to an average particle diameter of about 100 to 200 microns is suspended in water containing a wetting agent and a dispersant. The suspension is then added to 10
While heating to 0 to 180 ° C., the mixture is treated with a homomixer or a pressure shock type homogenizer, and the treatment is adjusted so as to obtain a desired average particle diameter. Then, the aqueous dispersion obtained by cooling and solidifying has an average particle size of 0.3 to 5 microns, and it is more difficult to obtain a dispersion having a large average particle size by these methods.

Examples of the wetting agent or dispersant used herein include anionic surfactants, anionic high molecular weight dispersants such as sulfonated polyvinyl alcohol salts and sulfonated polystyrene salts, polyvinyl alcohol, and partially saponified polyvinyl alcohol. Preferred are high-molecular nonionic dispersants such as alcohols, water-soluble cellulose derivatives, acrylamide polymers and acrylamide / acrylate copolymers, and frequently use cationic surfactants and low molecular weight nonionic surfactants. Is not preferred.

The average particle diameter of the thus obtained developer composition is preferably adjusted to 0.3 to 5 microns. More preferably, the particle size is between 0.5 and 3 microns, most preferably, between 0.6 and 1.8 microns. In addition, the requirements for the particle size of the developer composition are different between the copy paper type pressure-sensitive recording material and the self-coloring type pressure-sensitive recording material. It is better to be smaller than the particle size of the agent composition.

The necessary materials such as extender and adhesive are mixed with the aqueous suspension or the aqueous dispersion of the color developer composition to prepare the paint necessary for forming the color development layer of the pressure-sensitive recording material. Is done. As extenders used here, kaolinite, talc, calcium carbonate, silicic anhydride, zinc oxide,
Inorganic pigments such as aluminum hydroxide or barium sulfate are preferred. As the adhesive, a coating such as starch, starch derivative, methylcellulose, hydroxyethylcellulose, acrylamide polymer, acrylamide / acrylate copolymer, acrylamide / acrylate / acrylate copolymer, polyvinyl alcohol or partially saponified polyvinyl alcohol Formable water-soluble polymer compound, styrene-butadiene copolymer, styrene-butadiene-itaconic acid copolymer, vinyl acetate polymer, acrylate ester polymer, its copolymer, methacrylate ester polymer or its copolymer A latex of a water-insoluble polymer compound such as a polymer is preferred. Depending on the requirements of the workability of the coating site of the paint, the paint may further be mixed with an antifoaming agent or a thickener.

The amount of the coating material for the color developing layer applied on the support is the same for the copy paper type pressure-sensitive recording material and the self-coloring type pressure-sensitive recording material. Is preferably adjusted to be 0.2 to 3 grams. Then, the color developing layer of the copy paper type pressure-sensitive recording material to which the paint is applied and dried is finished with a smooth surface using a super calender or the like.

Dyes used in the pressure-sensitive recording material include lactone dyes typified by crystal violet lactone, oxidized leuco dyes typified by benzoyl leucomethylene blue, fluoran compounds and indolylphthalide compounds And indolylazaphthalide compounds. These dyes include synthetic oils such as alkyl naphthalenes, alkyl biphenyls, alkylated diphenylethane or chlorinated paraffin,
It is dissolved in a solvent composed of a natural oil such as cottonseed oil, castor oil, animal oil or mineral oil, then dispersed in water, and microencapsulated. As a wall material of the microcapsule, a geracene / formaldehyde-based, melamine-resin-based or urethane-resin-based material is generally used. The average particle size of the microcapsules containing the dye solution is usually preferably 2 to 10 microns. A paint is prepared by adding an adhesive or the like to the aqueous suspension of the microcapsules. The paint containing the microcapsules is applied to the surface of the support or the back of the support already having the color developer layer and dried to form the dye layer, in order to form a dye layer.

In the case of the self-coloring type pressure-sensitive recording material, a coating containing microcapsules is first applied to the surface of the support, and then a coating containing the developer composition is further applied and dried to finish. There are known a layer type and a one-layer type in which a coating containing a microcapsule and a developer composition is applied and dried to finish.

The developer composition for a pressure-sensitive recording material of the present invention can be suitably used for both copy paper type pressure-sensitive recording materials and self-coloring type pressure-sensitive recording materials.

[0050]

EXAMPLES The production examples and examples of the present invention and some comparative examples are shown below. % In Production Examples, Examples and Comparative Examples represents% by weight unless otherwise specified. Production Example-1 (Production of zinc salt of 3-methyl-5-secondary dodecylsalicylic acid) A hard glass made of hard glass having an inner volume of 3,000 ml equipped with a stirrer, a thermometer, a gas inlet, a reflux condenser, and a dropping funnel. Orthocresol in a five-necked flask
620 g (15 mol) and 100 g of activated clay were charged, and the flask was heated with stirring. When the temperature of the content reached 160 ° C., the temperature was maintained, and 840 g of 1-dodecene (5 mol, Purity 99
%) Was added dropwise over 5 hours. After completion of the dropwise addition, the flask was kept at that temperature for 10 hours for aging. When a small amount was sampled and analyzed by gas chromatography, 1-dodecene was almost eliminated. The reaction mixture contained 47.4% of unreacted orthocresol and 28.0% of 2-methyl-4-secondary dodecylphenol.
%, 2-methyl-6-secondary dodecylphenol was 18.6% and 2-methyl-4,6-disecondary dodecylphenol was 6.0%. The reaction mixture was filtered under pressure to remove activated clay. The filtrate was transferred to a 3,000 ml hard glass distiller equipped with a rectification column 30 cm high, 4 cm in diameter and packed with a Raschig ring and containing approximately 1 Torr.
Distill at r vacuum. A fraction at 140 ° -155 ° C. was collected to give about 1,090 grams. Analysis of this fraction by gas chromatography indicated that it was 2-methyl-4
61.8% secondary dodecylphenol and 2
-Methyl-6-secondary dodecylphenol 38.
It was a 2% mixture. Furthermore, the result of analysis by gas chromatography with a capillary column, 2-methyl-4
-Secondary dodecylphenol was found to be a mixture of 5 isomers. These are presumed to be mixtures in which linear dodecyl groups are attached to the phenol nucleus at positions 2, 3, 4, 5 and 6. FIG. 1 shows the temperature-rise type capillary gas chromatogram. In FIG. 1, the peak is a solvent (acetone), the peak is a 4-secondary dodecyl group, a 1-pentylheptyl group, the peak is a 1-butyloctyl group, the peak is a 1-propylnonyl group,
The peak is 1-ethyldecyl group and the peak is 1
-Methylundecyl group, 2-methyl-4-secondary dodecylphenol.

332 g of a fraction collected in a 1,000 ml hard glass five-necked flask equipped with a stirrer, a thermometer, a reflux condenser equipped with a water separator, a gas inlet and a dropping funnel, was prepared. Toluene 15
0 ml was charged and nitrogen gas was blown. Heat the flask with stirring and bring the contents to a boil.
63 grams of an aqueous sodium hydroxide solution was dropped from the dropping funnel. The distilled water was separated by a water separator and dehydrated until no more water distilled. It is mainly the sodium salt of 2-methyl-4-secondary dodecylphenol. The total volume is 500 stainless steel inner volume.
After transferring to a milliliter autoclave and sealing, carbon dioxide gas was blown in at a pressure of 20 kgf / cm ² . By heating the autoclave and raising the temperature of the contents to 150 ° C,
Since carbon dioxide gas was consumed as the reaction proceeded, carbon dioxide gas was replenished so that the pressure inside the autoclave was constantly maintained at 20 kgf / cm ² . After continuing the reaction at 150 ° C. for 5 hours, the content was cooled to 100 ° C., and then depressurized, and the autoclave was opened.

In a 5,000 ml hard glass three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 2,000 ml of water and 5 ml of methanol were added.
00 ml, 200 ml of toluene and the entire contents of the autoclave were charged, and the contents were boiled by heating the flask while stirring. This was transferred to a separating funnel, the separated upper layer oil was removed, and the lower layer was returned to the original flask. Again, 200 ml of toluene was added thereto, and the flask was heated to boiling while stirring and transferred to a separating funnel to remove the upper layer. This operation was repeated once more, and the aqueous layer was returned to the flask.
The reflux condenser was replaced with a distillation port, and the flask was heated to remove the solubilized toluene and methanol, thereby removing the organic solvent. Adjust the pH of the contents with dilute sulfuric acid
When adjusted to, the contents are intermediate 3-methyl-5-
The main component is the sodium salt of secondary dodecylsalicylic acid. 200 ml of toluene and 300 g of a 28% aqueous zinc sulfate solution were added, and the mixture was stirred at 70 ° C. for 30 minutes, and then transferred to a separating funnel to remove an aqueous layer. The oily layer contained about 56% zinc 3-methyl-5-secondary dodecylsalicylate. Comparative Production Example-1 The same operation as in Production Example-1 was carried out except that 560 g (5 mol) of 1-octene was used instead of 840 g of 1-dodecene in Production Example-1, and 3-methyl-5-secondary was used. A zinc octyl salicylate was obtained. Production Example-2 (Production of zinc salt of 3-secondary dodecyl-5-methylsalicylic acid) 1,620 g of paracresol and 100 g of activated clay were placed in a 3,000 ml five-necked flask in the same manner as in Production Example-1. The contents were heated to 160 ° C. while stirring and heating the flask while stirring. While maintaining the temperature, 840 grams of 1-dodecene was dropped from the dropping funnel over 5 hours. Further aged at that temperature for 10 hours,
When a small amount was sampled and analyzed by gas chromatography, it was found that 1-dodecene as a raw material had almost disappeared. The reaction mixture was 44.3% paracresol, 52.4% 2-secondary dodecyl-4-methylphenol, and 3.3% 2,6-disecondary dodecyl-4-methylphenol. The reaction mixture was filtered under pressure to remove the activated clay, then transferred to the same still as in Example 1, and distilled under a vacuum of about 1 Torr. A fraction at 135-155 ° C was collected to give about 1,240 grams. Analysis by gas chromatography indicated that it was almost 100% 2-secondary dodecyl-4-methylphenol. Further, as a result of analysis by gas chromatography equipped with a capillary column, it was confirmed that this was a mixture of five isomers. They are presumed to be those in which the linear dodecyl group is attached to the phenol nucleus at positions 2, 3, 4, 5, and 6.

2-Secondary dodecyl-4 was placed in the same 1,000-ml five-necked flask as in Production Example-1.
-248.5 grams of methylphenol and toluene 2
Then, the contents were boiled by heating the flask while introducing nitrogen gas. Distilled water was removed by a water separator while 83 g of a 60% aqueous potassium hydroxide solution was dropped from the dropping funnel. When the water distills off, it is considered that the formation of the potassium salt of 2-secondary dodecyl-4-methylphenol is completed. Production Example-1
The whole amount was transferred to the same autoclave and sealed, and carbon dioxide gas was blown in at a pressure of 20 kgf / cm ² . When the temperature of the contents was raised to 150 ° C. by heating the autoclave, the reaction proceeded and carbon dioxide gas was consumed. Therefore, carbon dioxide gas was replenished so that the inside of the autoclave was constantly maintained at a pressure of 20 kgf / cm ² . After 10 hours, remove the autoclave
It was cooled to 00 ° C and opened.

2,000 ml of water was placed in a three-necked flask having the same internal volume of 5,000 ml as in Production Example-1.
500 ml of methanol, 200 ml of toluene and the entire contents of the autoclave were charged, and the contents were boiled by heating the flask while stirring.
The contents were transferred to a separatory funnel, the upper layer was removed of oil, and the lower layer was returned to the original flask. 200 ml of toluene was added thereto, and the flask was heated to boiling while stirring, and transferred to a separating funnel to remove the upper layer. This operation was repeated once more. Return the aqueous layer to the flask,
The reflux condenser was attached to the distillation port and the flask was heated.
Toluene and methanol distilled off from the distillation port were removed, and the content was adjusted to pH 7 with dilute sulfuric acid. This content was mainly composed of potassium salt of 3-secondary dodecyl-5-methylsalicylic acid. 250 ml of toluene and 350 g of a 28% aqueous zinc sulfate solution were added, and the mixture was stirred at 70 ° C. for 30 minutes, and then transferred to a separating funnel to remove an aqueous layer. The oily layer contained 56.3% zinc 3-secondary dodecyl-5-methylsalicylate. Production Example-3 (Production of zinc salt of polycyclic nucleus-substituted salicylic acid-1) 2,4-di (α-methylbenzyl) phenol 241 was placed in the same 1,000-ml five-necked flask as in Production Example-1. 0.6 g and 200 ml of toluene were charged, and nitrogen gas was blown therein. Since the content was boiled by heating the flask, 65 g of a 48% aqueous sodium hydroxide solution was dropped from the dropping funnel. Distilled water was removed until no more water was distilled. When the water has ceased to evaporate, the formation of the sodium salt of 2,4-di (α-methylbenzyl) phenol is considered to be completed. The whole amount was transferred to the same autoclave as in Production Example-1, sealed, and then carbon dioxide gas was blown in at a pressure of 20 kgf / cm ² . When the temperature of the contents was raised to 135 ° C. by heating the autoclave, the reaction proceeded and carbon dioxide gas was consumed. Therefore, carbon dioxide gas was replenished so that the inside of the autoclave became 20 kgf / cm ² .
After continuing the reaction at 135 ° C for 4 hours, the contents were brought to 100 ° C.
After cooling, the autoclave was opened.

3,000 ml of water and the entire contents of the autoclave were charged into a 5,000 ml three-necked flask as in Production Example 1, and the contents were boiled by heating the flask while stirring. This was transferred to a separating funnel to remove the separated upper layer oil, and the lower layer was returned to the flask. 200 ml of toluene was added to the mixture, and the flask was heated and boiled while stirring, and was again transferred to a separating funnel to remove the upper layer. This operation was repeated once more. The lower layer was returned to the flask to remove toluene. This was a sodium salt of 3,5-di (α-methylbenzyl) salicylic acid as the main component. Again, 220 ml of toluene and 350 g of a 28% aqueous zinc sulfate solution were added, and the mixture was stirred at 70 ° C. for 30 minutes, and then transferred to a separating funnel to remove the lower aqueous phase. The oil layer contained 59.5% zinc 3,5-di (α-methylbenzyl) salicylate. Production Example-4 (Production of zinc salt of polycyclic nucleus-substituted salicylic acid-2) 2- (α-methylbenzyl) phenol was added to a 1,000-ml five-necked flask in the same manner as in Production Example-1. 8%, 6.5% of 4- (α-methylbenzyl) phenol, 81.6% of 2,4-di (α-methylbenzyl) phenol and 8% of 2,6-di (α-methylbenzyl) phenol 230 g of a 0.1% mixture and 200 ml of toluene were charged and the contents were boiled by heating the flask while blowing in nitrogen gas. The water was removed while 75 g of a 48% aqueous sodium hydroxide solution was dropped from the dropping funnel, and water did not evaporate, so the flask was cooled to 80 ° C. Production Example-1
After transferring to the same autoclave and sealing, carbon dioxide gas was blown in at a pressure of 20 kgf / cm ² and the autoclave was heated to bring the temperature of the contents to 135 ° C. Carbon dioxide gas was consumed as the reaction proceeded, so carbon dioxide gas was replenished so as to maintain a pressure of 20 kgf / cm ² . After keeping at 135 ° C. for 4 hours, the autoclave was cooled to 100 ° C. and opened.

3,000 ml of water and the contents of the autoclave were charged into a three-necked flask having the same internal volume of 5,000 ml as in Production Example 1, and the flask was heated to boiling while stirring. This was transferred to a separating funnel to remove the separated upper oil layer, and the lower aqueous phase was returned to the flask. 200 ml of toluene was added thereto, and the mixture was boiled again with stirring and transferred to a separating funnel to remove the upper layer oil. This operation was repeated once more, and the lower aqueous phase was returned to the flask. Toluene 1
60 ml and 350 g of 28% zinc sulfate were added, and the mixture was stirred at 70 ° C. for 30 minutes and transferred to a separating funnel to remove the lower aqueous phase. The oil layer contains about 55% solids, and the contents of the solids are 4.6% zinc 3- (α-methylbenzyl) salicylate and 7.2% zinc 5- (α-methylbenzyl) salicylate. % And 3,5-di (α
-Methylbenzyl) salicylate was 88.2%. Example-1 (Binary developer composition-1) A toluene solution of zinc 3-methyl-5-secondary dodecylsalicylate obtained in Production Example 1 and 3,5-di obtained in Production Example-3 A mixture of (α-methylbenzyl) zinc salicylate and a toluene solution of zinc salicylate was mixed so that the total solid content was 100 g and the solid content ratio was 40:60.
0, 100 g of an aqueous solution containing 5 g of polyvinyl alcohol having a saponification rate of 98%, 0.1 g of sodium lauryl sulfate and 0.2 g of sodium carbonate, and a homomixer (Special Kika Kogyo Co., Ltd .: Model)
The mixture was emulsified and dispersed in M) and adjusted to a desired particle size. The average particle size of the emulsion containing the organic solvent is 1.1.
Since it was empirically known that the particle diameter after removal of the solvent would be 1.0 micron if the particle diameter was micron, the average particle diameter was adjusted to 1.1 micron here. The average particle diameter was measured by a laser diffraction type particle size distribution analyzer (Shimadzu: SALAD-2000). Stirring machine,
An emulsified dispersion and 80 ml of water were charged into a 500 ml hard glass three-necked flask equipped with a thermometer and a distillation port, and the flask was heated with gentle stirring. Since the contents were boiled and toluene and water were distilled off from the distillation port, condensed toluene was removed and water was returned to the flask. When no more toluene was distilled off, the water was removed to a solids content of 42%. The average particle size of the aqueous dispersion of the developer composition was 0.98 μm. Example-2 (Binary developer composition-2) The toluene solution of zinc 3-methyl-5-secondary dodecylsalicylate used in Example-1 was obtained in Production Example-2. 3-Secondary dodecyl-5 An aqueous dispersion of a developer composition having a solid content of 42% and an average particle diameter of 0.97 micron was obtained in exactly the same manner as in Example 1 except that the toluene solution of zinc methylsalicylate was used. Was. Example-3 (Ternary developer composition-1) A toluene solution of zinc 3-methyl-5-secondary dodecylsalicylate obtained in Production Example-1 and 3,5-diene obtained in Production Example-3 A mixture of (α-methylbenzyl) zinc salicylate and a toluene solution of zinc salicylate was mixed so that the total solid content was 60 g and the solid content ratio was 40 to 60, and 50% of a styrene polymer (Sanyo Chemical Industries, Ltd .: Hymer ST95) was added. 80 grams of a 1% toluene solution was added to make it homogeneous. This was added to 100 g of an aqueous solution containing 3 g of polyvinyl alcohol having a degree of polymerization of 500 and a saponification ratio of 85%, 0.3 g of sodium salt of sulfonated polystyrene and 0.2 g of sodium carbonate, and emulsified and dispersed with a homomixer. Thus, an emulsified dispersion having an average particle diameter of 1.1 μm was obtained. The emulsified dispersion and 80 ml of water were charged into the same three-necked flask having an internal volume of 500 ml as in Example 1, and the solid content was 42% in the same manner as in Example 1.
An aqueous dispersion of the developer composition having an average particle size of 1.01 μm was obtained. Example-4 (Ternary developer composition-2) The toluene solution of zinc 3-methyl-5-secondary dodecylsalicylate used in Example-3 was obtained in Production Example-2. 3-Secondary dodecyl-5 An aqueous dispersion of a developer composition having a solid content of 42% and an average particle size of 1.03 was obtained in exactly the same manner as in Example 3 except that the toluene solution of zinc methyl salicylate was used. . Example-5 (Binary developer composition-3) The intermediate 3-secondary dodecyl-5-methylsalicylic acid potassium salt obtained in the same manner as in Production Example-2 was added to 0.1%.
An aqueous solution containing 25 moles and an aqueous solution containing 0.35 moles of an intermediate sodium salt of 3,5-di (α-methylbenzyl) salicylic acid obtained in the same manner as in Production Example-3 were mixed, and the mixture was stirred. 5,000 with inner volume
In a milliliter beaker, add 7% zinc sulfate aqueous solution
While stirring 0 g, the mixture was slowly dropped. A metathesis reaction occurred simultaneously with the dropwise addition to produce a water-insoluble suspension. When the beaker is gradually heated after dropping to bring the content to 50 to 65 ° C., the suspension in the beaker appears to be in an agglomerated state, so the heating is stopped, the mixture is stirred for 20 minutes, and then cooled. After cooling to 30 ° C. or less, the contents of the beaker were filtered to collect a solid, washed with water and dried. A composition containing, in a solid matter, zinc 3-secondary dodecyl-5-methylsalicylate and zinc 3,5-di (α-methylbenzyl) salicylate in a weight ratio of 1: 1.5. there were.

Sodium dioctyl sulfosuccinate 0.1.
An aqueous solution 35 containing 1 gram, 2.5 grams of polyvinyl alcohol having a degree of polymerization of 500 and a saponification rate of 98%.
0 g and 50 g of the above composition having an internal volume of 1.0
The mixture was charged into a pot of a 00 ml stainless steel sand grinder, added with 600 ml of glass beads having a diameter of 1.5 mm, and then ground at 1,000 rpm for 1 hour. The contents of the pot were sieved through a 60 mesh sieve to remove the glass beads. The resulting suspension of the developer composition has an average particle size of 1.
It was 6 microns, 13.1% solids, thixotropic and viscous. Example-6 (Ternary developer composition-3) Potassium salt of 3-secondary dodecyl-5-methylsalicylic acid as an intermediate obtained in the same manner as in Production Example-2 was prepared as follows.
An aqueous solution containing 2 moles and an aqueous solution containing 1.2 moles of an intermediate sodium salt of 3,5-di (α-methylbenzyl) salicylic acid obtained in the same manner as in Production Example 3 were mixed, and the mixture was stirred. In a 10,000 ml flask with an internal volume of 2.5%
00 g, sodium dioctylsulfosuccinate 0.1 g.
4 grams and hydrogenated petroleum resin (Tonex: ESC
OREZ 5380) Finely pulverized product (100 mesh) 6
While stirring, 00 g was added dropwise while stirring. When the addition is complete, heat the flask to bring the contents temperature to 5
0 to 60 °. The content became agglomerated, and was stirred at this temperature for 20 minutes. The flask was cooled and filtered to collect the solid. Wash it with water and dry it for about 1,
450 grams of solids were obtained. This solid comprises 28 mg of zinc 3-secondary dodecyl-5-methylsalicylate.
6%, 30.7% zinc 3,5-di (α-methylbenzyl) salicylate, and 40% ESCOREZ5380.
The composition contained 7%.

2,000 g of an aqueous solution containing 50 g of polyvinyl alcohol having a degree of polymerization of 500 and a saponification ratio of 98%, 30 g of sodium salt of sulfonated polystyrene, 1.0 g of sodium lauryl sulfate and 1.4 g of sodium carbonate. And 1,400 grams of the composition pulverized to 200 mesh were added and dispersed.

The dispersion was subjected to a pressure shock type homogenizer (Nippon Seiki Seisakusho, NPH-100) at a temperature of 150.
By treating at a temperature of 800 ° C. and a pressure of 800 kgf / cm ² , an aqueous dispersion of the developer composition having an average particle diameter of 1.1 μm was obtained. The solid content of this aqueous dispersion was 42.7%. Example-7 to Example-16 (Ternary developer composition) The zinc 3-secondary dodecyl-5-methylsalicylate obtained in Production Example-2, the polycyclic nucleus-substituted zinc salicylate, and the organic polymer compound were used. Using this, a developer composition aqueous dispersion was prepared in the same manner as in Example-3, and the average particle diameter was adjusted to 1.0.
The micron, solids content was adjusted to 42%. The composition is shown in the table below.

The percentages in parentheses in the following table are the percentages by weight of the polycyclic nucleus-substituted zinc salicylate used and the percentages by weight of the organic polymer compound, and the remainder from 100% is 3-secondary dodecyl-5-methyl. % By weight of zinc salicylate.
The examples in the column of polycyclic nucleus-substituted salicylate show production examples of the used polycyclic nucleus-substituted zinc salicylate, and the columns of organic polymer compounds show the trade names and product numbers of the used ones. * 1: Hydrogenated C5 petroleum resin registered by Tonex * 2: Hydrogenated C5 petroleum resin registered by Tonex * 3: Hydrogenated modified alicyclic hydrocarbons registered by Tonex * 4: Idemitsu Petrochemical Company Registered trademark partially hydrogenated petroleum resin * 5: Idemitsu Petrochemical Company registered trademark Partially hydrogenated petroleum resin * 6: Idemitsu Petrochemical Company registered trademark Fully hydrogenated petroleum resin * 7: Mitsui Petrochemical Industry Co., Ltd. Polystyrene * 8: Mitsui Petrochemical Co., Ltd. registered trademark α-methylstyrene polymer * 9: Tosoh Corporation, registered trademark petroleum resin Example-17 (Composite binary developer composition) 3- obtained in Production Example-2 Secondary toluene dodecyl-5-methylsalicylate zinc solution in toluene and ESCORE
A 50% toluene solution of Z5380 was mixed so that the solid content ratio was 55:45 and the total solid content was 100 g, and in the same manner as in Example-8, the solid content was 42%, and the average particle size was 0.1 g. An aqueous dispersion of the composition which was 75 microns was obtained.
Next, a 60% toluene solution of zinc 3,5-di (α-methylbenzyl) salicylate and a 50%
A toluene solution having a solid content ratio of 55:45 and a total solid content of 10
The resulting mixture was mixed to give 0 g, and an aqueous dispersion of a composition having a solid content of 42% and an average particle diameter of 0.72 μm was obtained in the same manner as in Example-13. Further, the two aqueous dispersions were mixed at a ratio of 1: 1.5 to complete a composite aqueous developer composition aqueous dispersion. Example-18 (Binary developer composition) A toluene solution of zinc 3-secondary dodecyl-5-methylsalicylate obtained in Production Example-2 and a product obtained by adding 2.3 mol of styrene to 1 mol of salicylic acid 50 of zinc salt
% Toluene solution and a solids weight ratio of 40:60 and a total solids content of 100 grams, and the same as in Example 1, having a solids content of 42% and an average particle diameter of 40%. An aqueous dispersion of the developer composition measuring 1.03 microns was obtained. Example -19 (Binary developer composition) Toluene solution of zinc 3-secondary dodecyl-5-methylsalicylate obtained in Production Example 2 and 2.2 mol of benzyl chloride and 1.2 mol of styrene in 1 mol of salicylic acid A 50% toluene solution of the zinc salt of the product obtained by reacting the moles is reacted with the solids at a weight ratio of 40:60 and a total solids content of 100%.
The aqueous dispersion of the developer composition having a solid content of 42% and an average particle diameter of 1.00 micron was obtained in the same manner as in Example-1. Example -20 (Examples of zinc and other metals) Toluene solution of zinc 3-secondary dodecyl-5-methylsalicylate obtained in Production Example-2, Intermediate 3 obtained in the same manner as in Production Example-2 -Secondary dodecyl-5-
A 60% toluene solution of nickel 3-secondary dodecyl-5-methylsalicylate produced by metathesis from an aqueous solution of potassium methylsalicylate and an aqueous solution of nickel chloride, and 3,5-di (α-methylbenzyl) obtained in Production Example-3 A toluene solution of zinc salicylate was mixed so that the weight ratio of the solid content was 40:10:50 and the total solid content was 100 g, and the solid content was 42% and the average particle size was the same as in Example-1. Was 0.97 microns to obtain an aqueous dispersion of the developer composition. Comparative Example-1 A solid solution having a solid content of 42% was prepared in the same manner as in Example-5, except that the toluene solution of 3-methyl-5-secondary zinc dodecylsalicylate obtained in Production Example-1 had a solid content of 100 g.
An aqueous dispersion of a developer having an average particle size of 0.97 microns was obtained. Comparative Example-2 A solid solution having a solid content of 42% was prepared in the same manner as in Example 1, except that 100 g of a solid solution of the toluene solution of zinc 3-secondary dodecyl-5-methylsalicylate obtained in Production Example-2 was used.
An aqueous dispersion of a developer having an average particle size of 1.02 microns was obtained. Comparative Example-3 A solid solution having a solid content of 42% was prepared in the same manner as in Example-5, except that the toluene solution of zinc 3,5-di (α-methylbenzyl) salicylate obtained in Production Example-3 was equivalent to 100 g of solid content. ,
An aqueous dispersion of a developer having an average particle diameter of 1.04 μm was obtained. Comparative Example-4 A mixture of zinc 3- (α-methylbenzyl) salicylate, zinc 5- (α-methylbenzyl) salicylate and zinc 3,5-di (α-methylbenzyl) salicylate obtained in Production Example-4 An aqueous dispersion of a developer having a solid content of 42% and an average particle diameter of 0.99 micron was obtained in the same manner as in Example 5 except that the solid content of the toluene solution was 100 g. Comparative Example-5 60 grams of a toluene solution of zinc 3-secondary dodecyl-5-methylsalicylate obtained in Production Example-2 and FTR0100 (α-methylstyrene polymer) 4
A 50% toluene solution containing 0 g was treated in the same manner as in Example 7 to obtain an aqueous dispersion of a developer composition having a solid content of 42% and an average particle size of 1.01 μm. Comparative Example-6 Except that the zinc salt of 3-methyl-5-secondary octylsalicylate obtained in Comparative Production Example 1 was used instead of the zinc salt of 3-methyl-5-secondary dodecylsalicylate in Production Example-1 An aqueous dispersion of the developer composition was obtained in the same manner as in Example-1. Example -21 An aqueous suspension or dispersion of the developer composition obtained in Examples -1 to -20 and the developer or developer obtained in Comparative Examples -1 to -5 Using the aqueous dispersion of the colorant composition, a paint was prepared with the following composition. Light calcium carbonate (50% aqueous suspension) 85 g as solids polyvinyl alcohol (Wako Pure Chemical Industries, Ltd .: degree of polymerization 500) 〃 5 g carboxy-modified SBR latex (Sumitomo Dow: SN-307) １０ 10 g sodium polyacrylate ( Reagent) ０．１ 0.1 g Water was added to this to make the total amount 210 g. To this, an aqueous dispersion of the color developer or the color developer composition is added so that the total amount of the nuclear-substituted zinc salicylate therein becomes 6 g, and further water is added so that the total amount of the paint becomes 370 g. did. This was mixed well to finish the paint for the color developer layer.

Next, the paint was uniformly applied to the surface of plain paper and dried to obtain a weight increase of 4.5 to 4.7 grams per square meter of paper. Apply this coated surface to a mini super calender (Yuri Roll Machine Co., Ltd .: IS
C-167) to finish the color developer layer.

The resulting developer layer and the dye layer of the upper paper having a dye layer made of commercially available CVL are printed so as to face each other,
The following tests were performed to evaluate the properties of the color developer layer.

(1) Coloring property: The density of a recorded image was visually determined by printing with an electric typewriter.

2 Color development at low temperature: Density of a recorded image was visually observed and determined one minute after printing with an electric typewriter in a refrigerator at -20 ° C.

3 Light fastness of white paper: The developed surface was set at a right angle to the sun on a sunny day in June, exposed for 8 hours, printed with an electric typewriter, and the density of the recorded image was compared with the unexposed one. Visual comparison was made.

4 Lightfastness of Print: The printed test piece was exposed to the sun on a sunny day in June for 8 hours so that its surface was at a right angle, and the degree of fading of the recorded image was visually determined.

5 Water resistance of blank paper: The developed surface was exposed to running water at 25 ° C. for 30 minutes, dried and printed, and the density of the recorded image was visually observed and judged.

6 Water resistance of printing: The developed surface immediately after printing was 2
After exposure to running water at 5 ° C. for 30 minutes, the density of the recorded image or the degree of bleeding was visually observed and judged.

7 Moisture resistance of white paper: 90 ° C, 90 °
% For 24 hours, dry and print.
The density of the recorded image was visually observed and determined.

8 Moisture resistance of printed image:
It was left for 24 hours at 90 ° C. and 90% humidity, and the degree of fading of the recorded image was visually observed and determined.

9 Heat resistance of blank paper: Developed surface at 70 ° C. 24
After standing for a while, printing was performed and the density of the recorded image was visually observed and determined.

10 Plasticizer resistance of printing: Three sheets of commercial polyvinyl chloride wrap containing a plasticizer were placed on a recorded image left for 24 hours after printing, and a load of 200 g per square centimeter was applied thereon. Contact 25
After standing in a room at room temperature for one week, the degree of fading or bleeding of the recorded image was visually observed and judged.

The rating evaluated was expressed on a 5-point scale, with 5 being very good, 4 being fairly good, 3 being standard, 2 being slightly poor and 1 being very poor. Table 2 shows the results. Example-22 Developer or developer composition obtained in Example-3, Example-4, Example-6, Example-7, Example-20 and Comparative examples -1 to -5. Using a water suspension or dispersion of the product, the paint was finished in exactly the same manner as the paint for the developer layer of Example-20. This is uniformly coated on a dye layer of upper paper using a commercially available CVL as a dye so that the weight increase after drying is 4 to 4.5 g per square meter, and then dried to develop a self-coloring type. Finished the surface. The developed surface was printed by an electric typewriter without using an ink ribbon, and the characteristics of the self-coloring type pressure-sensitive recording material were tested. The test methods 1 to 10 of the characteristic evaluation items and the results were very similar to those of Example 21 and were omitted, and evaluation items 11 of the characteristic test unique to the self-coloring type pressure-sensitive recording material were omitted.
Table 3 shows the results for Nos. 1 to 15.

The test method was as described above, and the evaluation was based on a 5-point method. 5: No contamination is observed. 4:
Slightly contaminated but slight. 3: Slight contamination is observed but practically acceptable. 2: Pollution is a major problem. 1: Pollution is severe and lacks practicality.

[0075]

As can be understood from the results of Examples -1 to -20, all of the developer compositions of the present invention are smoothly pulverized or emulsified and dispersed using water as a medium.
It has been found that an aqueous dispersion suitable for application in paints is obtained, indicating that this industrial implementation is easy.

Further, as can be judged from Examples 21 and 22, the developer composition of the present invention, as compared with Comparative Examples, is particularly superior in light resistance of white paper, light resistance of printing, water resistance of printing and printing. In various properties of the pressure-sensitive recording material such as the plasticizer resistance, a remarkable well-balanced improvement effect was observed. In particular, in light fastness of printing, the developer composition of the present invention in which monocyclic and polycyclic nucleus-substituted zinc salicylate are used in combination is better than the comparative example using nucleus-substituted zinc salicylate alone as a developer component. The results obtained demonstrate the excellent synergistic effect of the present invention.

Further, as can be seen from Table 3, the developer composition of the present invention can be suitably used not only for a copying paper type pressure-sensitive recording material but also for a self-coloring type pressure-sensitive recording material. Can be said to be the effect of the present invention.

[0078]

[Brief description of the drawings]

FIG. 1 is a gas chromatogram of a heated capillary column of 2-methyl-4-secondary dodecylphenol obtained in Production Example-1. The vertical axis indicates the retention time (minutes), and the horizontal axis indicates the peak height.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Tomoyuki Tanemura 1-10-24 Itikaichi, Ibaraki-shi, Osaka

Claims (11)

[Claims] 1. A pressure-sensitive recording material utilizing a color development reaction between an electron-donating colorless dye and an electron-accepting color developing agent, wherein the color developing agent is represented by the general formula (1): ## STR1 ## [In the formula (1), one of R ₁ and R ₂ represents a methyl group,
The other is of the general formula (2) で In the formula (2), n is an integer of 1 to 5, takes at least two or more values, and the total number of carbons is 12. Represents｝. M represents a polyvalent metal atom, and m represents the valence of M. ]
Characterized by containing a polyvalent metal salt of 3-methyl-5-secondary dodecylsalicylic acid or 3-secondary dodecyl-5-methylsalicylic acid and a polyvalent metal salt of a polycyclic nucleus-substituted salicylic acid represented by A developer composition for pressure recording materials. 2. The polycyclic nucleus-substituted salicylic acid is 3- (α
-Methylbenzyl) salicylic acid, 5- (α-methylbenzyl) salicylic acid, 3,5-di (α-methylbenzyl)
At least one selected from salicylic acid, a reaction product of addition reaction of styrene with salicylic acid, a reaction product of salicylic acid with benzyl chloride and styrene, or a copolycondensation reaction product of salicylic acid and phenol with formaldehyde. Item 4. The developer composition for a pressure-sensitive recording material according to Item 1. 3. The method according to claim 2, wherein the polycyclic nucleus-substituted salicylic acid is 3,5-
The developer composition for a pressure-sensitive recording material according to claim 1, which is di (α-methylbenzyl) salicylic acid. 4. The developer according to claim 1, wherein said 3-methyl-5-secondary dodecylsalicylic acid or 3-secondary dodecyl-
4. The composition according to claim 1, comprising 10 to 90% by weight of the polyvalent metal salt of 5-methylsalicylic acid and 90 to 10% by weight of the polyvalent metal salt of the polycyclic nucleus-substituted salicylic acid. A developer composition for pressure recording materials. 5. The method according to claim 1, wherein the developer is 3-methyl-5-secondary dodecylsalicylic acid or 3-secondary dodecyl-
It is characterized by containing a polyvalent metal salt of 5-methylsalicylic acid, a polyvalent metal salt of the above-mentioned polycyclic nucleus-substituted salicylic acid, and an organic polymer compound mainly composed of hydrocarbon and having a molecular weight of 300 to 50,000. Developer composition for pressure-sensitive recording materials. 6. The developer according to claim 1, wherein said 3-methyl-5-secondary dodecylsalicylic acid or 3-secondary dodecyl-
The polyvalent metal salt of 5-methylsalicylic acid and the polyvalent metal salt of the polycyclic nucleus-substituted salicylic acid are in a total amount of 20 to 95% by weight and mainly composed of the above hydrocarbon and having a molecular weight of 300
The developer composition for a pressure-sensitive recording material according to claim 5, further comprising 80 to 5% by weight of an organic polymer compound having a molecular weight of from 50,000 to 50,000. 7. The organic polymer compound mainly comprising a hydrocarbon is at least one selected from a styrene polymer, an α-methylstyrene polymer, a styrene / α-methylstyrene copolymer or a petroleum resin. 7. The developer composition for a pressure-sensitive recording material according to 6. 8. The method according to claim 1, wherein the polyvalent metal salt is a zinc salt.
A developer composition for a pressure-sensitive recording material according to claim 6. 9. The developer composition for a pressure-sensitive recording material according to claim 1, which is dissolved in an organic solvent which is practically insoluble in water, and emulsified and dispersed in water containing a dispersant. The average particle diameter obtained by removing the organic solvent by distillation is 0.3.
Aqueous dispersion of the composition which is between 5 and 5 microns. 10. An average particle diameter obtained by emulsifying and dispersing the developer composition for a pressure-sensitive recording material according to claim 1 in water containing a dispersant under heating, followed by cooling and solidification, wherein the average particle diameter is 0. .
An aqueous dispersion of the composition which is 3 to 5 microns. 11. An aqueous dispersion of the developer composition for a pressure-sensitive recording material according to claim 1, or an aqueous dispersion of the developer composition for a pressure-sensitive recording material according to claim 9. A pressure-sensitive recording material characterized by the following.