JP3119515B2 - Developer composition, aqueous dispersion thereof, and pressure-sensitive recording sheet manufactured using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a developer composition, an aqueous dispersion thereof, and a pressure-sensitive recording sheet produced by using the same. The present invention relates to a pressure-sensitive recording sheet having excellent properties such as light resistance of a recorded image and water resistance of a recorded image, a color developer composition providing those properties, and an aqueous dispersion having good storage stability of the color developer composition. .

[0002]

2. Description of the Related Art A pressure-sensitive recording sheet is disclosed in U.S. Pat.
No. 07, No. 2800457 and No. 3418250
As described in the specification, it is composed of a combination of an electron-donating colorless dye (hereinafter referred to as “dye”) solution and an electron-accepting compound (hereinafter referred to as “developer”). When the microcapsules enclosing the dye solution are destroyed by pressure, the dye solution and the developer come into contact with and react with each other to form a color, and a recording image corresponding to the pressure is obtained. It is widely known as paper.

As a developer for a pressure-sensitive recording sheet, an inorganic compound represented by activated clay, a polycondensate of formaldehyde of para-substituted phenol and a polyvalent metal salt of nucleus-substituted salicylic acid (Japanese Patent Application Laid-Open No. 51-1979) No. 25174, 62-19
No. 486, No. 62-17687, No. 62-17838
7, JP-A-62-178388 and JP-A-1-14551
No. 89) has already been put to practical use, and the present invention relates to a polyvalent metal salt of a nuclear-substituted salicylic acid.

A polyvalent metal salt of a nuclear-substituted salicylic acid is generally hardly soluble or insoluble in water, and is particularly excellent in high color density and stable recorded image as compared with other color developers. Has been widely put into practical use. Conventionally, this type of developer is finely pulverized in water with a fine grinding medium such as a ball mill, attritor or sand grinder,
After dispersing, it is common to use such a method that a necessary paint such as an inorganic pigment, a clay mineral, an adhesive, a dispersant or an antifoaming agent is added to prepare a paint. For this reason, the developer is preferably ground as small as possible, and the polyvalent metal salt of the nuclear-substituted salicylic acid is selected to have a relatively high softening point so as to be easily ground, and the softening point is further reduced. Even the presence of such contaminants as to reduce it was disliked.

[0005]

However, it has been known that such an organic developer having a high softening point generally has the following two drawbacks.

(1) The reaction between an inorganic color developer and a dye solution is said to be a surface adsorption reaction, and the color development reaction is usually extremely rapid. On the other hand, since the color developing reaction proceeds while the organic color developer is dissolved in the dye solution, the color development speed is determined by the dissolution speed of the color developer in the dye solution. The dissolution rate is related to the size of the developer particles, the molecular weight of the components constituting the developer, the solubility of the developer in the dye solution, the softening point of the developer, and other conditions. If constant, the dissolution rate will be lower if the softening point of the developer is higher. Therefore, with a developer having a high softening point, it takes a long time from the destruction of the microcapsules due to the pressure until the density or the color tone of the color image becomes constant. This tendency is problematic because the lower the temperature, the slower the change in color density is considered as the instantaneous color development at low temperatures, and the slower the change in color tone is particularly the case with multiple mixed dyes. Is a problem with the black coloration of

(2) Since a developer having a high softening point or a high melting point is softened or melted at a heating temperature for drying a coating on a substrate and does not adhere to itself, particles of the developer are adhered to the substrate. A slightly more adhesive is needed to fix.
In addition, this tendency becomes more remarkable as the particles of the color developer are made finer for the purpose of improving the color density or the instantaneous color developability. In many cases, the purpose is not sufficiently achieved due to the color development inhibiting action of the adhesive.

A first object of the present invention is to improve the color developing speed of a pressure-sensitive recording sheet at a low temperature, and to provide a stable aqueous dispersion of a developer composition which can achieve this object. It is. The second object is to further improve the color density of the recording of the pressure-sensitive recording sheet, the light fastness of the recorded image and the water fastness of the recorded image by examining and limiting the polyvalent metal salt of the nuclear-substituted salicylic acid. .

[0009]

According to the present invention, a compound represented by the general formula (1):

[0010]

Embedded image (Wherein, R ₁ and R ₂ are each a tertiary butyl group,
A tertiary mil group, a tertiary octyl group, an isononyl group, or an isododecyl group, at least one of R ₁ and R ₂ is an isononyl group or an isododecyl group, M is a polyvalent metal atom, and n is a polyvalent metal atom. Indicates valence. )
97 to 80% by weight of a nuclear-substituted salicylic acid polyvalent metal salt represented by the following formula:

[0011]

Embedded image (Wherein, R ₃ and R ₄ each represent a hydrogen atom or an alkyl group, and the total number of carbon atoms is from 8 to 24). A developer composition, an aqueous dispersion characterized in that the developer composition is dispersed in water, and a paint prepared using the aqueous dispersion applied to a substrate and dried. A pressure-sensitive recording sheet characterized by being finished is provided.

This pressure-sensitive recording sheet is found to have particularly remarkable improvements in the recording color density, the recording color development speed at low temperatures, the light fastness of the recorded image, and the water fastness of the recorded image. The aqueous dispersion of the composition is also sufficiently stable without increasing the viscosity or aggregating during long-term storage.

The developer composition of the present invention is non-crystalline,
It has a relatively low softening point, and it is difficult to finely pulverize it in water using a medium as in the prior art to make it suitable for application to a pressure-sensitive recording sheet. However, a new technique for dispersing a developer in water has been established (Japanese Patent Laid-Open No. 62-241549).
Nos. 63-173680 and 64-34782), it is possible to make fine particles suitable for application to a pressure-sensitive recording sheet even if the developer has a considerably low softening point. Together, they make the present invention valuable.

R ₁ and R ₂ in the general formula (1) are a tertiary butyl group, a tertiary mil group, a tertiary octyl group, an isononyl group or an isododecyl group, respectively.
At least one of R ₁ and R ₂ is an isononyl group or an isododecyl group. However, the isononyl group is defined as a propylene trimer (isononene), and the isododecyl group is defined as a group formed by adding a propylene tetramer (isododecene) to the core of salicylic acid. R ₁ and R ₂ are particularly limited because they give good results on the color developer or the light fastness of the recorded image.

The total number of carbon atoms of R ₁ and R ₂ is 1
If it is 2 or less, the water resistance of the recorded image of the obtained pressure-sensitive recording sheet is not sufficient, and if it is 25 or more, the color developing ability of the color developer is reduced by being diluted by the large substituent, and the sufficient color density becomes insufficient. Although it is limited to 13 to 24 for the reason that it cannot be obtained, any combination of R ₁ and R ₂ does not deviate from this range in the definition of R ₁ and R _{2 in} the general formula (1).

In the present invention, the reason that at least one of R ₁ and R ₂ is an isononyl group or an isododecyl group is that the polyvalent metal salt of the nucleus-substituted salicylic acid is non-crystalline, and the color density of recording is high. Also, a stable aqueous dispersion of the developer composition can be obtained. As is already known, both propylene trimer and propylene tetramer are a mixture of a large number of isomers, and the nucleus-substituted salicylic acid added to the core of salicylic acid is also a collection of a large number of isomers. This is also considered to be the cause of the non-crystallinity, and is particularly preferable for the purpose of the present invention. Incidentally, it does not contain isononyl group or isododecyl group 3,
The polyvalent metal salt of 5-ditertiaryoctylsalicylic acid has a total of 16 carbon atoms in the substituents, but has strong crystallinity and cannot be used alone to obtain a stable aqueous dispersion. Has low color density and poor practicality.

M in the general formula (1) is a polyvalent metal atom, and specific preferred examples include magnesium, aluminum, calcium, cobalt, nickel, zinc, strontium, tin and cerium, and most preferably. Zinc.

Of the polyvalent metal salts of the nucleus-substituted salicylic acid represented by the general formula (1), preferred examples of the present invention include zinc 3-tert-butyl-5-isononylsalicylate and 3-isononyl- Zinc 5-tert-butylsalicylate, 3-tert-butyl-5-isododecylsalicylate, 3-isododecyl-5-zinc tert-butylsalicylate, 3-tertiaryoctyl-5-isononylzinc-salicylate, 3-isononyl- Zinc 5-tertiaryoctyl salicylate or zinc 3,5-diisononyl salicylate;
Zinc diisononyl salicylate. This is selected for reasons such as good light fastness and water fastness, high color density, or the most economical production. All of these zinc salts of the nuclear-substituted salicylic acid are non-crystalline and are suitable for preparing a stable aqueous dispersion. Further, it is very suitable for the purpose of the present invention because it has good miscibility with the alkylphenol represented by the general formula (2). Further, they alone provide a pressure-sensitive recording sheet having excellent light fastness and water fastness of a recorded image as a developer.

R ₃ and R ₄ in the general formula (2) each represent a hydrogen atom or an alkyl group, and the total number of carbon atoms is 8
To 24. Preferred specific examples of the alkyl group include a methyl group, an ethyl group, an isopropyl group, a secondary butyl group, a tertiary butyl group, a tertiary mil group, a secondary hexyl group, a secondary octyl group, a tertiary octyl group, an isononyl group, and an isododecyl group. Is mentioned. Alkylphenols having a total number of carbon atoms of R ₃ and R ₄ of less than 8 have relatively high volatility, and may evaporate slightly when the pressure-sensitive recording sheet is dried, possibly causing contamination of the drying zone of the coater. It is not preferable. Alkyl phenols having a total of 25 or more carbon atoms of R ₃ and R ₄ naturally have a large molecular weight and a large viscosity.
The contribution of the present invention to the improvement of the color development speed at low temperatures is small.

Preferred examples of the alkylphenol represented by the general formula (2) for the purpose of the present invention include:
2,4-di-tert-butyl phenol, 2-secondary octyl phenol, 4-secondary octyl phenol, 2-tert-octyl phenol, 4-tert-octyl phenol, 2-tert-octyl phenol Methyl-4-secondary octyl phenol, 2-secondary octyl-4-methyl phenol, 2-methyl-4-tert-sharyoctyl phenol, 2-t-sharyoctyl-4-methyl phenol, 2- Isononylphenol, 4-isononylphenol, 2-methyl-4-isononylphenol, 2
-Isononyl-4-methylphenol, 2-secondary-octyl-4-ethylphenol, 2-tert-sharyoctyl-4-ethylphenol, 2,4-di-tert-amylphenol, 2-secondary-decylphenol, 4
-Secondary decylphenol, 2-isopropyl-4
-Tert-octylphenol, 2-tert-octyl-4-isopropylphenol, 2-tert-butyl-4-tert-octylphenol, 2-tert-octyl-4-tert-butylphenol, 2-
Isododecylphenol, 4-isododecylphenol, 2-methyl-4-isododecylphenol, 2-isododecyl-4-methylphenol, 2-tert-butyl-4-isononylphenol, 2-isononyl-4
-Tert-butylphenol, 2-tert-butyl-4-isododecylphenol, 2-isododecyl-4
-Tert-butylphenol, 2,4-ditertiooctylphenol, 2-tertiooctyl-4-isononylphenol, 2-isononyl-4-tertiooctylphenol, 2,4-diisononylphenol, 2-tertiooctyl-4-iso Dodecylphenol, 2-isododecyl-4-tertiooctylphenol, 2-isononyl-4-isododecylphenol, 2-isododecyl-4-isononylphenol or 2,4-diisododecylphenol, and more preferably 4- Isononylphenol, 2-isododecylphenol, 4-isododecylphenol, 2-tert-butyl-4-isononylphenol, 2-isononyl-4-tert-butylphenol, 2-tert-butyl-4-iso Decyl phenol, 2-isododecyl-4-tert-butylphenol, 2,4-ditertiary-octylphenol, 2-tertiary-octyl-4-isononylphenol, 2-isononyl-4
Tertiary octyl phenol, 2,4-diisononyl phenol, 2,4-diisododecyl phenol and the like can be mentioned.

Most preferably, it is 2,4-diisononylphenol, which is low in volatility, has good miscibility with the nucleus-substituted zinc salicylate, has a large effect of improving the color-forming speed, and is most economical. However, the fact that they are the same as the raw materials obtained by the method of synthesizing the most preferred core-substituted salicylic acid Kolbeschmidt cannot be regarded as an industrial advantage. These alkyl phenols have good miscibility with the polyvalent metal salt of the nucleus-substituted salicylic acid represented by the general formula (1), and a completely uniform composition can be obtained. In addition, these compounds have an effect of improving the color-forming speed at low temperature with the smallest addition amount, and furthermore, the inhibitory effect on the color-forming ability of the polyvalent metal salt of the nuclear-substituted salicylic acid is minimized. It is suitable.

For the purpose of improving the long-term storability of the pressure-sensitive recording sheet, an antioxidant called a hindered phenol is sometimes added to the polyvalent metal salt of the nuclear-substituted salicylic acid. Equation (3)

[0023]

Embedded image (Wherein R ₅ , R ₆ and R ₇ represent an alkyl group or an aralkyl group) and are usually phenolic compounds or polyphenolic compounds which improve the color-forming speed at low temperatures. In addition to its poor effect, it has a large inhibitory effect on the color-forming ability of polyvalent metal salts of nuclear substituted salicylic acids,
Therefore, it cannot be used in a large amount like the alkylphenol of the general formula (2) used in the present invention.

In some cases, a formaldehyde polycondensate of an alkylphenol is added to a polyvalent metal salt of a nuclear-substituted salicylic acid.

[0025]

Embedded image Wherein R ₈ is an alkyl group, an aralkyl group or an aryl group, and m represents the degree of polymerization. These are phenol compounds represented by the following formulas, which inhibit the color-forming ability of a polyvalent metal salt of a nuclear-substituted salicylic acid. Although the effect is small, the effect of improving the coloring speed at low temperatures is hardly observed. For the above reasons, the effects of the alkylphenol of the general formula (2) used in the present invention can be clearly distinguished from these phenol compounds.

In general, the rate of color development at low temperatures is closely related to the rate of dissolution of a color developer in a dye solution. In the present invention, while trying to solve the problem by emphasizing the relationship between the softening point of the color developer and the dissolution rate in the dye solution, the dissolution rate, besides, the color development on the surface of the pressure-sensitive recording sheet Agent particle size,
Since the amount of the developer used per unit area or the type and amount of the adhesive used to fix the developer is also affected, the preferable range of the softening point of the developer is determined centrally. I can't. Therefore, the determination of the quantitative ratio between the polyvalent metal salt of the nuclear-substituted salicylic acid and the alkylphenol in the developer composition cannot be determined only from the softening point. If the particles of the developer composition are small and the amount used per unit area is large, even if the amount of alkylphenol is small, the effect of improving the color development rate at low temperatures is large, and the lower limit is 3% by weight of alkylphenol and nuclear-substituted salicylic acid. Of the polyvalent metal salt of 97% by weight. or,
Under the same conditions, the higher the ratio of alkylphenol added, the lower the softening point of the developer composition, and the color development speed at low temperatures alone can be improved to any extent. Is not preferable because it causes the following three problems. (1) The color developing ability per unit weight of the color developing composition is reduced due to the dilution effect of the alkylphenol. (2) Yellowing of the pressure-sensitive recording sheet due to nitrogen oxides increases. (3) The long-term storage stability of the aqueous dispersion at a high temperature is reduced because the softening point of the developer composition is too low.

For this reason, the upper limit for the addition of the alkylphenol is a weight ratio of 20% by weight of the alkylphenol and 80% by weight of the polyvalent metal salt of the nuclear-substituted salicylic acid. Also, preferably, the polyvalent metal salt of the nuclear-substituted salicylic acid is in the range of 95 to 85% by weight and the alkylphenol is in the range of 5 to 15% by weight.

In addition to the polyvalent metal salt of a nuclear-substituted salicylic acid and an alkyl phenol, a polymer compound for the purpose of further increasing water resistance, and an ultraviolet absorber for the purpose of further improving light resistance, For the purpose of improving the heat resistance, the composition may contain an antioxidant and other polyvalent metal salts of nucleus-substituted salicylic acid as long as the object of the present invention is not impaired.

The method for producing a nuclear-substituted salicylic acid includes a synthesis method by an addition reaction of salicylic acid or a salicylic acid ester and an olefin as described in JP-A-54-160335, etc .; There is a reaction between salt and carbon dioxide, a so-called Kolbe-Schmidt synthesis method. For the purpose of the present invention, a nuclear-substituted salicylic acid obtained by any of the synthesis methods can be used. According to the former synthesis method, the nucleus-substituted salicylic acid obtained from salicylic acid or salicylic acid ester as a raw material contains almost no phenolic component. On the other hand, the latter synthesis method is a reaction for generating an alkali metal salt of a nuclear-substituted salicylic acid from an alkali metal salt of a nuclear-substituted phenol and carbon dioxide, and it is already known that this is an equilibrium reaction. Therefore, if an attempt is made to obtain a nuclear-substituted salicylic acid by this method, the content of unreacted nuclear-substituted phenol cannot be avoided as it is. It is very convenient that this unreacted nucleus-substituted phenol is in agreement with the preferred alkylphenol of the general formula (2) used in the present invention, but its content is determined by the nucleus content in the developer composition of the present invention. It exceeds the preferred amount of alkylphenol relative to the polyvalent metal salt of the substituted salicylic acid. In producing the nuclear-substituted salicylic acid used in the present invention, it is difficult to adjust the amount of the unreacted nuclear-substituted phenol or alkylphenol to a preferable range for the purpose of the present invention by this known synthesis method. is there. Therefore, when obtaining a nuclear-substituted salicylic acid by this synthesis method, unreacted substances are removed by means such as an extraction method or mixed with a nuclear-substituted salicylic acid containing no alkylphenol to adjust the amount of alkylphenol. Must.

Since the developer composition of the present invention has a relatively low softening point, it is difficult to finely pulverize using a medium to obtain particles suitable for application to a pressure-sensitive recording sheet. It is. JP-A Nos. 62-241549 and 63-173
In JP-A-680 and JP-A-64-34782, a developer containing a polyvalent metal salt of a nuclear-substituted salicylic acid as a main component is dissolved in an organic solvent, and this is emulsified and dispersed in water, and then the organic solvent is distilled off. A method for producing an aqueous dispersion of a coloring agent is disclosed. The developer composition of the present invention is obtained by such a method.
Most preferably, it is used as an aqueous dispersion dispersed in water at a particle size suitable for application to a pressure-sensitive recording sheet.

An inorganic pigment, a clay mineral, an adhesive, a dispersant, an antifoaming agent, and the like are added to an aqueous dispersion of the developer composition of the present invention to prepare a paint, which is applied and fixed on a substrate. Finish the color developing surface of the pressure-sensitive recording sheet.

[0032]

EXAMPLES In order to further clarify the present invention, specific examples and comparative examples will be described. In the examples, what is simply described as percent means percent by weight.

Example 1 2-tert-butyl was placed in a 10-liter hard glass four-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser capable of azeotropically separating water. -4-isononylphenol (hydroxyl number 20
3.1) 4,976 grams (18 moles) and 3,600 grams of toluene were charged. The contents were boiled by heating the flask while stirring. 48% sodium hydroxide aqueous solution 1,500 from dripping funnel
Grams (18 moles) when the temperature of the flask contents is 110
The solution was slowly dropped so that the temperature did not fall below ℃. During this time,
The water separated by the reflux condenser was appropriately removed. After the addition of the aqueous sodium hydroxide solution was complete, salt formation was terminated when water was no longer separated in the reflux condenser (the amount of water removed so far is about 1,050 grams).
After dehydration, the contents of the flask were transferred to a stainless steel autoclave having an internal volume of 10 liters. Oh
The temperature of the contents of the reactor was 170 ° C., and the reaction was carried out at a carbon dioxide gas pressure of 20 kgf / cm ² for 3 hours. The reaction mixture contained 69 mole percent sodium 3-tert-butyl-5-isononylsalicylate and 31 mole percent sodium salt of the unreacted 2-tert-butyl-4-isononylphenol. Was.

Comparative Example 1-1 One-third of the reaction mixture of the autoclave obtained in Example 1 was mixed with a stirrer, a thermometer and a reflux condenser and made of a hard-glass three-neck having a capacity of 5 liters. The mixture was transferred to a flask, 1 liter of a 10% aqueous solution of sodium sulfate was added, and the contents were heated to 80 ° C. while stirring. Unreacted 2-tert-butyl-
The sodium salt of 4-isononylphenol was decomposed into sodium carbonate or sodium hydrogencarbonate and 2-tert-butyl-4-isononylphenol by the action of the remaining carbon dioxide and the added water. If this is transferred to a separatory funnel and allowed to stand, an aqueous solution of sodium sulfate and sodium carbonate or sodium bicarbonate is present in the lower layer, and sodium 3-tert-butyl-5-isononylsalicylate and 2-tert-butyl-4- are present in the upper layer. A toluene solution of isononylphenol separated. The lower layer aqueous solution was removed, and the upper layer was again transferred to a 5 liter three-necked flask, and stirred, and a 36% zinc sulfate aqueous solution 1,
680 grams (7.5 equivalents) were added. The flask was heated while stirring, and the temperature of the contents was maintained at 80 ° C. for 1 hour to complete the double decomposition. When this was transferred to a separating funnel and allowed to stand, the lower layer was a mixed aqueous solution of excess zinc sulfate and sodium sulfate formed by metathesis, and the upper layer was zinc 3-tert-butyl-5-isononylsalicylate and 2-tert-butyl-. Separated as a toluene solution of 4-isononylphenol. The weight ratio of the two in the toluene solution was 73.5% and 26.5% by weight.
The aqueous solution in the lower layer was removed and the upper
Transferred to a liter stainless steel beaker, 2,500 grams of an aqueous solution containing 30 grams of a copolymer of 92 mole percent acrylamide and 8 mole percent butyl acrylate and 3 grams of sodium carbonate was added. Subsequently, a homomixer model M (manufactured by Tokushu Kika Kogyo Co., Ltd.) was operated at a rotation speed of 8,500 times per minute for 35 minutes to perform an emulsification dispersion operation of the contents of the beaker. By this operation, the average particle size of the dispersoid was adjusted to 1.1 microns.
Add 1,000 grams of water to this dispersion, stirrer,
The mixture was transferred to a hard glass three-necked flask having an internal volume of 10 liters equipped with a thermometer and a distillation port. The flask was heated while stirring the contents, and toluene and water were taken out from the distillation port. Toluene was completely removed from the contents, and the amount of water removed was adjusted so that the content of non-volatile components in the contents was 40 percent. The aqueous dispersion thus obtained had an average particle size of the dispersoid of 0.97 micron, and the finally measured zinc 3-tert-butyl-5-isononylsalicylate and 2-tert-butyl-4-isobutyl were used. The amount ratio of nonylphenol was 72.8 percent and 27.2 percent.

Comparative Example 1-2 The next third volume of the autoclave reaction mixture obtained in Example 1 was mixed with a 5 liter hard glass bottle equipped with a stirrer, thermometer and reflux condenser. Comparative Example 1
-1 was treated in exactly the same way. Stirring a mixed toluene solution of sodium 3-tert-butyl-5-isononylsalicylate and 2-tert-butyl-4-isononylphenol in the upper layer, a thermometer, a reflux condenser, and an inner volume with a liquid outlet at the bottom It was transferred to a 30 liter hard glass flask and 15 liters of water, 7 liters of methanol and 1 liter of n-octane were added. The flask was heated with stirring to bring the temperature of the contents to 80 ° C. 8
The stirring was stopped at 0 ° C., and the mixture was allowed to stand. The oil phase was separated in the upper layer and the aqueous phase was separated in the lower layer. The aqueous phase was set aside in another container, and the oil phase was removed. The aqueous phase was returned to the same flask, 1 liter of n-octane was added, and the mixture was stirred at 80 ° C., and then allowed to stand to remove the oil phase. When this operation was repeated three more times, the aqueous phase contained almost no 2-tert-butyl-4-isononylphenol. The aqueous phase was returned to the same flask, and the reflux condenser was replaced with a distillation port to distill off methanol and dissolved or solubilized n-octane. 1,300 grams of toluene and 36
1,680 grams (7.5 equivalents) of a percent aqueous zinc sulfate solution was added and stirred at 80 ° C. for 1 hour. When this was allowed to stand, a toluene solution of zinc 3-tert-butyl-5-isononylsalicylate separated into the upper layer. The upper layer toluene solution was transferred to a stainless steel beaker having an internal volume of 10 liters, and an aqueous solution containing 22 g of the acrylamide-butyl acrylate copolymer used in Comparative Example 1-1 and 2.2 g of sodium carbonate 1,900 was used. Grams were added. Subsequently, Comparative Example 1-1 was performed using the homomixer model M.
In the same manner as in the above, an emulsified dispersion having an average particle size of the dispersoid of 1.1 μm was obtained. To this dispersion, 730 g of water was added, and an aqueous dispersion having a nonvolatile component content of 40% was obtained in the same manner as in Comparative Example 1-1. The average particle size of the dispersoid of this dispersion was 0.99 micron, and 3-tert-butyl-5-
Zinc isononyl salicylate and 2-tert-butyl-4
The amount ratio of -isononylphenol was 98.8% and 1.2%.

Example 1-1 The last third of the autoclave reaction mixture obtained in Example 1 was treated in the same manner as in Comparative Example 1-2 to give 3-tert-butyl-5-isononylsalicylic acid. A toluene solution of zinc was obtained. To this, 150 g of 2-tert-butyl-4-isononylphenol was added and transferred to a stainless steel beaker having an internal volume of 10 liters, and 25 g of the acrylamide-butyl acrylate copolymer used in Comparative Example 1-1 and carbonic acid 2,100 grams of an aqueous solution containing 2.5 grams of sodium was added. Subsequently, an emulsified dispersion having an average particle size of the dispersoid of 1.1 μm was obtained using the homomixer M in the same manner as in Comparative Example 1-1. 800 g of water was added to this dispersion to obtain an aqueous dispersion having a nonvolatile component content of 40% in the same manner as in Comparative Example 1-1. The average particle size of this dispersion is 1.00 micron, and the quantitative ratio of zinc 3-tert-butyl-5-isononylsalicylate to 2-tert-butyl-4-isononylphenol is 87.
9 percent and 12.1 percent.

Example 2 The 2-tert-butyl-4-isononylphenol used in Example 1 was converted to 2-isononyl-4-tert-butylphenol (hydroxyl value: 202.6) 4,976.
An autoclave reaction mixture was obtained in exactly the same manner as in Example 1 except that the amount was changed to gram (18 mol). The resulting reaction mixture contained 67.5 mole percent sodium 3-isononyl-5-tert-butylsalicylate and 32.5 mole percent unreacted sodium salt of 2-isononyl-4-tert-butylphenol. It had been.

Comparative Example 2-1 One-third of the autoclave reaction mixture obtained in Example 2 was treated in exactly the same manner as in Comparative Example 1-1 to obtain an aqueous dispersion containing 40% of nonvolatile components. I got The resulting aqueous dispersion has an average particle size of the dispersoid of 0.96 microns,
The amount ratio of zinc 3-isononyl-5-tert-butylsalicylate to 2-isononyl-4-tert-butylphenol was 71.1 percent and 28.9 percent.

Comparative Example 2-2 One-third of the autoclave reaction mixture obtained in Example 2 was treated in exactly the same manner as in Comparative Example 1-2 to obtain an aqueous dispersion containing 40% of non-volatile components. I got The resulting aqueous dispersion has an average particle size of the dispersoid of 0.98 microns,
The amount ratio of zinc 3-isononyl-5-tert-butylsalicylate to 2-isononyl-4-tert-butylphenol was 99.0 percent and 1.0 percent.

Example 2-1 One-third of the autoclave reaction mixture obtained in Example 2 was replaced with 2-tert-butyl-4-isononylphenol used in Example 1-1. 4-
Except that 150 g of tertiary butyl phenol was used, the same treatment as in Example 1-1 was carried out to obtain an aqueous dispersion having a nonvolatile component content of 40%. The resulting aqueous dispersion had an average particle size of the dispersoid of 0.99 μm, and contained 3-isononyl-5-tert-butylsalicylate zinc and 2-
The amount ratio of isononyl-4-tert-butylphenol was 87.1 percent and 12.9 percent.

Example 3 130 g of zinc 3-tert-butyl-5-isododecylsalicylate and 20 g of 2-tert-butyl-4-isododecylphenol were dissolved in 120 g of toluene, and 1 liter of hard glass was used. Into a tall beaker. To this was added 320 grams of an aqueous solution containing 4.5 grams of a copolymer of 94 mole percent acrylamide and 6 mole percent butyl acrylate and 0.3 gram of sodium carbonate. Of 1.15 microns. 250 g of water was added thereto, and the mixture was transferred to a 2-liter hard glass three-necked flask equipped with a stirrer, a thermometer, and a distillation port. The flask was heated with stirring to remove toluene and water from the distillation port. Toluene was completely removed from the flask, and the amount of water was adjusted so that the amount of the non-volatile components in the dispersion in the flask became 40 percent. The resulting aqueous dispersion had an average particle size of the dispersoid of 0.94 micron, and zinc 3-tert-butyl-5-isododecylsalicylate and 2
The ratio by weight of tert-butyl-4-isododecylphenol was 85.9% to 14.1%.

Example 4 A solution of 140 grams of zinc 3-isododecyl-5-tert-butylsalicylate, 10 grams of 2-isododecyl-4-tert-butylphenol and 120 grams of toluene was treated exactly as in Example 3 to obtain a non-volatile solution. An aqueous dispersion having a component amount of 40% was obtained. This dispersion had an average particle size of the dispersoid of 0.93 μm, and the amount ratio of zinc 3-isododecyl-5-tert-butylsalicylate to 2-isododecyl-4-tert-butylphenol was 9%.
3.1 percent and 6.9 percent.

Example 5 130 grams of zinc 3-tert-octyl-5-isononylsalicylate and 20 grams of 2-tert-octyl-4-isononylphenol were treated exactly as in Example 3 to determine the amount of non-volatile components. Gave a 40% aqueous dispersion. This dispersion had an average particle size of the dispersoid of 0.99 microns, and the ratio by weight of zinc 3-tert-octyl-5-isononylsalicylate to 2-tert-octyl-4-isononylphenol was 86.1% 13. 0.9%.

Example 6 140 grams of zinc 3-isononyl-5-tert-octylsalicylate and 10 grams of 2-isononyl-4-tert-octyloctyl phenol were prepared in exactly the same manner as in Example 4 and the water content of non-volatile components was 40 percent. A dispersion was obtained. This dispersion had an average particle size of the dispersoid of 0.95 micron, and the amount ratio between zinc 3-isononyl-5-tert-octylsalicylate and 2-isononyl-4-tert-octyloctylphenol was 93.4% and 6. 6 percent.

Example 7 In a 10-liter hard glass four-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 2,740 g (18 mol) of methyl salicylate and 50 parts of trifluoromethanesulfonic acid were added. Grams were charged. Heat the flask while stirring to raise the temperature of the contents to 60 ° C.
And 460 g (43.2 mol) of propylene trimer (isononene) was added dropwise from the dropping funnel in about 10 hours. The temperature in the flask was appropriately adjusted to 60 ° C. because there was some heat generation during the dropwise addition. 5 hours after dropping 6
It was kept at 0 ° C. and then cooled. In a 50 liter stainless steel reactor equipped with a stirrer, thermometer, gas inlet, reflux condenser and liquid outlet at the bottom, 10,000 grams of methanol and 1,520 grams of a 50% aqueous sodium hydroxide solution were placed. (19 mol)
Was added, and the reaction mixture in the above flask was further added. The reactor was heated while stirring, so that the contents were slowly boiled. After about 6 hours, the saponification reaction of the contents was completed. Here, 20,000 grams of water was added to the reactor, and the reflux condenser was replaced with a distillation port, from which methanol, excess isononene and water were azeotropically removed in a carbon dioxide gas atmosphere. When the temperature of the contents reaches 97 ° C., the distillation operation is stopped, the temperature of the contents is reduced to 80 ° C. or less, and then toluene 8,8
2,000 grams and 200 grams of sodium sulfate,
The temperature of the contents was again raised to 80 ° C. while stirring. After one hour, stop the stirrer and let it stand still.
Sodium diisononyl salicylate solution in toluene
An aqueous solution of sodium sulfate, sodium hydrogen carbonate, methanol and a small amount of sodium 5-isononylsalicylate separated in the lower layer. The lower aqueous solution is removed, and
10,000 grams of a 5% sodium sulfate aqueous solution was added, and the mixture was stirred at 80 ° C. for 1 hour and allowed to stand again to remove the aqueous solution. Next, 6,000 grams (22.3 equivalents) of a 30 percent aqueous solution of zinc sulfate was added to the reactor and added.
The mixture was stirred at 2 ° C. for 2 hours and then allowed to stand. A toluene solution of zinc 3,5-isononylsalicylate was separated in the upper layer, and an aqueous solution of sodium sulfate and excess zinc sulfate was separated in the lower layer.
The toluene solution in the upper layer had a non-volatile component amount of 48.2%, and the non-volatile component composition was 96.6% zinc 3,5-diisononylsalicylate, 2.9% zinc 5-isononylsalicylate, and , 5-diisononylphenol was 0.2 percent and unknown was 0.3 percent.

Comparative Example 7-1 300 grams of the toluene solution obtained in Example 7 was charged into a 1-liter tall beaker, and 3 grams of a copolymer of 93 mole percent of acrylamide and 7 mole percent of butyl acrylate and sodium carbonate were added. 250 g of an aqueous solution containing 0.3 g was added, and the mixture was emulsified and dispersed using a homomixer model M such that the average particle size of the dispersoid became 1.2 μm. 150 g of water was added thereto, and the mixture was transferred to a 1-liter three-necked flask equipped with a stirrer, a thermometer, and a distillation port. The flask was heated while stirring to remove toluene and water from the distillation port, and the removal amount was adjusted so that the amount of nonvolatile components in the dispersion was 40%. The resulting aqueous dispersion had an average particle size of the dispersoid of 0.95 μm, and the amount ratio of zinc 3,5-diisononylsalicylate to 2,4-diisononylphenol was 9%.
9.5 percent and 0.5 percent.

Example 7-1 300 g of the toluene solution obtained in Example 7 and 2,2
Comparative Example 7-1 15 g of 4-diisononylphenol
And treated in the same manner as in Comparative Example 7-1 to obtain an aqueous dispersion having a nonvolatile component content of 40%. This dispersion had an average particle size of the dispersoid of 1.
01 micron and the quantitative ratio of zinc 3,5-diisononylsalicylate to 2,4-diisononylphenol is 90.
0 percent and 10.0 percent.

Example 7-2 A non-volatile compound was treated in the same manner as in Example 7-1 except that 15 grams of 2,4-diisononylphenol used in Example 7-1 was replaced with 15 grams of 4-isononylphenol. An aqueous dispersion was obtained in which the amount of the water-soluble component was 40%. This dispersion has an average particle size of the dispersoid of 0.97 microns,
The ratio by weight of zinc 3,5-diisononylsalicylate to alkylphenol was 90.4 percent and 9.6 percent. The breakdown of alkylphenol was 96% of 4-isononylphenol and 4% of 2,4-diisononylphenol.

Example 7-3 The procedure of Example 7-1 was repeated, except that 15 grams of 2,4-diisononylphenol used in Example 7-1 was replaced with 15 grams of 4-isododecylphenol. An aqueous dispersion having a nonvolatile content of 40% was obtained. This dispersion had an average particle size of the dispersoid of 0.94 microns and the ratio by weight of zinc 3,5-diisononylsalicylate to alkylphenol was 90.3% to 9.7%. The breakdown of alkylphenol was 96.2% of 4-isododecylphenol and 3.8% of 2,4 diisononylphenol.

Example 7-4 300 g of the toluene solution obtained in Example 7, 2,4
-10 grams of diisononylphenol and styrene and α
-Methylstyrene copolymer (average degree of polymerization: about 10) 1
0 g was treated in exactly the same manner as in Example 7-1 to obtain an aqueous dispersion having a nonvolatile component content of 40%. This dispersion had an average particle size of the dispersoid of 1.02 microns,
The amount ratio of zinc 5-diisononylsalicylate to 2,4-diisononylphenol was 93.1 percent and 6.9 percent.

Example 8 4,4-Diisononylphenol 4,160 was placed in a 10-liter hard glass four-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser capable of separating water. Grams (12 moles) and xylene 3,5
The flask was heated while stirring and the contents were boiled. 960 grams (12 moles) of a 50 percent aqueous sodium hydroxide solution was added dropwise from the dropping funnel.

The water separated by the reflux condenser is appropriately removed,
When the temperature of the contents is 1
The temperature was adjusted so as not to be lower than 45 ° C. During this time, the water separated by the reflux condenser was appropriately removed. After the addition of the aqueous sodium hydroxide solution was completed, if the water was no longer separated in the reflux condenser (the amount of water removed so far was about 880 grams), the dehydration operation was completed. This was transferred to a stainless steel autoclave having an internal volume of 10 liters, and a carbon dioxide gas pressure of 20 kgf / cm ² at 160 ° C.
The reaction was performed for 3 hours under the conditions described above. The reaction mixture contained 72 mole percent sodium 3,5-diisononylsalicylate and 28 mole percent unreacted sodium salt of 2,4-diisononylphenol. Stirring machine,
Water 5,000 was placed in a 20-liter hard glass flask with a thermometer, reflux condenser, and a liquid outlet at the bottom.
Grams and the entire amount of the autoclave reaction mixture were charged, and the flask was heated with stirring to bring the contents to 85 ° C. After stirring at 85 ° C. for 1 hour, the mixture was allowed to stand, and the xylene solution of sodium 3,5-diisononylsalicylate and 2,4-diisononylphenol was separated in the upper layer, and the aqueous solution of sodium hydrogen carbonate was separated in the lower layer. After removing the lower layer, 2% aqueous sodium sulfate solution
Then, the mixture was stirred at 85 ° C. for 30 minutes and allowed to stand again to remove the lower aqueous solution. Next, 3,800 grams (about 14 equivalents) of a 30% aqueous zinc sulfate solution was added, and the mixture was stirred at 85 ° C. for 2 hours and allowed to stand. Since the liquid separated into two layers, the lower aqueous solution was removed. The upper layer was a xylene solution having a nonvolatile content of 58.0 percent and containing zinc 3,5-diisononylsalicylate and 2,4-diisononylphenol in a ratio by weight of 75.7 percent to 24.3 percent. .

Comparative Example 8-1 300 g of the xylene solution obtained in Example 8 was treated in exactly the same manner as in Comparative Example 7-1 to obtain an aqueous dispersion having a nonvolatile content of 40%. This dispersion had an average particle size of the dispersoid of 1.05 microns, and the ratio by weight of zinc 3,5-diisononylsalicylate to 2,4-diisononylphenol was 75.1% to 24.9%.

Comparative Example 8-2 220 g of the xylene solution obtained in Example 8, 40 g of a copolymer of styrene and α-methylstyrene, and 40 g of xylene were uniformly dissolved. Exactly the same treatment was performed to obtain an aqueous dispersion having a nonvolatile content of 40%. This dispersion had an average particle size of the dispersoid of 0.96 micron, and the amount ratio of zinc 3,5-diisononylsalicylate to 2,4-diisononylphenol was 7%.
5.3 percent and 24.7 percent.

Example 8-1 140 g of the xylene solution obtained in Example 8 and 160 g of the toluene solution obtained in Example 7 were mixed.
Thereafter, the same treatment as in Comparative Example 7-1 was carried out to obtain an aqueous dispersion having a nonvolatile component of 40%. This dispersion has an average particle size of the dispersoid of 0.93 micron, and the quantitative ratio of zinc 3,5-diisononylsalicylate to 2,4-diisononylphenol is 87.2% and 12.8%. Was a cent. Example 9 (test of storage stability) Comparative Example 1-1, Comparative Example 1-2, Example 1-1, Comparative Example 2
-1, Comparative Example 2-2, Example 2-1, Example 3, Example 4, Example 5, Example 6, Comparative Example 7-1, Example 7-
1. Take 80 grams each of the aqueous dispersions obtained in Example 7, Example 7-2, Example 7-3, Example 7-4, Comparative Example 8-1, Comparative Example 8-2, and Example 8-1. Into a 0.1 liter flask. The flask was fitted with a stirrer having blades 2 cm long and 1 cm wide so that it could be kept airtight except for the connection to the atmosphere through a cooling pipe. Each flask was immersed in a 35 ° C. bath and agitated at a rate of 500 revolutions per minute. While maintaining this state for one week, the viscosity of the dispersion was measured. The viscosities of the initial dispersions were all between 15 and 35 centipoise. If the viscosity after one week is 50 centipoise or less, the storage stability is ◎, if the viscosity is 50 to 100 centipoise, ○, if the viscosity is 100 to 500 centipoise, and if the viscosity is 500 centipoise or more, the result is indicated by ×. And are shown in Table 1. Example 10 (Evaluation of pressure-sensitive copying paper) Preparation of developer coating solution Comparative Example 1-1, Comparative Example 1-2, Example 1-1, Comparative Example 2
-1, Comparative Example 2-2, Example 2-1, Example 3, Example 4, Example 5, Example 6, Comparative Example 7-1, Example 7-
1, 40% aqueous dispersions of the developers obtained in Example 7-2, Example 7-3, Example 7-4, Comparative Example 8-1, Comparative Example 8-2, and Example 8-1 Using, 18 types of developer coating liquids were prepared according to the following formulations.

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

Production of developer for pressure-sensitive recording paper The developer coating solution obtained above was applied to one side of a base paper of 40 g / m ^{2 at} a dry weight of 4 g / m ² , dried and dried.
Various kinds of color developing paper for pressure-sensitive recording paper were obtained.

A quality evaluation test was performed on the 18 types of color-developed paper for pressure-sensitive recording paper obtained as described above in accordance with the following method. Table 1 shows the results.

[0059] dissolving crystal violet lactone in the manufacture alkylation naphthalene above paper, coated with the oily liquid so that 4g / m ² by dry weight of the microcapsules the coating liquid prepared by microencapsulation on one surface of woodfree paper Then, it was dried to obtain the upper paper.

Low-Temperature Color Forming Test The color- developed paper and the upper paper obtained as described above were left in an atmosphere of 0 ° C. for 10 hours. Thereafter, the coated surfaces of the color-developed paper and the upper paper are opposed to each other, and the color is developed by a drop-type color tester (weight: 150 g, height: 15 cm) in an atmosphere of 0 ° C., and then struck with a Macbeth reflection densitometer. The color density was measured 10 seconds after the pressure (the larger the value, the better).

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

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

Photo-yellowing The developing paper obtained as described above was exposed to sunlight for 2 days, and the degree of yellowing of the developing layer was visually evaluated. The evaluation criteria were as follows: ◎: little yellowing was observed; ：: slight yellowing was observed; Δ: yellowing was considerably observed.

[0065]

[Table 1]

[0066]

The pressure-sensitive recording paper of the present invention is excellent in color density, low-temperature recording color-forming speed, recorded image light fastness and water fastness, and the aqueous dispersion of the present invention can withstand long-term storage.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Eiji Kawabata 1-110-24, Itikaichi, Ibaraki-shi, Osaka Inside the Sanko Development Research Institute, Inc. (72) Masato Tanaka 4-3-1 Jokoji, Amagasaki-shi, Hyogo No. Kanzaki Paper Co., Ltd. Kanzaki Mill (72) Inventor Toshio Kimura 4-3-1 Jokoji, Amagasaki City, Hyogo Prefecture Kanzaki Paper Co., Ltd. Kanzaki Mill (56) References JP-A-60-107384 (JP, A) JP-A-60-72786 (JP, A) JP-A-56-75892 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B41M 5/124-5/165

Claims (18)

(57) [Claims] 1. A compound of the general formula (1) (Wherein, R ₁ and R ₂ are each a tertiary butyl group,
A tertiary mil group, a tertiary octyl group, an isononyl group, or an isododecyl group, at least one of R ₁ and R ₂ is an isononyl group or an isododecyl group, M is a polyvalent metal atom, and n is a polyvalent metal atom. Indicates valence. )
97 to 80% by weight of a polyvalent metal salt of a nuclear-substituted salicylic acid represented by the general formula (2): (Wherein, R ₃ and R ₄ each represent a hydrogen atom or an alkyl group, and the total number of carbon atoms is from 8 to 24). Developer composition. 2. 95 to 85% by weight of a polyvalent metal salt of a nuclear-substituted salicylic acid represented by the general formula (1), and 5 to 15 alkylphenols represented by the general formula (2).
The developer composition according to claim 1, wherein the developer composition comprises a weight percentage. 3. The developer composition according to claim 1, wherein the polyvalent metal M is zinc. 4. R ₁ in the above general formula (1) and R ₃ in the above general formula (2) are the same group, and R 1 in the above general formula (1)
_4. The developer composition according to claim 1, wherein R _{2 in the} formula and R ₄ in the formula (2) are the same group. 5. The polyvalent metal salt of a nucleus-substituted salicylic acid represented by the above general formula (1) is zinc 3-tert-butyl-5-isononyl salicylate, zinc 3-isononyl-5-tert-butyl salicylate, -Tert-butyl-5-
Zinc isododecyl salicylate, 3-isododecyl-5
Zinc tert-butyl salicylate, zinc 3-tert-octyl-5-isononyl salicylate, zinc 3-isononyl-5-tert-octyl salicylate and 3,5-
4. The developer composition according to claim 1, wherein the developer composition is selected from the group consisting of zinc diisononylsalicylate. 6. The polyvalent metal salt of a nuclear-substituted salicylic acid represented by the above general formula (1) is zinc 3,5-diisononylsalicylate, and the alkylphenol represented by the above general formula (2) is 2,4- The developer composition according to claim 1, 2, 3, 4, or 5, which is diisononylphenol. 7. An aqueous dispersion, wherein the developer composition according to claim 1 is dispersed in water. 8. An aqueous dispersion, wherein the color developer composition according to claim 2 is dispersed in water. 9. An aqueous dispersion, wherein the developer composition according to claim 3 is dispersed in water. 10. An aqueous dispersion, wherein the color developer composition according to claim 4 is dispersed in water. 11. An aqueous dispersion, wherein the developer composition according to claim 5 is dispersed in water. 12. An aqueous dispersion, wherein the color developer composition according to claim 6 is dispersed in water. 13. A pressure-sensitive recording sheet, characterized in that a paint prepared using the aqueous dispersion according to claim 7 is applied to a substrate and dried to finish. 14. A pressure-sensitive recording sheet, characterized in that a paint prepared using the aqueous dispersion according to claim 8 is applied to a substrate and dried to finish. 15. A pressure-sensitive recording sheet, characterized in that a paint prepared using the aqueous dispersion according to claim 9 is applied to a substrate and dried to finish. 16. A pressure-sensitive recording sheet, characterized in that a coating prepared using the aqueous dispersion according to claim 10 is applied to a substrate and dried to finish. 17. A pressure-sensitive recording sheet, characterized in that a paint prepared using the aqueous dispersion according to claim 11 is applied to a substrate and dried to finish. 18. A pressure-sensitive recording sheet, characterized in that a paint prepared using the aqueous dispersion according to claim 12 is applied to a substrate and dried to finish.