JP3107854B2 - Process for producing 3,5-di (α-methylbenzyl) salicylic acid derivative and use of polyvalent metallized product as color developer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a novel process for producing a 3,5-di (α-methylbenzyl) salicylic acid derivative useful as a color developer for pressure-sensitive copying paper or thermal paper and a polyvalent metal compound thereof. It relates to the developer contained.

[0002]

2. Description of the Related Art In general, salicylic acid compounds as color developers for pressure-sensitive paper and thermal paper are excellent in clarity of a color image and storage stability. On the other hand, in the pressure-sensitive paper, the color development speed is delayed due to lack of compatibility with the capsule oil in which the colorless dye is dissolved, and the water resistance is poor, such as the disappearance of the color image with water. Various attempts have been made. For example, a method has been proposed in which an aromatic substituent or the like is introduced into a salicylic acid skeleton to compensate for the above-mentioned disadvantage.

(1) As a method for producing 3,5-disubstituted salicylic acid, there is known a method for producing from a corresponding substituted phenol and carbon dioxide by a Kolbe-Schmitt reaction. For example, 3,5-di (α, α-dimethylbenzyl) salicylic acid disclosed in JP-B-49-10856 can be obtained from phenol and α-methylstyrene.
It is manufactured using di (α, α-dimethylbenzyl) phenol as a raw material. However, this method requires a long reaction step,
In addition to the drawback that the yield is low, the introduction of a carboxyl group involves a disadvantage that the reaction is generally carried out under high temperature and high pressure, resulting in high cost.

(2) There has been an attempt to produce a similar salicylic acid compound for the purpose of overcoming such a problem in production cost. For example, there is an alkylation reaction of salicylic acid or salicylic acid ester.

[0005] One mole of salicylic acid is reacted with 2 moles of 1-phenylethanol to give 5- [α-methyl-4- (α-
Methylbenzyl) -benzyl] salicylic acid or 3,5
Method for obtaining a mixture with -di (α-methylbenzyl) salicylic acid (Japanese Patent Application Laid-Open No. 61-100493, 62-9644)
9) is known. In this method, the substituted salicylic acid is produced as various mixtures, and is separated as a metal salt of a mixture with the mono-substituted salicylic acid or the di-substituted salicylic acid by a complicated operation. When used as a coloring agent, there is a problem that it is difficult to obtain reproducibility in quality such as color development performance and storage stability of a color developing sheet.

(3) A method of obtaining a di-substituted salicylic acid by reacting a styrene compound with salicylic acid using an organic sulfonic acid or an inorganic acid as a catalyst in the presence of an aliphatic carboxylic acid has been proposed (JP-A-2-91043). ).

[0007] In this case, 90-
Since the reaction is carried out at 130 ° C. and the amount of the acid used is 50% by weight or more based on salicylic acid, the treatment of this waste acid is also a problem and is not an industrially advantageous method. In this method, the reaction product is, for example, 3,5-di (α-methylbenzyl) salicylic acid and 3-α-methylbenzyl-5-
(1,3-diphenylbutyl) salicylic acid and 3-
It is a mixture of (1,3-diphenylbutyl) -5-α-methylbenzylsalicylic acid. When such a reaction product is used as a developer for pressure-sensitive paper, there is a problem similar to (2).

(4) For the alkylation reaction of salicylic acid alkyl ester, for example, styrene is reacted with methyl salicylate in the presence of alkanesulfonic acid to give 3,5
A method for obtaining methyl-di (α-methylbenzyl) salicylate is known (JP-B-61-26772). In this method, since styrene is used, various polymers of styrene and other by-products are generated. This method is similar to the method for producing a salicylate resin disclosed by the present inventors in Japanese Patent Application Laid-Open No. 1-133780, and even when the catalyst, the molar ratio of salicylate to styrene, the reaction temperature, etc. are changed, It is not possible to suppress the side reaction to be changed.

Example 4 of Japanese Patent Publication No. 61-26772
In Comparative Example 1 to be described later, the selectivity of methyl 3,5-di (α-methylbenzyl) salicylate was 43%. This is because a styrene polymer, a dimer adduct, and the like are formed in addition to the formation of the mono-substituted product and the tri-substituted product.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a 3,5-di (α) which is excellent as a color developer and has excellent color-forming performance and light yellowing resistance.
-Development of an economical process for producing a (-methylbenzyl) salicylic acid derivative and a color developing agent using the same, and a color developing composition having improved water stability and especially low temperature color developing properties of a color image. It is in.

[0011]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have reacted salicylic esters with α-methylbenzyl halides in the presence of an acid catalyst to give 3,5- The inventors have found a method of producing a di (α-methylbenzyl) salicylate and then hydrolyzing to obtain a 3,5-di (α-methylbenzyl) salicylate derivative.

In this case, prior to the hydrolysis, the reaction product is subjected to vacuum distillation to separate 3,5-di (α-methylbenzyl) salicylate, whereby 3,3 having a purity of 99% or more is obtained. A 5-di (α-methylbenzyl) salicylic acid derivative can be obtained.

Further, the salicylic esters and α-
Methylbenzyl halides are reacted in the presence of an acid catalyst, and the reaction product is hydrolyzed to obtain 3,5-di (α-
60-90% by weight of methylbenzyl) salicylic acid derivative
It has been found that the above object can be achieved by using a polyvalent metallized product of an α-methylbenzyl group-substituted salicylic acid derivative composition as a color developer.

That is, the present invention provides the following: (1) General formula (I)

[0015]

Embedded image (Wherein, R ₁ represents an alkyl group, an aralkyl group or a cycloalkyl group having 1 to 12 carbon atoms) represented by the general formula (II)

[0016]

Embedded image Wherein R ₂ and R _{3 each} represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents a halogen atom, in the presence of an acid catalyst. Characterized in that the resulting 3,5-di (α-methylbenzyl) salicylate is hydrolyzed.
A method for producing a 5-di (α-methylbenzyl) salicylic acid derivative, and (2) obtained by hydrolyzing a reaction product of the above reaction,
A metallized α-methylbenzyl group-substituted salicylic acid derivative composition containing 60 to 90% by weight of a 3,5-di (α-methylbenzyl) salicylic acid derivative, and a color developing sheet using the same as a color developer. is there.

The salicylates used in the present invention include methyl salicylate, ethyl salicylate, n-propyl salicylate, isopropyl salicylate, isoamyl salicylate, tert-octyl salicylate, nonyl salicylate, dodecyl salicylate, cyclohexyl salicylate, benzyl salicylate, and benzyl salicylate. -Α-methylbenzyl and the like, but are not limited thereto. Industrially preferably inexpensive methyl salicylate,
And ethyl salicylate.

Examples of the kind of halogen in the α-methylbenzyl halides used in the present invention include chlorine and bromine, but chlorine is preferred. Accordingly, α-methylbenzyl halides include α-methylbenzyl chloride, o-methyl-α-methylbenzyl chloride,
p-methyl-α-methylbenzyl chloride, m-methyl-α-methylbenzyl chloride, o-ethyl-α-
Methylbenzyl chloride, p-ethyl-α-methylbenzyl chloride, p-isopropyl-α-methylbenzyl chloride, 2,3-dimethyl-α-methylbenzyl chloride, 2,4-dimethyl-α-methylbenzyl chloride, 2, Examples include, but are not limited to, 5-dimethyl-α-methylbenzyl chloride, 3,4-dimethyl-α-methylbenzyl chloride, and the like. Of these, α-methylbenzyl chloride and p-methyl-α-methylbenzyl chloride are preferred.

The amount of the various α-methylbenzyl halides used in the production method of the present invention is preferably 1.5 to 3 mol, more preferably less than 1.5 mol, per mol of the salicylic acid ester represented by the above general formula (I). Alternatively, the use of more than 3 moles is not preferred because the production rate of 3,5-di (α-methylbenzyl) salicylate, which is the main target precursor, is reduced.

The acid catalyst used in this reaction is, for example, a Lewis acid type catalyst such as ferric chloride, zinc chloride, aluminum chloride, stannic chloride, titanium tetrachloride, boron trifluoride, etc. Fluoroalkanesulfonic acids such as trifluoromethanesulfonic acid and Nafion H (trade name Du) as perfluoroalkanesulfonic acid resin
Pont) can be used. Among them, zinc chloride is particularly preferred.

The amount of the catalyst to be used is in the range of 0.05 to 200 mol%, preferably 0.1 to 100 mol%, based on salicylic acid esters in view of economy.

The reaction temperature ranges from 0 to 180 ° C., preferably from 5 to 80 ° C., more preferably from 10 to 180 ° C.
40 ° C. The reaction time is usually 1 to 120 hours.

In the reaction between salicylic esters and α-methylbenzyl halides, a solvent may be used if necessary. As the solvent, those inert to the reaction, for example, 1,2
Halogenated hydrocarbons such as dichloroethane and 1,1,2-trichloroethane, and organic acids such as acetic acid and propionic acid can be used. When these solvents are used, the ratio is preferably 30 (volume / weight) or less in consideration of the economical efficiency of the raw material.

In the present invention, a general method for reacting a salicylic acid ester with an α-methylbenzyl halide is as follows: a salicylic acid ester represented by the aforementioned general formula (I) and an α-methylbenzyl halide represented by the aforementioned formula (II) And a predetermined amount of the catalyst are charged at once and reacted at a predetermined temperature as it is, or after adding the salicylic acid ester and the catalyst, reacting while dropping α-methylbenzyl halides.

The end point of this reaction can be determined while observing the reduction of salicylic acid esters and α-methylbenzyl halides as raw materials by high performance liquid chromatography.

For the hydrolysis, a usual method using an acid or alkali aqueous solution is used. That is, in the hydrolysis with an acid, mineral acids such as hydrochloric acid and sulfuric acid, a combined use of sulfuric acid and acetic acid, organic sulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid, chlorobenzenesulfonic acid, and methanesulfonic acid, aluminum chloride, and zinc chloride. , A Lewis acid such as stannic chloride, and even trifluoromethanesulfonic acid,
It is carried out with super strong acids such as Nafion H and water.

In the hydrolysis with alkali, caustic soda,
The method using caustic potassium and water is common.

The ratio of acid or alkali to water can be selected at an arbitrary ratio, but is usually in the range of 1: 100 to 99: 1, preferably 5:95 to 95: 5 (weight ratio).

The amount of the acid or alkali used in the hydrolysis can be determined in any ratio with respect to the salicylate used as the raw material. Usually, it is carried out in the range of 0.05 to 30 times mol depending on the strength of the acid. In the case of an alkali, the equivalent is 30 or more.
The range is twice as high.

The reaction temperature ranges from 50 to 200 ° C., preferably from 80 to 160 ° C.

The reaction time ranges from 1 to 50 hours.

For the purpose of shortening the reaction time, a phase transfer catalyst such as a quaternary ammonium salt, a quaternary phosphonium salt, crown ether, cryptate or polyethylene glycol may be added as a reaction accelerator.

The hydrolysis reaction is usually carried out without using an organic solvent, but an organic solvent may be used.
Examples of the solvent include N-methylformamide, N, N-dimethylformamide, N, N-dimethylacetamide,
Aprotic polar solvents such as dimethylsulfoxide, sulfolane, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, and hexamethylphosphotriamide;
Glycols such as ethylene glycol, polyethylene glycol dialkyl ether, 2-methoxyethanol and 2-ethoxyethanol can be used, and water such as toluene, xylene, monochlorobenzene, 1,2-dichloroethane and 1,1,2-trichloroethane can be used. Immiscible solvents can also be used. The amount of the solvent used is sufficient to be 0.5 to 10 (volume / weight) times the amount of the raw material.

The composition of the reaction product in the hydrolyzate thus obtained is 3,5-di (α-methylbenzyl)
60-90% by weight of salicylic acid derivative, 3 or 5-
0 to 40% by weight of (α-methylbenzyl) salicylic acid derivative (abbreviated as mono-substituted salicylic acid derivative)
0 to 40% by weight of a salicylic acid compound (abbreviated as a tri-substituted salicylic acid derivative) obtained by reacting a di (α-methylbenzyl) salicylic acid derivative with an α-methylbenzyl group, and these constitute 95% by weight or more in total. The remainder is an aromatic salicylic acid resin and oligomers of α-methylbenzyl halides. Since the hydrolysis is performed almost quantitatively, it is considered that the proportion of each component in the form of the ester before hydrolysis is almost the same.

According to the present invention, the substance containing a 3,5-di (α-methylbenzyl) salicylic acid derivative as a main component and sometimes containing a mono- and / or tri-substituted salicylic acid derivative is used in the present invention. Things.

High-purity (99% or more) 3,5-di (α-
To obtain a methylbenzyl) salicylic acid derivative, 3,5-di (α-methylbenzyl) salicylate is separated from the reaction product before the hydrolysis by vacuum distillation,
This is hydrolyzed.

Such a production method is inexpensive as compared with a conventionally known method derived from phenol, and has a high selectivity as compared with a method produced from salicylic esters and styrenes. This is extremely advantageous in producing the same.

When salicylic acid is used in place of salicylic acid esters in the method of the present invention, the reactivity becomes low due to the presence of a carboxyl group of an electron-withdrawing group. However, under such conditions, the selectivity of the di-substituted salicylic acid derivative is 40 to 40.
50%.

In order to obtain a reaction product from the reaction solution after the completion of the hydrolysis reaction, the reaction solution is neutralized and, if crystals are precipitated, isolated as crystals. If a solvent is used and it is in a dissolved state, the solvent can be distilled off, or it can be directly discharged into water and taken out as crystals.

In some cases, recrystallization of an appropriate solvent can be performed to obtain crystals. The progress of the reaction and the purity of the isolated product can be determined by high-performance liquid chromatography analysis.

Next, 3,5-di (α-methylbenzyl)
A method for producing a polyvalent metal compound of a salicylic acid derivative and an α-methylbenzyl-substituted salicylic acid derivative composition (both will be simply referred to as a salicylic acid compound hereinafter) will be described.

The polyvalent metal compound is produced by reacting an alkali metal salt of a salicylic acid compound with a water-soluble polyvalent metal salt in water or a solvent in which both are soluble.

That is, the salicylic acid compound is dispersed in an aqueous solution, an alcohol solution or a water-alcohol solution containing a hydroxide, carbonate or alkoxide of an alkali metal in an amount equivalent to or more than the carboxyl group in the salicylic acid compound, The salicylic acid compound is dissolved as a precipitate by dissolving under water temperature conditions of 0 to 100 ° C and adding and reacting the water-soluble polyvalent metal salt as it is or as an aqueous solution, alcohol solution or water-alcohol solution at 0 to 100 ° C. To obtain a polyvalent metal salt of About 0.5 to 1 based on the carboxyl group in the salicylic acid compound
It is desirable to react an equivalent amount of a water-soluble polyvalent metal salt.

The metal of the metal used in the present invention includes
Including metals excluding alkali metals such as lithium, sodium, potassium, etc., preferred polyvalent metals include calcium, magnesium, aluminum, copper, zinc, tin, barium, cobalt, nickel and the like. Of these, zinc is particularly effective.

The polyvalent metalated salicylic acid compound obtained by the above-described method has excellent properties as a color developer. In order to use the metal compound as a color developer, the metal compound may be pulverized with a pulverizer such as a sand grinding mill to have an appropriate particle size. For actual use, the developer may be further suspended or dissolved in a solvent and used in a desired form, and used in combination with a known developer, that is, an inorganic solid acid such as activated clay. Can be used in combination with an organic polymer such as a phenol-formaldehyde resin or other metal salts of aromatic carboxylic acids, and further, zinc, magnesium, aluminum,
It may be used in combination with at least one of oxides, hydroxides and carbonates of polyvalent metals selected from the group consisting of lead, titanium, calcium, cobalt, nickel, manganese and barium.

The method for preparing a color developing sheet for pressure-sensitive copying paper using the color developing agent of the present invention is as follows: (1) A water-based coating is prepared by using the aqueous suspension of the metallized product and is applied to a support such as paper. A method of coating, (2) a method of shaping the metallized material during papermaking,
(3) A method in which a coating material is prepared by dissolving or suspending the metalized product in an organic solvent and applied to a support can be used.

In order to form a color developer layer on a support such as paper by coating, it is desirable that the color developer has appropriate viscosity and coating suitability. Liquid,
After dissolved or suspended in a solvent, kaolin clays,
Calcium carbonate, starch, synthetic or natural latex, etc. are blended to adjust to appropriate viscosity and coating suitability, and used as a paint. The ratio of the developer component in the paint is desirably 10 to 70% of the total solid content. If the ratio of the developer component is less than 10%, sufficient color developability cannot be exhibited.
If it exceeds, the paper surface characteristics of the color developing sheet will deteriorate. The coating amount of the paint is 0.5 g / m ² or more by dry weight, preferably 1 to
10 g / m ² .

[0048]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments.

The preparation of a pressure-sensitive copying paper color development sheet using the products obtained in each of the examples and comparative examples as a color developer and a method for measuring the performance of the color development sheet are described below. The performance measurement results are collectively shown in Tables 1 and 2.

1. Preparation of a Developing Sheet A metal suspension of a salicylic acid compound obtained in Examples 2, 5 to 8 described later was used as a developing agent, and was dispersed by a sand grinding mill with the following composition to prepare a suspension.

Developer 6 parts by weight Polyvinyl alcohol (Kuraray # 117) 10% aqueous solution 3 parts by weight Water 22.5 parts by weight Next, a coating material having the following composition was prepared using the suspension.

Suspension 10 parts by weight Light calcium carbonate 10 parts by weight Starch 0.8 parts by weight Synthetic rubber latex 0.8 parts by weight Water 32.5 parts by weight The amount of these paints applied to high quality paper when dried is 5.0. ~ 5.5
g / m ² and dried to obtain a color developing sheet.

2. Coloring speed and density (5 ° C, 60% R
H and 20 ° C., 65% RH in a constant-temperature and constant-humidity chamber) Commercially available blue-colored paper using crystal violet lactone (CVL) as the main pressure-sensitive dye (NJ-4 manufactured by Jujo Paper)
0T), the coated surface and the developing sheet (lower paper) coated with the water-based paint are superposed on each other, and the color is applied with an electronic typewriter.

1 minute and 30 seconds after embossing and 2 hours after 24 hours
The points are measured and displayed as Y values.

3. Lightfastness of Colored Image The developed sheet developed by the method of 2 was exposed to a carbon arc fade meter (manufactured by Suga Test Instruments) for 2 hours (and 4 hours), and the reflectance after irradiation was measured using a Σ-80 color difference meter. And measured and indicated by Y value.

The lower the Y value and the smaller the difference from the pre-test value, the less the discoloration due to light, and thus the more preferable.

4. Plasticizer resistance A melamine / formaldehyde resin film microcapsule having an average particle diameter of 5.0 μm using dioctyl phthalate (DOP) as a core substance is prepared, and a small amount of a liquid starch-based binder is added to form a coating liquid, which is then coated on a high-quality paper with an air knife coater. The coated DOP microcapsule is coated and dried so that the dry coating amount is 5 g / m ² . After making the color-developing surface of the color-developing sheet colored with the DOP microcapsule-coated paper 2 face, the DOP microcapsule is passed through a super calender roll having a linear pressure of 100 kg / cm to uniformly penetrate the color-developing surface.

The reflectance after one hour is measured using a Σ-80 color difference meter, and is displayed as a Y value. The lower the Y value and the smaller the difference from the value before the test, the better the plasticizer resistance of the color image.

5. Water resistance of the color-developed image The color-developed sheet developed by the method of 2 was immersed in water for 2 hours, and the density change of the color-developed image was visually observed.

6. Yellowing of Developed Sheet (6-1) Yellowing by NO _{x Based on} JIS L-1055 [Testing method for nitrogen oxide gas fastness of dyed materials and dyes], the developed sheet was made of NaNO ₂
(Sodium nitrite) and H ₃ PO ₄ (phosphoric acid) are stored for 1 hour in a closed container in an atmosphere of NO _x gas generated by the reaction, and the degree of yellowing is examined.

At the end of the first hour after storage, the data is displayed as a WB value using a Σ-80 color difference meter. WB value is large and NO (Table 2 displays untested sheet) sheet which is not exposed to _x gas means that yellowing in NO _x atmosphere smaller the difference between the WB value of is small.

(6-2) Yellowing due to light The developed sheet is irradiated with a carbon arc fade meter (manufactured by Suga Test Instruments) for 4 hours, and after irradiation, the sheet is indicated by WB value using a Σ-80 color difference meter. The smaller the difference between the WB value and the WB value of the unirradiated sheet (indicated as an untested sheet in Table 1), the smaller the yellowing due to light irradiation.

Example-1 152.2 g (1 mol) of methyl salicylate, 281.
2 g (2 mol) of 1-chloroethylbenzene and 3 g
Of trifluoromethanesulfonic acid was charged into a flask and reacted at room temperature (20 ° C.) for 5 days.

After the completion of the reaction, 1500 ml of toluene is charged and dissolved, then 100 ml of water is added, and the mixture is stirred at 60 to 70 ° C. for 0.5 hour to separate the liquid into an organic layer and an aqueous layer (lower layer). After standing still to remove the lower aqueous layer, the solvent was distilled off from the organic layer. As a result of measurement of the residue by high performance liquid chromatography (HLC), it was found that monosubstituted methyl salicylate was 3%, disubstituted methyl salicylate was 89.5%, and trisubstituted methyl salicylate was 7.5%. Then 1 ~
Vacuum distillation was performed at 3 mmHg, and a fraction at 213 to 218 ° C was collected to obtain 291 g (yield 81%) of methyl 3,5-di (α-methylbenzyl) salicylate.

Then, 90 g (0.25 mol) of the obtained methyl 3,5-di (α-methylbenzyl) salicylate and 4
28.9 g of a 0% aqueous sodium hydroxide solution (NaOH 0.27
5 mol) into a 500 ml flask and add 95-105
The reaction was carried out at a temperature of ° C. for 3 hours to complete the hydrolysis. Thereafter, 430 ml of water was charged and dissolved, neutralized with sulfuric acid, filtered, washed with water, and dried to obtain 84.7 g (yield 98%) of 3,5-di (α-methylbenzyl) salicylic acid having a purity of 99% or more. Obtained.

Melting point: 147 to 150 ° C.

[0067]

[Table 1] H-NR (DMS-d6) 1.6 (m, 6H), 4.1 (m, 1H), 4.6
(M, 1H) 7.1-7.3 (m, 1H), 7.65 (m, 1H) 9.4 (Br, 1H), 10.5 (s, 1H) MS: m / z = 346 (M ⁺ ) The measurement results by HLC are shown in FIG.

The measurement conditions are as follows.

Model: LIQIOD CHOROMATOGRAPH
LC-3A (Shimadzu) Column: YMC-Pack AM-312 Moving layer: acetonitrile / MeOH / water / trifluoroacetic acid = 725 ml / 100 ml / 175 ml / 0.5 g Flow rate: 1 ml / min. Detector: SPD-2A (UV-254nm) Waveform processing: Model Shimadzu Chromatopack C-R3
A Example-2 69.2 g (0.2 mol) of 3,5-di (α-methylbenzyl) salicylic acid obtained in Example-1 was added to 8.8 g (0.21 mol) of 95% caustic soda and 500 g of water. And dissolved in an alkaline aqueous solution dissolved therein. This aqueous solution was previously mixed with 31.6 g of zinc sulfate of heptahydrate in 300 ml of water.
The solution was added dropwise over 1 hour to the aqueous solution dissolved in the above, aged for 1 hour, filtered, washed with water and dried to obtain 70 g of zinc 3,5-di (α-methylbenzyl) salicylate.

Example 3 An acid catalyst prepared by dissolving 190.3 g (1.25 mol) of methyl salicylate and 5 g of zinc chloride in 2 g of concentrated hydrochloric acid was charged into a flask, and then heated to 35 ° C. At the same temperature, 404.3 g (2.87) of 1-chloroethylbenzene
Mol) is added dropwise over 2 hours. After dropping, at the same temperature 2
Aged for 0 hours. Thereafter, 750 ml of toluene was charged and dissolved, and then 150 ml of water was added and the mixture was dissolved at 60 to 70 ° C. and dissolved in 0.1 ml.
After stirring for 5 hours, the solution was allowed to stand until the liquid was separated into two layers, an organic layer and an aqueous layer (lower layer). After removing the lower aqueous layer, the solvent was distilled off from the organic layer. As a result of measurement of the residue by HLC,
2.9% of mono-substituted methyl salicylate, 80% of di-substituted methyl salicylate and 11.2% of tri-substituted methyl salicylate. Then, vacuum distillation is performed at 1-3 mmHg, and 2
A fraction at 13 to 218 ° C. is collected, and 338 g of methyl 3,5-di (α-methylbenzyl) salicylate (75% yield)
I got Thereafter, hydrolysis was carried out using a 40% aqueous solution of sodium hydroxide in the same manner as in Example 1 to give 318 g of 3,5-di (α-methylbenzyl) salicylic acid having a purity of 99% (yield 98%).
%).

Example 4 16.6 g (0.1 mol) of ethyl salicylate;
8 g (0.24 mol) of 1-chloroethylbenzene and 0.3 g of trifluoromethanesulfonic acid were charged into a flask and reacted at 20 ° C. for 30 hours. After completion of the reaction, 150 ml of toluene is charged and dissolved, and then 50 ml of water is added.
And stirred at 60 to 70 ° C. for 0.5 hour. The solution was allowed to stand until the liquid was separated into two layers, an organic layer and an aqueous layer. After removing the lower aqueous layer, the organic layer was removed in the same manner as in Example-1. The solvent was distilled off. As a result of measurement of the residue by HLC, ethyl salicylate was 6%, mono-substituted ethyl salicylate was 4.5%, di-substituted ethyl salicylate was 76.8%, and tri-substituted ethyl salicylate was 12.7%. Then, 26.2 g of ethyl 3,5-di (α-methylbenzyl) salicylate was obtained by vacuum distillation.
(Yield 70%), and then hydrolyzed with 40% sodium hydroxide to obtain 23.7 g (98% yield) of 3,5-di (α-methylbenzyl) salicylic acid with a purity of 99%.

Example-5 76.1 g (0.5 mol) of methyl salicylate, 1.5
g stannic chloride (SnCl ₂ ) and 154.6 g
(1.1 mol) of 1-chloroethylbenzene was charged into a flask and reacted at 20 to 25 ° C. for 5 hours. Then 7
The temperature was raised to 0 ° C., and 200 ml of warm water was charged.
The temperature was raised to 98 ° C, 170 g of 15% caustic soda was added dropwise over 2 hours, and the mixture was aged at 98 to 100 ° C for 5 hours to complete the hydrolysis. The measurement result of the hydrolyzate by HLC is as follows:
Salicylic acid 2%, mono-substituted salicylic acid 13%, di-substituted salicylic acid 67%, tri-substituted salicylic acid 17%, and 1%. Thereafter, 700 ml of water was added to dilute the mixture, and the pH was adjusted to 9 with sulfuric acid.
0 g was dropped over 1 hour, aged for 1 hour, filtered, washed with water,
After drying, 200 g of a zinc salt of the α-methylbenzyl-substituted salicylic acid composition was obtained. Example -6 methyl salicylate 76.1 g (0.5 mol), 1 g of antimony chloride (SbCl ₅₎ and 147.6g
(1.05 mol) of 1-chloroethylbenzene was charged into a flask and reacted at 30 to 35 ° C. for 8 hours. Then 7
The temperature was raised to 0 ° C, 200 ml of warm water was charged, and 95 to 9
The temperature was raised to 8 ° C., 170 g of a 15% aqueous solution of caustic soda was added dropwise over 2 hours, and the mixture was aged at 98 to 100 ° C. for 5 hours to complete the hydrolysis. The results of the HLC measurement of the hydrolyzate were as follows: monosubstituted salicylic acid 12%, disubstituted salicylic acid 68
%, Trisubstituted salicylic acid 18%, and other 2%. Thereafter, 700 ml of water was added to dilute the mixture, the pH was adjusted to 9 with sulfuric acid, 180 g of a 43% aqueous zinc sulfate solution was added dropwise at 30 ° C. over 1 hour, the mixture was aged for 1 hour, filtered, washed with water, and dried to obtain α-.
200 g of a zinc salt of methylbenzyl-substituted salicylic acid was obtained.

Example -7 76.1 g (0.5 mol) of methyl salicylate and an acid previously prepared by dissolving 2 g of zinc chloride in 0.8 g of concentrated hydrochloric acid were charged into a flask, and then heated to 35 ° C. 1- at temperature
Chloroethylbenzene 161.7 g (1.15 mol) is added dropwise over 2 hours. After the completion of the dropwise addition, the reaction was carried out at the same temperature for 20 hours. Thereafter, the temperature was raised to 70 ° C., 200 ml of warm water was charged, the temperature was further raised to 95 to 98 ° C., and 170 g of a 15% aqueous solution of caustic soda was added dropwise over 2 hours.
The hydrolysis was completed by aging at 5 ° C. for 5 hours. H of the hydrolyzate
As a result of measurement by LC, monosubstituted salicylic acid was 7%, disubstituted salicylic acid was 80%, and trisubstituted salicylic acid was 13%. Thereafter, 700 ml of water was added to dilute the mixture, and p
Adjusted to H9, 180 g of 43% aqueous zinc sulfate solution at 30 ° C
Was dropped over 1 hour, aged for 1 hour, filtered, washed with water and dried to obtain a zinc salt of α-methylbenzyl-substituted salicylic acid 200.
g was obtained.

Example-8 1.5 g of 76.1 g (0.5 mol) of methyl salicylate
Trifluoromethanesulfonic acid, and 154.6 g
(1.1 mol) of 1-chloroethylbenzene was charged into a flask and reacted at 20 to 25 ° C. for 5 days. Then 70
The temperature was raised to 200 ° C., and 200 ml of warm water was charged.
The temperature was raised to 70 ° C., 170 g of a 15% aqueous sodium hydroxide solution was added dropwise over 2 hours, and the mixture was aged at 98 to 100 ° C. for 5 hours to complete the hydrolysis. The result of measurement of the hydrolyzate by HLC was as follows: di-substituted salicylic acid 88%, tri-substituted salicylic acid 11
% And other 1% (FIG. 2). In this figure, RT
8.427 is 3,5- (α-methylbenzyl) salicylic acid. Thereafter, 700 ml of water was added to dilute the mixture, and the pH was adjusted to 9 with sulfuric acid.
80 g was added dropwise over 1 hour, aged for 1 hour, filtered, washed with water and dried to obtain 200 g of zinc salt of 3,5-di (α-methylbenzyl) salicylic acid.

Comparative Example 1 76.1 (0.5 mol) of methyl salicylate and 10
g of methanesulfonic acid into a flask at 60 to 65 ° C.
While maintaining the temperature at 140 g, styrene (140 g, 1.346 mol) is added dropwise over 14 hours. After completion of the dropwise addition, the reaction solution obtained by aging at the same temperature for 30 minutes was hydrolyzed with a 40% aqueous sodium hydroxide solution in the same manner as in Example-1. Then neutralized with sulfuric acid to obtain an oily product containing 3,5-di (α-methylbenzyl) salicylic acid.

The result of the analysis by HLC was 3,5-di (α
The content of (-methylbenzyl) salicylic acid was 43.3%. This is shown in FIG. In the figure, RT8.437 is 3,
5-di (α-methylbenzyl) salicylic acid.

Further, subchlorination was attempted in the same manner as in Example 8, but it turned into a gum and a block, and it was difficult to filter, wash and dry.

[0078]

[Table 2]

[0079]

[Table 3]

[0080]

The production method of the present invention can be said to be an industrially suitable method because a 3,5-di (α-methylbenzyl) salicylic acid derivative can be obtained with inexpensive raw materials and simple operations.

Further, in a color developing sheet using a polyvalent metal compound of an α-methylbenzyl-substituted salicylic acid derivative composition containing a 3,5-di (α-methylbenzyl) salicylic acid derivative as a main component obtained by the method of the present invention. Is suitable for use in cold regions, which has conventionally been a problem, because of its excellent color development at low temperatures. Further, since the problem of disappearance of the color image in water is also solved, it can be stably used in the field where the use has been restricted in the past.

[Brief description of the drawings]

FIG. 1. 3,5-Di (α) isolated by the method of the present invention.
An example of the result of HLC analysis of -dimethylbenzyl) salicylic acid is shown.

FIG. 2 shows an example of an HLC analysis result of the α-methylbenzyl-substituted salicylic acid derivative composition obtained by the method of the present invention.

FIG. 3 shows an example of an HLC analysis result of a 3,5-di (α-dimethylbenzyl) salicylic acid-containing oil obtained by a conventional method.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-B-51-25174 (JP, B2) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 65/105 B41M 5/155 B41M 5 / 30 C07C 51/09 CA (STN) REGISTRY (STN)

Claims (7)

(57) [Claims] 1. A compound of the general formula (I) (Wherein R ₁ represents an alkyl group, an aralkyl group or a cycloalkyl group having 1 to 12 carbon atoms) with respect to 1 mol of the salicylic acid ester represented by the general formula (II): (Wherein, R ₂ and R _{3 each} represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents a halogen atom). 3,5-di (α-methylbenzyl) salicylate produced by reacting at a temperature of 10 ° C. to 40 ° C. in the presence of 3,5-di (α)
-Methylbenzyl) salicylic acid derivative production method. 2. The process according to claim 1, wherein before the hydrolysis, 3,5-di (α-methylbenzyl) salicylate is separated from the reaction solution by vacuum distillation. 3. A compound of the general formula (I) (Wherein R ₁ represents an alkyl group having 1 to 12 carbon atoms, an aralkyl group or a cycloalkyl group) with respect to 1 mol of the salicylates represented by the general formula (II): (Wherein, R ₂ and R _{3 each} represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents a halogen atom.) 1.5 to 3 mol of α-methylbenzyl halides represented by the following formula: At a temperature in the range of 10C to 40C in the presence of
The resulting α-methylbenzyl-substituted salicylic acid ester derivative is obtained by hydrolyzing the mono-substituted salicylic acid derivative having an α-methylbenzyl group in the range of 0 to 15 % by weight.
10 to 10 tri-substituted salicylic acid derivatives of methylbenzyl group
20 % by weight and 3,5-di (α-methylbenzyl) salicylic acid derivative in the range of 60 to 90% by weight, and these α-methylbenzyl-substituted salicylic acid derivatives constitute 95% by weight or more as a whole. Characteristic composition for developer. Claim 3 composition monosubstituted salicylic acid derivative polyvalent metal compound is 0-15 weight α- methylbenzyl made by reacting a polyvalent metal salt containing α- methylbenzyl-substituted salicylic acid derivative according % range, trisubstituted salicylic acid derivative polyvalent metal products of α- methylbenzyl group 1
In the range of 0 to 20 % by weight and 60 to 90% of the polyvalent metal compound of the 3,5-di (α-methylbenzyl) salicylic acid derivative.
% Of the polyvalent metallized product of the α-methylbenzyl-substituted salicylic acid derivative is 95% by weight as a whole.
A composition for a color developer comprising the above. 5. The method according to claim 2, wherein
A method for producing a polyvalent metalated 3,5-di (α-methylbenzyl) salicylic acid derivative, comprising reacting a di (α-methylbenzyl) salicylic acid derivative with a polyvalent metal salt. 6. A developer sheet using the developer composition according to claim 3 as a developer. 7. A color developing sheet using the polyvalent metal compound according to claim 4 as a color developer.