JPH05998A - Production of 3,5-di(alpha-methylbenzyl) salicylic acid derivative and its use as color-developing agent of multi-valent metal compound - Google Patents

Abstract

PURPOSE:To produce the compound having good color-developing property, good image-coloring property and good water resistance and useful as a color- developing agent for pressure-sensitive sheet and thermosensitive sheet, etc., by reacting a salicylate ester with an alpha-methylbenzyl halide in the presence of an acid catalyst and subsequently hydrolyzing the reaction product. CONSTITUTION:A salicylate ester of formula I (R1 is 1-12C alkyl, aralkyl, cycloalkyl) (e.g. methyl salicylate) is reacted with an alpha-methylbenzyl halide (e.g. 1-chloroethyl benzene) in the presence of an acid catalyst (e.g. trifluoromethane sulfonic acid), and the produced 3,5-di(alpha-methylbenzyl) salicylic acid ester [e.g. 3,5-di(alpha-methyl) salicylic acid methyl ester] is hydrolyzed in an sodium hydroxide aqueous solution at 95-105 deg.C for 3hr into the objective 3,5-di(alpha-methylbenzyl) salicylic acid derivative.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art In general, salicylic acid compounds as developers for pressure-sensitive papers and thermal papers are excellent in sharpness of color images 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 a colorless dye is dissolved, and the color development image is poor in water resistance such as disappearance with water, in order to compensate for these drawbacks, Various attempts have been made. For example, a method has been proposed in which an aromatic substituent or the like is introduced into the salicylic acid skeleton to compensate for the above-mentioned drawbacks.

(1) As a method for producing a 3,5-disubstituted salicylic acid, a method of producing the corresponding substituted phenol and carbon dioxide by a Kolbe-Schmidt reaction is known. For example, 3,5-di (α, α-dimethylbenzyl) salicylic acid disclosed in JP-B-49-10856 is 2,4-obtained from phenol and α-methylstyrene.
It is manufactured using di (α, α-dimethylbenzyl) phenol as a raw material. However, this method has a long reaction step,
In addition to the drawback that the yield is low, there is a drawback that the reaction is generally carried out at high temperature and high pressure when the carboxyl group is introduced, so that it is generally expensive.

(2) Attempts have been made to produce similar salicylic acid compounds for the purpose of overcoming the above problems in production cost. For example, there is an alkylation reaction of salicylic acid or a salicylic acid ester.

2-mol of 1-phenylethanol is reacted with 1 mol of salicylic acid 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 (JP-A-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 mono-substituted salicylic acid or di-substituted salicylic acid by a complicated operation. When used as a colorant, there is a problem that it is difficult to obtain reproducibility in quality such as color development performance and storage stability in the color developing sheet.

(3) A method has been proposed in which a styrene compound is reacted with salicylic acid in the presence of an aliphatic carboxylic acid using an organic sulfonic acid or an inorganic acid as a catalyst to obtain a di-substituted salicylic acid (Japanese Patent Laid-Open No. 2-91043). ).

In this case, an aliphatic carboxylic acid such as acetic acid or propionic acid is used in combination with sulfuric acid or methanesulfonic acid to obtain 90-
Since the reaction is carried out at 130 ° C. and the amount of the acid used is 50% by weight or more with respect to 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, it has the same problem as (2).

(4) Regarding the alkylation reaction of salicylic acid alkyl ester, for example, methyl salicylate is reacted with styrene in the presence of alkanesulfonic acid to give 3,5
A method for obtaining methyl-di (α-methylbenzyl) salicylate is known (Japanese Patent Publication No. 61-26772). Since styrene is used in this method, various polymers of styrene and other by-products are produced. This method is similar to the method for producing a salicylic acid ester resin disclosed by the present inventors in JP-A-1-133780, and the resin can be prepared even if the catalyst, the molar ratio of salicylic acid ester and styrene, the reaction temperature and the like are changed. It is not possible to suppress the side reaction that is converted into.

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, in addition to the production of mono-substituted products and tri-substituted products, styrene polymers, further dimer adducts, etc. are produced, and the amount of alkanesulfonic acid used as a catalyst is large, so it cannot be said to be an advantageous method.

[0010]

DISCLOSURE OF THE INVENTION The object of the present invention is 3,5-di (α) which is excellent as a color developer in color developing performance and light yellowing resistance.
The present invention provides an economical production method of a (methylbenzyl) salicylic acid derivative, a developer using the same, and a developer composition having improved stability of a color image to water and color developability at low temperature. Especially.

[0011]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the inventors have made salicylic acid esters and α-methylbenzyl halides react in the presence of an acid catalyst to give 3,5- We have found a method for producing a di (α-methylbenzyl) salicylic acid ester and then hydrolyzing it to obtain a 3,5-di (α-methylbenzyl) salicylic acid derivative.

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

Further, the salicylates and α-
3,5-di (α-, obtained by reacting methylbenzyl halides in the presence of an acid catalyst and hydrolyzing the reaction product.
Methylbenzyl) salicylic acid derivative 60 to 90% by weight
It has been found that the above object can be achieved by using a polyvalent metal compound of an α-methylbenzyl group-substituted salicylic acid derivative composition containing the compound as a developer.

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

[0015]

[Chemical 5] (In the formula, R ₁ represents an alkyl group having 1 to 12 carbon atoms, an aralkyl group or a cycloalkyl group), the salicylic acid ester represented by the general formula (II)

[0016]

[Chemical 6] (Wherein R ₂ and R ₃ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents a halogen atom), and reacted with α-methylbenzyl halides in the presence of an acid catalyst, 3,5-di (α-methylbenzyl) salicylic acid ester produced is hydrolyzed.
A method for producing a 5-di (α-methylbenzyl) salicylic acid derivative and (2) a reaction product obtained by hydrolyzing a reaction product of the above reaction,
A metallized product of an 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. is there.

The salicylic acid esters used in the present invention include methyl salicylate, ethyl salicylate, salicylic acid-n-propyl, isopropyl salicylate, isoamyl salicylate, salicylic acid-tert-octyl, nonyl salicylate, dodecyl salicylate, cyclohexyl salicylate, benzyl salicylate, salicylate. Examples thereof include, but are not limited to, -α-methylbenzyl and the like. Industrially preferably cheap methyl salicylate,
And ethyl salicylate.

The type of halogen of the α-methylbenzyl halides used in the present invention includes chlorine and bromine, and chlorine is preferable. Therefore, as α-methylbenzyl halides, 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 thereof include 5-dimethyl-α-methylbenzyl chloride and 3,4-dimethyl-α-methylbenzyl chloride, but are not limited thereto. Of these, α-methylbenzyl chloride and p-methyl-α-methylbenzyl chloride are preferable.

The amount of various α-methylbenzyl halides used in the production method of the present invention is preferably 1.5 to 3 mol, and less than 1.5 mol, per 1 mol of salicylic acid ester represented by the general formula (I). Alternatively, if it is used in excess of 3 moles, the production rate of 3,5-di (α-methylbenzyl) salicylic acid ester, which is the main purpose precursor, becomes low, which is not preferable.

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, or a peracid known as a super strong acid. Fluoroalkane sulfonic acids such as trifluoromethane sulfonic acid and Nafion H (trade name Du as a perfluoroalkane sulfonic acid resin
can be used. Of these, zinc chloride is particularly preferable.

The amount of the catalyst used is 0.05 to 200 mol% with respect to salicylic acid esters, and preferably 0.1 to 100 mol% in view of economy.

The reaction temperature is in the range of 0 to 180 ° C, preferably 5 to 80 ° C, more preferably 10 to 80 ° C.
40 ° C. The reaction time is usually 1 to 120 hours.

A solvent may be used for the reaction between salicylic acid esters and α-methylbenzyl halides, if necessary. As this solvent, one that is inert to the reaction, such as 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, it is preferable to be 30 (volume / weight) times or less in consideration of economy with respect to the raw material.

In the present invention, a general method for reacting salicylic acid esters with α-methylbenzyl halides is a salicylic acid ester represented by the general formula (I) and an α-methylbenzyl halide represented by the above formula (II). Then, a predetermined amount of the catalyst is charged all at once, and the reaction is carried out at the predetermined temperature as it is, or after the salicylic acid ester and the catalyst are charged, the reaction is carried out while dropping the α-methylbenzyl halides.

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

For the hydrolysis, a usual method using an acid or alkaline aqueous solution is used. That is, in acid hydrolysis, mineral acids such as hydrochloric acid and sulfuric acid, 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, zinc chloride. , Lewis acids such as stannic chloride, and even trifluoromethanesulfonic acid,
It is carried out with superacids such as Nafion H and water.

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

The ratio of acid or alkali to water can be selected at any ratio, but it 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 may be any ratio with respect to the salicylic acid ester used as the starting material. Usually, it is carried out in the range of 0.05 to 30 times by mole depending on the strength of the acid. Equivalent or more to 30 for alkali
It is in the double molar range.

The reaction temperature is in the range of 50 to 200 ° C, preferably 80 to 160 ° C.

The reaction time is in the range of 1 to 50 hours.

Phase transfer catalysts such as quaternary ammonium salts, quaternary phosphonium salts, crown ethers, cryptates and polyethylene glycols may be added as reaction accelerators for the purpose of shortening the reaction time.

The hydrolysis reaction is usually carried out without using an organic solvent, but an organic solvent may be used.
As the solvent, N-methylformamide, N, N-dimethylformamide, N, N-dimethylacetamide,
Aprotic polar solvents such as dimethyl sulfoxide, sulfolane, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, 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 solvent may be used in an amount of 0.5 to 10 (volume / weight) times 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-
0-40% by weight of (α-methylbenzyl) salicylic acid derivative (abbreviated as mono-substituted salicylic acid derivative), 3,5
-0 to 40% by weight of a salicylic acid compound (abbreviated as a tri-substituted salicylic acid derivative) obtained by further reacting a di (α-methylbenzyl) salicylic acid derivative with an α-methylbenzyl group, and these constitute 95% by weight or more in total. The balance is an aromatic salicylic acid resin and an oligomer of α-methylbenzyl halides. Since the hydrolysis is carried out almost quantitatively, the proportion of each component in the ester form before the hydrolysis is considered to be almost the same.

According to the present invention, the above-mentioned substance containing a 3,5-di (α-methylbenzyl) salicylic acid derivative as a main component and optionally containing a mono- and / or tri-substituted salicylic acid derivative is used as the α-methylbenzyl-substituted salicylic acid derivative composition. It is called a thing.

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

Such a production method is less expensive than conventionally known methods derived from phenol, and has higher selectivity than methods produced from salicylic acid esters and styrenes. It is extremely advantageous for manufacturing.

When salicylic acid is used in place of the salicylic acid ester as the raw material in the method of the present invention, the reactivity becomes low because of the carboxyl group of the electron-withdrawing group, and the reaction must be carried out at a higher temperature than in the case of the present invention. Under such conditions, the selectivity of the di-substituted salicylic acid derivative is 40-
50%.

In order to obtain a reaction product from the reaction solution after completion of the hydrolysis reaction, the reaction solution is neutralized, and if crystals are precipitated, they are 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 a suitable solvent can be performed to obtain crystals. The progress of the reaction and the purity of the isolated product can be determined by analysis by high performance liquid chromatography.

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 are collectively referred to as salicylic acid compounds hereinafter) will be described.

The polyvalent metal compound is produced by reacting an alkali metal salt of a salicylic acid compound and 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 an alkali metal hydroxide, carbonate or alkoxide 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 it under a temperature condition of 0 to 100 ° C. and adding a water-soluble polyvalent metal salt to the solution as it is or as an aqueous solution, an alcohol solution or a water-alcohol solution at 0 to 100 ° C. To obtain a polyvalent metal salt of. About 0.5 to 1 with respect to the carboxyl group in the salicylic acid compound
It is desirable to react an equivalent amount of water-soluble polyvalent metal salt.

As the metal of the metallization used in the present invention,
Although metals excluding alkali metals such as lithium, sodium and potassium are included, preferable polyvalent metals include calcium, magnesium, aluminum, copper, zinc, tin, barium, cobalt and nickel. Of these, zinc is particularly effective.

The polyvalent metal compound of the salicylic acid compound obtained by the method described above has excellent properties as a developer. In order to use the metal compound as a developer, it is preferable to grind it with a grinder such as a sand grinding mill to obtain an appropriate particle size. For practical use, the developer may be further suspended in a solvent or dissolved to obtain a desired form, and used in combination with a known developer, that is, an inorganic solid acid such as activated clay. , An organic polymer such as phenol-formaldehyde resin or other aromatic carboxylic acid metal salt can be used in combination, and further zinc, magnesium, aluminum,
You may use together with at least 1 sort (s) of the oxide, hydroxide, or carbonate of the polyvalent metal selected from the group which consists of lead, titanium, calcium, cobalt, nickel, manganese, and barium.

The method for preparing a color-developing sheet for pressure-sensitive copying paper with the color-developing agent of the present invention includes (1) preparing an aqueous paint using an aqueous suspension of the metallized product and applying it to a support such as paper. A method of applying, (2) a method of incorporating the metallized product at the time of paper making,
(3) Any of a method of preparing a coating material using a solution or suspension of the metal compound in an organic solvent and applying the coating material to a support can be used.

In order to form a developer layer on a support such as paper by coating, it is desirable that the developer has an appropriate viscosity and coating suitability. As a liquid
After dissolving or suspending in a solvent, kaolin clays,
Calcium carbonate, starch, synthetic or natural latex, etc. are added to adjust the viscosity and coating suitability to be used as a paint. The proportion of the developer component in the coating composition is preferably 10 to 70% of the total solid content, and if the proportion of the developer component is less than 10%, sufficient color developability cannot be exhibited, and 70% is sufficient.
If it exceeds, the paper surface characteristics of the color-developing sheet deteriorate. The coating amount of the coating material is 0.5 g / m ² or more on a dry basis, preferably 1 to
It is 10 g / m ² .

[0048]

EXAMPLES The present invention will be described in detail below with reference to examples.

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

1. Preparation of Developer Sheet A metallized salicylic acid compound obtained in Examples 2 to 5 to be described later was used as a developer and dispersed with a sand grinding mill in the following composition to prepare a suspension.

[0051]     Developer 6 parts by weight     Polyvinyl alcohol (Kuraray # 117) 10% aqueous solution 3 parts by weight     22.5 parts by weight of water Next, the suspension was used to prepare a coating material having the following composition.

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 These paints are applied to high-quality paper at a dry amount of 5.0. ~ 5.5
The coated sheet was dried so as to be g / m ² to obtain a color-developing sheet.

2. Color development speed and density (5 ℃, 60% R
H and 20 ° C., 65% RH in a constant temperature and humidity room) Commercially available blue coloring top paper (JW NW-4 made by Crystal Violet Lactone (CVL) as a main pressure-sensitive dye)
(0T) and a developer sheet (lower paper) coated with a water-based paint are made to face each other with their coated surfaces facing each other, and color is formed by pressing with an electronic typewriter.

2 minutes after 1 minute 30 seconds and 24 hours after stamping
The points are color-measured and displayed as Y values.

3. The color development sheet developed by the method of light fastness 2 of the color image is exposed to a carbon arc fade meter (manufactured by Suga Test Instruments) for 2 hours (and 4 hours), and the reflectance after irradiation is measured using a Σ-80 color difference meter. Was measured and displayed as Y value.

The lower the Y value and the smaller the difference from the value before the test, the less fading due to light is preferable.

4. Preparation of melamine-formaldehyde resin film microcapsules with an average particle size of 5.0μ using a plasticizer-resistant dioctyl phthalate (DOP) as a core substance, add a small amount of liquid starch-based binder to prepare a coating liquid, and use an air knife coater to print on fine paper. And coated and dried to give a dry coating amount of 5 g / m ² to obtain DOP microcapsule coated paper. The DOP microcapsule-coated paper and the color-developing sheet colored in 2 are made to face each other, and then passed through a super calender roll having a linear pressure of 100 kg / cm to uniformly permeate DOP into the color-developing surface.

The reflectance after 1 hour is measured using a Σ-80 color difference meter and displayed as a Y value. The lower the Y value and the smaller the difference from the pre-test value, the better the plasticizer resistance of the color image.

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

6. Yellowing of the color-developing sheet (6-1) based on the yellowing JIS L-1055 by NO _x [dyeings and nitrogen oxide gas fastness test method of the dye], a color-developing sheet NaNO ₂
It is stored for 1 hour in a closed container in an NO _x gas atmosphere generated by the reaction of (sodium nitrite) and H ₃ PO ₄ (phosphoric acid), and the degree of yellowing is examined.

At the first hour after the storage, the WB value is displayed using a Σ-80 color difference meter. A larger WB value and a smaller difference from the WB value of the sheet that is not exposed to NO _x gas (indicated as an untested sheet in Table 2) means less yellowing in a NO _x atmosphere.

(6-2) A carbon arc fade meter (manufactured by Suga Test Instruments Co., Ltd.) is irradiated with the yellow color-developing sheet by light for 4 hours, and after irradiation, it is displayed as a WB value using a Σ-80 color difference meter. The larger the WB value and the smaller the difference from 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
The trifluoromethanesulfonic acid of was charged in a flask and reacted at room temperature (20 ° C.) for 5 days.

After completion of the reaction, 1500 ml of toluene was charged and dissolved, 100 ml of water was added, and the mixture was stirred at 60 to 70 ° C. for 0.5 hours to separate the liquid into two layers, 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), the content was 3% for mono-substituted methyl salicylate, 89.5% for di-substituted methyl salicylate and 7.5% for tri-substituted methyl salicylate. Then 1
Vacuum distillation was performed at 3 mmHg, and a fraction at 213 to 218 ° C. was collected to obtain 291 g of methyl 3,5-di (α-methylbenzyl) salicylate (yield 81%).

Then, 90 g (0.25 mol) of methyl 3,5-di (α-methylbenzyl) salicylate thus obtained and 4
28.9 g of 0% aqueous sodium hydroxide solution (NaOH 0.27
5 mol) into a 500 ml flask and put at 95-105
Hydrolysis was completed by reacting at a temperature of ° C for 3 hours. After that, 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 147-150 ° C.

[0067]

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

The measurement conditions are as follows.

[0069] Model: LIQIOD CHOROMATOGRAPH
LC-3A (Shimadzu) column: YMC-Pack AM-312 mobile phase: 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 69.5 g (0.2 mol) of 3,5-di ([alpha] -methylbenzyl) salicylic acid obtained in Example-1 was added with 8.8 g (0.21 mol) of 95% caustic soda and 500 g of water. It was charged by dissolving in an alkaline aqueous solution dissolved in. This aqueous solution is preliminarily treated with 31.6 g of zinc sulfate of 7 hydrate and 300 ml of water.
Was added dropwise to the aqueous solution dissolved in 1 hour, aged for 1 hour, filtered, washed with water and dried to obtain 70 g of 3,5-di (α-methylbenzyl) salicylic acid zinc salt.

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

Example-4 16.6 g (0.1 mol) of ethyl salicylate, 33.
8 g (0.24 mol) of 1-chloroethylbenzene and 0.3 g of trifluoromethanesulfonic acid were charged in a flask and reacted at 20 ° C. for 30 hours. After the reaction was completed, 150 ml of toluene was charged and dissolved, and then 50 ml of water was added.
Was added and the mixture was stirred at 60 to 70 ° C. for 0.5 hour, allowed to stand until the liquid separated into two layers of an organic layer and an aqueous layer, and the lower aqueous layer was removed. The solvent was distilled off. As a result of HLC measurement of the residue, it was 6% ethyl salicylate, 4.5% mono-substituted ethyl salicylate, 76.8% di-substituted ethyl salicylate, and 12.7% tri-substituted ethyl salicylate. Then by vacuum distillation, 26.2 g of ethyl 3,5-di (α-methylbenzyl) salicylate
(Yield 70%) was obtained, and then hydrolyzed with 40% caustic soda to obtain 23.7 g (yield 98%) of 3,5-di (α-methylbenzyl) salicylic acid having a purity of 99%.

Example-5 76.1 g (0.5 mol) of methyl salicylate, 1.5
g stannous 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., 200 ml of warm water was charged, and 95-
The temperature was raised to 98 ° C., 170 g of 15% caustic soda was added dropwise over 2 hours, and then aged at 98 to 100 ° C. for 5 hours to complete hydrolysis. The measurement result of the hydrolyzate by HLC is
The salicylic acid was 2%, the mono-substituted salicylic acid was 13%, the di-substituted salicylic acid was 67%, the tri-substituted salicylic acid was 17%, and the others were 1%. After that, 700 ml of water was added to dilute the solution, and the pH was adjusted to 9 with sulfuric acid.
0 g was added dropwise 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 further 95 to 9
The temperature was raised to 8 ° C., 170 g of a 15% aqueous sodium hydroxide solution was added dropwise over 2 hours, and then aged at 98 to 100 ° C. for 5 hours to complete hydrolysis. The HLC measurement result of the hydrolyzate was as follows: mono-substituted salicylic acid 12%, di-substituted salicylic acid 68
%, Tri-substituted salicylic acid 18%, and other 2%. After that, 700 ml of water was added to dilute, the pH was adjusted to 9 with sulfuric acid, 180 g of 43% zinc sulfate aqueous solution was added dropwise at 30 ° C. over 1 hour, aged for 1 hour, filtered, washed with water, dried and α-
200 g of a methylbenzyl-substituted salicylic acid zinc salt was obtained.

Example 7 76.1 g (0.5 mol) of methyl salicylate and 2 g of zinc chloride were dissolved in 0.8 g of concentrated hydrochloric acid in advance, the prepared acid was charged into a flask, and the temperature was raised to 35 ° C. 1 at temperature
161.7 g (1.15 mol) of chloroethylbenzene are added dropwise over 2 hours. After the dropping was completed, 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., 170 g of a 15% aqueous sodium hydroxide solution was added dropwise over 2 hours, and then 98 to 100.
The hydrolysis was completed by aging at 5 ° C for 5 hours. Hydrolyzate H
The measurement results by LC were mono-substituted salicylic acid 7%, di-substituted salicylic acid 80%, and tri-substituted salicylic acid 13%. After that, add 700 ml of water to dilute, and add p with sulfuric acid.
Adjusted to H9, 180g of 43% zinc sulfate aqueous solution at 30 ℃
Was added dropwise 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 76.1 g (0.5 mol) of methyl salicylate (1.5 g)
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 ℃ and charged with 200 ml of warm water, then 95-98.
The temperature was raised to 0 ° C., 170 g of a 15% aqueous sodium hydroxide solution was added dropwise over 2 hours, and then aged at 98 to 100 ° C. for 5 hours to complete hydrolysis. The HLC measurement result of the hydrolyzate was 88% for di-substituted salicylic acid and 11 for tri-substituted salicylic acid.
% And the other 1% (FIG. 2). In this figure, RT
8.427 is 3,5- (α-methylbenzyl) salicylic acid. After that, 700 ml of water was added to dilute the solution, 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) methyl salicylate and 10
Charge 60 g of methanesulfonic acid to a flask at 60 to 65 ° C.
While maintaining the temperature, 140 g (1.346 mol) of styrene is added dropwise over 14 hours. After completion of the dropping, the reaction solution obtained by aging at the same temperature for 30 minutes was hydrolyzed with a 40% sodium hydroxide aqueous solution in the same manner as in Example-1. Then, it was neutralized with sulfuric acid to obtain an oily product containing 3,5-di (α-methylbenzyl) salicylic acid.

The result of the HLC analysis 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,
It is 5-di (α-methylbenzyl) salicylic acid.

Further, an attempt was made to form chlorite in the same manner as in Example 8, but gum-like and block-like forms were formed, and filtration, washing with water and drying were difficult.

[0078]

[Table 2]

[0079]

[Table 3]

[0080]

INDUSTRIAL APPLICABILITY 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 an inexpensive raw material and a simple operation.

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

[Brief description of 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 analysis result by HLC of an α-methylbenzyl-substituted salicylic acid derivative composition obtained by the method of the present invention.

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

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location B01J 27/125 27/128 27/132 27/138 31/10 B41M 5/155 5/30 // C07B 61/00 300

Claims (10)

[Claims] 1. A compound represented by the general formula (I): (Wherein R ₁ represents an alkyl group having 1 to 12 carbon atoms, an aralkyl group or a cycloalkyl group), the salicylic acid ester represented by the general formula (II) (Wherein R ₂ and R ₃ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents a halogen atom), and reacted with α-methylbenzyl halides in the presence of an acid catalyst, 3,5-di (α-methylbenzyl) salicylic acid ester produced is hydrolyzed.
A method for producing a 5-di (α-methylbenzyl) salicylic acid derivative. 2. The method according to claim 1, wherein 3,5-di (α-methylbenzyl) salicylic acid esters are separated from the reaction solution by vacuum distillation before the hydrolysis. 3. A compound represented by the general formula (I): (Wherein R ₁ represents an alkyl group having 1 to 12 carbon atoms, an aralkyl group or a cycloalkyl group), the salicylic acid ester represented by the general formula (II) (Wherein R ₂ and R ₃ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents a halogen atom), and α-methylbenzyl halides are reacted in the presence of an acid catalyst. , 3,5-di (α-methylbenzyl) produced
Hydrolyzed salicylate derivative 3,5-
Di (α-methylbenzyl) salicylic acid derivative 60 ~ 9
An α-methylbenzyl-substituted salicylic acid derivative composition, which is contained in an amount of 0% by weight. 4. A mono-substituted salicylic acid derivative having an α-methylbenzyl group in a range of 0 to 40% by weight, a tri-substituted salicylic acid derivative having an α-methylbenzyl group in a range of 0 to 40% by weight, and 3,5-di (α). The α-methylbenzyl-substituted salicylic acid derivative composition according to claim 3, wherein the -methylbenzyl) salicylic acid derivative is in the range of 60 to 90% by weight, and these constitute 95% by weight or more as a whole. 5. A polyvalent metal compound of 3,5-di (α-methylbenzyl) salicylic acid, which is obtained by reacting the α-methylbenzyl-substituted salicylic acid derivative composition according to claim 3 with a polyvalent metal salt, in an amount of 60 to 60%. A polyvalent metallized product of an α-methylbenzyl-substituted salicylic acid derivative composition, which is contained in an amount of 90% by weight. 6. The mono-substituted salicylic acid derivative polyvalent metal compound of α-methylbenzyl group obtained by reacting the α-methylbenzyl-substituted salicylic acid derivative composition according to claim 4 with a polyvalent metal salt is contained in an amount of 0 to 40% by weight. Range, α-methylbenzyl group tri-substituted salicylic acid derivative polyvalent metal compound 0-40
Wt% range and 3,5-di (α-methylbenzyl)
The polyvalent metallized product of the α-methylbenzyl-substituted salicylic acid derivative composition, wherein the polyvalent metallized product of the salicylic acid derivative is in the range of 60 to 90% by weight, and the total content of these is 95% by weight or more. 7. A 3,5-obtained by the method according to claim 2.
A method for producing a polyvalent metal compound of a 3,5-di (α-methylbenzyl) salicylic acid derivative, which comprises reacting a di (α-methylbenzyl) salicylic acid derivative with a polyvalent metal salt. 8. A color developing sheet using the polyvalent metal compound according to claim 5 as a color developing agent. 9. A color developing sheet using the polyvalent metal compound according to claim 6 as a color developing agent. 10. A developer sheet using the polyvalent metal compound according to claim 7 as a developer.