JPH02142747A - Nucleus-substituted salicylic acid and salt thereof - Google Patents

Abstract

NEW MATERIAL:The nucleous-substituted salicylic acid of formula I (R1 and R2 are tert-butyl, tert-amyl, tert-hexyl, tert-octyl, alpha,alpha-dialkylbenzyl or nucleus- substituted alpha,alpha-dialkylbenzyl) and its salt. EXAMPLE:3,5-Di-tert-butyl-6-methylsalicylic acid. USE:It has especially good solubility in organic solvent or organic polymer compound and is useful as a fungicide, a stabilizer for polymer compound or a color-developing agent for recording material. It develops dense color at a high rate of color development. PREPARATION:The sodium or potassium salt of the compound of formula I is produced by reacting sodium or potassium salt of a nucleus-substituted phenol of formula II with carbon dioxide gas (Kolbe-Schmitt's reaction). The reaction is carried out at 120-200 deg.C. The starting compound of formula II can be synthesized by the nucleus-substitution reaction of m-cresol.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to novel nuclear-substituted salicylic acids and salts thereof.

The novel nuclear-substituted salicylic acids and their salts have good solubility in water, organic solvents, or organic polymer compounds, and are suitable for application as bactericides, stabilizers for polymer compounds, or color developers for recording materials.

[Conventional technology]

Nuclear substituted salicylic acid and its salts have high bactericidal activity and are used as bactericidal agents. (Unexamined Japanese Patent Publication No. 62-1532
No. 45) Polyvalent metal salts of nuclear-substituted salicylic acid are used as stabilizers for polymeric compounds containing carbon dioxide, such as polyvinyl chloride. (% JP-A No. 56-112955) Polyvalent metal salts of nuclear-substituted salicylic acid, especially zinc salts, are used as color developers for recording materials. (% opening 48-9
No. 8914, No. 62-25086 and No. 63-186
No. 729) [Object of the Invention] The object of the present invention is to provide a compound which has particularly good solubility in water, organic solvents or organic polymer compounds, and which can be applied as a bactericide, a stabilizer for polymer compounds, or a color developer for recording materials. An object of the present invention is to provide a specific nuclear-substituted salicylic acid and a salt thereof suitable for use in the present invention.

[Structure of the invention]

According to the present invention, the general formula [I] (wherein R4 and R2 are a tert-butyl group, a tert-aryamyl group, a tert-hexyl group, a tert-aryoctyl group, an α, α-soalkylpenzyl group or a nuclear substituted A novel nuclear-substituted salicylic acid and its salts are provided. These are characterized by extremely high solubility in water, organic solvents, or organic polymer compounds.

A highly water-soluble fungicide is most preferred because it can be easily formulated or applied using water as a medium. Since the alkali metal salt, amine salt, or ammonium salt of the nuclear-substituted salicylic acid represented by the general formula [1] is easily dissolved in water, a highly concentrated aqueous solution can be specially prepared. Furthermore, since they do not particularly exhibit photoallergenic properties to the skin, they are safe and suitable for use as disinfectants over a wide range of areas.

Various metal compounds are used as stabilizers for halodane-containing polymer compounds, but especially when transparency is required for the polymer composition, metal compounds that have good solubility in the polymer compound are used. To be elected. The polyvalent metal salt of nuclear-substituted salicylic acid represented by the general formula [■] has good solubility in polymer compounds, forms a completely transparent composition, and has excellent stability, especially against heat and light. give.

Since the color development reaction of color developers for recording materials is generally carried out in a relatively polar organic medium, it can be said that solubility in the medium is the most important characteristic of the color developer. can. Polyvalent metal salts of nuclear-substituted salicylic acid represented by general formula [I], especially zinc salts, dissolve well even in organic solvents with low polarity and have a strong color developing effect, so when applied as a color developer, they are It has advantages such as color density and color development speed.

These solubility are closely related to the structure of general formula III]. In the general formula CD, R1 and R2 are a tert-butyl group, a tert-aryamyl group, a tert-hexyl group, a tertiary octyl group, an α,α-dialkylpencyl group, or a nuclear-substituted α,α-dialkylbenzyl group; All of these groups act as a cap and increase the solubility of the nuclear-substituted salicylic acid and its salts in organic solvents or organic polymer compounds. However, the effect alone is still 1
Good solubility as aimed at by the present invention cannot be obtained.

The 6-position of the nuclear-substituted salicylic acid represented by the general formula CD is a methyl group, and this is the most characteristic feature of the structure of the present invention, and its contribution to solubility is due to the bulky groups of R1 and R2. , is amazing. As described above, the nuclear-substituted salicylic acid with good solubility, which is the object of the present invention, is formed by having a methyl group at the 6-position and bulky groups of R1 and R2 at the 3- and 5-positions. I am forced to do so.

Specific examples of the nuclear-substituted salicylic acid represented by the general formula [■] include 3.5-ditertibutyl-6-methylsalicylic acid, 3-tert-butyl-5-tert-aryamyl-6-methylsalicylic acid, and 3-tert-butyl-6-methylsalicylic acid. Tertiarybutyl-5
-tert-hexyl-6-methylsalicylic acid, 3-tert-butyl-5-tert-octyl-6-methylsalicylic acid.

3-tert-butyl-5-(α,α-dimethylbenzyl)-6-methylsalicylic acid, 3-tert-butyl-
5-(α,α,3-trimethylbenzyl)-6-methylsalicylic acid, 3-tert-butyl-5-(α,α,4
-trimethylbenzyl)-6-methylsalicylic acid, 3-
tert-butyl-5-(α-methyl-α-ethylbenzyl)-6-methylsalicylic acid, 3-tert-butyl-5-tert-butyl-6-methylsalicylic acid, 3,
5-ditertiaryamyl-6-methylsalicylic acid, 3-
Tert-hexyl-5-tert-butyl-6-methylsalicylic acid, 3,5-diterhexyl-6-methylsalicylic acid, 3-tert-octyl-5-tert-butyl-6-methylsalicylic acid, 3,5-diter Charioctyl-6-methylsalicylic acid, 3-(α, α-
Examples include dimethylbenzyl)-5-tert-butyl-6-methylsalicylic acid or 3,5-di(α,α-trimethylbenzyl)-6-methylsalicylic acid,
Furthermore, from the viewpoint of ease of industrial implementation, 3,5-ditertiarybutyl-6-methylsalicylic acid, 3-tertiarybutyl-
5-(α,α-dimethylbenzyl)-6-1+rusalicylic acid, 3,5-ditertiamyl-6-methylsalicylic acid, 3-tert-octyl-5-tert-butyl-6-methylsalicylic acid or 3-( [alpha],[alpha]-dimethylbenzyl)-5-tajarizotyl-6-methylsalicylic acid is chosen and these are also more preferred for the purposes of the present invention.

These nuclear-substituted salicylic acids represented by the general formula [1) have the general formula [11] (wherein R1 and R2 are respectively the same as defined in the general formula [1)]. ) Reaction between the sodium salt or potassium salt of a nuclear-substituted phenol represented by and carbon dioxide gas (Colbecy Mits reaction)
It can be obtained as IJum salt or potassium salt. Both the sodium salts and potassium salts of general formula [I] and general formula [11] dissolve well in various organic solvents as intended by the present invention, so the series of operations is preferably carried out in an organic solvent. The reaction temperature is preferably in the range of 120°C to 200°C.

The nuclear substituted phenol represented by the general formula [11] can be obtained by subjecting metacresol to a nuclear substitution reaction. Reagents for introducing substituents include inbutylene, tert-butyl chloride, tert-liptanol, 2-methyl-1-butene, 2-methyl-2-butene, 2-methyl-
1--'8! Ntene, 2-methyl-2-ntenthene, 2-
Ethyl-1-hexene, zoisobutylene, α-methylstyrene, α,3-dimethylstyrene, α,4-dimethylstyrene, α-ethylstyrene, α,β-dimethylstyrene α-methyl-β-globylstyrene or α, Examples include β-diethylstyrene. As a catalyst for introducing a substituent, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, radruenesulfonic acid, xylene sulfonic acid, sec-butylbenzenesulfonic acid,
Acidic catalysts such as heteropolyacids, boron trifluoride, aluminum chloride or zinc chloride are preferred. When R1 and 82 in general formula [I] or general formula [n] are the same, the substituents are introduced into metacresol all at once using one reagent. R1 and R
2 is different, first introduce R1, then R
2 will be introduced.

As described above, the nuclear-substituted salicylic acid of the present invention is produced as its sodium salt or potassium salt. Free nuclear-substituted salicylic acid can be obtained by adding an acid such as dilute sulfuric acid or dilute hydrochloric acid to an aqueous solution of the sodium salt or potassium salt for acid precipitation. Furthermore, it can also be purified by recrystallization with an organic solvent.

These are generally insoluble in water but soluble in organic solvents, so they are used as oil-soluble fungicides in cutting oils and the like.

Since the alkali metal salt, amine salt, or ammonium salt of nuclear-substituted salicylic acid is water-soluble, an aqueous solution thereof can be obtained by neutralizing free nuclear-substituted salicylic acid with alkali hydroxide, amine, or ammonia in water as a medium. Preferred alkali hydroxides include lithium hydroxide, sodium hydroxide, or potassium hydroxide, and preferred amines include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethanolamine, jetanolamine, triethanolamine, and isonoamine. Ropanolamine, diisofo zf7-
Examples include /l/7amine, triisopropro, f/-ruamine, trimethylaminoethanol, diethylaminoethanol, and morpholine. These water-soluble nuclear-substituted salicylic acid ti have uses as water-soluble bactericides or fungicides.

Although polyvalent metal salts of nuclear-substituted salicylic acid are poorly soluble or insoluble in water, they are well soluble in organic solvents or organic polymer compounds. These are produced as water-insoluble salts by the metathesis method from an aqueous solution of a water-soluble salt of a nuclear-substituted salicylic acid and an aqueous solution of a water-soluble polyvalent metal salt. be done. At this time, heating or addition of an organic solvent can be carried out if desired.

Preferred polyvalent metals include magnesium, aluminum, calcium, iron, cobalt, nickel, zinc, strontium, cadmium, tin, barium, and lead, with magnesium, calcium, and zinc being the most preferred. Examples of water-soluble polyvalent metal salts include magnesium sulfate, aluminum sulfate, calcium chloride, zinc sulfate, and lead acetate. Polyvalent metal salts of nuclear-substituted salicylic acids, including % magnesium, calcium or zinc salts, are used as stabilizers for chlorine-containing polymeric compounds. At this time, compounds in which R1 and R2 of the general formula [1] are different are preferred because they have better solubility. Polyvalent metal salts of nuclear-substituted salicylic acids, especially zinc salts, are also used as color developers for recording materials. In this case, when the total number of carbon atoms of R1 and R2 in the general formula [1] is 9 or more, more preferably 12 or more, the recorded image has good resistance to humidity or water.

[Examples of the Invention] Next, in order to further clarify the present invention, specific examples and reference examples will be given and described.

Example 1 Internal volume with stirrer, thermometer and reflux condenser capable of separating and removing water 2. 330 grams (1,5 moles) of 2,4-tata-butyl-5-methylphenol in an OOO milliliter hard glass three-necked flask.
, 1,000 grams of diethylene glycol dimethyl ether, 100 grams of toluene, and 120 grams of 50 percent aqueous sodium hydroxide solution. Heat the flask while stirring to remove water that azeotropes with toluene. The contents of the dehydrated flask are transferred to a stainless steel autoclave having an internal volume of 2,000 ml. Add carbon dioxide gas to the autoclave at 20'Q/cm2
and reacted at 180°C for 3 hours. Once the autoclave is cooled and the temperature of the contents is below 90°C,
5. Depressurize the contents and reduce the internal volume. Oooomi! J! Transfer to a large beaker. Add 3,000g of boiling water and 50g of
Add 0 grams of toluene and stir.

This f'L is allowed to stand, and the oil layer that separates into the upper layer is removed.

While stirring, gradually add 170 ml of dilute sulfuric acid at 1O. When cooled, crystals precipitate out, which are completely filtered and recrystallized with 600 milliliters of toluene to obtain 262 grams of white crystals.

It has a melting point of 178°C and an acid value of 210.9 (theoretical value; 2
12.2) The nuclear magnetic resonance absorption spectrum is shown in Figure 1, confirming that it is 3,5-ditertiarybutyl-6-methylsalicylic acid.

Example 2 Internal volume with stirrer, thermometer, reflux condenser and dropping funnel 1. o o o Mi! J! 2-tert-butyl-5- in a J.T.L. hard glass four-hole flask.
Charge 492 grams (3 moles) of methylphenonol and 10 grams of dehydrated para-toluenesulfonic acid. Cool the flask to maintain a temperature of about 30°C to 35°C. Stir vigorously to remove α-methylstyrene 319 grams A (2
, 7 mol) 1 over a period of about 10 hours. 10 hours after the completion of the dropping, 200 g of water was added, the temperature was raised while stirring, and the mixture was boiled for about 1 hour. Transfer this to a separatory funnel and remove the aqueous layer. Furthermore, the washing operation was repeated three times using 200 grams of boiling water each time. This total internal volume is 1.0
Transfer to a vacuum distillation apparatus of 00 mm IJ IJ liter and reduce to 1.5
Approximately 610 grams of the fraction from 153°C to 158°C is collected using a toll. It has a melting point of 92°C and a hydroxyl number of 1.
99.1 (theoretical value: 198.7), and it is confirmed that it is 2-tert-butyl-4-[α,α-dimethylbenzyl]-5-methylphenol.

Example 2-2 Internal volume equipped with a stirrer, a thermometer, and a reflux condenser that can separate water2. In an ooo milliliter hard glass three-neck flask were placed 423 g (1.5 mol) of 2-tert-butyl-4-(α,α-tumethylbenzyl)-5-methylphenol obtained in Example 2 and diethylene glycol dimethyl ether. 800 grams, 350 grams of toluene, and 120 grams of 50/f-cent sodium hydroxide aqueous solution. Heat the flask while stirring to remove water that azeotropes with the toluene. The contents of the dehydrated flask are transferred to a stainless steel autoclave having an internal volume of 2,000 ml. Pressure carbon dioxide gas f20 kg7cm2 into the autoclave,
React at 180°C for 3 hours. Cool the autoclave, and when the temperature of the contents falls below 90℃, remove the contents and reduce the internal volume to 10,000 ml! Transfer to a 7'/liter flask. Add 5,000 ml of water to this,
While stirring, raise the temperature to 85°C, then let stand. After removing the upper oil layer, stir again and add 170 ml of 10N dilute sulfuric acid! j! Gradually drip 1 liter. An oily substance separates and crystallizes when cooled. When this is recrystallized from n-hexane, 368 grams of white crystals are obtained. It has a melting point of 172°C and an acid value of 172.2 (
Theoretical value; 171.9), and the nuclear magnetic resonance absorption spectrum is shown in Figure 2, 3-Tarjarichru5-(
It is confirmed to be α,α-dimethylbenzyl)-6-methylsalicylic acid.

Example 3 Internal volume 1.00CB with stirrer, thermometer, dropping funnel and reflux condenser! J! A 7-tall hard glass back-door flask is charged with 378 grams (3.5 moles) of metacresol and 5 grams of xylene sulfonic acid. While stirring the contents vigorously, 420 g (3 mol) of 2-methyl-2-butene containing a small amount of 2-methyl-1-butene was added dropwise from the dropping funnel over about 10 hours. Since the temperature rises due to heating during dropping, the flask is cooled to maintain a temperature of 30°C to 35°C. 10 hours after the completion of the dripping, add 200 grams of water and heat while stirring to give about 1 hour.
Boil for an hour. Transfer to a separatory funnel, remove the aqueous layer, and wash three times with 200 ml of boiling water each time. Transfer this to a vacuum distillation apparatus and reduce the temperature from 110°C to 1 torr.
510 grams of fraction up to 20° C. are obtained. It has a melting point of 64°C and a hydroxyl number of 226.5 (theoretical value; 225
．． 9) It is confirmed that it is 2,4-ditertiaryamyl-5-methylphenol.

Example 3-2 2,4-ditertiaryamyl-5- obtained in Example 3
From 372 grams (165 moles) of methylphenol, 278 grams of white crystals are obtained in exactly the same manner as in Example 1. It has a melting point of 125°C, an acid value of 193.0 (theoretical value; 191.9), and a nuclear magnetic resonance absorption (17) absorption spectrum shown in Figure 3). It is confirmed that it is 6-methylsalicylic acid.

Example 4 Distillation 5 from 100°C to 105°C at 1.5 torr was prepared in exactly the same manner as in Example 3 from 540 grams (5 moles) of metacresol and 336 grams (3 moles) of diisobutylene.
90 grams are obtained. This is a colorless, transparent, slightly viscous liquid with a hydroxyl value of 253.5 (theoretical value; 25
4.6). Further, gas chromatography confirms that this is 2-tert-octyl-5-methylphenol containing about 0.5 percent 3-methyl-4-tert-octylphenol.

Example 4-2 Internal volume 1 with stirrer, thermometer, gas inlet and reflux condenser with top connected to dry ice trap
．． 550 grams (2.5 moles) of the 2-tert-octyl-5-methylphenol obtained in Example 4 and 5 grams of hissecandabutylbenzenesulfonic acid were placed in a 000 milliliter hard glass back-door flask. While stirring, blow in butylene from the gas inlet.

As the reaction generates heat, the flask is cooled so that the temperature of the contents is between 30°C and 45°C.

The contents are sampled from time to time and the progress of the reaction is monitored by gas chromatography. Approximately 2 times until the reaction is fully completed
Blow in isobutylene so that it takes 0 hours. When the desired reaction is completed, stop blowing inbutylene and wash the contents with hot water.

The contents are a reddish-brown transparent viscous liquid with a hydroxyl number of 192.4 (theoretical value: 202.9). The deviation of the hydroxyl value from the theoretical value is considered to be due to impurities such as inbutylene polymers. Also, gas chromatography confirmed that this was pure i93? -Seventh 2-tert-octyl-4-tert-butyl-
It is confirmed to be 5-methylphenol. Moreover, the melting point of this purified product by k f# W is 72°C.

Example 4-3 341 grams of white crystals are obtained analogously to Example 2-2 from 60/f-cents (1.5 mol) of the product of Example 4-2. It has a melting point of 165℃ and an acid value of 176.
．． 4 (theoretical value; 175.1), and the nuclear magnetic resonance absorption spectrum is as shown in Figure 4, and is 3-(1,1, 3,3tetramethylbutyl)-5-
It is confirmed to be tert-butyl-6-methylsalicylic acid.

Example 5 540 grams of metacresol (540 grams) was prepared in the same manner as in Example 3.
mol) and α-methylstyrene 354 grams (3 mol)
From, 618 fractions from 105°C to 115°C at 1 torr
grams are obtained. It is an almost colorless, very viscous liquid with a hydroxyl number of 245.9 (theoretical value; 247.
9). Also, from gas chromatography, this is 1
．． It is confirmed that it is 2-(α,α-trimethylpennol)-5-methylphenol containing 3-methyl-4-(α,α-trimethylbenzyl)phenol of 3/#-cent.

Example 5-2 2-(α,α-tumethylbenzyl) obtained in Example 5
From 565 g (2.5 mol) of -5-methylphenol, a light brown, extremely viscous liquid is obtained in exactly the same manner as in Example 4-2. This has a hydroxyl value of 187.2 (
Theoretical value: 198.7) It was confirmed by gas chromatography that it was 2-(α,α-trimethylbenzyl)-4-tert-butyl-5-methylphenol with a purity of 94%.

Example 5-3 White crystals were obtained in exactly the same manner as in Example 4-3 from 2-(α,α-dimethylbenzyl)-4-tert-butyl-5-methylphenol obtained in Example 5-2. 362 grams are obtained. It has a melting point of 181℃ and an acid value of 170.
．． 2 (theoretical value: 171.9) and the nuclear magnetic resonance absorption spectrum is as shown in Figure 5, indicating that it is 3-(α,α-dimethylbenzyl)-5-tert-butyl-6-methylsalicylic acid. is confirmed.

Example 6 3,5-ditertiarybutyl-6- obtained in Example 1
264 grams (1 mole) of methylsalicylic acid are dissolved in 700 grams of an aqueous solution containing 1 mole of sodium hydroxide.

This is an aqueous solution containing about 30 percent sodium 3,5-ditertibutyl-6-methylsalicylate.

Example 7 In the same manner as in Example 6, the sodium salts of the nuclear-substituted salicylic acids obtained in Examples 2-2, 3-2, 4-3, and 5-3 are obtained.

Example 8 By replacing the aqueous sodium hydroxide solution in Examples 6 and 7 with an aqueous triethanolamine or morpholine solution, the corresponding triethanolamine or morpholine salt of a nuclear-substituted salicylic acid is obtained.

Example 9 In a stainless steel beaker with an internal volume of 2.000 milliliters, 400 grams of a 25% zinc sulfate aqueous solution was charged, and while stirring vigorously, the 3,5-Ivy butyl obtained in Example 6 was prepared. The entire aqueous solution of sodium 6-methylsalicylate is injected in about 20 minutes. After further stirring for 20 minutes, the precipitated zinc 3,5-ditertiarybutyl-6-methylsalicylate was filtered, and further 1.
Rinse with 1,000ml of water. This is vacuum dried at 110°C to obtain 297 grams of white powder. This has a zinc content of 10.9 mm (theoretical value; 11.
Oz? It is confirmed that it is zinc 3,5-ditertiarybutyl-6-methylsalicylate.

Example 10 A pure white powder was obtained from the nuclear-substituted sodium salicylate obtained in Example 7 in the same manner as in Example 9, and the fact that it was the desired product was confirmed by measuring the zinc content in each powder.

Comparative Example 1 (3,5-ditertiarybutylsalicylic acid) 3
．． From 5-ditertiarybutylsalicylic acid, Example 6,
The sodium salt thereof in the same manner as in Example 8 and Example 9,
Morpholine and zinc salts are obtained.

〔Effect of the invention〕

The nuclear-substituted salicylic acid and its salt of the present invention are characterized by excellent solubility in water and organic compounds, and have utility as a bactericidal agent, a stabilizer for polymeric compounds, or a color developer for recording paper. is large.

Table 1 shows the test results. Regarding solubility, ◎ means 50% or more, ○ means 20 to 50%,
Δ represents a solubility of 5 to 20 percent and × represents a solubility of less than 5 percent;
0 parts by weight and 3 parts by weight of nuclear substituted zinc salicylate f: 220
Kneaded at ℃ for 10 minutes, ◎ is completely transparent, ○ is almost transparent,
△ indicates that there is a slight cloudiness, and × indicates that there is a lot of turbidity.
After coating the paper surface so that fi0.7 grams per square meter is applied and drying, printing is done using the top sheet of commercially available pressure-sensitive recording paper.
The color is rich, △ is slightly inferior, and X is 'Jk' which does not develop color.

[Brief explanation of the drawing]

Figures 1 to 5 are all nuclear magnetic resonance absorption spectrum charts, Figure 1 is Example 1 and Figure 2 is Example 2-2.
, FIG. 3 shows each nuclear-substituted salicylic acid obtained in Example 3-2, FIG. 4 shows Example 4-3, and FIG. 5 shows each nuclear-substituted salicylic acid obtained in Example 5-3. DMSO-d6 was used as the solvent and tetramethylsilane was used as the reference. Agent Patent Attorney Ms. Yamashita Hiracho Adhesive C Nyama 1'Sei 1i 1OJ12fi Special, rll+Chief Bunsatsu 1, 1, ``1<'' Name of the Invention Nuclear Substitution Sally r- Ruic acid and salt: 3. Relationship with Sodewo-→Ruishi i?E1 Patent applicant name: Hikari Kaihatsu Science Institute 4, Agent 31 [) 3 (4: Ri l) +8: N 5. Patent of the subject specification of the supplement, 11. Scope of the invention, 1.''Detailed explanation column and drawings 6. Contents of amendment (1) Amend the scope of the claims as shown in the attached sheet. The following parts of the specification are amended as follows: Claim (1) General formula [I] (wherein R1 and R2 are tert-butyl group, t-aryamyl group, t-hexyl group, tertiary-hexyl group, lyoctyl group, α,α-dialkylbenzyl group, or a nuclear-substituted α,α-dialkylbenzyl group.) Nucleically substituted salicylic acid and its salts. (2) An acid represented by the general formula [I] and The salt is 35-
Ditert-butyl-6-methylsalicylic acid, 3-tert-butyl-5-(α,α-dimethylbenzyl)-6
-Methylsalicylic acid, 3,5-ditertiaryamyl-6
-methylsalicylic acid, 3-tert-octyl-5-diter-butyl-6-methylsalicylic acid and 3-(α
α-dimethylbenzyl)-5-ditertibutyl-6
The nuclear-substituted salicylic acid and its salt according to claim 1, which is an acid selected from -methylsalicylic acid and its salt. (3) The nuclear substituted salicylate according to claim 1 or 2, wherein the salt is a polyvalent metal salt. (4) The nuclear substituted salicylate according to claim 3, wherein the polyvalent metal salt is a zinc salt.

Claims (4)

[Claims] (1) General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼...[I] (In the formula, R_1 and R_2 are tert-butyl group, tert-aryamyl group, t-hexyl group, tert-rioctyl group) group, an α,α-dialkylbenzyl group or a nuclear-substituted α,α-dialkylbenzyl group) and its salts. (2) The acid represented by the general formula [I] and its salt are 3,
5-ditertibutyl-6-methylsalicylic acid, 3-
Tert-butyl-5-(α,α-dimethylbenzyl)
-6-methylsalicylic acid, 3,5-ditertiaryamyl-6-methylsalicylic acid, 3-tertiaryoctyl-5
-tert-butyl-6-methylsalicylic acid and 3-(
α,α-dimethylbenzyl)-5-tert-butyl-
The nuclear-substituted salicylic acid and its salt according to claim 1, which is an acid selected from 6-methylsalicylic acid and its salt. (3) The nuclear substituted salicylate according to claim 1 or 2, wherein the salt is a polyvalent metal salt. (4) The nuclear substituted salicylate according to claim 1 or 2, wherein the salt is a zinc salt.