JP2008137969A - Hydroxybenzene derivative and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound while maintaining processability and a high moist heat resistant bonding property of a rubber composition obtained by blending the same with a rubber, suppressing bloom observed by blending with resorcin or an RF (resorcin-formaldehyde) resin as much as possible, having less bonding property reduction while storing the rubber composition and exhibiting a stable bonding property. <P>SOLUTION: This compound is expressed by formula (1) [wherein, Rs are each independently a 1-8C aliphatic group, an alkoxy, hydroxy, carboxyl or amino which may be protected; Xs are each independently -CONH- or -COO-; (n) is an integer of 2 to 4; and (m) is an integer of 0 to 4, provided that (n+m) is 3 to 6]. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a novel composition or compound that improves adhesion durability with a metal reinforcing material such as a steel cord used for rubber articles such as pneumatic tires and industrial belts, and more particularly when blended with rubber. A compound having a specific structure, which has good processability of the rubber composition, and can stably exhibit initial adhesiveness and wet heat resistant adhesiveness to a metal reinforcing material regardless of the storage period of the rubber composition And a composition containing the compound as a main component.

  For rubber products that require particularly high strength, such as automobile tires, conveyor belts, hoses, etc., composites in which a metal reinforcing material such as a steel cord is coated with a rubber composition to reinforce the rubber and improve its strength and durability. Material is used. In order for the rubber-metal composite material to exhibit a high reinforcing effect and to obtain reliability, stable adhesion that is not affected by the conditions of mixing, blending, storage and the like is necessary between the rubber-metal reinforcing material. In order to obtain such a composite, a metal reinforcing material such as a steel cord plated with zinc, brass or the like is embedded in a rubber composition containing sulfur and bonded at the same time as rubber vulcanization at the time of heat vulcanization. Vulcanization bonding is widely used, and various studies have been made so far for improving adhesion between a rubber and a metal reinforcing material in the direct vulcanization bonding, in particular, wet heat resistance.

  For example, there has been reported a rubber composition containing resorcin or resorcin-formaldehyde resin (hereinafter abbreviated as “RF resin”) obtained by condensing resorcin and formalin for the purpose of improving moisture and heat resistance. (Patent Document 1). By blending the RF resin, the moisture and heat resistance of the steel cord and rubber will certainly improve dramatically.

  However, resorcin and RF resin have very high polarity, so they are poorly compatible with rubber. Depending on conditions such as mixing, blending, and storage, so-called blooms that precipitate resorcin and RF resin are generated. There is a risk of damage. In addition, due to the occurrence of bloom, there is a problem that the adhesiveness decreases when the rubber composition is compounded and then stored for a long time from vulcanization adhesion. Therefore, the rubber composition formulated with resorcin or RF resin is vulcanized and bonded quickly. This may impair the productivity of rubber articles.

  In addition, an adhesive material made of a mixed polyester having a resorcin skeleton having a weight average molecular weight of 3000 to 45000 has been reported (Patent Document 2). However, mixed polyester having a large molecular weight is not completely satisfactory, although the compatibility with rubber is improved as compared with RF resin. Furthermore, when a high molecular weight mixed polyester is blended with rubber, there is a problem that the viscosity of the blended rubber is increased and the processability is lowered, and the wet heat resistance is not sufficient.

JP 2001-234140 A JP-A-7-118621

  The present invention suppresses bloom as seen when compounding resorcinol and RF resin as much as possible while maintaining the processability and high heat-and-moisture resistance adhesion when the rubber composition is compounded with rubber. It is an object of the present invention to provide a compound having a specific structure that can reduce the decrease in adhesiveness and can exhibit excellent adhesion stability.

  As a result of intensive investigations to achieve the above-mentioned problems, the present inventors have blended a compound having a specific structure with rubber so that the heat and heat resistance equal to or higher than that of resorcin or RF resin is maintained, while resorcin or RF resin is maintained. While maintaining the processability of the rubber composition obtained by blending with rubber, which is a problem of the above, it has been found that it suppresses the occurrence of bloom and exhibits excellent adhesion stability regardless of the conditions of blending, storage, etc. The invention has been completed.

（式中、Ｒは、それぞれ独立して炭素数１〜８の脂肪族基、アルコキシ基、水酸基、カルボキシル基、保護されていてもよいアミノ基を表し、Ｘは、それぞれ独立して−ＣＯＮＨ−あるいは−ＣＯＯ−を表す。ｎは２〜４の整数を、ｍは０〜４の整数を表す。但し、ｎ＋ｍは３〜６である。） That is, the hydroxybenzene derivative of the present invention is a compound represented by the following general formula (1).

(In the formula, each R independently represents an aliphatic group having 1 to 8 carbon atoms, an alkoxy group, a hydroxyl group, a carboxyl group, or an amino group which may be protected, and each X independently represents —CONH—. Or represents -COO-, n represents an integer of 2 to 4, m represents an integer of 0 to 4, provided that n + m is 3 to 6.

（式中、Ｘは、それぞれ独立して−ＣＯＮＨ−あるいは−ＣＯＯ−を表す。ｎは３または４である。）ここで、前記一般式（２）中におけるｎは３である事が望ましく、また、前記一般式（２）で表される化合物としては、下記式（５）で表わされるベンゼントリカルボン酸系化合物が特に好ましい。

In a preferred embodiment of the present invention, the compound represented by the general formula (1) is a compound represented by the following general formula (2).

(In the formula, each X independently represents -CONH- or -COO-. N is 3 or 4.) Here, n in the general formula (2) is preferably 3. Moreover, as a compound represented by the said General formula (2), the benzene tricarboxylic acid type compound represented by following formula (5) is especially preferable.

  According to the present invention, the rubber composition obtained by blending with rubber maintains the workability and high moisture and heat resistance adhesion, while suppressing the bloom seen when blending resorcinol and RF resin as much as possible, and the rubber composition Thus, it is possible to provide a compound capable of exhibiting stable adhesiveness with little decrease in adhesiveness during storage.

  The present invention is described in detail below. The compound of the present invention is represented by the general formula (1). R in the general formula (1) represents an aliphatic group having 1 to 8 carbon atoms, an alkoxy group, a hydroxyl group, a carboxyl group, or an amino group that may be protected, and X represents —CONH— or —COO—. n represents an integer of 2 to 4, and m represents an integer of 0 to 4. However, n + m is 3-6. Here, each X may be the same or different, and when m is 2 or more, each R may be the same or different. In addition, it is preferable that m in General formula (1) is 0. In this case, the compound represented by General formula (1) turns into a compound represented by the said General formula (2). X in the general formula (2) has the same meaning as X in the general formula (1). Further, n in the general formula (2) is 3 or 4, but is preferably 3.

  Examples of the aliphatic group having 1 to 8 carbon atoms include a linear or branched alkyl group such as a methyl group, an ethyl group, a butyl group, an isobutyl group, an octyl group, and a 2-ethylhexyl group, a vinyl group, a butenyl group, Examples thereof include linear or branched alkenyl groups such as octenyl group, alkyl groups or alkenyl groups in which hydrogen atoms of these alkyl groups or alkenyl groups are substituted with hydroxyl groups or amino groups, and alicyclic groups such as cyclohexyl groups. It is done. Examples of the alkoxy group include a methoxy group and an ethoxy group, and examples of the protective group for the amino group include an acetyl group, a formyl group, a Boc group, and a Z group.

  Specific examples of the compound represented by the general formula (1) include 2-methyl-terephthalic acid bis (3-hydroxyphenyl) ester, 2-methyl-terephthalic acid bis (4-hydroxyphenyl) ester, 3-methyl- Terephthalic acid bis (3-hydroxyphenyl) ester, 3-methyl-terephthalic acid bis (4-hydroxyphenyl) ester, 4-methyl-isophthalic acid bis (3-hydroxyphenyl) ester, 4-methyl-isophthalic acid bis (4 -Hydroxyphenyl) ester, 1,3,5-benzenetricarboxylic acid tris (3-hydroxyphenyl) ester, 1,3,5-benzenetricarboxylic acid tris (4-hydroxyphenyl) ester, 1,3,5-benzenetricarboxylic acid Acid tris (1-hydroxyphenyl) ester, 1,3,5-benzene Zentricarboxylic acid-1,3-bis (3-hydroxyphenyl) ester, 1,3,5-benzenetricarboxylic acid-1,3-bis (4-hydroxyphenyl) ester, 1,3,5-benzenetricarboxylic acid- 1,3-bis (1-hydroxyphenyl) ester, 1,3,5-benzenetricarboxylic acid-1,5-bis (3-hydroxyphenyl) ester, 1,3,5-benzenetricarboxylic acid-1,5- Bis (4-hydroxyphenyl) ester, 1,3,5-benzenetricarboxylic acid-1,5-bis (1-hydroxyphenyl) ester, 1,2,4-benzenetricarboxylic acid tris (3-hydroxyphenyl) ester, 1,2,4-benzenetricarboxylic acid tris (4-hydroxyphenyl) ester, 1,2,4-benzenetricarboxylic acid Lis (1-hydroxyphenyl) ester, 1,2,4-benzenetricarboxylic acid-1,2-bis (3-hydroxyphenyl) ester, 1,2,4-benzenetricarboxylic acid-1,2-bis (4- Hydroxyphenyl) ester, 1,2,4-benzenetricarboxylic acid-1,2-bis (1-hydroxyphenyl) ester, 1,2,4-benzenetricarboxylic acid-1,4-bis (3-hydroxyphenyl) ester 1,2,4-benzenetricarboxylic acid-1,4-bis (4-hydroxyphenyl) ester, 1,2,4-benzenetricarboxylic acid-1,4-bis (1-hydroxyphenyl) ester, 2-methyl -Terephthalic acid bis (3-hydroxyphenyl) amide, 2-methyl-terephthalic acid bis (4-hydroxyphenyl) amide, 3-methyl -Terephthalic acid bis (3-hydroxyphenyl) amide, 3-methyl-terephthalic acid bis (4-hydroxyphenyl) amide, 4-methyl-isophthalic acid bis (3-hydroxyphenyl) amide, 4-methyl-isophthalic acid bis ( 4-hydroxyphenyl) amide, 1,3,5-benzenetricarboxylic acid tris (3-hydroxyphenyl) amide, 1,3,5-benzenetricarboxylic acid tris (4-hydroxyphenyl) amide, 1,3,5-benzene Tricarboxylic acid tris (1-hydroxyphenyl) amide, 1,3,5-benzenetricarboxylic acid-1,3-bis (3-hydroxyphenyl) amide, 1,3,5-benzenetricarboxylic acid-1,3-bis ( 4-hydroxyphenyl) amide, 1,3,5-benzenetricarboxylic acid-1,3-bis (1-hydroxyphenyl) amide, 1,2,4-benzenetricarboxylic acid tris (3-hydroxyphenyl) amide, 1,2,4-benzenetricarboxylic acid tris (4-hydroxyphenyl) amide, 1,2,4- Benzenetricarboxylic acid tris (1-hydroxyphenyl) amide, 1,2,4-benzenetricarboxylic acid-1,2-bis (3-hydroxyphenyl) amide, 1,2,4-benzenetricarboxylic acid-1,2-bis (4-hydroxyphenyl) amide, 1,2,4-benzenetricarboxylic acid-1,2-bis (1-hydroxyphenyl) amide, 1,2,4-benzenetricarboxylic acid-1,4-bis (3-hydroxy Phenyl) amide, 1,2,4-benzenetricarboxylic acid-1,4-bis (4-hydroxyphenyl) amide, 1,2,4- Emissions Zen tricarboxylic acid-1,4-bis (1-hydroxy-phenyl) amide. Among these, 1,3,5-benzenetricarboxylic acid tris (3-hydroxyphenyl) ester, 1,3,5-benzenetricarboxylic acid-1,3-bis (3-hydroxyphenyl) ester, 1,2,4 Benzenetricarboxylic acid tris (3-hydroxyphenyl) ester, 1,2,4-benzenetricarboxylic acid-1,2-bis (3-hydroxyphenyl) ester, 1,2,4-benzenetricarboxylic acid-1,4- Resorcinesters such as bis (3-hydroxyphenyl) ester, 1,3,5-benzenetricarboxylic acid tris (3-hydroxyphenyl) amide, 1,3,5-benzenetricarboxylic acid-1,3-bis (3- Hydroxyphenyl) amide, 1,2,4-benzenetricarboxylic acid tris (3-hydroxyphenyl) amide, M-amino such as 1,2,4-benzenetricarboxylic acid-1,2-bis (3-hydroxyphenyl) amide, 1,2,4-benzenetricarboxylic acid-1,4-bis (3-hydroxyphenyl) amide, etc. Phenol-based amides are preferred, especially 1,3,5-benzenetricarboxylic acid tris (3-hydroxyphenyl) ester, 1,3,5-benzenetricarboxylic acid-1,3-bis (3-hydroxyphenyl) ester, Benzenetricarboxylic acid triesters or diesters such as 2,4-benzenetricarboxylic acid tris (3-hydroxyphenyl) ester are preferred.

（式中、Ｒは、それぞれ独立して炭素数１〜８の脂肪族基、アルコキシ基、水酸基、カルボキシル基、保護されていてもよいアミノ基を表し、Ｙはハロゲン原子を表す。ｎは２〜４の整数を、ｍは０〜４の整数を表す。但し、ｎ＋ｍは３〜６である。）
下記一般式（４）で表される化合物

（式中、Ａは水酸基またはアミノ基を表す。）
とを塩基の存在下または非存在下で反応させて製造される。 Although the manufacturing method of the compound represented by General formula (1) is not specifically limited, For example, the polyvalent carboxylic acid halide represented by following General formula (3),

(In the formula, each R independently represents an aliphatic group having 1 to 8 carbon atoms, an alkoxy group, a hydroxyl group, a carboxyl group, or an amino group which may be protected, Y represents a halogen atom, and n represents 2. An integer of -4, m represents an integer of 0-4, provided that n + m is 3-6.
Compound represented by the following general formula (4)

(In the formula, A represents a hydroxyl group or an amino group.)
Is reacted in the presence or absence of a base.

  R in the general formula (3) has the same meaning as R in the general formula (1), and Y represents a halogen atom. As a halogen atom, a chlorine atom or a bromine atom is preferable.

  Examples of the compound represented by the general formula (3) include 2-methyl-terephthalic acid dichloride, 3-methyl-terephthalic acid dichloride, 4-methyl-isophthalic acid dichloride, 1,3,5-benzenetricarboxylic acid trichloride, 1 , 3,5-benzenetricarboxylic acid dichloride, 1,2,4-benzenetricarboxylic acid trichloride, 1,2,4-benzenetricarboxylic acid dichloride, and the like. Among these, 1,3,5-benzenetricarboxylic acid trichloride is preferable.

  Examples of the compound represented by the general formula (4) include catechol, resorcin, hydroquinone, o-aminophenol, m-aminophenol and p-aminophenol. Resorcin and m-aminophenol are particularly preferable.

  The base used for reacting the compound represented by the general formula (3) with the compound represented by the general formula (4) is usually pyridine, β-picoline, N-methylmorpholine, dimethylaniline, diethylaniline. Organic bases such as trimethylamine, triethylamine, and tributylamine are used.

  When the compound represented by the general formula (3) and the compound represented by the general formula (4), particularly catechol, resorcin and hydroquinone are reacted, the carboxylic acid in the compound represented by the general formula (3) is usually used. The compound represented by the general formula (4) is reacted with respect to the acid halide skeleton so as to have a molar ratio of 3 to 20 times. If the molar ratio is lower than this, the formation of a polymer is concerned, which is not preferable. On the other hand, even if the molar ratio is higher than this, an improvement in selectivity is not particularly observed, and the volumetric efficiency is deteriorated, which is disadvantageous for product isolation.

  When the compound represented by the general formula (3) is reacted with the compound represented by the general formula (4), a solvent can be used for the purpose of dissolving the raw materials. As the solvent, the above-described organic base may be used as it is, or another organic solvent that does not inhibit the reaction may be used. Examples of such a solvent include ether solvents such as dimethyl ether, diethyl ether, and dioxane.

  The reaction temperature for reacting the compound represented by the general formula (3) with the compound represented by the general formula (4) is usually -20 ° C to 120 ° C.

  The compound represented by the general formula (1) obtained by the above reaction can be isolated from the reaction mixture by a known method. That is, the organic base used in the reaction and the compound represented by the general formula (4) by an operation such as distillation under reduced pressure, and when an organic solvent is used in the reaction, the organic solvent is distilled off and dried. Examples include a method of reprecipitation by adding a poor solvent of the compound represented by the general formula (1) to the mixture, a method of adding water and an organic solvent immiscible with water to the reaction mixture, and extracting to the organic layer. . Moreover, you may refine | purify by recrystallization depending on the case.

  As a poor solvent for the compound represented by the general formula (1), water is usually used. Examples of the organic solvent immiscible with water include esters such as ethyl acetate and butyl acetate, and ketones such as methyl isobutyl ketone and diisobutyl ketone.

で表される二量体が副生する事があるが、該二量体を分離すること無く使用する事が出来る。尚、式（６）の二量体は、通常、式（５）で表わされる化合物に対して１〜２０質量％含まれる。 When 1,3,5-benzenetricarboxylic acid trichloride is used as the compound represented by the general formula (3) and resorcin is used as the compound represented by the general formula (4), the above formula ( The compound represented by 5) is obtained. In this case, the following formula (6):

The dimer represented by the formula may be by-produced, but the dimer can be used without separation. In addition, the dimer of Formula (6) is contained normally 1-20 mass% with respect to the compound represented by Formula (5).

  The compound of the present invention is characterized by being easily mixed with a rubber component as compared with resorcin or RF resin. Therefore, the rubber composition containing the compound of the present invention tends to be less likely to bloom than the rubber composition containing resorcin or RF resin. This is presumably because the compound of the present invention has a lower polarity than resorcin or RF resin. Further, the rubber composition containing the compound of the present invention is excellent in adhesion stability regardless of the storage period. Therefore, the compound of the present invention is useful as an adhesion improver.

  Hereinafter, the present invention will be described in more detail with reference to Examples, Reference Examples, and Comparative Examples, but the present invention is not limited to the following Examples.

(Example 1)
Preparation of 1,3,5-benzenetricarboxylic acid-triresorcin ester A solution of 176.2 g (1.60 mol) of resorcin in 176.2 g of pyridine is cooled to 10 to 15 ° C. Then, 24.8 g (0.0934 mol) of 1,3,5-benzenetricarboxylic acid trichloride, which was heated and melted, was added dropwise over 1 hr. Then, after aging at room temperature for 2 hr, the temperature was raised to 115 ° C. to 120 ° C. and aging was performed at the same temperature for 6 hr. From the obtained mass, pyridine was distilled off at 120 ° C. under reduced pressure. The final degree of vacuum reached 20 torr.

  After 200 g of water was charged into the mass from which pyridine had been distilled off, the pH was adjusted to 3 with hydrochloric acid, and an additional 500 g of water was added. Thereafter, extraction was performed 4 times with 100 ml of ethyl acetate, and the ethyl acetate layer was washed with water, dried over Mg sulfate and concentrated to distill off the ethyl acetate to obtain 250 g of syrup. Thereafter, when water was added and the whole became cloudy, this solution was discharged into 2 kg of water, and the resulting precipitate was filtered, washed with water, and dried under reduced pressure at 60 ° C. to obtain 38.52 g of powder. It was. The crude yield was 85% based on 1,3,5-benzenetricarboxylic acid.

  As a result of analyzing the obtained powder by HPLC, 84.1 area% (85.3 mass%) of 1,3,5-benzenetricarboxylic acid-triresorcin ester and 11.0 area% of dimer ( 11.1% by mass) and resorcin was 0.5% by mass.

  The identification data of 1,3,5-benzenetricarboxylic acid-triresorcin ester and dimer are as follows.

<Identification data of 1,3,5-benzenetricarboxylic acid triresorcin ester>
MS spectral data FAB (pos.) M / z = 487 (M + H) ⁺
IR spectral data 1745 cm ⁻¹ , 1227 cm ⁻¹ and 1136 cm ⁻¹
The NMR spectrum data are shown in Table 1-1 and Table 1-2.

<Identification data of dimer>
The NMR spectrum data are shown in Table 2-1 and Table 2-2.

The HPLC analysis conditions are as follows.
Analysis of 1,3,5-benzenetricarboxylic acid-triresorcin ester, dimer and resorcin Column: YMC A-312 ODS
Column temperature: 40 ° C
Eluent: Methanol / water = 7/3 (adjusted to pH = 3 with phosphoric acid)
Detection: UV (254 nm)

(Reference Example 1)
Using the composition produced in Example 1 as a test compound, a 2200 mL Banbury mixer was kneaded and mixed with the rubber compounding formulation shown in Table 3 to prepare an unvulcanized rubber composition. The bloom resistance, Mooney viscosity, adhesiveness immediately after compounding, and adhesiveness after leaving the compounded rubber were measured and evaluated. The results are shown in Table 3.

<Broom resistance>
After storing the unvulcanized rubber composition at 40 ° C. for 7 days, whether or not the compounding agent was deposited on the rubber surface was visually confirmed, and judged by ○, Δ, and ×.
○: No compounding agent is deposited on the surface.
Δ: Precipitated in part ×: Precipitating agent deposited on the entire surface

<Mooney viscosity>
The unvulcanized rubber composition was measured for ML (1 + 4) 130 ° C. according to JIS K6300-2001. A result shows that it is so favorable that a numerical value is low.

<Adhesion test>
Steel cords (1x5 structure, strand diameter 0.25mm) plated with brass (Cu; 63% by mass, Zn: 37% by mass) are arranged in parallel at 12.5mm intervals. After coating with the composition, this was immediately vulcanized under conditions of 160 ° C. × 15 minutes to prepare a sample having a width of 12.5 mm. For each of the following adhesive properties, in accordance with ASTM-D-2229, the steel cord was pulled out from each sample, the rubber coating state was visually observed, displayed in 0 to 100%, and each adhesive index It was. It shows that it is so favorable that a numerical value is large. Initial adhesion was measured immediately after the vulcanization. The wet heat adhesiveness was measured after aging and after aging at 70 ° C., 100% humidity and 4 days of wet heat conditions.

<Adhesion stability test>
The steel cord-rubber composite obtained by coating the unvulcanized steel cord with each rubber composition from both the upper and lower sides is left in a constant temperature and humidity chamber of 40 ° C. × 80 RH% for 7 days, and then vulcanized at 160 ° C. for 15 minutes. Then, initial adhesiveness was measured and used as an index of adhesive stability.

(Comparative Example 1)
A rubber composition was prepared and evaluated in the same manner as in Reference Example 1 except that the composition of the present invention was not used as a test compound. The results are shown in Table 3.

(Comparative Example 2)
A rubber composition was prepared and evaluated in the same manner as in Reference Example 1 except that 2 parts by mass of resorcin as a test compound was added to the basic rubber compound. The results are shown in Table 3.

(Comparative Example 3)
A rubber composition was prepared and evaluated in the same manner as in Reference Example 1 except that 2 parts by mass of RF resin was added to the basic rubber compound as a test compound. The results are shown in Table 3. In addition, RF resin was manufactured with the following method.

  First, 1100 g of water, 1100 g (10 mol) of resorcin, and 1.72 g (10 mmol) of p-toluenesulfonic acid were charged into a four-necked flask equipped with a cooling tube, a stirrer, a thermometer, a dropping funnel, and a nitrogen introducing tube at 70 ° C. The temperature was raised to. 477 g (5.9 mol) of 37% formalin solution was added dropwise over 2 hours, and kept at the same temperature for 5 hours to complete the reaction. After the completion of the reaction, 4 g of 10% aqueous sodium hydroxide solution was added to neutralize, and then the condenser was changed to a Dean-Stark type refluxing device. The temperature was raised to 150 ° C. while distilling off water, and further under reduced pressure of 20 mmHg for 1 hour. Water was removed to obtain an RF resin. The obtained RF resin had a softening point of 124 ° C. and a residual resorcin content of 17%.

(Comparative Example 4)
A rubber composition was prepared and evaluated in the same manner as in Reference Example 1 except that 2 parts by mass of the mixed polyester described in JP-A-7-118621 (Patent Document 2) was mixed as a test compound in the rubber basic compound. . The results are shown in Table 3. The mixed polyester was synthesized according to Example 1 described in the above patent.

  A 300 ml four-necked flask equipped with a reflux condenser and a thermometer was charged with 108.9 g (0.99 mol) of resorcin, 131.4 g (0.90 mol) of adipic acid, 222.0 g (2.175 mol) of acetic anhydride and 0.54 g of pyridine. (0.5% by weight based on resorcin) was charged, and after substitution with nitrogen, the mixture was stirred at room temperature for 15 minutes, then heated to 100 ° C. and subjected to 2 hr acetylation at the same temperature. Thereafter, the temperature was raised while distilling acetic acid produced as a by-product out of the system, and the mixture was aged at 140 ° C. for 1 hour, further heated and aged at 240 ° C. for 2 hours. Next, aging was continued at 240 ° C. under reduced pressure (50 mmHg). The reaction mixture was discharged into a magnetic dish to obtain 195.6 g of an ocher candy. It gradually crystallized by kneading with a glass rod. As a result of the analysis, it contained 0.1% by weight of resorcin, 0.5% by weight of resorcin monoacetate, and 0.8% by weight of resorcin diacetate. Moreover, as a result of measuring molecular weight by GPC, the weight average molecular weight was about 30000 (PS conversion).

Claims (6)

A compound represented by the following general formula (1).

(In the formula, each R independently represents an aliphatic group having 1 to 8 carbon atoms, an alkoxy group, a hydroxyl group, a carboxyl group, or an amino group which may be protected, and each X independently represents —CONH—. Or represents -COO-, n represents an integer of 2 to 4, m represents an integer of 0 to 4, provided that n + m is 3 to 6. The compound according to claim 1, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

(In the formula, each X independently represents -CONH- or -COO-, and n is 3 or 4.)   The compound according to claim 2, wherein n in the general formula (2) is 3. A polyvalent carboxylic acid halide represented by the following general formula (3):

(In the formula, each R independently represents an aliphatic group having 1 to 8 carbon atoms, an alkoxy group, a hydroxyl group, a carboxyl group, or an amino group which may be protected, Y represents a halogen atom, and n represents 2. An integer of -4, m represents an integer of 0-4, provided that n + m is 3-6.
The following general formula (4)

(In the formula, A represents a hydroxyl group or an amino group.)
The manufacturing method of the compound represented by General formula (1) characterized by making the compound represented by these react. The compound according to claim 1, wherein the compound represented by the general formula (2) is a benzenetricarboxylic acid compound represented by the following formula (5).

The benzenetricarboxylic acid-based compound according to claim 5, comprising a dimer represented by the following formula (6).