Novel trihydroxybenzene derivatives

Abstract

An object of the present invention is to provide a novel compound that has good solubility in solvents, high storage stability (dissolution stability) during storage at refrigerated or frozen temperatures, and can be used as a crosslinking agent. As a solution, there is provided a substituted triphenol compound represented by the following formula (2).

Description

Technical Field

[0001] The present invention relates to a novel triphenol derivative having good solubility in solvents and excellent storage stability. Background Art

[0002] Conventionally, in order to improve the film properties of photosensitive resins, phenolic hydroxymethyl compounds or methoxymethyl compounds have been used as crosslinking agents. From the viewpoint of high crosslinking reaction efficiency and stable film properties, crosslinking agents are preferably compounds having a large number of crosslinking groups per molecule. For example, regarding phenolic compounds containing methoxymethyl that have sufficient hard film properties even in small amounts, a group of compounds represented by the following chemical structures have been reported (for example, Patent Documents 1 and 2, etc.).

[0003] [Chemical Formula 1]

[0004]

[0005] Patent Documents

[0006] Patent Document 1: Japanese Patent Laid-Open No. 07-017888

[0007] Patent Document 2: Japanese Patent Laid-Open No. 2007-016214 Summary of the Invention

[0008] Since phenolic hydroxymethyl compounds or methoxymethyl compounds crosslink when stored at temperatures above room temperature, refrigerated or frozen storage is preferred. For solution products such as photosensitive resin compositions (varnishes), photoresists, and coatings that use the above compounds, from the perspective of quality storage stability during storage, storage under refrigeration is required. On the other hand, from the perspective of manufacturing efficiency, the raw materials may sometimes be solubilized in advance for use.

[0009] The inventors have recognized that the compound (x) or compound (y) represented by the above chemical structure has the characteristic of being easily crystallized due to the symmetry of the mother skeleton. Therefore, as described in the experimental examples below, there is a problem that the amount dissolved in the solvent is not much. In addition, it has also been recognized that even if a desired high-concentration solution can be prepared at room temperature, crystals will precipitate when the solution is stored under refrigeration or freezing. Therefore, when stored under refrigeration or freezing, only a low-concentration solution that does not precipitate crystals can be prepared, and there is a problem that the amount added as a crosslinking agent is limited.

[0010] The present invention has been completed against the above background, and its object is to provide a novel compound having good solubility in solvents, high storage stability (dissolution stability) during refrigerated or frozen storage, and usable as a crosslinking agent.

[0011] The present inventors conducted in-depth research to solve the above problems and found that, by introducing a mother skeleton containing a linear alkylene group instead of the mother skeletons of conventionally known compounds (for example, the above Patent Documents 1 and 2), especially by utilizing the flexibility of the mother skeleton of raspberry ketone (4-(hydroxyphenyl)-2-butanone), crystallization can be inhibited and the solubility in solvents can also be improved, thus completing the present invention. The inhibition of crystallization and the improvement of solubility in solvents are considered to be due to the introduction of the above mother skeleton, which makes it difficult for molecules to stack with each other.

[0012] The present invention is as follows.

[0013] 1. A substituted triphenol compound, characterized in that it is represented by the following formula (1),

[0014] [Chemical formula 2]

[0015]

[0016] In the formula, each R1 independently represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a phenyl group, and each R a independently represents a hydrogen atom or a substituted carbonyl group, and each R b independently represents a substituent, n represents an integer of 1 to 2, m represents 0 or an integer of 1 to 3, p represents an integer of 1 to 6, and among them, m + n is an integer of 1 to 4.

[0017] 2. A substituted triphenol compound, characterized in that it is represented by the following formula (2),

[0018] [Chemical formula 3]

[0019]

[0020] In the formula, each R1 independently represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a phenyl group, each R2 independently represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, n represents an integer of 1 to 2, m represents 0 or an integer of 1 to 3, p represents an integer of 1 to 6, and among them, m + n is an integer of 1 to 4.

[0021] 3. A substituted triphenol compound, characterized in that it is represented by the following formula (3),

[0022] [Chemical formula 4]

[0023]

[0024] In the formula, each R1 independently represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms or a phenyl group, R3 and R4 each independently represent a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 8 carbon atoms, R3 and R4 may be bonded to each other to form, as a whole, a cyclic secondary amino group having 5 to 10 carbon atoms which may contain an oxygen atom or a sulfur atom, n represents an integer of 1 to 2, m represents an integer of 0 or 1 to 3, P represents an integer of 1 to 6, and m + n is an integer of 1 to 4.

[0025] 4. A substituted triphenol compound, characterized in that it is represented by the following formula (4):

[0026] [Chemical formula 5]

[0027]

[0028] In the formula, each R1 independently represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms or a phenyl group, each R5 independently represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 8 carbon atoms, n represents an integer of 1 to 2, m represents an integer of 0 or 1 to 3, p represents an integer of 1 to 6, and m + n is an integer of 1 to 4.

[0029] The novel compound of the present invention can exhibit excellent effects of good solubility in solvents and high storage stability (dissolution stability) during storage under refrigeration or freezing.

[0030] In addition, by using the novel compound of the present invention as a crosslinking agent, a photosensitive resin with improved film properties can be expected to be created, and thus it is useful.

[0031] Furthermore, the novel compound of the present invention can also be used as a curing agent for epoxy resins. Detailed Description of the Invention

[0032] Hereinafter, the present invention will be described in detail.

[0033] <Compound of the Present Invention>

[0034] The compound of the present invention is a substituted triphenol compound represented by the following formula (1).

[0035] [Chemical formula 6]

[0036]

[0037] (In the formula, each R1 independently represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms or a phenyl group, R a each independently represents a hydrogen atom or a substituted carbonyl group, R bEach independently represents a substituent, n represents an integer from 1 to 2, m represents 0 or an integer from 1 to 3, and p represents an integer from 1 to 6. Among them, m + n is an integer from 1 to 4.)

[0038] Among the substituted triphenol compounds represented by the above formula (1), the preferred compounds are the substituted triphenol compounds represented by the above formulas (2) to (4). That is, R in the above formula (1) a , preferably a hydrogen atom or a -COR5 group (R5 represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 8 carbon atoms), R b is preferably an -OR2 group (R2 represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms), an -NR3R4 group (R3 and R4 each independently represent a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 8 carbon atoms), or an -OCOR5 group (R5 represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 8 carbon atoms).

[0039] R1 in the above formulas (1) to (4) each independently represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a phenyl group. Among them, a linear or branched alkyl group having 1 to 4 carbon atoms, a cyclohexyl group, or a phenyl group is preferred, and a linear or branched alkyl group having 1 to 4 carbon atoms or a cyclohexyl group is more preferred, and a methyl group or a cyclohexyl group is particularly preferred.

[0040] m in the above formulas (1) to (4) represents 0 or an integer from 1 to 3. Among them, 0, 1 or 2 is preferred, and 0 or 1 is more preferred. When M is 1, the substitution position of R1 in the benzene ring is preferably ortho to the hydroxyl group or the -OCOR5 group.

[0041] p in the above formulas (1) to (4) represents an integer from 1 to 6. Among them, an integer from 1 to 4 is preferred, 1 or 2 is more preferred, and 2 is particularly preferred.

[0042] R2 in the above formula (2) each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. Among them, a linear or branched alkyl group having 1 to 4 carbon atoms is preferred, methyl or ethyl is more preferred, and methyl is particularly preferred. The substitution position of the -CH2OR2 group on the benzene ring in the above formula (2) is preferably ortho to the hydroxyl group.

[0043] R3 and R4 in the above formula (3) each independently represent a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 8 carbon atoms. Among them, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms is preferred, a linear or branched alkyl group having 1 to 6 carbon atoms is more preferred, a linear or branched alkyl group having 1 to 4 carbon atoms is further preferred, and a methyl group is particularly preferred.

[0044] In addition, when a cyclic secondary amino group having 5 to 10 carbon atoms which may contain an oxygen atom or a sulfur atom is formed as a whole, specifically, for example, a cyclic secondary amino group represented by the following formula can be cited, and the following is particularly preferred.

[0045] [Chemical formula 7]

[0046]

[0047] (In the formula, * refers to a bonding group.)

[0048] The substitution position of the -CH2NR3R4 group on the benzene ring in the above formula (3) is preferably ortho to the hydroxyl group.

[0049] R5 in the above formula (4) each independently represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 8 carbon atoms. Among them, a linear or branched alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 8 carbon atoms is preferred, a linear or branched alkyl group having 1 to 6 carbon atoms, or a phenyl group is more preferred, and a linear or branched alkyl group having 1 to 4 carbon atoms is further preferred, and methyl is particularly preferred.

[0050] The substitution position of the -CH2OCOR5 group on the benzene ring in the above formula (4) is preferably ortho to the -OCOR5 group.

[0051] <Substituted triphenol compound represented by formula (2)>

[0052] Regarding the substituted triphenol compound represented by the above formula (2) as the compound of the present invention, a preferred compound is a substituted triphenol compound represented by the following formula (2a) in which the hydroxyl groups are in the para position, and a more preferred compound is a substituted triphenol compound represented by the following formula (2b) in which "p" in the following formula (2a) is 2.

[0053] [Chemical formula 8]

[0054]

[0055] (In the formula, R1, R2, m, n, and p have the same definitions as in formula (2).)

[0056] Specific examples or preferred examples of R1, R2, m, n, and p in the above formula (2a) are the same as those in the above formula (2).

[0057] [Chemical formula 9]

[0058]

[0059] (In the formula, R1, R2, m, and n have the same definitions as in formula (2).)

[0060] Specific examples or preferred examples of R1, R2, m, and n in the above formula (2b) are the same as those of the above formula (2).

[0061] Among the substituted triphenol compounds represented by the above formula (2b) as a further preferred group of compounds, the group of compounds represented by the following chemical structural formula is particularly preferred.

[0062] [Chemical Formula 10]

[0063]

[0064] <Substituted Triphenol Compound Represented by Formula (3)>

[0065] Regarding the substituted triphenol compound represented by the above formula (3) as the compound of the present invention, the preferred compound is the substituted triphenol compound represented by the following formula (3a) in which the hydroxyl group is in the para position, and the further preferred compound is the substituted triphenol compound represented by the following formula (3b) in which "p" in the following formula (3a) is 2.

[0066] [Chemical Formula 11]

[0067]

[0068] (In the formula, R1, R3, R4, m, n, and p have the same definitions as in formula (3).)

[0069] Specific examples or preferred examples of R1, R3, R4, m, n, and p in the above formula (3a) are the same as those of the above formula (3).

[0070] [Chemical Formula 12]

[0071]

[0072] (In the formula, R1, R3, R4, m, and n have the same definitions as in formula (3).)

[0073] Specific examples or preferred examples of R1, R3, R4, m, and n in the above formula (3b) are the same as those of the above formula (3).

[0074] Among the substituted triphenol compounds represented by the above formula (3b) as a further preferred group of compounds, the group of compounds represented by the following chemical structural formula is particularly preferred.

[0075] [Chemical Formula 13]

[0076]

[0077] <Substituted Triphenol Compound Represented by Formula (4)>

[0078] Regarding the substituted triphenol compound represented by the above formula (4) of the compound of the present invention, a preferred compound is a substituted triphenol compound represented by the following formula (4a) in which the -OCOR5 group is in the para position, and a more preferred compound is a substituted triphenol compound represented by the following formula (4b) in which "p" in the following formula (4a) is 2.

[0079] [Chemical Formula 14]

[0080]

[0081] (In the formula, R1, R5, m, n, and p have the same definitions as in formula (4).)

[0082] Specific examples or preferred examples of R1, R5, m, n, and p in the above formula (4a) are the same as those in the above formula (4).

[0083] [Chemical Formula 15]

[0084]

[0085] (In the formula, R1, R5, m, and n have the same definitions as in formula (4).)

[0086] Specific examples or preferred examples of R1, R5, m, and n in the above formula (4b) are the same as those in the above formula (4).

[0087] Among the substituted triphenol compounds represented by the above formula (4b) which are a group of further preferred compounds, a group of compounds represented by the following chemical structural formula are particularly preferred.

[0088] [Chemical Formula 16]

[0089]

[0090] <Manufacturing Method of the Compound of the Present Invention>

[0091] As shown in the following reaction formula, the raw material (7) of the compound of the present invention is produced by the condensation reaction of a ketone (5) having a hydroxyphenyl group and a phenol (6). This condensation reaction can be carried out according to known reaction conditions.

[0092] [Chemical Formula 17]

[0093]

[0094] (In the formula, R1, m, and p have the same definitions as in formulas (1) to (4).)

[0095] As the ketones (5) having a hydroxyphenyl group in the above manufacturing method, they can be manufactured, for example, by the method described in Japanese Patent Laid-Open No. 51-32532. Specifically, for example, 4-(4-hydroxyphenyl)butan-2-one (CAS registry number 5471-51-2), 4-(4-hydroxy-3-methylphenyl)butan-2-one (CAS registry number 125101-98-6), 4-(4-hydroxy-2-methylphenyl)butan-2-one (CAS registry number 91969-86-7), 4-(4-hydroxy-3-isopropylphenyl)butan-2-one (CAS registry number 96713-34-7), 4-(4-hydroxy-3-tert-butylphenyl)butan-2-one (CAS registry number 54685-33-5), 4-(4-hydroxy-3-cyclohexylphenyl)butan-2-one (CAS registry number 60561-24-2), 4-(4-hydroxy-2,6-dimethylphenyl)butan-2-one (CAS registry number 125102-00-3), 4-(4-hydroxy-2,3-dimethylphenyl)butan-2-one (CAS registry number 125102-01-4), 4-(4-hydroxy-3,5-dimethylphenyl)butan-2-one (CAS registry number 91374-58-2), 4-(4-hydroxy-3,5-dibutylphenyl)butan-2-one (CAS registry number 5082-72-4), etc. Among them, 4-(4-hydroxyphenyl)butan-2-one is particularly preferred.

[0096] In addition, as shown in the following reaction formula, the raw material (7) of the compound of the present invention can also be manufactured by the reaction of a halogenated ketone (8) and a phenol (6). This reaction can be carried out according to known reaction conditions.

[0097] [Chemical formula 18]

[0098]

[0099] (In the formula, R1, m, and p have the same definitions as in formulas (1) to (4), and X represents a halogen atom.)

[0100] As the halogenated ketones (8) in the above manufacturing method, specifically, for example, fluoroacetone, chloroacetone, bromoacetone, iodoacetone, 4-fluoro-2-butanone, 4-chloro-2-butanone, 4-bromo-2-butanone, 4-iodo-2-butanone, 5-chloro-2-pentanone, 5-bromo-2-pentanone, 5-iodo-2-pentanone, 6-chloro-2-hexanone, 6-bromo-2-hexanone, 6-iodo-2-hexanone, 7-chloro-2-heptanone, 7-bromo-2-heptanone, 7-iodo-2-heptanone, 8-chloro-2-octanone, 8-bromo-2-octanone, 8-iodo-2-octanone, etc. can be cited.

[0101] <Manufacturing method 1>

[0102] As the production method 1 of the compound of the present invention, taking the production method of the following preferred compound as an example, the method via a hydroxymethyl compound will be specifically described. Hereinafter, the compounds in the following reaction formula will be referred to as "compound (A1)", "compound (B1)", and "compound (C1)".

[0103] [Chemical formula 19]

[0104]

[0105] (Step I)

[0106] The following description is made for the initial step (I).

[0107] It can be obtained by using compound (A1) as a raw material, reacting 1 mole of compound (A1) with 6 to 12 moles, preferably 9 moles of formaldehyde in the presence of a basic catalyst in an aqueous solvent or a mixed solvent of water and an organic solvent, and then neutralizing the resulting reaction product. In the above production method, as formaldehyde, commercially available 35% formalin aqueous solution can be directly used. In addition, in the presence of water, paraformaldehyde or trioxane having the same effect as formaldehyde can also be used, but formalin is preferably used.

[0108] Examples of the basic catalyst include hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, and magnesium hydroxide, or organic strong bases such as tetramethylammonium hydroxide. Among them, alkali metal hydroxides such as sodium hydroxide or potassium hydroxide or organic strong bases such as tetramethylammonium hydroxide are preferred, and an aqueous solution of 10 to 40 wt% of these bases is preferably used. In step (I), the basic catalyst is preferably used in an amount of 2.5 to 3.5 molar times, more preferably 3 molar times, based on compound (A1) as the raw material.

[0109] The reaction of step (I) is usually carried out in an aqueous solvent or a mixed solvent of water and an organic solvent. Regarding the solvent, if the basic aqueous solution of the basic catalyst can partially or completely dissolve compound (A1) as the raw material and the reaction mixture can be stirred, there is no need to specifically use these solvents. However, when a solvent is required, generally, it is preferably used in a range of about 1 to 5 times, more preferably about 2 to 3 times, by weight based on compound (A1) as the raw material.

[0110] As the above-mentioned organic solvent, within the range that does not impair the solubility of the aforementioned basic catalyst and the aqueous solvent mixture of the compound (A1) as a raw material, for example, the following can be used: alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol, ethylene glycol monomethyl ether, diethylene glycol, carbitol, etc.; aromatic hydrocarbons such as toluene and xylene; and water-soluble aprotic polar solvents such as dimethyl sulfoxide, N-methylpyrrolidone, and dimethylformamide.

[0111] Regarding the reaction in step (I), it is usually carried out within the range of 20 to 50 °C, preferably within the range of 25 to 40 °C, more preferably within the range of 30 to 35 °C, and usually carried out for 1 to 72 hours, preferably about 4 to 16 hours. If the reaction temperature is lower than 20 °C, the reaction proceeds slowly, and when it is higher than 50 °C, various undesired by-products such as a large amount of polybody impurities are generated, so it is not preferred.

[0112] In the presence of a basic catalyst, after the reaction between the compound (A1) as a raw material and formaldehyde is completed, in order to separate and recover the target compound (B1) from the resulting reaction mixture, after the reaction is completed, an acid such as sulfuric acid is added to the reaction-completed mixture to neutralize the basic salt of the target substance and the basic catalyst. Then, in order to separate and remove the aqueous layer, a water-separable solvent such as an aromatic hydrocarbon such as toluene or xylene is added as needed, and then the aqueous layer is separated. After the obtained oil layer is washed with water, the solvent or low-boiling compounds such as formaldehyde are distilled off from the oil layer, and the target compound (B1) can be obtained.

[0113] The obtained compound (B1) can be purified or directly used in the subsequent step (II).

[0114] (Step II)

[0115] The following description is made for the subsequent step (II).

[0116] Using the compound (B1) obtained from the above step (I) as a raw material, in the presence of an acid catalyst, it is reacted with methanol, whereby the target compound (C1) can be obtained. Here, instead of methanol, it can also be reacted with a saturated aliphatic alcohol having 2 to 4 carbon atoms, such as ethanol, n-propanol, isopropanol, n-butanol, etc., to change the methoxymethyl of the compound (C1) to various alkoxymethyls.

[0117] As the above acid catalyst, concentrated sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, cation exchange resin (acid type), oxalic acid, etc. are preferably used. More preferably, inorganic strong acids such as concentrated sulfuric acid are used. In addition, relative to compound (B1), the acid catalyst is usually used in the range of 20 to 40% by weight, preferably 30% by weight. If the acid catalyst is less than 20% by weight, the reaction proceeds slowly, and if it exceeds 40% by weight, the reaction proceeds excessively, resulting in a large amount of impurities being generated, so it is not preferred.

[0118] The above methanol usually also serves as a reaction solvent and can be used in excess relative to compound (B1). The usage amount is not particularly limited, and usually, relative to compound (B1), it is used in the range of 6 to 12 times by weight, preferably 9 times by weight.

[0119] The reaction temperature of step (II) is usually in the range of 40 to 70 °C, preferably in the range of 50 to 65 °C, and more preferably in the range of 55 to 60 °C. If the reaction temperature is lower than 40 °C, polymers will be preferentially generated, so it is not preferred. When it is higher than 70 °C, the reaction proceeds rapidly, resulting in a large amount of polymers being generated, so it is not preferred. The reaction time is usually about 1 to 240 hours, preferably about 5 to 100 hours.

[0120] After the reaction is completed, the target compound (C1) can be isolated from the obtained reaction mixture according to conventional methods. For example, after the reaction is completed, the obtained reaction mixture is neutralized with an alkali such as an aqueous sodium hydroxide solution, and then, if necessary, the excess methanol that also serves as a reaction solvent is removed by distillation, etc. The salt formed by neutralization is filtered off to obtain a crude product of the target compound. If necessary, the crude product is dissolved in a solvent such as an aromatic hydrocarbon such as toluene or xylene, washed several times with water, and the aqueous layer is separated to remove inorganic salts. If further purification is required, it can be separated and purified by column chromatography.

[0121] <Manufacturing Method 2>

[0122] As Manufacturing Method 2 of the compound of the present invention, taking the reaction formula of the following preferred compounds as an example, the method via an aminomethyl body and an acetyl body will be specifically described. Based on the above-mentioned "Compound (A1)" and "Compound (C1)", the compounds in the following reaction formula are referred to as "Compound (D1)" and "Compound (E1)".

[0123] [Chemical Formula 20]

[0124]

[0125] (Step (III))

[0126] For the initial step (III), the following description is provided.

[0127] Step (III) is a step of using compound (A1) as a raw material and reacting it with formaldehyde and dimethylamine in a solvent to obtain compound (D1). This reaction can be easily carried out by a method based on the well-known Mannich reaction. As the formaldehyde, it can be an aqueous formaldehyde solution or paraformaldehyde. In addition, if a secondary amine such as diethylamine, dibutylamine, diisopropylamine, pyrrolidine, piperidine, piperazine, morpholine, oxazolidine, etc. is used instead of dimethylamine, the dimethylamino group of compound (D1) can be changed to various amino groups.

[0128] In this step (III), if acetic acid is added as a catalyst, the reaction rate increases, which is preferred. However, if the addition amount of acetic acid relative to dimethylamine exceeds 1 molar equivalent, the reaction rate will instead slow down, which is not preferred.

[0129] In this step (III), the usage amounts of formaldehyde and dimethylamine relative to compound (A1) as the raw material are preferably stoichiometric or more. Specifically, the usage amount of dimethylamine relative to compound (A1) as the raw material is preferably in the range of 6 to 12 molar equivalents, more preferably in the range of 8 to 10 molar equivalents. Similarly, the usage amount of formaldehyde relative to compound (A1) as the raw material is preferably in the range of 6 to 12 molar equivalents, more preferably in the range of 8 to 10 molar equivalents.

[0130] A reaction solvent can be used during the reaction, or it can be not used. When using a reaction solvent, there is no particular limitation as long as it is a well-known solvent for this reaction. Specifically, for example, water, or ether solvents such as diethyl ether, dibutyl ether, and tetrahydrofuran, alcohol solvents such as methanol, ethanol, propanol, and butanol, aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as acetone and methyl isobutyl ketone, ester solvents such as ethyl acetate and γ-butyrolactone, nitrile solvents such as acetonitrile, and aprotic polar solvents such as N-methylpyrrolidone, N-methyl-2-pyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide, etc. Such solvents can be used alone or in combination of two or more.

[0131] The usage amount of the solvent is not particularly limited. Relative to compound (A1) as the raw material, it is preferably in the range of 0.5 to 20 weight equivalents, more preferably in the range of 1 to 5 weight equivalents.

[0132] The reaction temperature of step (III) is preferably in the range of 30 to 100 °C, more preferably in the range of 60 to 90 °C, and further preferably in the range of 75 to 80 °C. The reaction temperature can be appropriately selected within the above temperature range. If the reaction temperature is lower than 30 °C, the reaction proceeds slowly and the reaction cannot be completed. At temperatures higher than 100 °C, raw materials such as dimethylamine will volatilize, which is not preferred.

[0133] The reaction time is generally 0.5 to 24 hours, preferably about 1 to 10 hours.

[0134] In addition, in step (III), there is no particular limitation on the order of adding the raw materials. For example, the compound (A1) as a raw material, dimethylamine, aqueous formaldehyde solution, and a solvent as required can be added simultaneously, or after adding the compound (A1) and dimethylamine as raw materials, the aqueous formaldehyde solution can be added dropwise thereto.

[0135] After step (III) of the compound (A1) as a raw material with formaldehyde and dimethylamine is completed, the compound (D1) as the target reaction product can be separated and recovered from the obtained reaction mixture by a known method and used as the raw material for the subsequent step (IV).

[0136] For example, after the reaction is completed, if necessary, a solvent immiscible with water such as aromatic hydrocarbons like toluene and xylene is added to the reaction-completed mixture, and then the aqueous layer is separated. Water can be added to the obtained oil layer to wash the oil layer, and if necessary, the solvent is removed from the oil layer by distillation or the like, whereby the obtained crude product containing the target substance is directly used as the raw material for the subsequent step. In addition, the compound (D1) can be isolated and purified from the oil layer obtained by the treatment after the reaction is completed.

[0137] (Step IV)

[0138] The following description is made for the subsequent step (IV).

[0139] Step (IV) is a step of manufacturing the compound (E1) using the compound (D1) obtained from the above step (III) as a raw material. The reaction in step (IV) can be easily carried out according to a known method of reacting the compound (D1) with acetic anhydride. Here, acetic anhydride can also be replaced with a carboxylic anhydride, such as propionic anhydride, butyric anhydride, benzoic anhydride, etc., to react, and the acetyl group of the compound (E1) can be changed to various acyloxy groups.

[0140] In step (IV), the usage amount of acetic anhydride relative to the compound (D1) is preferably stoichiometric or more, specifically preferably in the range of 9 to 15 molar times, more preferably 12 molar times.

[0141] During the reaction, since acetic anhydride can also be used as a solvent, there is no need to particularly use other solvents, but non-aqueous solvents such as toluene and xylene can also be used according to the needs of the reaction operation. The reaction temperature is preferably in the range of 80 to 130 °C, more preferably in the range of 100 to 130 °C, and particularly preferably in the range of 120 to 125 °C. If the reaction temperature is lower than 80 °C or higher than 130 °C, a large amount of impurities will be generated, so it is not preferred. The reaction time is generally about 0.5 to 40 hours, preferably about 5 to 20 hours.

[0142] After the reaction is completed, the target compound (E1) can be separated and recovered from the resulting reaction mixture by known methods and used as a raw material for the subsequent step (V). For example, after the reaction is completed, unreacted acetic anhydride, solvents added as needed, etc. are distilled off from the reaction mixture to obtain a crude product containing the target compound, which can be directly used as a raw material for the subsequent step (V). In addition, the obtained crude product can be isolated and purified to obtain compound (E1).

[0143] (Step V)

[0144] The following is an explanation of the subsequent step (V).

[0145] Step (V) is a step of reacting compound (E1) obtained in the above step (IV) with methanol in the presence of a catalyst to obtain compound (C1) as the target compound. Here, instead of methanol, it can also be reacted with saturated aliphatic alcohols having 2 to 4 carbon atoms, such as ethanol, n-propanol, isopropanol, n-butanol, etc., to change the methoxymethyl group of compound (C1) to various alkoxymethyl groups.

[0146] Regarding the amount of methanol used in step (V) relative to compound (E1), it is preferably a molar ratio of stoichiometric amount or more. Generally, it also serves as a reaction solvent and can be used in excess relative to compound (E1). The amount used is not particularly limited as long as it is stoichiometric amount or more. Specifically, for example, in the range of 6 to 12 times by weight, preferably 7 times by weight.

[0147] Specific examples of the catalyst used in step (V) include acid catalysts such as sulfuric acid and p-toluenesulfonic acid, base catalysts such as potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, and sodium methoxide, and carboxylates such as sodium acetate and potassium acetate. Acid catalysts are preferred. The amount of catalyst used varies depending on the type of catalyst required. For example, in the case of sulfuric acid, relative to compound (E1), it is preferably in the range of 1 to 20 mol%, more preferably 10 mol%. If the amount of this catalyst used exceeds 20 mol%, the reaction proceeds excessively and a large amount of impurities are generated, so it is not preferred.

[0148] During the reaction, since saturated aliphatic alcohols having 1 to 4 carbon atoms can also be used as solvents, generally no other solvents need to be used specifically. However, depending on the requirements of the reaction operation, non-aqueous solvents such as toluene and xylene can also be used.

[0149] The reaction temperature is preferably in the range of 40 to 70 °C, more preferably in the range of 50 to 65 °C, and particularly preferably in the range of 55 to 60 °C. If the reaction temperature is lower than 40 °C, the formation of polymers will be preferred, so it is not preferred. If it is higher than 70 °C, the reaction proceeds rapidly and a large amount of polymers are formed, so it is not preferred. The reaction time is usually about 1 to 240 hours, preferably about 5 to 100 hours.

[0150] In addition, in step (V), there is no particular limitation on the addition order of the raw materials. For example, compound (E1), methanol, and the catalyst can be added simultaneously, or methanol and the catalyst can be mixed and then compound (E1) can be added thereto.

[0151] After the completion of step (V), the target compound (C1) can be separated and purified from the resulting reaction mixture according to conventional methods and isolated as a crude product or a high-purity product. For example, after the completion of the reaction, in the case of using an acid catalyst, an alkali can be added to the reaction mixture to neutralize it. After distilling off excess methanol or the like as needed, a solvent immiscible with water is added for washing with water, and the solvent is removed by distillation or the like as needed, thereby obtaining the target compound as a crude product. In addition, the crude product can be further purified by column chromatography or the like to obtain a high-purity compound (C1).

[0152] The substituted triphenol compounds represented by the above formula (2) of the compounds of the present invention, especially the substituted triphenol compounds represented by the above formula (2b), are a group of compounds useful as crosslinking agents for photosensitive resins. In addition, the substituted triphenol compounds represented by the above formula (3) of the compounds of the present invention are important intermediates in the production of the substituted triphenol compounds represented by the above formula (2). Further, the substituted triphenol compounds represented by the above formula (4) of the compounds of the present invention are important intermediates in the production of the substituted triphenol compounds represented by the above formula (2), and among them, especially the substituted triphenol compounds represented by the above formula (4b) are a group of compounds useful as curing agents for epoxy resins.

[0153] Examples

[0154] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by these examples.

[0155] The analysis method is as follows.

[0156] <Analysis apparatus and analysis conditions>

[0157] (1) Analysis conditions for compound (B1) and compound (B2)

[0158] Measuring apparatus: Shimadzu HPLC LC-20 series (manufactured by Shimadzu Corporation)

[0159] Pump: LC-20AT

[0160] Column oven: CTO-20A

[0161] Detector: SPD-20A (HPLC), flow cell length 1 cm

[0162] Chromatographic column: Shim-pack CLC-ODS (chromatographic column 6.0×150 mm, particle size 5 μm, manufactured by Shimadzu GLC Co., Ltd.)

[0163] Oven temperature: 50 °C

[0164] Flow rate: 1.0 ml / min

[0165] Mobile phase: (i) 0.2 vol% acetic acid aqueous solution, (ii) MeOH

[0166] Gradient condition: (i) volume % (time elapsed since the start of analysis)

[0167] 30% (0 min) → 82.5% (30 min) → 100% (35 min) → 100% (45 min)

[0168] Detection wavelength: 280 nm

[0169] Sample concentration: 50 mg / 50 ml

[0170] Sample injection volume: 20 μl

[0171] (2) Analytical conditions for Compound (C1), Compound (C2), Compound (E1), and Compound (E2)

[0172] Measuring device: Shimadzu HPLC LC-20 series (manufactured by Shimadzu Corporation)

[0173] Pump: LC-20AT

[0174] Column oven: CTO-20A

[0175] Detector: SPD-20A (HPLC), flow cell length 1 cm

[0176] Chromatographic column: Shim-pack CLC-ODS (chromatographic column 6.0×150 mm, particle size 5 μm, manufactured by Shimadzu GLC Co., Ltd.)

[0177] Oven temperature: 50 °C

[0178] Flow rate: 1.0 ml / min

[0179] Mobile phase: (i) 0.2 vol% acetic acid aqueous solution, (ii) MeOH

[0180] Gradient conditions: (i) volume % (time elapsed since the start of analysis)

[0181] 50% (0 min) → 100% (30 min) → 100% (45 min)

[0182] Detection wavelength: 280 nm

[0183] Sample concentration: 50 mg / 50 ml

[0184] Sample injection volume: 20 μl

[0185] (3) Analytical conditions for compound (D1) and compound (D2)

[0186] Measuring device: Shimadzu HPLC LC-20 series (manufactured by Shimadzu Corporation)

[0187] Pump: LC-20AT

[0188] Column oven: CTO-20A

[0189] Detector: SPD-20A (HPLC), flow cell length 1 cm

[0190] Chromatographic column: Shim-pack CLC-ODS (column 6.0 × 150 mm, particle size 5 μm, manufactured by Shimadzu GLC Co., Ltd.)

[0191] Oven temperature: 50 °C

[0192] Flow rate: 1.0 ml / min

[0193] Mobile phase: (i) 0.1 vol% phosphoric acid aqueous solution, (ii) MeOH

[0194] Gradient conditions: (i) volume % (time elapsed since the start of analysis)

[0195] 5% (0 min) → 100% (30 min) → 100% (45 min)

[0196] Detection wavelength: 280 nm

[0197] Sample concentration: 50 mg / 50 ml

[0198] Sample injection volume: 20 μl

[0199] (4) Solubility measurement, analytical conditions for comparative compounds (x) and (y)

[0200] Measuring device: Shimadzu UFLC LC-20 series (manufactured by Shimadzu Corporation)

[0201] Pump: LC-20AD

[0202] Column oven: CTO-20A

[0203] Detector: SPD-20A (UFLC), flow cell length 5 mm

[0204] Chromatographic column: HALO-C18 (column 3.0×75 mm, particle size 2.7 μm, manufactured by advanced materials technology)

[0205] Oven temperature: 50 °C

[0206] Flow rate: 0.7 ml / min

[0207] Mobile phase: (i) 0.2 vol% acetic acid aqueous solution, (ii) MeOH

[0208] Gradient conditions: (i) volume % (time elapsed since the start of analysis)

[0209] 50% (0 min) → 100% (7.5 min) → 100% (10 min)

[0210] Detection wavelength: 280 nm

[0211] Sample concentration: compound (x) 50 mg / 50 ml, compound (y) 120 mg / 50 ml

[0212] Sample injection volume: 5 μl

[0213] <Example 1: Synthesis of compound (B1): Step (I)>

[0214] Step (I): Into a 2 L four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooler, 80.0 g (0.24 mol) of compound (A1) and 191.4 g (0.72 mol) of a 15% aqueous sodium hydroxide solution were added. While maintaining the temperature at 25 - 30°C, 184.6 g (2.15 mol) of 35% formalin was added dropwise over 1 hour, and the mixture was stirred at 25 - 30°C for 11 hours. Compound (B1) in the reaction solution was 85% (HPLC area %). The reaction solution was added to a mixed solvent of methyl ethyl ketone and toluene, and neutralized by adding dilute sulfuric acid dropwise and stirring. Then, the aqueous layer was separated, distilled water was added to the obtained oil layer and stirred, and the mixture was washed with water to separate and remove the aqueous layer. Further, the obtained oil layer was subjected to the same water washing operation twice, and the obtained oil layer was concentrated under reduced pressure and the solvent was distilled off to obtain 123.1 g of compound (B1). The obtained compound (B1) was purified by preparative HPLC to obtain compound (B1) with a purity of 98.6% (HPLC area %).

[0215] The analysis results are as follows.

[0216] Molecular weight of compound (B1) (liquid chromatography - mass spectrometry / atmospheric pressure chemical ionization method): 513.2 (M - H) -

[0217] 1H-NMR (400 MHz, Methanol-d4 / TMS): δ1.65 (s, 3H), 2.27 - 2.34 (m, 4H), 4.65 (s, 12H), 4.89 (br.s, 9H), 6.87 (s, 2H), 7.03 (s, 4H).

[0218] <Example 2: Synthesis of compound (C1): Step (I) → Step (II)>

[0219] Step (I): Into a 2 L four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooler, 80.0 g (0.24 mol) of compound (A1) and 191.4 g (0.72 mol) of a 15% aqueous sodium hydroxide solution were added. While maintaining the temperature at 25 - 30°C, 184.6 g (2.15 mol) of 35% formalin was added dropwise over 1 hour, and the mixture was stirred at 25 - 30°C for 11 hours. Compound (B1) in the reaction solution was 85% (HPLC area %). The reaction solution was added to a mixed solvent of methyl ethyl ketone and toluene, and neutralized by adding dilute sulfuric acid dropwise and stirring. Then, the aqueous layer was separated, distilled water was added to the obtained oil layer and stirred, and the mixture was washed with water to separate and remove the aqueous layer. Further, the obtained oil layer was subjected to the same water washing operation twice, and the obtained oil layer was concentrated under reduced pressure and the solvent was distilled off.

[0220] Step (II): Methanol was added to the obtained concentrate, and the solvent was distilled off. 1107.9 g of methanol and 36.9 g of 98% sulfuric acid were added, and the temperature was raised to an internal temperature of 58 - 60 °C, followed by stirring for 16 hours. The compound (C1) in the reaction solution was 74.5% (HPLC area %). Subsequently, a 16% aqueous sodium hydroxide solution and 75% phosphoric acid were added to the obtained reaction-terminated solution. After distilling off methanol and the like, toluene and water were added. After stirring, the operation of separating the aqueous layer was carried out, and toluene was distilled off by vacuum distillation to obtain the compound (C1) with a purity of 74.4% (HPLC area %).

[0221] <Example 3: Synthesis of Compound (D1): Step (III)>

[0222] Step (III): 250 g (0.75 mol) of compound (A1), 250.1 g of 2-propanol, and 513.4 g (5.98 mol) of 35% formalin were added to a 3 L four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooler. Then, 537.7 g (5.96 mol) of 50% aqueous dimethylamine solution was added to the liquid, and the mixture was stirred for 3 hours while maintaining the internal temperature at 80 - 85 °C. The compound (D1) in the reaction solution was 96% (HPLC area %).

[0223] Subsequently, the obtained reaction-terminated solution was distilled. Toluene was added to the obtained distillation residue, and the oil layer was washed twice with water. Then, a Dean-Stark tube was connected for reflux operation to remove the water in the system. Then, toluene was distilled off by vacuum distillation to obtain the compound (D1) with a purity of 95.0% (HPLC area %).

[0224] The analysis results are as follows.

[0225] Molecular weight (liquid chromatography - mass spectrometry / atmospheric pressure chemical ionization method): 675.5 (M - H) -

[0226] 1H-NMR (400 MHz, Methanol-d4 / TMS): δ1.62 (s, 3H), 2.22 (s, 24H), 2.27 - 2.31 (m, 16H), 3.51 (s, 4H), 3.52 (s, 8H), 4.93 (br.s, 3H), 6.76 (s, 2H), 6.91 (s, 4H).

[0227] <Example 4: Synthesis of Compound (E1): Step (III) → Step (IV)>

[0228] Step (III): Add 250 g (0.75 mol) of compound (A1), 250.1 g of 2-propanol, and 513.4 g (5.98 mol) of 35% formalin to a 3 L four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooler. Then add 537.7 g (5.96 mol) of 50% aqueous dimethylamine solution to the liquid, and stir for 3 hours while maintaining the internal temperature at 80 - 85°C. The compound (D1) in the reaction solution is 96% (HPLC area%).

[0229] Next, distill the obtained reaction-terminated liquid, add toluene to the obtained distillation residue, perform two water washing operations on the oil layer, connect a Dean-Stark tube, and perform a reflux operation to remove the water in the system.

[0230] Step (IV): Then, cool the internal temperature to 78°C, and add 918.0 g (12.0 mol) of acetic anhydride over 2 hours. After the addition, stir for 3 hours while maintaining the internal temperature at 120 - 125°C. The compound (E1) in the reaction solution is 92% (HPLC area%). Then, distill off unreacted acetic anhydride, etc. by performing vacuum distillation on the obtained reaction-terminated liquid to obtain compound (E1) with a purity of 92.9% (HPLC area%).

[0231] The analysis results are as follows.

[0232] Molecular weight (liquid chromatography - mass spectrometry / atmospheric pressure chemical ionization method): 915.3 (M + Na) +

[0233] 1H-NMR (400 MHz, Methanol-d4 / TMS): δ1.75 (s, H), 1.97 (s, 12H), 2.00 (s, 6H), 2.28 (s, 3H), 2.30 (s, 6H), 2.39 - 2.48 (m, 4H), 5.00 (s, 4H), 5.01 (s, 8H), 7.22 (s, 2H), 7.34 (s, 4H).

[0234] <Example 5: Synthesis of compound (C1): Step (III) → Step (IV) → Step (V)>

[0235] Step (III): Add 250 g (0.75 mol) of compound (A1), 250.1 g of 2-propanol, and 513.4 g (5.98 mol) of 35% formalin to a 3 L four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooler. Then add 537.7 g (5.96 mol) of 50% aqueous dimethylamine solution to the liquid, and stir for 3 hours while maintaining the internal temperature at 80 - 85°C. The compound (D1) in the reaction solution is 96% (HPLC area%).

[0236] Subsequently, the obtained reaction-terminated solution was distilled, toluene was added to the obtained distillation residue, the oil layer was washed twice with water, and then a Dean-Stark tube was connected for reflux operation to remove the water in the system.

[0237] Step (IV): Then, the internal temperature was cooled to 78 °C, and 918.0 g (12.0 mol) of acetic anhydride was added over 2 hours. Thereafter, the mixture was stirred for 3 hours while maintaining the internal temperature at 120 - 125 °C. The compound (E1) in the reaction solution was 92% (HPLC area %).

[0238] Step (V): Subsequently, unreacted acetic anhydride and the like were distilled off by subjecting the obtained reaction-terminated solution to vacuum distillation and then cooling. At around 50 °C, 4,687.7 g of methanol and 14.3 g (0.075 mol) of p-toluenesulfonic acid monohydrate were added, and the mixture was stirred for 11 hours while maintaining the internal temperature at 59 - 60 °C. The compound (C1) in the reaction solution was 98.0% (HPLC area %).

[0239] Next, 16% sodium hydroxide and 75% phosphoric acid were added to the obtained reaction-terminated solution, methanol and the like were distilled off, toluene and water were added, and after stirring, the operation of separating the aqueous layer was carried out. Then, toluene was distilled off by vacuum distillation, ethyl lactate widely used as an anti-resist solvent was added and distilled again, and ethyl lactate was added again to adjust the solid content concentration to 42.9% (ethyl lactate was quantified and calculated using an HPLC absolute calibration curve), thereby calculating the yield. An oily compound (C1) was obtained with a purity of 97.5% (HPLC area %) and a yield of 95 mol% (relative to compound (A1)).

[0240] The analysis results are as follows.

[0241] Molecular weight (liquid chromatography - mass spectrometry / atmospheric pressure chemical ionization method): 597.3 (M - H) -

[0242] 1H-NMR (400 MHz, Methanol-d4 / TMS): δ1.62 (s, 3H), 2.27 (br.s, 4H), 3.34 (s, 12H), 3.37 (s, 6H), 4.48 (s, 4H), 4.49 (s, 8H), 4.88 (br.s, 3H), 6.88 (s, 2H), 7.04 (s, 4H).

[0243] <Example 6: Synthesis of Compound (D2): Step (III)>

[0244] [Chemical formula 21]

[0245]

[0246] Step (III): Add 30 g (0.06 mol) of the above compound (A2), 30.0 g of 2-propanol, and 39.8 g (0.46 mol) of 35% formalin to a 500 mL four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooler. Then add 40.1 g (0.44 mol) of 50% dimethylamine to the liquid, and stir for 13.5 hours while maintaining the internal temperature at 80 - 85°C. The compound (D2) in the reaction solution is 97.1% (HPLC area%).

[0247] Next, distill the obtained reaction-terminated solution, add toluene to the obtained distillation residue, perform two water washing operations on the oil layer, connect a Dean-Stark tube and perform a reflux operation to remove the water in the system. Then distill off the toluene by vacuum distillation to obtain the compound (D2) with a purity of 98.6% (HPLC area%).

[0248] The analysis results are as follows.

[0249] Molecular weight (liquid chromatography - mass spectrometry / atmospheric pressure chemical ionization method): 727.6 (M + H) +

[0250] 1H-NMR (400 MHz, Methanol-d4 / TMS): δ1.21 - 1.48 (m, 10H), 1.60 (s, 3H), 1.73 - 1.82 (m, 10H), 2.24 - 2.32 (m, 28H), 2.93 (t, 2H), 3.57 (d, 8H), 4.90 (br.s, 3H), 6.74 - 6.86 (m, 6H).

[0251] <Example 7: Synthesis of Compound (E2): Step (III) → Step (IV) >

[0252] [Chemical formula 22]

[0253]

[0254] Step (III): Add 30 g (0.06 mol) of the above compound (A2), 30.0 g of 2-propanol, and 39.8 g (0.46 mol) of 35% formalin to a 500 mL four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooler. Then add 40.1 g (0.44 mol) of 50% dimethylamine to the liquid, and stir for 13.5 hours while maintaining the internal temperature at 80 - 85°C. The compound (D2) in the reaction solution is 97.1% (HPLC area%).

[0255] Next, the resulting reaction-terminated solution was distilled. Toluene was added to the resulting distillation residue, and after performing two water washing operations on the oil layer, a Dean-Stark tube was connected for a reflux operation to remove water in the system.

[0256] Step (IV): Then, the internal temperature was cooled to 80 °C, and 74.2 g (0.73 mol) of acetic anhydride was added over 2 hours. After the addition was completed, the mixture was stirred for 18.5 hours while maintaining the internal temperature at 120 - 125 °C. The compound (E2) in the reaction solution was 90.7% (HPLC area %). Subsequently, unreacted acetic anhydride and the like were distilled off by performing vacuum distillation on the resulting reaction-terminated solution, and a compound (E2) with a purity of 90.6% (HPLC area %) was obtained.

[0257] The analysis results are as follows.

[0258] Molecular weight (liquid chromatography - mass spectrometry / atmospheric pressure chemical ionization method): 913.5 (M + H) +

[0259] 1H-NMR (400 MHz, Methanol-d4 / TMS): δ 1.23 - 1.43 (m, 10H), 1.72 - 1.85 (m, 13H), 2.02 (d, 12H), 2.34 (d, 9H), 2.45 (s, 4H), 2.54 (t, 2H), 5.03 (d, 8H), 7.15 - 7.23 (m, 6H).

[0260] <Example 8: Synthesis of compound (C2): Step (III) → Step (IV) → Step (V)>

[0261] [Chemical formula 23]

[0262]

[0263] Step (III): 30 g (0.06 mol) of the above compound (A2), 30.0 g of 2-propanol, 39.8 g (0.46 mol) of 35% formalin were added to a 500 mL four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooler. Then, 40.1 g (0.44 mol) of 50% dimethylamine was added to the liquid, and the mixture was stirred for 13.5 hours while maintaining the internal temperature at 80 - 85 °C. The compound (D2) in the reaction solution was 97% (HPLC area %).

[0264] Next, the resulting reaction-terminated solution was distilled. Toluene was added to the resulting distillation residue, and after performing two water washing operations on the oil layer, a Dean-Stark tube was connected for a reflux operation to remove water in the system.

[0265] Step (IV): Then, cool the internal temperature to 80 °C, and add 74.2 g (0.73 mol) of acetic anhydride over 2 hours. After the addition is complete, stir for 18.5 hours while maintaining the internal temperature at 120 - 125 °C. The compound (E2) in the reaction solution is 90.7% (HPLC area %).

[0266] Step (V): Next, distill off unreacted acetic anhydride and the like by performing vacuum distillation on the obtained reaction-terminated solution, then cool it, add 246.1 g of methanol and 1.0 g (0.005 mol) of p-toluenesulfonic acid monohydrate at around 50 °C, and stir for 10 hours while maintaining the internal temperature at 60 °C. The compound (C2) in the reaction solution is 95.9% (HPLC area %).

[0267] Next, add 16% sodium hydroxide and 75% phosphoric acid to the obtained reaction-terminated solution, distill off methanol and the like, then add butyl acetate and water, stir, and perform the operation of separating the aqueous layer. Then, distill off butyl acetate by vacuum distillation to obtain an oily compound (C2) with a purity of 97.1% (HPLC area %). The yield is 83.8 mol% (relative to compound (A2)).

[0268] The analysis results are as follows.

[0269] Molecular weight (liquid chromatography - mass spectrometry / atmospheric pressure chemical ionization method): 673.5 (M - H) -

[0270] 1H-NMR (400 MHz, Methanol-d4 / TMS): δ1.22 - 1.45 (m, 10H), 1.62 (s, 3H), 1.71 - 1.80 (m, 10H), 2.27 (s, 4H), 2.95 (t, 2H), 3.38 (d, 12H), 4.52 (d, 8H), 4.90 (br.s, 3H), 6.90 - 6.96 (m, 6H).

[0271] <Evaluation Test 1: Solubility at 30 °C>

[0272] Regarding the compound (C1) and compound (C2) obtained from the examples, and the following 2 compounds reported as crosslinking agents that also have 6 functional groups, measure the solubility in ethyl lactate, which is widely used as a resist solvent, at 30 °C. In addition, the following compounds are referred to as "Comparative Compound (x)" and "Comparative Compound (y)".

[0273] Comparative Compound (x) and Comparative Compound (y) are compounds synthesized using the synthesis methods described in Synthesis Examples 3 and 4 of Patent Document 2 above for reference.

[0274] [Chemical Formula 24]

[0275]

[0276] (Evaluation method)

[0277] Add a magnetic stir bar and 10 g of ethyl lactate to a 100-ml test tube. After adding 10 g of Comparative Compound (x) (or (y)), with a reflux condenser installed and nitrogen sealed in, set a pre-temperature-controlled water bath to 30 °C and stir with a stirrer for 3 hours. After stirring for 3 hours, sample the inner liquid with a pipette, pass it through a syringe filter, filter the solid matter from the sampled liquid to obtain the supernatant, and transfer the supernatant to a 50-ml volumetric flask. Dilute the supernatant with HPLC-grade methanol to the 50-ml mark and analyze it using a high-performance liquid chromatography analyzer. Using the peak area of Comparative Compound (x) (or (y)), quantify Comparative Compound (x) (or (y)) in the above supernatant from the obtained results, and calculate the solubility (= quantitative value of Comparative Compound (x) or (y) (mg) / (weight (mg) passing through the syringe filter and transferred to the 50-ml volumetric flask - quantitative value of Comparative Compound (x) or (y) (mg))).

[0278] Calibration curve preparation method: Analyze Comparative Compound (x) (or (y)) used in the test by HPLC. Using the peak area of Comparative Compound (x) (or (y)) as the horizontal axis and the concentration (mg / 50 ml) as the vertical axis, take the approximate straight line obtained from "intercept = 0" as the calibration curve of Comparative Compound (x) (or (y)).

[0279] [Table 1]

[0280]

[0281] As shown in Table 1, it is clear that Compound (C1) as a compound of the present invention has about twice the solubility in ethyl lactate compared to Comparative Compound (x) reported to be useful as a crosslinking agent. In addition, it has a slightly lower solubility in ethyl lactate compared to Comparative Compound (y) reported to be useful as a crosslinking agent.

[0282] In addition, it is clear that the solubility of Compound (C2) as a compound of the present invention is 100.0 g / 100 g or more, which is a very high solubility. It is also clear that its solubility in ethyl lactate is more than twice that of Comparative Compound (x), and in addition, its solubility in ethyl lactate is higher than that of Comparative Compound (y).

[0283] <Evaluation Test 2: Low-temperature storage stability (dissolution stability)>

[0284] In the above “Evaluation Test 1”, Compound (C1) of the present invention, which has the same solubility of ethyl lactate as Comparative Compound (y) at 30°C, and Compound (C2) of the present invention, which has a higher solubility than Comparative Compound (y), were used to conduct a low-temperature storage test of an ethyl lactate solution at refrigeration (5°C) and freezing (-5°C).

[0285] (Evaluation Method)

[0286] To a 50 ml screw tube, 4.29 g of Compound (C1) as the compound of the present invention and 5.71 g of ethyl lactate were added and mixed, and the mixture was placed in a water bath set at 30°C and stirred while shaking by hand. After visually confirming complete dissolution, an ethyl lactate solution with a concentration of 42.9% by weight of Compound (C1) was prepared.

[0287] In addition, in the same manner as Compound (C1), an ethyl lactate solution with a concentration of 40% by weight of Compound (C2), an ethyl lactate solution with a concentration of 50% by weight of Compound (C2), and an ethyl lactate solution with a concentration of 40% by weight of Compound (y) were prepared.

[0288] For the above solutions, a 30-day solution storage test was conducted in a refrigerator (5°C) and a freezer (-5°C).

[0289] According to the following evaluation criteria, the evaluation results are summarized in Table 2.

[0290] [Evaluation Criteria]

[0291] 〇: Completely dissolved, and no precipitation of crystals or separation of oily components can be visually confirmed.

[0292] ×: Precipitation of crystals or separation of oily components can be visually confirmed.

[0293] [Table 2]

[0294]

[0295] As shown in Table 2, it was confirmed that for Compound (C1) and Compound (C2) as the compounds of the present invention, even at a refrigeration temperature of 5°C and a freezing temperature of -5°C, and after 30 days of storage, no crystals precipitated at all, and a transparent solution could be maintained.

[0296] On the other hand, it was also clarified that for Comparative Compound (y), which has a slightly higher solubility at 30°C than the compounds of the present invention, crystals precipitated even at a refrigeration temperature of 5°C and a freezing temperature of -5°C, although the concentration was low. And even when the test sample with precipitated crystals was left at room temperature (22°C) for 1 day, no redissolution of the precipitated crystals was confirmed.

[0297] From the results of the above “Evaluation Tests 1 and 2”, it is considered that both Comparative Compound (x) and Comparative Compound (y) have a rigid chemical structure as the mother skeleton, so the movement of the molecules is restricted, or it is easy to generate stacking between the molecules, and thus it is easy to crystallize. On the other hand, it is considered that by introducing the flexibility of the mother skeleton containing a linear alkylene group into the compound of the present invention, it is difficult to generate stacking between the molecules, and as a result, crystallization is suppressed, and even under low-temperature storage conditions such as 5 °C or -5 °C, crystals will not precipitate.

Claims

1. A substituted triphenol compound, characterized in that, Any one of the compounds represented by the following chemical structural formulas, [Chemical formula 1] 。 2. A substituted triphenol compound, characterized in that, Any one of the compounds represented by the following chemical structural formulas, [Chemical formula 2] 。 3. A substituted triphenol compound, characterized in that, Any one of the compounds represented by the following chemical structural formulas, [Chemical formula 3] 。

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