Method for producing new polynuclear poly(formylphenol)

Abstract

Produce the target substance, or a polynuclear poly(formylphenol) expressed by general Formula (2), in an industrial setting with ease and at high purity by causing a polynuclear poly(hydroxymethylphenol) or polynuclear poly(alkoxymethylphenol) to react with hexamethylene tetramine in the presence of an acid and then hydrolyzing the obtained reaction product.

Description

This application is the U.S. National Phase under 35 U.S.C. §371 of International Application PCT/JP2007/061107, filed May 31, 2007, which claims priority to Japanese Patent Application No. 2006-151973, filed May 31, 2006, and No. 2006-161694, filed Jun. 9, 2006. The International Application was published under PCT Article 21(2) in a language other than English.

TECHNICAL FIELD

The present invention relates to a method for producing a polynuclear poly(formylphenol) in an industrial setting with ease and at high purity. To be specific, the present invention relates to a method for producing a polynuclear poly(formylphenol) in an industrial setting with ease and at high yield and high purity by using as the material a polynuclear poly(hydroxymethylphenol) or polynuclear poly(alkoxymethylphenol) that can be obtained easily from a polynuclear polyphenol, and causing the material to react with hexamethylene tetramine in the presence of an acid and then hydrolyzing the obtained reaction product.

PRIOR ART

Traditionally, the Reimer-Tiemann reaction that uses chloroform and aqueous sodium hydroxide solution, as well as the Duff reaction that uses hexamethylene tetramine and an acid catalyst such as trifluoroacetate, are known as ways to introduce a formyl group to a phenol. These methods are both based on a reaction to directly introduce a formyl group to a phenyl nucleus by means of substitution, where the former method uses a large amount of halogenated hydrocarbon and provides a low yield, while the latter method, based on an examination by the inventors for the present invention, in many cases is unable to synthesize the target substance at a high yield even when applied to a polynuclear phenol as shown in a comparative example included in the present application for patent, or requires a very long reaction time.

Also, a method to cause a given amount of phenol to react with the same amount of alkyl magnesium bromide and then cause the obtained reaction product to react with formaldehyde to achieve formylation is described in J. Chem. Soc., Perkin Trans. (1978, 318 to 321). However, this method has a drawback of requiring a large amount of expensive alkyl magnesium bromide.

A method to cause a phenol to react with tin tetrachloride and then cause the obtained reaction product to react with formaldehyde to achieve formylation is described in J. Chem. Soc., Perkin Trans. (1978, 1862 to 1865). However, this method uses a large amount of expensive tin tetrachloride and also requires treatment of a large amount of wastewater generated from the reaction, which is undesirable. Also in this literature, a salicylaldehyde is synthesized from tin tetrachloride by also using 2-hydroxy benzyl alcohol. However, an examination by the inventors for the present application found that this method could not be applied favorably to a polynuclear polyphenol.

A method to oxidize a hydroxy methyl phenol to produce a hydroxy methyl benzaldehyde is described in Japanese Patent Laid-open No. 52-136141. However, this method is based on a gas/liquid reaction and therefore the reaction yield changes easily according to the agitation condition, etc. Also, pure oxygen is used, which makes it difficult to use this method in an industrial setting.

On the other hand, among the various methods to synthesize a bis(formylphenol) or polynuclear poly(formylphenol), a method to cause salicylaldehyde and formaldehyde to react with each other using an acid catalyst is described in Chungnam National University Industrial Technology Lab Papers Vol. 4, No. 2 (1977). However, the substituted benzaldehyde, which is used as the material, is expensive and if the reaction uses a carbonyl compound other than formaldehyde, the low reactivity causes benzaldehyde itself to polymerize under conditions where the carbonyl compound undergoes reaction. These factors make it difficult to apply this method.

Also, a method to tetraformylate a bisphenol is described in Toku-Kai-Hei 5-125032. However, the yield is low and, because a large amounts of hexamethylene tetramine and acid are used compared to the bisphenol, the volumetric efficiency is poor and therefore this method cannot be implemented in an industrial setting.

Furthermore, a method to cause 5-iodine-3-tert-butyl salicylaldehyde and 1,3,5-triethynyl benzene with each other in the presence of bis(triphenolphosphine)palladium, iodinated copper and triethyl amine to obtain 1,3,5-tris[(5-tert-butyl-3-formyl-4-hydroxyphenyl)ethynyl]benzene is described in WO Laid-open No. 2004/050231. However, this method uses expensive materials.

As explained above, it was difficult under any conventional method to produce a polynuclear formyl phenol in an industrial setting with ease and at high yield and high purity.

Patent Literature 1:     Japanese Patent Laid-open No. Sho 52-136141
Patent Literature 2:     Japanese Patent Laid-open No. Hei 5-125032
Patent Literature 3:     WO Laid-open No. 2004/050231
Non-patent Literature 1: J. Chem. Soc., Perkin Trans.
                         (1978, 318 to 321, 1862 to 1865)
Non-patent Literature 2: Chungnam National University Industrial
                         Technology Lab Papers Vol. 4, No. 2 (1977)

SUMMARY OF THE INVENTION

Problems to be Solved by the Invention

The present invention relates to a method for producing a polynuclear formyl phenol in an industrial setting with ease and at high yield and high purity. To be specific, the present invention relates to a method for producing a polynuclear formyl phenol by using as the material a polynuclear poly(hydroxymethylphenol) or polynuclear poly(alkoxymethylphenol) that can be obtained easily from a polynuclear polyphenol.

Means for Solving the Problems

After examining diligently to achieve the aforementioned purpose, the inventors found that the desired polynuclear formyl phenol could be obtained at high yield as a bis(formylphenol) or a polynuclear poly(formylphenol) having three or more hydroxy-substituted phenol nuclei, by using as the direct material a hydroxymethyl-substituted or alkoxymethyl-substituted bisphenol or polynuclear poly(hydroxymethylphenol) or polynuclear poly(alkoxymethylphenol) that can be obtained easily by, for example, methylolation of a polynuclear polyphenol being a subject of the present invention, such as a bisphenol or a polynuclear polyphenol having three or more hydroxy-substituted phenol nuclei, and then causing the material to react with hexamethylene tetramine in the presence of an acid, followed by hydrolyzation of the obtained reaction product to convert into a formyl group the hydroxy methyl group or alkoxy methyl group substituted to the phenyl nucleus. Based on the above findings, the inventors completed the present invention.

To be specific, the present invention provides a method for producing a polynuclear poly(formylphenol) expressed by General Formula (2), wherein said method is characterized in that a polynuclear polyphenol expressed by General Formula (1) is caused to react with hexamethylene tetramine in the presence of an acid and then the reaction product is hydrolyzed.

##STR00001##
(In the formula, all Rs may be the same or different and respectively represent a hydrogen atom or
(In the formula, R represents an
(In the formula, R represents an
(In the formula, R represents an
(In the formula, R represents an aliphatic hydrocarbon group that may have an aromatic hydrocarbon group, hydroxyl group, or aliphatic hydrocarbon group that may have an ether group.)

Also, under a production method conforming to the present invention, the selection of whether to use a polynuclear poly(hydroxymethylphenol) or polynuclear poly(alkoxymethylphenol) corresponding to the target compound is not specifically limited when a polynuclear polyphenol expressed by General Formula (1) is used as the starting material. A desired material can be determined as deemed appropriate by considering the production method, ease of achieving high purity, stability and toxicity of the compound, reaction selectivity, and the like.

EFFECTS OF THE INVENTION

According to a production method conforming to the present invention, a polynuclear formyl phenol which is useful as a resist material, polymerization catalyst or resin or other material can be produced with ease and at high yield and high volumetric efficiency by causing a polynuclear polyphenol expressed by General Formula (1) to react with hexamethylene tetramine in the presence of an acid and then hydrolyze the reaction product.

Furthermore, the material polynuclear poly(hydroxymethylphenol) or polynuclear poly(alkoxymethylphenol) can be produced easily from the corresponding polynuclear polyphenol depending on the substitution position of the hydroxy methyl group or alkoxy methyl group as well as the details of substitution numbers a, b, c and substitution groups R₁, R₂, R₃, X and Y, which allows for production of a polynuclear poly(formylphenol) consistently from a polynuclear polyphenol in an industrial setting with ease and at high yield and high efficiency.

BEST MODE FOR CARRYING OUT THE INVENTION

EXAMPLES

Example 1

Synthesis of 4,4′-methylene bis(2-methyl-6-formylphenol) (Chemical Formula 17)

1140.0 g (10.0 mols) of trifluoroacetic acid was put in a four-way flask with a capacity of 5 liters and the reaction container was substituted by nitrogen, after which 315.0 g (2.25 mols) of hexamethylene tetramine was added at a temperature of approx. 30° C., and then 288.0 g of 4,4′-methylene bis(2-methyl-6-hydroxymethylphenol) (1.0 mol; purity 93% based on high-speed liquid chromatograph (HPLC)) was added under agitation over 3 hours at a temperature of 40° C. to cause reaction. After the entire amount of the material had been added, the temperature was raised to 85° C., and then the mixture was further agitated for 3 hours as a post-reaction. After the reaction, the obtained liquid was partially collected and hydrolyzed, and then analyzed based on HPLC. As a result, the main component that appeared to be the target substance had a composition ratio of 70%. Next, 800.0 g of water was added to the liquid obtained from the reaction to implement hydrolysis reaction for 1 hour at a temperature of 60° C. Crystal precipitated during this reaction. After the reaction, 1471.0 g of 16% aqueous sodium hydroxide solution was added to neutralize the obtained mixture liquid, and then 50 g of methyl isobutyl ketone and 50 g of methanol were added further, after which the mixture was cooled and precipitated crystal was filtered out to obtain 302.3 g of a composition. The obtained composition was put in a four-way flask with a capacity of 2 liters, and 369.2 g of methyl isobutyl ketone and 255.6 g of toluene were added, and then the mixture was maintained at a temperature of 70° C. and agitated for 30 minutes in a slurry state. The mixture was cooled and precipitated crystal was filtered out and dried to obtain 196.8 g of yellow powder crystal having a purity of 95.8% based on HPLC. The yield with respect to 4,4′-methylene bis(2-methyl-6-hydroxymethylphenol) was 69.3%. Based on the results of NMR and mass spectrometry, the obtained crystal was confirmed to be the target substance.

##STR00040##

Melting point: 155.4° C. (based on peak top by differential scanning calorimetry)

Molecular weight: 283 (M—H)⁻ (by mass spectrometry LC-MS (APCI⁻))

Proton NMR identification result (400 MHz, solvent: DMSO-d6, internal standard: tetramethyl silane)

TABLE 1
Shift value (ppm)	Proton number	Signal	Attribution
2.17	6	s	—CH3
3.86	2	s	—CH2—
7.37 to 7.44	4	m	Ph—H
10.00	2	s	Ph—OH
10.88	2	s	—CHO

Example 2

Synthesis of 2,2′-methylene bis(4-methyl-6-formylphenol) from bis(hydroxymethylphenol) Compound (Chemical Formula 18)

546.4 g (4.8 mols) of trifluoroacetic acid was put in a four-way flask with a capacity of 2 liters and the reaction container was substituted by nitrogen, after which 123.2 g (0.88 mol) of hexamethylene tetramine was added at a temperature of approx. 30° C., and then 115.3 g of 2,2′-methylene bis(4-methyl-6-hydroxymethylphenol) (0.4 mol; purity 89% based on HPLC) was added under agitation over 2 hours at a temperature of 60° C. to cause reaction. After the entire amount of the material had been added, the temperature was raised to 85° C., and then the mixture was further agitated for 4 hours as a post-reaction. After the reaction, the obtained mixture liquid was partially collected and then analyzed based on HPLC in the same manner as in Example 1. As a result, the main component that appeared to be the target substance had a composition ratio of 76%.

Next, 320.0 g of water was added to the liquid obtained from the reaction to implement hydrolysis reaction for 1 hour at a temperature of 60° C. Crystal precipitated during this reaction. After the reaction, 830.0 g of 16% aqueous sodium hydroxide solution was added to neutralize the obtained mixture liquid, and then 220.0 g of toluene and 280.0 g of cyclohexane were added further, after which the mixture was cooled and precipitated crystal was filtered out and dried to obtain 81.5 g of yellow powder having a purity of 95.6% based on HPLC. The yield with respect to 2,2′-methylene bis(4-methyl-6-hydroxymethylphenol) was 71.7%.

Based on the results of NMR and mass spectrometry, the obtained crystal was confirmed to be the target substance.

##STR00041##

Melting point: 160.3° C., 168.5° C. (based on peak top by differential scanning calorimetry)

Molecular weight: 283 (M—H)⁻ (by mass spectrometry LC-MS (APCI⁻))

Proton NMR identification result (400 MHz, solvent: DMSO-d6, internal standard: tetramethyl silane)

TABLE 2
Shift value (ppm)	Proton number	Signal	Attribution
2.23	6	s	—CH3
3.90	2	s	—CH2—
7.20 to 7.44	4	m	Ph—H
9.98	2	s	Ph—OH
10.96	2	s	—CHO

Example 3

Synthesis of 2,2′-methylene bis(4-methyl-6-formylphenol) from bis(alkoxymethylphenol) Compound

13.7 g (0.12 mol) of trifluoroacetic acid was put in a four-way flask with a capacity of 200 ml and the reaction container was substituted by nitrogen, after which 2.8 g (0.02 mol) of hexamethylene tetramine was added at a temperature of 30° C., and then 6.3 g of 2,2′-methylene bis(4-methyl-6-methoxymethylphenol) (0.01 mol; purity 90% based on HPLC) was added under agitation over 2 hours at a temperature of 60° C. to cause reaction. After the entire amount of the material had been added, the temperature was raised to 85° C., and then the mixture was further agitated for 4 hours as a post-reaction. After the reaction, the obtained liquid was partially collected and analyzed based on HPLC in the same manner as in Example 2. As a result, the main component corresponding to the target substance had a composition ratio (area %) of 73%.

Example 4

Synthesis of 4,4′-methylene bis(2,5-dimethyl-6-formylphenol) (Chemical Formula 17)

171.0 g (1.5 mol) of trifluoroacetic acid was put in a four-way flask with a capacity of 1 liter and the reaction container was substituted by nitrogen, after which 47.3 g (0.34 mol) of hexamethylene tetramine was added at a temperature of approx. 25° C., and then 47.4 g (0.15 mol) of 4,4′-methylene bis(2,5-dimethyl-6-hydroxymethylphenol) was added under agitation over 2.5 hours at a temperature of 50° C. to cause reaction. After the entire amount of the material had been added, the temperature was raised to 80° C., and then the mixture was further agitated for 20 hours as a post-reaction. Next, 150.0 g of water was added to the mixture liquid obtained from the reaction to implement hydrolysis reaction for 1 hour at a temperature of 70° C. (crystal precipitated during this reaction). 245.7 g of 16% aqueous sodium hydroxide solution was added to neutralize the obtained mixture liquid, which was then kept at a temperature of 80° C. for 1 hour. Thereafter, the mixture was cooled and precipitated crystal was filtered out to obtain 72.3 g of coarse crystal. Next, the obtained coarse crystal was put in a four-way flask with a capacity of 1 liter, and then 70.0 g of methyl isobutyl ketone and 50.0 g of toluene were added and the mixture was kept at a temperature of 80° C. for 1 hour (the solution was in a slurry state), after which the mixture was cooled and precipitated crystal was filtered out and dried to obtain 45.3 g of yellow powder having a purity of 94.6% based on HPLC.

The yield with respect to 4,4′-methylene bis(2,5-dimethyl-6-hydroxymethylphenol) was 82.1%.

Based on the results of NMR and mass spectrometry, the obtained crystal was confirmed to be the target substance.

##STR00042##

Melting point: 200.7° C. (based on peak top by differential scanning calorimetry)

Molecular weight: 311 (M—H)⁻ (by mass spectrometry LC-MS (APCI⁻))

Proton NMR identification result (400 MHz, solvent: DMSO-d6, internal standard: tetramethyl silane)

TABLE 3
Shift value (ppm)	Proton number	Signal	Attribution
2.07	6	s	—CH3 ([2])
2.46	6	s	—CH3 ([1])
3.84	2	s	—CH2
7.00	2	s	Ph—H
10.41	2	s	Ph—OH
12.25	2	s	—CHO

Comparative Example 1

Synthesis of 4,4′-methylene bis(2-methyl-6-formylphenol) from 4,4′-methylene bis(2-methylphenol) via Duff Reaction (Reaction Formula 8)

13.7 g (0.12 mol) of trifluoroacetic acid was put in a four-way flask with a capacity of 200 ml and the reaction container was substituted by nitrogen, after which 2.8 g (0.02 mol) of hexamethylene tetramine was added at a temperature of approx. 30° C., and then 2.3 g (0.01 mol) of 4,4′-methylene bis(2-methylphenol) was added under agitation over 2 hours at a temperature of 40° C. to cause reaction. After the entire amount of the material had been added, the temperature was raised to 85° C., and then the mixture was further agitated for 3 hours as a post-reaction. After the post-reaction, the obtained liquid was partially collected and analyzed based on HPLC in the same manner as in Example 1. As a result, the main component that appeared to be the target substance had a low selectivity. When the post-reaction was continued for 12 hours and the obtained liquid was analyzed based on HPLC in the same manner, the main component that appeared to be the target substance had a composition ratio (area %) of only 7%.

##STR00043##

Example 5

Synthesis of 1-[α-methyl-α-(3-formyl-5-methyl-4-hydroxyphenyl)ethyl]-4-[α,α-bis(3-formyl-5-methy 1-4-hydroxyphenyl)ethyl]benzene

410.4 g (3.6 mol) of trifluoroacetic acid was put in a four-way flask with a capacity of 1 liter and the reaction container was substituted by nitrogen, after which 92.4 g (0.66 mol) of hexamethylene tetramine was added at a temperature of approx. 30° C., and then 111.4 g of 1-[α-methyl-α-(3-hydroxymethyl-5-methyl-4-hydroxyphenyl)ethyl]-4-[α,α-bis(3-hydrox ymethyl-5-methyl-4-hydroxyphenyl)ethyl]benzene (0.2 mol; purity 92.4% based on high-speed liquid chromatography (HPLC)) was added under agitation over 2 hours at a temperature of 60° C. to cause reaction. After the entire amount of the material had been added, the temperature was raised to 85° C., and then the mixture was further agitated for 5 hours as a post-reaction.

Next, 240 g of water was added to the mixture liquid obtained from the reaction to implement hydrolysis reaction for 1 hour at a temperature of 60° C. Viscous solids precipitated during this reaction. After the reaction, 220 g of toluene was added to the obtained mixture liquid, which was then heated to a temperature of 70° C. to dissolve the solids and then kept stationary for 10 minutes to separate the water layer. 32.8 g of 16% aqueous sodium hydrochloride solution was added to neutralize the obtained oil layer, and water was added further to agitate the mixture, which was then kept stationary to separate the water layer and the obtained oil layer was decompressed and condensed up to 10 kPa at 70° C. Thereafter, 30 g of ethyl acetate was added and the mixture was cooled to 50° C., and then 200 g of cyclohexane was added further, with the mixture cooled and precipitated crystal filtered out and dried to obtain 52.7 g of light yellow powder (purity 93.2% based on high-speed liquid chromatography). Based on the results of NMR and mass spectrometry, the obtained crystal was confirmed to be the target substance.

Melting point (peak top by differential scanning calorimetry): 143.0° C.

Molecular weight: 549 (M—H)⁻ (by mass spectrometry LC-MS (APCI⁻))

Proton nuclear magnetic resonance analysis method (400 MHz, solvent: DMSO-d6)

##STR00044##

TABLE 4
1H-NMR (400 MHz) measurement results (Internal
standard: Tetramethyl silane)
Shift value (ppm)	Proton number	Signal	Attribution
1.64	6	s	—CH3 ([1])
2.11	3	s	—CH3 ([2])
2.14	9	s	—CH3 ([3])
6.98 to 7.53	10	m	Ph—H
9.94	2	s	Ph—OH ([4])
10.02	1	s	Ph—OH ([5])
10.92	3	s	—CHO

Example 6

2.85 g (0.025 mol) of trifluoroacetic acid was put in a four-way flask with a capacity of 100 ml and the reaction container was substituted by nitrogen, after which 0.64 g (0.0046 mol) of hexamethylene tetramine was added at a temperature of 30° C., and then 0.77 g of 1-[α-methyl-α-(3-hydroxymethyl-5-methyl-4-hydroxyphenyl)ethyl]4-[α,α-bis(3-hydrox ymethyl-5-methyl-4-hydroxyphenyl)ethyl]benzene (0.00139 mol; purity 92.4% based on high-speed liquid chromatography) was added under agitation over 5 minutes at a temperature of 50° C. to cause reaction. After the entire amount of the material had been added, 2.85 g of toluene was added and the temperature was raised to 85° C., and then the mixture was further agitated for 4 hours as a post-reaction. After the reaction, the obtained liquid was partially collected and hydrolyzed, and then analyzed by high-speed liquid chromatography. As a result, the main component that appeared to be the target substance had a composition ratio (area ratio) of 60.9%.

Comparative Example 2

2.85 g (0.025 mol) of trifluoroacetic acid was put in a four-way flask with a capacity of 100 ml and the reaction container was substituted by nitrogen, after which 0.64 g (0.0046 mol) of hexamethylene tetramine was added at a temperature of 30° C., and then 0.65 g of 1-[α-methyl-α-(3-methyl-4-hydroxyphenyl)ethyl]-4-[α,α-bis(3-methyl-4-hydroxyphenyl)ethyl]benzene (0.00139 mol; purity 97.6% based on HPLC) was added under agitation over 5 minutes at a temperature of 50° C. to cause reaction. After the entire amount of the material had been added, 2.85 g of toluene was added and the temperature was raised to 85° C., and then the mixture was further agitated for 4 hours. However, a lot of material crystal remained undissolved, and therefore the mixture was agitated further for 4 hours as a post-reaction. After the reaction, the obtained liquid was partially collected and hydrolyzed, and then analyzed by high-speed liquid chromatography. As a result, although the material had almost entirely reacted, the main component that appeared to be the target substance had a composition ratio (area ratio) of 18.4%.

Claims

1. A method for producing a polynuclear poly(formylphenol) expressed by general Formula (2), characterized in that a polynuclear polyphenol expressed by general Formula (1) is caused to react with hexamethylene tetramine in the presence of an acid, and then the obtained reaction product is hydrolyzed:

2. The method for producing a polynuclear poly(formylphenol) according to claim 1, wherein, with respect to a polynuclear polyphenol expressed by the aforementioned general Formula (1), if m is 0, X is a bivalent bond group or single bond and l+n is 2 in the formula, then the polynuclear polyphenol is a bisphenol expressed by general Formula (3) specified below, and wherein similarly the polynuclear poly(formylphenol) expressed by the aforementioned general Formula (2) is a bis(formylphenol) expressed by general Formula (4) specified below:

3. The method for producing a polynuclear poly(formylphenol) according to claim 2, characterized in that a bis(hydroxymethylphenol) expressed by general Formula (6), being a bisphenol expressed by the aforementioned general Formula (3) where R is a hydrogen atom, is obtained by causing a bisphenol expressed by general Formula (5) to react with formaldehyde in the presence of an alkali catalyst:

4. The method for producing a polynuclear poly(formylphenol) according to claim 2, characterized in that a bis(alkoxymethylphenol), being a bisphenol expressed by the aforementioned general Formula (3) where R is an aliphatic hydrocarbon group that may have an aromatic hydrocarbon group, hydroxyl group or aliphatic hydrocarbon group that may have an ether group, is obtained by causing a bisphenol expressed by general Formula (5) to react with formaldehyde in the presence of an alkali catalyst and then causing the obtained bis(hydroxymethylphenol) expressed by general Formula (6) to further react with an alcohol expressed by the general Formula (7) specified below in the presence of an acid catalyst:

5. The method for producing a polynuclear poly(formylphenol) according to claim 1, wherein, with respect to a polynuclear polyphenol expressed by the aforementioned general Formula (1), the polynuclear polyphenol where m in the formula indicates an integer of 0, 1 or 2, but where if m is 0, then X is a trivalent to hexavalent bond group and l+n is 3 to 6, is a polynuclear polyphenol expressed by general Formula (8) specified below, and wherein similarly the polynuclear (formylphenol) expressed by the aforementioned general Formula (2) is a polynuclear poly(formylphenol) expressed by general Formula (9) specified below:

6. The method for producing a polynuclear poly(formylphenol) according to claim 5, characterized in that a polynuclear poly(hydroxymethylphenol) expressed by general Formula (11) specified below, being a polynuclear polyphenol expressed by the aforementioned general Formula (8) where R is a hydrogen atom, is obtained by causing a polynuclear polyphenol expressed by general Formula (10) specified below to react with formaldehyde in the presence of an alkali catalyst:

7. The method for producing a polynuclear poly(formylphenol) according to claim 5, characterized in that a polynuclear poly(alkoxymethylphenol), being a polynuclear polyphenol expressed by the aforementioned general Formula (8) where R is an aliphatic hydrocarbon group that may have an aromatic hydrocarbon group, hydroxyl group or aliphatic hydrocarbon group that may have an ether group, is obtained by causing a polynuclear polyphenol expressed by general Formula (10) to react with formaldehyde in the presence of an alkali catalyst and then causing the obtained polynuclear poly(hydroxymethylphenol) expressed by general Formula (11) to further react with an alcohol expressed by general Formula (12) specified below in the presence of an acid catalyst: