JPWO2014156713A1 - Benzyl ether type phenolic resin, resin composition thereof, and binder and carbide obtained using the same - Google Patents

Abstract

Provided is a benzylic ether type phenolic resin and a resin composition thereof which can advantageously provide a dense and highly resistant carbide with a higher carbon content than a conventional phenolic resin. Moreover, the carbide | carbonized_material which has the outstanding characteristic obtained using such a benzylic ether type phenol resin and its resin composition, and the binder for carbon product or a refractory product manufacture are provided. In the benzylic ether type phenol resin having an ortho-conversion rate of 70% or more, the total of methylene bond substitution ratio, benzylic ether bond substitution ratio and methylol group substitution ratio respectively obtained as the substituent ratio per mole of phenol nucleus is 100. %, The ratio of the benzylic ether bond substitution ratio was 10.0 to 40.0%, and the ratio of the methylol group substitution ratio was 13.0 to 40.0%.

Description

  The present invention relates to a benzylic ether type phenolic resin, a resin composition thereof, and a binder and a carbide obtained by using them, and is particularly suitable for use in refractory products, carbon products, grindstones, friction materials, and the like. , Benzylic ether type phenol resins and their resin compositions that give a carbide with a high residual carbon ratio, as well as carbides, carbon products or refractory products obtained by using these benzylic ether type phenol resins and their resin compositions It relates to a binder.

  Conventionally, when manufacturing carbon products and refractory products, various bonding agents or binders (binders) have generally been used for bonding carbon materials and refractory materials as raw materials. For example, pitches and various phenol resins are widely used as such binders. And in the case where a phenol resin is used as a binder, in order to enjoy the blending effect advantageously and from an economical viewpoint, it is necessary to use a phenol resin having a high residual carbon ratio after firing. This is preferable. For example, in JP-A-4-367556 (Patent Document 1), a phenol resin is used as a binder for magnesia-carbon brick, which is a refractory material, and a carbon bond is formed between the refractory materials by firing. It has become so. For this reason, it has been clarified that the residual carbon ratio of the phenol resin greatly contributes to the strength of the obtained refractory product. However, “Thermosetting Resin”, Vol. 2, no. 4 (1981), pp. 36-51 (Non-patent Document 1), in various conventionally known phenol resins, the residual carbon ratio in the carbonization is relatively low of about 50%. It was a thing.

  For this reason, research and development have been actively conducted on a phenol resin (composition) that can be advantageously used as such a binder and has an improved residual carbon ratio after firing. -132696 (Patent Document 2) proposes a phenol resin composition having a high residual carbon ratio obtained by blending a predetermined amount of hexamethylenetetramine and phenol into a novolac type phenol resin and / or a resol type phenol resin. However, although the phenol resin composition proposed there has a relatively high residual carbon ratio, it is numerically only having a residual carbon ratio in the range of 50%. Moreover, the phenol resin compositions with a high residual carbon ratio proposed there are those of semi-cured or cured products, and they are blended with carbon sources and refractory particles in the production process of carbon products and refractory products. When melted, the phenol resin composition may not be able to sufficiently exhibit the fluidity required as a binder. Moreover, since such a phenol resin composition contains hexamethylenetetramine, it is generated by decomposition of hexamethylenetetramine when it is used as a binder to produce carbon products and refractory products. Problems such as the need to take measures against the odor of ammonia are also inherent.

  On the other hand, it is known that the carbide of a phenol resin has an undesirable property of poor oxidation resistance. For example, in Japanese Patent Application Laid-Open No. 2010-31079 (Patent Document 3), a refractory brick using a novolac type phenolic resin as a binder has poor oxidation resistance, and the brick of the refractory brick is easily oxidized by oxidation of carbon in the refractory brick. The problem of causing a decrease in strength has been pointed out. Therefore, there has been proposed a boric acid-modified phenol novolak resin in which boric acid is used as a reaction catalyst to react phenols and aldehydes and boric acid itself is incorporated into the phenol resin skeleton. However, since the proposed boric acid-modified phenolic resin is a novolak type resin, a curing agent such as hexamethylenetetramine must be used, and therefore, measures against the odor of ammonia generated during curing are required. There was a problem that it was necessary to carry out the process, and the residual carbon ratio was only about 50%.

JP-A-4-367556 JP-A-9-132696 JP 2010-31079 A

“Thermosetting resin”, Vol. 2, no. 4 (1981), pp. 36-51

  Here, the present invention has been made in the background of such circumstances, and the problem to be solved is that it has a higher residual carbon ratio than conventional phenol resins, and has a dense and high oxidation resistance. It is to provide a benzylic ether type phenolic resin and a resin composition thereof that can advantageously give a carbide having the same, and excellent obtained by using such a benzylic ether type phenolic resin and the resin composition thereof The object is to provide a carbide having properties and a binder for producing a carbon product or a refractory product.

  And, as a result of intensive studies on the phenol resin and its resin composition in order to solve the above-mentioned problems, the present inventors have found that the structure of the phenol resin has a substitution position of the substituent mainly with respect to the phenol skeleton. A so-called high-ortho structure, and a substitution ratio of methylene bond, benzylic ether bond, and methylol group in the phenol resin within a specific region, and a benzylic ether type phenol resin and its resin composition The present inventors have found that a carbide having a high residual carbon ratio, denseness, and good oxidation resistance can be obtained by calcination, and the present invention has been completed.

  That is, in order to solve the above-described problems, the present invention is required to obtain a benzylic ether type phenol resin having an ortho-conversion rate of 70% or more and a substituent ratio per mole of the phenol nucleus of the resin. When the total of the methylene bond substitution ratio, the benzylic ether bond substitution ratio, and the methylol group substitution ratio is 100%, the ratio of the benzylic ether bond substitution ratio is 10.0 to 40.0%, and the methylol group The gist of the present invention is a benzylic ether type phenol resin characterized in that the ratio of the substitution ratio is 13.0 to 40.0%.

  According to one of the preferred embodiments of the benzylic ether type phenol resin according to the present invention, the ratio of the benzylic ether bond substitution ratio is 20.0 to 39.5%, and the methylol group substitution is performed. The ratio is 13.5 to 38.0%.

  In the benzylic ether type phenol resin according to the present invention, the methylene bond substitution ratio is 0.42 to 0.55 mol per mole of phenol nucleus, and the benzylic ether bond substitution ratio is 0. It is desirable that the methylol group substitution ratio is 0.13 to 0.20 mol.

  Furthermore, the benzylic ether type phenolic resin according to the present invention is preferably obtained by reacting phenols and aldehydes using a divalent metal salt as a catalyst. As the valent metal salt, at least one selected from the group consisting of zinc chloride, zinc acetate, a mixture of boric acid and zinc hydroxide, and zinc borate is in a ratio of 0.1 mol% or more with respect to phenols. It is desirable to be used. Moreover, the aspect whose molar ratio of phenols and aldehydes exists in the range of 1.0: 1.0-1.0: 2.0 will also be employ | adopted advantageously.

  In addition, the benzylic ether type phenolic resin according to the present invention preferably has a weight average molecular weight (Mw) of more than 2,000 and less than 30,000, so that it falls within such a molecular weight range. By preparing a benzylic ether type phenol resin, the ratio of methylene bond, benzylic ether bond and methylol group in the phenol resin can be advantageously within the range defined in the present invention.

  And in this invention, the benzylic ether type phenol resin composition which contains the benzylic ether type phenol resin as mentioned above as an essential component is also made into the object.

  The gist of the present invention is a carbide obtained by firing the above-mentioned benzylic ether type phenolic resin or a resin composition thereof.

  Furthermore, in the present invention, the above-mentioned benzylic ether type phenolic resin is used as a bonding agent having a high residual carbon ratio that is used for bonding carbon materials or refractory materials to give a target carbon product or refractory product. Alternatively, the gist of the present invention is also a carbon product or a refractory product manufacturing binder comprising the resin composition.

  In such a benzylic ether type phenolic resin and a resin composition thereof according to the present invention, the residual carbon ratio is 60% or more in firing in a nitrogen atmosphere up to 800 ° C. and up to 300 to 800 ° C. It has the characteristic that the carbide | carbonized_material whose weight reduction | decrease rate in the baking area | region becomes 30% or less can be obtained. Moreover, the carbide | carbonized_material according to such this invention has the characteristic that it has higher oxidation resistance than other conventionally well-known phenol resins, and is a dense carbide | carbonized_material.

It is explanatory drawing which shows the mechanism of carbonization by baking of a phenol resin in the mode of a chemical structure change. It is the scanning electron microscope (SEM) photograph which shows the state of the carbide | carbonized_material of the benzylic ether type phenol resin obtained in Example 1, Comprising: (a) shows the whole image of the carbide particle (magnification: 50 times), ( b) and (c) respectively show the state of the fracture surface of such carbide particles at different magnifications (100 times or 1000 times). It is a scanning electron microscope (SEM) photograph about the carbide | carbonized_material of the novolak-type phenol resin prepared in the comparative example 11, Comprising: (a) shows the whole image of such a carbide particle (magnification: 50 times), (b ) And (c) show the state of the fracture surface of the carbide particles at different magnifications (100 times or 1000 times), respectively. 2 is a diagram showing a TG chart for a carbide of a benzylic ether type phenol resin obtained in Example 1 and a carbide of a novolac type phenol resin prepared in Comparative Example 11. FIG.

  By the way, as described above, the benzylic ether type phenol resin according to the present invention has (A) a high-ortho structure, and (B) a methylene bond ratio (methylene bond substitution ratio) per mole of phenol nucleus of the resin, When the total amount of rickether bond ratio (benzylic ether bond substitution ratio) and methylol group ratio (methylol group substitution ratio) is 100%, the ratio of the benzylic ether bond substitution ratio is 10.0 to 40.0. %, And the ratio of methylol group substitution ratio is in the range of 13.0 to 40.0%.

  And, regarding the high ortho structure according to the structural requirement (A) in such a benzylic ether type phenol resin according to the present invention, the ortho ratio, which is the ratio of the substituents bonded to the ortho position of the phenol nucleus of the resin, It is necessary to be 70% or more of the proportion of ortho-bonding that normally known high ortho resole has, and preferably it is 75 to 90%. Note that 90% of the upper limit is an assumed numerical value that can be manufactured, and in fact, there is no upper limit of the ortho-ratio, and it can be said that a higher value is desirable. Further, the higher the ratio of such ortho-bonds, the more easily a dense carbide is formed in the carbonization step, and the residual carbon ratio is improved. As shown in FIG. 1, when the resin has a high-ortho-linear structure, there is no gap between the cyclization and aromatization in the carbonization step and the polycondensation in the solid phase. It is considered that a flat surface is easily formed.

  Here, the ortho-ratio can be easily obtained by performing 13C-NMR measurement on a resin sample using a nuclear magnetic resonance apparatus according to a known method. That is, the chemical shift of 13C-NMR of each ortho of the phenol nucleus in the benzylic ether type phenol resin, the methylene bond bonded to the para position, the benzylic ether bond and the methylol group is known (Andre Knop., Louis A. Pilato., Translated by Shoji Seto, “Phenolic Resin”, p. 110), based on their chemical shift information, they are linked to ortho-ortho, ortho-para, para-para position. Obtain the integrated intensity ratio of each carbon peak of the methylene bond, benzylic ether bond and the methylol group bonded to the ortho or para position, and thereby calculate the ratio of the ortho bond when the total bond is 100%. It can be done.

  In addition, regarding the structural requirement (B) relating to the benzylic ether type phenol resin according to the present invention, the methylene bond substitution ratio, the benzylic ether bond substitution ratio, and the methylol group respectively obtained as the substituent ratio per mole of phenol nucleus in the resin In order to obtain a high residual carbon ratio in a benzylic ether type phenol resin with a total substitution ratio of 100%, in addition to the above-mentioned condition (A), the ratio of the benzylic ether bond substitution ratio is 10.0. It is necessary that the ratio of methylol group substitution ratio is 13.0 to 40.0%. Among these, the ratio of the benzylic ether bond substitution ratio is 20. In order to facilitate the production in only one cycle of the condensation step, the distillation under reduced pressure concentration step, and the discharge step, and to further improve the residual carbon ratio. It is desirable that it is 0 to 39.5%, and the ratio of methylol group substitution ratio is 13.5 to 38.0%. Regarding the individual proportions of these binding components, the lower limit of the benzylic ether bond substitution ratio may be 10% or more, preferably 15% or more, more preferably 20% or more, while the upper limit is , 40% or less, preferably 39.5% or less, more preferably 30% or less. The ratio of the methylol group substitution ratio is 13% or more, preferably 13.5% or more, more preferably 15% or more, while the upper limit is 40% or less, preferably 38%. Below, more preferably 30% or less. The ratio of the methylene bond substitution ratio is a value obtained by subtracting the total amount of each ratio of the benzylic ether bond substitution ratio and the methylol group substitution ratio from 100%.

  In addition, when it deviates from the regulation range of the above (B) in the present invention, for example, when the proportion of benzylic ether bonds is larger than the range of (B), the residual carbon ratio is lowered. Is heated, the formaldehyde is removed and a methylene bond is formed. At this time, the cross-linked structure is inhibited from becoming dense, or the densification of the carbide is inhibited by a large amount of formaldehyde that is eliminated. It seems to be because. Moreover, when the ratio of a methylol group increases from the range of (B), it will become difficult to manufacture the benzylic ether type | mold resol resin of such a composition. Furthermore, from the specified range of (B), when the benzylic ether bond and the methylol group, or both are lowered, the proportion of methylene bonds is relatively increased, and therefore the crosslinking density is lowered due to the lack of reactive groups, Residual carbon ratio will decrease.

  Further, in the benzylic ether type phenol resin according to the present invention, in order to increase the residual carbon ratio preferentially, the substitution ratio of the methylene bond is 0.42 to 0.55 mol with respect to 1 mol of the phenol nucleus of the resin. The substitution ratio of the benzylic ether bond is 0.26 to 0.38 mol, and the substitution ratio of the methylol group is 0.13 to 0.20 mol, which is advantageously employed. .

  Here, the benzylic ether type phenol resin targeted in the present invention is obtained by reacting phenols and aldehydes, and the benzylic ether type phenol resin according to the present invention is publicly known. As described above, it is obtained by reacting phenols and aldehydes in the presence of a predetermined catalyst, and the production method is not particularly limited, and there are known materials appropriately selected. Will be used.

  Specifically, as is well known, a benzylic ether type phenol resin is obtained by reacting phenols and aldehydes, generally using a catalyst such as a divalent metal salt. . In addition, about the usage-amount of phenols and aldehydes there, an aldehyde is preferably 1.0-2.0 mol with respect to 1.0 mol of phenol, More preferably, it is 1.1-1.6. Used in molar proportions. When the use ratio of the aldehydes is less than 1.0 mol, there is a shortage of reactive groups in the resin, and there is a possibility that a sufficient residual carbon ratio cannot be obtained by baking after curing. If it increases, the amount of formaldehyde generated during production and curing will increase, causing problems such as odor and blockage of the decompression line during production, as well as adversely affecting quality and reducing the carbon content. .

  Moreover, in the benzylic ether type phenol resin according to the present invention, its weight average molecular weight (Mw) is generally larger than 2,000 and smaller than 30,000, more preferably 3,000 to 20 1,000 is desirable. This is because when the weight average molecular weight is smaller than 2,000, the substitution ratio of the methylol group becomes too large, not only out of the specified range of (B) according to the present invention, but also the resin does not solidify at room temperature. Therefore, it is also disadvantageous from the viewpoint of handling, and when the weight average molecular weight is larger than 30,000, the substitution ratio of the methylene bond becomes too large, which is outside the specified range of (B) according to the present invention, This is because there is a possibility of causing gelation of the resin.

  Furthermore, the amount of unreacted phenol contained in the benzylic ether type phenol resin according to the present invention is not limited at all, but it is preferably 5% or less on a mass basis. If a large amount of unreacted phenol is contained, a large amount of phenol evaporates at the time of temperature rise before curing, which may lead to a decrease in the residual carbon ratio and foaming of the resin. From the viewpoint of environmental hygiene, the content of unreacted phenol is preferably 5% or less as described above.

  By the way, as phenols used for the production of the target benzylic ether type phenolic resin, various general phenols conventionally used for the production of phenolic resins can be exemplified.

  Specifically, as such phenols, for example, phenol; cresols such as m-cresol, p-cresol, o-cresol, 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, Xylenols such as 3,4-xylenol, m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4-tert-butylphenol, 3 Alkylphenols such as -tert-butylphenol, 2-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol, 6-tert-butyl-3-methylphenol; Methoxyphenol, m-methoxyphenol, -Alkoxyphenols such as ethoxyphenol, m-ethoxyphenol, p-propoxyphenol, m-propoxyphenol; o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol, 2-ethyl- Isopropenylphenols such as 4-isopropenylphenol; polyhydroxyphenols such as 4,4′-dihydroxybiphenyl, bisphenol A, resorcinol, hydroquinone, pyrogallol; phenylphenol, α-naphthol, β-naphthol, naphthalenediols, etc. Can be mentioned. Especially, in this invention, Preferably, the polynuclear body obtained by reaction of phenol and phenol, and formaldehyde will be used advantageously. Since phenols having other functional groups in the phenol nucleus tend to deteriorate the residual carbon ratio, phenols having no such functional groups are preferably used. Of course, it goes without saying that the present invention is not limited to such examples, and the above phenols can be used alone or in combination of two or more.

  In addition, as the aldehydes used in the present invention, any of the general aldehydes conventionally used in the production of phenol resins is targeted. For example, formaldehyde, formalin, paraformaldehyde, acetaldehyde, salicylaldehyde Preferably, formaldehydes such as formalin, paraformaldehyde and polyoxymethylene are used. In addition, this invention is not limited to the thing of such an illustration, Of course, those aldehydes will be used individually or in combination of 2 or more types. In particular, among formaldehydes, a formalin aqueous solution and paraformaldehyde are preferably used. However, the use of paraformaldehyde is more desirable because of the reaction rate during condensation and the decrease in internal temperature due to heat of evaporation during vacuum distillation.

  And as a catalyst for reacting the above phenols and aldehydes to obtain a benzylic ether type phenol resin according to the present invention, it is desirable to use a divalent metal salt, for example, a form of a divalent metal salt In addition to the use in, a divalent metal oxide or hydroxide, or both, and an acidic compound or a basic compound may be used in combination. The divalent metal salt as such a catalyst is not particularly limited as long as it can realize (A) and (B), which are constituents of the resin structure according to the present invention, and is not limited to anhydrides or hydrates. Any form is acceptable. Examples of acidic compounds include boric acid, acetic acid, and paratoluenesulfonic acid. Examples of basic compounds include sodium hydroxide, potassium hydroxide, zinc hydroxide, and triethylamine. By using this acidic compound or basic compound, the composition can be easily adjusted. In addition, the use of an acidic compound tends to increase the number of methylene bonds, while the use of a basic compound tends to decrease the number of methylene bonds.

  As such a divalent metal salt, a zinc compound such as zinc chloride, zinc acetate, zinc borate, or a mixture of boric acid and zinc hydroxide is advantageously used. Moreover, the zinc compound as such a bivalent metal salt may be used independently, and can also be used in combination of 2 or more type. When a plurality of divalent metal salts are used in combination, the divalent metal salt composed of a zinc compound is 0.1 mol% or more with respect to phenols, and the number of moles of other divalent metal salts is a zinc compound. It is preferable that the resin is contained in the range of the number of moles or less of the divalent metal salt consisting of

  Further, the amount of the catalyst used is appropriately determined depending on the kind thereof, and it is difficult to uniquely determine it. Generally, however, 0.01 to 100 parts per 100 parts by mass of phenol. It is used within a range of parts by mass, preferably 0.05 to 20 parts by mass, more preferably 0.1 to 5 parts by mass. If this amount of catalyst becomes too large, the reaction rate increases and it becomes difficult to produce a resin. On the other hand, if the amount of catalyst becomes too small, the residual carbon ratio tends to decrease.

  Furthermore, in the present invention, water can be appropriately added into the reaction vessel depending on the viscosity in the reaction system and the state of dissolution of the raw material. In that case, it is desirable to add water at a ratio of 0 to 50 parts by mass with respect to 100 parts by mass of the phenols. When the amount of water added exceeds 50 parts by mass, the condensation time becomes longer due to a decrease in the reaction rate, and it takes time to remove water in the distillation step, resulting in inefficiency.

  In addition, an antifoaming agent, an acid, an alkali, a granulating agent, or the like can be used as another additive to the reaction system. Therefore, antifoaming agents are used to suppress excessive resin foaming in the distillation process, acids and alkalis are used to adjust the reaction rate, and granulating agents granulate the resulting phenolic resin. And used as a particle.

  By the way, when manufacturing the benzylic ether type resole resin according to the present invention, the same manufacturing procedure as that of the prior art is adopted. Specifically, a raw material is charged into a reaction vessel, heated and heated, and then refluxed for a predetermined time to perform a condensation reaction, and a reaction product generated in the condensation reaction. Perform distillation under reduced pressure to remove residual phenol and water and increase the molecular weight, and discharge the reaction product (benzylic ether type phenol resin) when the molecular weight reaches a predetermined state (system) The removal process to the outside) is adopted.

  First, in the condensation step, the phenols, aldehydes, catalyst and water are put into a reaction vessel (container) and mixed, and then heated and heated, preferably at the reflux temperature. The condensation reaction of aldehydes with aldehydes proceeds. As the rate of temperature rise at this time, the heating starts from room temperature, and the range of 0.1 ° C./min to 5.0 ° C./min, more preferably the range of 0.3 ° C./min to 1.3 ° C./min. It is desirable that the temperature be increased to 80 to 120 ° C. This is because if the rate of temperature rise is too fast than 5.0 ° C./min, the reaction heat at the initial stage of the reaction increases, and there is a risk of gelation and aldehydes in the system are discharged out of the system. This is because, due to consumption of methylol groups due to a rapid reaction, the benzylic ether bond ratio and methylol group ratio in a predetermined resin cannot be obtained, leading to a decrease in the residual carbon ratio. On the other hand, if it is slower than 0.1 ° C./min, the production efficiency is deteriorated, and the condensation process takes time, which is disadvantageous from an economical viewpoint. From the above, it is possible to advantageously obtain a resin having a high residual carbon ratio by setting the temperature rising rate within the range of 0.1 ° C./min to 5.0 ° C./min. In addition, the condensation time is appropriately determined in consideration of the condensation temperature, the mixing ratio of the raw materials, the viscosity in the system, the degree of condensation, etc. Generally, it is about 1 to 10 hours. desirable.

  In general, the reaction rate of phenol in the condensation step is desirably 85% or less, preferably 40% to 85%, and more preferably 50% to 84%. That is, in the present invention, it is desirable to allow the condensation step to proceed so that the unreacted phenol is 15% or more. This is because when the reaction rate exceeds 85% or more, the viscosity in the system increases, and the viscosity increases during the subsequent distillation step under reduced pressure. This is because it becomes difficult for the resin to be discharged from the reaction can. Further, foaming becomes intense during vacuum distillation, and the reaction product is sucked into the vacuum distillation line and solidifies, thereby causing adverse effects such as the possibility of blocking the vacuum distillation line. Further, when the reaction rate is lower than 40%, there arises a problem that the yield decreases.

  Next, in the distillation step adopted after the completion of the above condensation step, the removal of unreacted raw materials and water from the reaction product is continued in the reaction kettle without using a special apparatus or steam distillation. This is done by stirring the product with a stirring blade. The distillation temperature is preferably 100 to 150 ° C., more preferably 100 to 120 ° C. under reduced pressure at a pressure of 8.0 kPa or less. The decompression in this distillation step is performed until the required molecular weight is reached. In this distillation step, unreacted phenol is removed. In that case, the residual amount of unreacted phenol is preferably 5.0% or less, and the residual phenol amount is 5.0%. If it is more, the phenol will evaporate at the time of curing, causing a problem that the residual carbon ratio decreases.

  In the vacuum distillation step, the weight average molecular weight of the reaction product is measured at the same time, and the resin (reaction product) in the system reaches a weight average molecular weight of more than 2,000 and less than 30,000. At that time, the vacuum distillation is stopped and the resin (reaction product) in the system is discharged out of the system as it is. In addition, since the molecular weight of the benzylic ether type resol resin increases rapidly as the molecular weight increases in the latter stage of the distillation process, it becomes gelled. Therefore, it is necessary to pay sufficient attention to end point management. Further, when the resin in the system is formed as a resin that can be solidified by cooling from the heat-melted state, if the molecular weight increases, the viscosity increases, making it difficult to discharge, so the weight average molecular weight is 10 It is preferable to discharge at a stage of 1,000 or less. In addition, when the resin in the system is formed as particles, it is not difficult to discharge the resin due to the increase in molecular weight. Therefore, the resin may be discharged in a state where the weight average molecular weight is less than 30,000. In order to discharge the resin in the system earliest, the resin may be discharged from the time when the weight average molecular weight becomes 2,000 or more so as to be within the specified range of (A) of the present invention.

  Here, the method for measuring the weight average molecular weight at the time of distillation under reduced pressure is not particularly limited as long as it is a method capable of measuring the weight average molecular weight of the resin in the system. In order to shorten the time lag until the molecular weight is increased by stopping the process, for example, while measuring the viscosity with a cone plate or the like, the viscosity is correlated with the molecular weight in advance, and the molecular weight is derived from the specified viscosity, A preferred method is to immediately shift to the discharging step when the molecular weight is reached. At this time, in order to adjust the resin composition or the like, it is possible to add a high ortho novolak resin, an alkali resole resin or the like to the reaction system and mix them.

  In the discharge step, when the unreacted phenol is removed in the previous vacuum distillation step, and the resin in the system reaches a predetermined molecular weight, it is discharged out of the system as it is. However, it is also possible to add a solvent in the middle of distillation under reduced pressure to form a solution and discharge it. In addition, a granulating agent such as water and gum arabic is added to remove the resin in the system. After granulating, it can be filtered and dried to be discharged as solid particles. In addition, in order to adjust the resin composition, it is possible to mix other high-ortho novolak resins or alkali resole resins after discharge.

  The benzylic ether type phenolic resin according to the present invention thus obtained is used as it is for various applications as it is, and as an essential component, other resins such as a high ortho novolac resin and an alkali resol resin are blended therewith, Moreover, various additives etc. can be mix | blended and a benzylic ether type phenol resin composition can be formed and used. In addition, the compounding of a resin composition will not be specifically limited if the resin composition finally completed satisfy | fills (A) and (B) which are the structural requirements of this invention.

  The benzylic ether type phenolic resin or the resin composition thereof according to the present invention exhibits the feature that a dense carbide can be formed by firing them in a nitrogen atmosphere. The carbonization of phenolic resin has been studied for a long time (Akio Shindo; “Science and Industry”, Vol. 53, No. 7 (1979), 248), and as shown in FIG. After completion of curing, a dehydration reaction takes place between the phenolic hydroxyl group and the methylene chain at 300 to 500 ° C., and then a condensed aromatic ring is formed via a dehydrogenation reaction, and then through a process toward carbonization. However, it is known that the benzylic ether type phenol resin according to the present invention advantageously gives a dense carbide by such a carbonization process.

  Moreover, the carbide | carbonized_material formed by baking the benzylic ether type phenol resin or resin composition according to this invention has the characteristics that the residual carbon rate will be 60% or more. When the residual carbon ratio is less than 60%, it is not desirable in terms of reducing the strength as a binder, and the yield of carbide is small, which is economically disadvantageous. When the residual carbon ratio is 60% or more, high strength can be obtained and economic efficiency can be improved by improving the yield. The weight reduction rate in the temperature range of 300 to 800 ° C. is desirably 30% or less. If the weight loss rate in the temperature range of 300 to 800 ° C. is higher than 30%, it becomes difficult to form a dense carbide, and volume shrinkage after curing is large, which is not preferable as a binder. When the weight reduction rate is 30% or less, a fine carbide having a small volume shrinkage after curing can be advantageously obtained.

  By the way, in the present invention, by satisfying the above conditions (A) and (B), a regular continuous ring structure as shown in FIG. 1 is efficiently formed in the dehydration reaction of the phenolic hydroxyl group and the methylene chain. It is thought that a dense condensed aromatic ring can be completed. That is, in the benzylic ether type phenolic resin and the resin composition according to the present invention that satisfy the conditions (A) and (B), sufficient fluidity is ensured when melted. At the same time, after the firing, it will give a high residual carbon ratio and a dense and oxidation-resistant carbide, so as to produce a carbon product and a refractory product, and also directly produce the carbide. As a raw material at that time, it can be suitably used.

For example, when producing a refractory product using the benzylic ether type phenolic resin or resin composition according to the present invention as a binder, a refractory material such as natural or artificial refractory particles and such a phenolic resin or resin according to the present invention. After blending and mixing with the composition, the resulting mixture is used to produce a predetermined molded body, and then the molded body is fired to produce the molded body.
Similarly, when producing a carbon product using the benzylic ether type phenol resin or the resin composition according to the present invention as a binder, for example, for a carbon material such as a powder (carbon source) such as coke, By blending and mixing the benzylic ether type phenolic resin or the composition thereof according to the present invention, using the resulting mixture, a predetermined molded body is produced, and further, the molded body is fired. Will be manufactured. Further, even in a carbon product called carbon-carbon composite material using carbon fiber as a carbon source, the benzylic ether type phenol resin or composition thereof according to the present invention dissolved in a predetermined solvent is carbon. The fiber is impregnated, the impregnated carbon fiber is molded in accordance with a predetermined molding method, and the obtained molded body is fired.

Some examples of the present invention will be shown below to clarify the present invention more specifically. However, the present invention is not limited by the description of such examples. Needless to say. In addition to the following examples, the present invention includes various changes and modifications based on the knowledge of those skilled in the art without departing from the spirit of the present invention, in addition to the specific description described above. It should be understood that improvements can be made.
In addition, the weight average molecular weight (Mw) of the benzylic ether type phenol resin obtained in the following Examples and Comparative Examples, the content of unreacted phenol, the orthorization rate, the resin composition, the residual carbon rate, the densification of the resin, and The oxidation resistance (TG chart) was measured or evaluated according to the following methods.

-Measurement of weight average molecular weight (Mw)-
Weight average molecular weight in terms of standard polystyrene (by means of gel filtration chromatograph 8020 series build-up system manufactured by Tosoh Corporation (column: G2000HXL + G4000HXL, detector: UV254 nm, carrier: tetrahydrofuran 1 ml / min, column temperature: 40 ° C.)) Mw).

-Measurement of unreacted phenol content-
Contains unreacted phenol by a calibration curve method using a gel filtration chromatograph 8020 series build-up system (column: G1000HL + G2000HL, detector: UV254 nm, carrier: tetrahydrofuran 1 ml / min, column temperature: 40 ° C.) manufactured by Tosoh Corporation Measure the amount (mass basis).

-Measurement of ortho ratio-
Using a nuclear magnetic resonance apparatus (manufactured by Varian: INOVA400), 13C-NMR (100 MHz, solvent: heavy pyridine) was measured for each resin sample. From the measured values, the ortho-ortho position and the ortho-para position were measured. Or the integral intensity ratio of each carbon peak of the methylene bond bonded to the para-para position, the benzylic ether bond bonded to the ortho-ortho position, and the methylol group bonded to the ortho or para position. Thus, the ratio of the ortho bond when the total bond is 100% is calculated by the following formula.
C1 (methylene-bonded carbon bonded to ortho-ortho position)
= Chemical shift 33.0-28.0 ppm peak integrated intensity ratio C2 (methylene-bonded carbon bonded to ortho-para position)
= Chemical shift 38.0 to 33.0 ppm peak integrated intensity ratio C3 (methylene-bonded carbon bonded to para-para position)
= Chemical shift 42.0 to 38.0 ppm peak integrated intensity ratio C4 (carbon of methylol group bonded to para position)
= Chemical shift 63.2 to 60.6 ppm peak integral intensity ratio C5 (carbon of methylol group bonded to ortho position)
= Chemical shift 66.8 to 64.2 ppm peak integrated intensity ratio C6 (carbon of benzylic ether bond bonded to ortho-ortho position)
)
= Chemical shift 71.0-66.8 ppm peak integrated intensity ratio Ortho ratio (%)
(OR) = (C1 × 2 + C2 + C5 + C6) /
(C1 × 2 + C2 × 2 + C3 × 2 + C4 + C5 + C6) × 10
0

-Measurement of resin composition-
Using a nuclear magnetic resonance apparatus (manufactured by Varian: INOVA400), 1H-NMR (400 MHz, solvent: heavy acetone) is measured on a resin sample acetylated by a conventional method, and a benzene ring, a methylene bond, and a benzylic ether bond. Then, each peak integral intensity ratio of protons bonded to carbon in the methylol group is obtained, and the total number of phenol nuclei is obtained by the following formula, and then the ratio of substituents per mole of phenol nuclei is calculated.
Thereafter, the total of the methylene bond substitution ratio, the benzylic ether bond substitution ratio, and the methylol group substitution ratio of the substituent ratio per mole of phenol nucleus is 100%, and the methylene bond, benzylic ether bond, and methylol group in the resin composition The ratio (mole) of each is determined.
A1 (proton bonded to carbon in the benzene ring)
= Chemical shift 7.70-6.50 ppm peak integrated intensity ratio A2 [acetylated hemiformal group: Ph-CH ₂ OCH ₂ OAc
Proton bonded to carbon (—OCH ₂ O—)]
= Peak integral intensity ratio of chemical shift of 5.42-5.18 ppm A3 (acetylated methylol group: bonded to carbon of Ph-CH ₂ OAc
Proton)
= Chemical shift 5.18-4.91 ppm peak integrated intensity ratio A4 [benzylic ether bond: Ph-CH ₂ OCH ₂ -Ph to carbon
Bonded proton and hemi-formal group: Ph-CH ₂ OCH ₂
Proton bonded to carbon of OAc (Ph—CH ₂ O—)]
= Chemical shift 4.91~4.17ppm of peak integral intensity ratio A5 (methylene linkages: Ph-CH ₂ -Ph of protons bonded to carbon
)
= Chemical shift 4.17 to 3.44 ppm peak integrated intensity ratio After obtaining the above integrated intensity ratio, the total number of phenol nuclei (P) is calculated according to the following equation.
P (total number of phenol nuclei) = {A1 + A2 / 2 + A3 / 2 + (A4-A2
) / 4 + A5 / 2} / 5
Subsequently, the substitution ratio (mol) of each substituent per mole of phenol nucleus is determined by the following formula.
Methylene bond substitution ratio R1 = A5 / (2 × P)
Benzyl ether bond substitution ratio R2 = (A4-A2) / (4 × P)
Methylol group substitution ratio R3 = A5 / (2 × P)
And the ratio of the methylene bond in a resin composition, a benzylic ether bond, and a methylol group is calculated | required by following Formula. That is, the methylene bond substitution ratio, the benzylic ether bond substitution ratio, and the methylol group substitution ratio, which are ratios of the methylene bond substitution ratio, the benzylic ether bond substitution ratio, and the methylol group substitution ratio, are respectively determined.
Methylene bond rate (%) = R1 / (R1 + R2 + R3) × 100
Benzyl ether bond percentage (%) = R2 / (R1 + R2 + R3) × 100
Methylol group ratio (%) = R3 / (R1 + R2 + R3) × 100
References: JCWoodbrey, HPHigginbottom, HMCulbertson, J.Polym.Sci
., PART A, Vol. 3, 1079-1106 (1965)

-Measurement of carbon residue-
Using a differential type differential thermal balance (Tg-DTA Thermoplus2 TG8120, manufactured by Rigaku Corporation; N ₂ flow rate: 500 ml / min, heating rate: 10 ° C./min, Pt pan: φ5 × 5 used) Measurement is performed by heating to room temperature to 830 ° C. From the weight reduction rate from room temperature to 800 ° C .: W1 (%), the residual carbon rate is obtained by the following formula.
Residual carbon ratio (%) = 100−W1
Here, the weight reduction rate from room temperature to 300 ° C. is the weight reduction rate until curing, and the weight reduction rate from 300 to 800 ° C. is the weight reduction rate after curing.

-Evaluation of densification of resin carbide-
In a differential type differential thermal balance (Tg-DTA Thermoplus2 TG8120, manufactured by Rigaku Corporation; N ₂ flow rate: 500 ml / min, heating rate: 10 ° C./min, Pt pan: φ5 × 5 used), heating rate: 2 The temperature is raised to 200 ° C. at a rate of about ° C./min to produce a cured product. Thereafter, the carbide is obtained by heating and heating to 830 ° C. at a rate of temperature increase of 10 ° C./min. Next, the obtained carbide is magnified from 50 times to 1000 times with a scanning electron microscope (JEM-6700F manufactured by JEOL Ltd.), and the state of the carbide is observed.

-Evaluation of densification (density) of resin carbide-
After the resin is cured by heating at 200 ° C. for about 5 hours in a dryer, it is 900 ° C. (nitrogen replacement, temperature rising condition in a baking furnace (vacuum purge type box furnace: μBF-WVP manufactured by Koyo Thermo Systems Co., Ltd.). After holding at 40 ° C. for 15 minutes, the heating rate was raised to 900 ° C. at a rate of 2 ° C./min. The carbide and the resin used to obtain the carbide were co-ground in a coffee mill at a weight ratio of 7: 3 to obtain a mixed powder of carbide and resin. Thereafter, a molded body of about 100 mm × 100 mm × 2 mm is formed on the carbide with a 20-ton press (load: 15 t, mold temperature condition: 180 ° C., molding time: 10 minutes, during which time gas is released until no gas is emitted). Made and again fired up to 900 ° C. under the above-mentioned conditions, fired at 2000 ° C. in a firing furnace (manufactured by Fuji Denpa Kogyo Co., Ltd .: High Multi 10000) (temperature rising rate under argon gas atmosphere: up to 2000 ° C. at 300 ° C./hr) After raising the temperature, the mixture was held at 2000 ° C. for 1 hour and then gradually cooled to obtain a carbide. The carbide was cut into a predetermined size, and the specific gravity was measured with a hydrometer (Electron hydrometer: MD-200S manufactured by Alpha Mirage Co., Ltd.).

-Evaluation of oxidation resistance of resin (measurement of TG chart)-
Resin carbide samples prepared by the above-described densification evaluation of the resin were subjected to differential type differential thermal balance (Tg-DTA Thermoplus2 TG8120 manufactured by Rigaku Corporation; air flow rate: 500 ml / min, heating rate: 10 ° C./min, Using a Pt pan: φ5 × 5), the temperature is raised from room temperature to 830 ° C. in an air atmosphere, and TG chart measurement is performed.

Example 1
In a reaction vessel equipped with a thermometer, a stirrer and a reflux condenser, 100 parts by mass of phenol (P), 52 parts by mass of 92% paraformaldehyde (F) (F / P = 1.5 on a molar basis) , 7.8 parts by mass of water, 0.28 parts by mass of zinc chloride as a catalyst (0.19 mol% with respect to phenol), and 0.011 of an antifoaming agent (manufactured by Shin-Etsu Chemical Co., Ltd .: KM-73E) After charging the parts by mass, the mixture was heated to a reflux temperature of 0.6 ° C./min while stirring and mixing, and a condensation reaction was carried out for 4 hours. Thereafter, the obtained reaction product was concentrated under reduced pressure in a reaction vessel under heating, while the Mw of the reaction product was measured, and the measured Mw was in the range of 5,000 to 8,000. At that time, the reaction product was discharged from the reaction vessel to obtain a benzylic ether type phenol resin.

Example 2
A benzylic ether type phenol resin was obtained in the same manner as in Example 1 except that the amount of 92% paraformaldehyde used was changed to 42 parts by mass (F / P = 1.2 on a molar basis).

Example 3
A benzylic ether type phenol resin was obtained in the same manner as in Example 1 except that the amount of 92% paraformaldehyde used was changed to 69 parts by mass (F / P = 2.0 on a molar basis).

Example 4
A benzylic ether type phenol resin was obtained in the same manner as in Example 1 except that the discharging was performed when the Mw measured in the vacuum concentration step became 2,000 to 2,500.

Example 5
A benzylic ether type phenol resin was obtained in the same manner as in Example 1 except that discharging was performed when Mw measured in the vacuum concentration step was in the range of 25,000 to 30,000.

Example 6
As catalysts, 0.14 parts by mass of zinc chloride (0.1 mol% with respect to phenol) and 0.13 parts by mass of manganese acetate (tetrahydrate) (0.05 mol% with respect to phenol) were used. Except for the above, condensation and concentration were carried out in the same manner as in Example 1, and when the Mw was in the range of 2,000 to 2,500, the reaction product was discharged, and the benzylic ether type phenol resin was obtained. Obtained.

Example 7
As catalysts, 0.14 parts by mass of zinc chloride (0.1 mol% with respect to phenol) and 0.26 parts by mass of manganese acetate (tetrahydrate) (0.1 mol% with respect to phenol) were used. Except for the above, condensation and concentration were carried out in the same manner as in Example 1, and when the Mw was in the range of 4,000 to 5,000, discharging was performed to obtain a benzylic ether type phenol resin.

Example 8
A condensation reaction was carried out in the same manner as in Example 1 except that 0.37 parts by mass of zinc acetate (dihydrate) (0.16 mol% based on phenol) was used as the catalyst. Thereafter, 29.8 parts by mass of 1% paratoluenesulfonic acid water was added, followed by concentration under reduced pressure under heating, and when the Mw measured in the process was in the range of 5,000 to 8,000, the reaction was performed. The reaction product was discharged from the container to obtain a benzylic ether type phenol resin.

Example 9
As a catalyst, a mixture of boric acid: zinc hydroxide = 2: 1 in a molar ratio was 0.24 parts by mass (0.2 mol% with respect to boric acid: phenol, 0 with respect to zinc hydroxide: phenol). 0.1 mol%), except that it was used in the same manner as in Example 1, to obtain a benzylic ether type phenol resin.

Example 10
A benzylic ether type phenol resin was used in the same manner as in Example 1 except that 0.43 parts by mass of zinc borate 3.5 hydrate (0.9 mol% based on phenol) was used as a catalyst. Obtained.

Example 11
Except that the amount of 92% paraformaldehyde used was changed to 49 parts by mass (F / P = 1.4 on a molar basis), and the internal temperature during the vacuum concentration step was always kept at 95 to 105 ° C. In the same manner as in No. 1, a benzylic ether type phenol resin was obtained.

Comparative Example 1
A benzylic ether type phenol resin was obtained in the same manner as in Example 1 except that the amount of 92% paraformaldehyde used was changed to 28 parts by mass (F / P = 0.8 on a molar basis).

Comparative Example 2
A benzylic ether type phenol resin was obtained in the same manner as in Example 1 except that the amount of 92% paraformaldehyde used was changed to 73 parts by mass (F / P = 2.1 on a molar basis).

Comparative Example 3
A benzylic ether type phenol resin was obtained in the same manner as in Example 1 except that the reaction product was discharged when the Mw measured in the vacuum concentration step became 1,000 to 1,500. .

Comparative Example 4
Although the reaction product was discharged when Mw measured in the vacuum concentration step exceeded 30,000, an attempt was made to produce a benzylic ether type phenol resin in the same manner as in Example 1, The target resin was not obtained due to gelation.

Comparative Example 5
A benzylic ether type phenol resin was obtained in the same manner as in Example 1 except that 0.49 parts by mass of manganese acetate (tetrahydrate) was used as a catalyst.

Comparative Example 6
A benzylic ether type phenol resin was obtained in the same manner as in Example 1 except that 1.74 parts by mass of 54% lead naphthenate was used as a catalyst.

Comparative Example 7
As a catalyst, a mixture of maleic anhydride: zinc oxide = 4: 1 (maleic anhydride: 0.32 mol% with respect to phenol, zinc oxide: 0.08 mol% with respect to phenol) in a molar ratio. A benzylic ether type phenol resin was obtained in the same manner as in Example 1 except that 0.4 part by mass was used.

Comparative Example 8
Example 1 except that 0.11 parts by mass of zinc chloride (0.08 mol% with respect to phenol) and 0.28 parts by mass of manganese acetate (0.11 mol% with respect to phenol) were used as catalysts. In the same manner as above, a benzylic ether type phenol resin was obtained.

Comparative Example 9
The catalyst was condensed and concentrated in the same manner as in Example 1 except that 0.11 part by mass of zinc chloride and 0.28 part by mass of manganese acetate were used as the catalyst, and the Mw was 25,000 to 30,000. At this point, the reaction product was discharged from the reaction vessel to obtain a benzylic ether type phenol resin.

Comparative Example 10
In a three-necked reaction flask equipped with a reflux, a thermometer, and a stirrer, 100 parts by mass of phenol, 58.9 parts by mass of 92% paraformaldehyde, and divalent metal salt of the catalyst, lead naphthenate. After charging 0.32 parts by mass and reacting at reflux temperature for 90 minutes, the mixture was concentrated under reduced pressure under heating to obtain a benzylic ether type phenolic resin A having a water content of 1% by mass or less. Subsequently, the obtained phenol resin A and novolak-type phenol resin B (Asahi Organic Materials Co., Ltd .: product name PAPS-PN4) at a ratio of A: B = 7: 3 in mass ratio at 130 ° C. The mixture was melted and mixed on a hot plate to obtain a phenol resin composition.

Comparative Example 11
A commercially available phenolic resin (manufactured by Asahi Organic Materials Co., Ltd .: product name KB5006N) prepared by adding hexamethylenetetramine to a novolak type phenolic resin was prepared.

-Experiment 1
For the various benzylic ether type phenol resins obtained in the above examples and comparative examples, respectively, the orthorization rate and the methylene bond rate, benzylic ether bond rate, and methylol group rate according to the resin composition were measured, Various characteristics were evaluated. The obtained results are shown in Table 1 and Table 2 below.

  As is clear from the results of Tables 1 and 2, the phenol resins obtained in Comparative Examples 1 to 9 satisfy the (A) high-ortho structure, but (B) the methylene bond substitution ratio in the benzylic ether type phenol resin. When the total of the benzylic ether bond substitution ratio and the methylol group substitution ratio is 100%, the ratio of the benzylic ether bond substitution ratio is in the range of 10.0 to 40.0%, and the ratio of the methylol group substitution ratio. Does not satisfy the range of 13.0 to 40.0%, the residual carbon ratio is lower than that of the benzylic ether type phenol resin of each example. Moreover, it is recognized that all of Examples 1 to 10 have cleared the residual carbon ratio of 60% or more. Moreover, even if the comparative example 10 satisfy | fills the range of (B), since it does not satisfy | fill the (A) high ortho structure, the residual carbon rate has fallen remarkably compared with an Example. Furthermore, Examples 1, 2, and 5 have a methylene bond substitution ratio of 0.42 to 0.55 mol and a benzylic ether bond substitution ratio of 0.26 to 0.38 mol per mol of phenol nucleus. In this range, the methylol group substitution ratio is in the range of 0.13 to 0.20 mol, and therefore the residual carbon ratio is higher than in the other examples.

-Experiment 2-
The carbide of the benzylic ether type phenolic resin of Example 1 and the carbide of the novolak type phenolic resin of Comparative Example 11 were produced, and these carbides were photographed with a scanning electron microscope (SEM) at a predetermined magnification. The densification of each resin was evaluated. The results are shown in FIGS.

  2 and 3, the carbide of the novolac type phenol resin of Comparative Example 11 has many bubbles, whereas the carbide of the benzylic ether type phenol resin of Example 1 has few bubbles and a dense structure. It can be seen that

-Experiment 3-
After producing carbides using the resins of Examples 1 and 11 and Comparative Examples 8 and 11, the specific gravity of the carbides was measured with an electronic hydrometer, and the densification (density) of each resin carbide was evaluated. . The results are shown in Table 3 below.

  From Table 3, the specific gravity of the novolac type phenol resin carbide using hexamethylenetetramine as the curing agent of Comparative Example 11 is less than 1.0, and the specific weight of the benzic ether type phenol resin carbide of Comparative Example 8 is 1. On the other hand, the carbides of the benzylic ether type phenol resins of Examples 1 and 11 have a specific gravity of 1.2 or more, and it can be seen that a finer carbide is formed than the resin of the comparative example.

-Experiment 4
Using the carbide of the benzylic ether type phenolic resin of Example 1 and the carbide of the phenol novolac resin of Comparative Example 11, the TG charts were measured to compare the oxidation resistance of the resins. The result is shown in FIG.

As apparent from FIG. 4, the temperature at which the carbide starts to decay due to oxidation is 554.0 ° C. in Comparative Example 11, whereas that in Example 1 is 603.7 ° C. In the benzylic ether type phenol resin according to the present invention, an improvement in oxidation resistance is observed.

Claims (10)

  A methylene bond substitution ratio, a benzylic ether bond substitution ratio, and a methylol group substitution ratio, each of which is obtained as a ratio of substituents per mole of phenolic nuclei of the resin, with an ortho-conversion rate of 70% or more. The ratio of the benzylic ether bond substitution ratio is 10.0 to 40.0%, and the percentage of the methylol group substitution ratio is 13.0 to 40.0% A benzylic ether type phenolic resin.   The ratio of the benzylic ether bond substitution ratio is 20.0 to 39.5%, and the ratio of the methylol group substitution ratio is 13.5 to 38.0%. Benzyl ether type phenolic resin.   The methylene bond substitution ratio is 0.42 to 0.55 mole, the benzylic ether bond substitution ratio is 0.26 to 0.38 mole, and the methylol group substitution ratio is 0.13 to 1 mole of phenol nucleus. The benzylic ether type phenol resin according to claim 1 or 2, wherein the amount is 0.20 mol.   The benzylic ether type phenol resin according to any one of claims 1 to 3, which is obtained by reacting phenols and aldehydes using a divalent metal salt as a catalyst. .   As the divalent metal salt, at least one selected from the group consisting of zinc chloride, zinc acetate, a mixture of boric acid and zinc hydroxide, and zinc borate is a ratio of 0.1 mol% or more based on phenols The benzylic ether type phenol resin according to claim 4, which is used in the above.   The benzylic ether type phenol according to claim 4 or 5, wherein a molar ratio of the phenols to the aldehydes is 1.0: 1.0 to 1.0: 2.0. resin.   The benzylic ether type phenol resin according to any one of claims 4 to 6, wherein the weight average molecular weight (Mw) is larger than 2,000 and smaller than 30,000.   A benzylic ether type phenol resin composition comprising the benzylic ether type phenol resin according to any one of claims 1 to 7 as an essential component.   A carbide formed by firing the benzylic ether type phenol resin or the resin composition thereof according to any one of claims 1 to 8. The benzylic resin according to any one of claims 1 to 8, wherein the binder is used for bonding a carbon material or a refractory material to form a binder having a high residual carbon ratio that gives a target carbon product or refractory product. A binder for producing a carbon product or a refractory product, comprising an ether type phenol resin or a resin composition thereof.

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