JP3207412B2 - Method for producing powdered phenolic resin - Google Patents

Description

The present invention relates to a method for producing a novel thermosetting powdery phenolic co-condensation resin. More specifically, it is a co-condensate of phenols and amino compounds and has excellent durability, heat resistance, hydrolysis resistance, fast curing, storage stability, molding materials, adhesives, laminates, foams The present invention relates to a phenolic co-condensation resin which is industrially useful as such.

[Conventional technology]

Conventionally, phenol resins formed by condensation of phenol and formaldehyde, which are thermosetting resins, urea resins formed by condensation of formaldehyde with amino compounds, and melamine resins have been widely used industrially as molding materials, adhesives, and the like. . Generally, phenolic resin has excellent durability, heat resistance,
It has hydrolysis resistance, but has the disadvantage of slow curing. Amino resins such as urea resins and melamine resins have good curability, but have insufficient durability, heat resistance and hydrolysis resistance. For example, urea resins do not withstand outdoor use. Therefore, a co-condensation resin having both advantages has been desired.

However, a mere mixture has little improvement in performance and poor storage stability, and has a drawback that it gels and separates in a relatively short time. And the condensation reaction between amino compounds is
It has been difficult to produce a resin having a high cocondensation rate because it has priority over the cocondensation reaction between a phenol and an amino compound. Since the bond between amino compounds is generally inferior in heat resistance and hydrolysis resistance to the bond between phenols and amino compounds or the bond between phenols, co-condensation resins in which bonds between amino compounds exist are durable. The properties are close to those of amino-based resins, and it is not a sufficiently improved co-condensation resin. The rapid development of instrumental analysis technology in recent years has made it possible to quantitatively determine the self-condensation ratio of phenol and amino compounds and the co-condensation between phenol and amino compounds in phenol-amino compound co-condensation resins. However, in the conventionally known production method, the co-condensation ratio is 0%.
It was as low as -2%.

[Means for solving the problem]

The present inventors have conducted intensive studies on the cocondensation of phenol and amino compounds, and as a result, the cocondensation rate was easily improved by reacting an initial condensate of phenols and aldehydes with urea in an acidic aqueous solvent. They have found that a co-condensate of a phenol and an amino compound having excellent curability and durability can be obtained, and have filed an application for a novel phenol derivative and a method for producing the same (Japanese Patent Application Laid-Open No. 3-95152). However, the co-condensation resin obtained by this method was a viscous liquid. The resin is easily soluble in a solvent such as acetone. If dissolved, the resin becomes a low-viscosity solution and is easy to handle. However, use of a solvent is not preferred due to health problems. For this reason, it is desirable that the particles be powdery for handling, but it was not possible to remove water from the resin and take out the resin as stable granular or powdery solids.

Therefore, as a result of further studies to overcome these difficulties, a phenolic co-condensation resin having a high co-condensation rate, a powdery form and excellent storage stability can be produced by a completely novel method, and the object can be satisfied. The present invention has been completed based on this finding.

That is, the present invention relates to a phenol, one or more compounds selected from the group consisting of compounds A obtained by reacting phenols and aldehydes, an amino compound (excluding melamine), and an amino compound ( One or two selected from the group consisting of compound B obtained by reacting aldehydes with melamine)
At least one kind is selected so as to always contain the compound B, and after reacting under acidic or neutral or alkaline conditions, the total molar ratio of aldehydes, phenols and amino compounds contained therein is At least one alkali metal salt or ammonium salt selected from the group consisting of sodium fluoride, potassium fluoride and ammonium fluoride, and a group consisting of calcium, magnesium and strontium. A method for producing a powdered phenolic resin, comprising adding one or more selected from at least one salt of an alkaline earth metal selected from the group consisting of: When the total molar ratio of the aldehydes and phenols to the amino compound contained in the above is 1 to 5: 1, in the case of the initial condensate, the initial condensate is returned to the raw material composition, and Is in the above range when is calculated.

The powdered phenolic resin obtained according to the present invention is preferably a condensate of a phenol, an amino compound and an aldehyde, and a ratio of a methylene group derived from a co-condensation of the phenol-amino compound to all methylene groups (co-condensation). Rate) is 20
% Phenol-based co-condensation resin containing an addition condensation reaction product of at least 10%.

In the co-condensation resin of the present invention, the co-condensation ratio is 20% or more, preferably 20% to 90%. When the co-condensation ratio is less than 20%, the performance is insufficiently improved, and when it exceeds 90%, the reaction process becomes complicated. May be economically disadvantaged.

The rate of this co-condensation can be easily known by ¹³ C-NMR analysis. Phenol and amino compounds -CH ₂ -, - CH ₂
Although they are bonded via —O—CH ₂ — or the like, the position of the signal of the methylene group (—CH ₂ —) is 30 to 100 ppm. Among them, the signals based on co-condensation are 40.5, 44.2, 4
Present at around 6.2 and 49.2 ppm. That is, the ratio of the sum of the signal intensities around 40.5, 44.2, 46.2, and 49.2 ppm to the integrated intensity of 30 to 100 ppm is the cocondensation rate.

The powdered phenolic co-condensation resin obtained according to the present invention is a fine powder of 10 to 400 microns in yellow to brown color, has good flow characteristics, and is extremely easy to handle. However, the particle size of the resin powder obtained by the present invention is not limited to the above range.

Hereinafter, a method for efficiently producing the powdered phenolic co-condensation resin which is the thermosetting resin of the present invention will be specifically described.

In the present invention, it can be obtained by dividing or adding the components to the mixture with the reaction components and / or the reaction product and reacting them.

The phenols used in the present invention are phenol,
One or two selected from the group consisting of resorcinol, catechol, phenylphenol, and alkylphenol
More than a species. The alkylphenol is a phenol substituted with an alkyl group having 12 or less carbon atoms, and specific examples thereof include cresol, xylenol, p-tert-butylphenol, p-octylphenol, mesitol, methylphenol, isopropylphenol, and isoamylphenol.

Amino compounds include urea, thiourea, guanamines,
One or more selected from the group consisting of guanidines and hydantoins. Guanamines are compounds in which one amino group of melamine is substituted with a hydrogen atom, an aliphatic / aromatic hydrocarbon or a derivative thereof, and examples thereof include formomoguanamine, acetoguanamine, benzoguanamine, and phenylacetoguanamine. Guanidines are guanidine and its salts, and examples thereof include guanidine hydrochloride and guanidine acetate. Hydantoins are hydantoin and hydantoin derivatives, and examples of hydantoin derivatives include dimethylhydantoin, diethylhydantoin, and hydantoin acetic acid.

Aldehydes are formaldehyde, acetaldehyde, n-butyraldehyde, paraformaldehyde,
And trioxane.

In the reaction components, compound A is obtained by reacting aldehydes and phenols, preferably in a molar ratio of 0.5 to 2.0: 1. When the reaction molar ratio is lower than 0.5, the physical strength of the co-condensation resin may be insufficient, and when it exceeds 2.0, the particle size of the co-condensation resin becomes large and the co-condensation resin tends to aggregate during storage. The reaction pH is desirably 8.0 to 13.0. If it is less than 8.0, the molecular weight tends to be high, and if it exceeds 13, the amount of the basic catalyst becomes too large and adversely affects the formation of fine particles. Examples of the basic catalyst include alkali metal compounds such as hydroxides and oxides of alkali metals, alkaline earth metal compounds such as hydroxides and oxides of alkaline earth metals, and amine compounds. For example, NaOH, KOH, Ca (OH) ₂ , CaO, Mg (OH) ₂ ,
Ammonia and the like can be exemplified. The weight average molecular weight of compound A is desirably 1000 or less. If it is more than 1000, a gel-like substance is apt to be formed during the reaction with the above, which is not preferable.

In the reaction components, compound B is an essential component of the present invention, and preferably contains aldehydes and amino compounds in a molar ratio of 2.
It is obtained by reacting at 0 to 10.0: 1 at pH 1 to 3.9. If the pH is lower than 1.0, an alkali catalyst required in the subsequent reaction step increases, which is not preferable. If it exceeds 3.9, it may be hardened during the reaction, which is not preferable. The compound B preferably has a weight average molecular weight of 500 or less. If it is more than 500, a gel-like substance may be generated, which is not preferable.

The reaction components are one or more selected from the group consisting of phenols and compound A, and it is desirable that the ratio of phenols is large. When the ratio of the compound A is large, a gel-like substance is likely to be formed without forming a powder-like substance. Compound A
Is preferably not more than 50% by weight of the whole mixture.

The reaction component is one or more selected from the group consisting of an amino compound and a compound B, and the compound B is an essential component. It is desirable that the ratio of the compound B is 50% by weight or more of the whole mixture.

The reaction with the reaction components takes place in two stages. The first stage is a reaction in which co-condensation substantially occurs, and the second stage is a reaction in which co-condensation and partial self-condensation occur. The first step must be carried out under acidic conditions, preferably at pH 1.0-5.5, more preferably at 2.0-5.0. If it is lower than 1.0, the reaction is too fast to control the reaction. If it is higher than 5.5, the reaction time is too long. Examples of the acidic catalyst include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, organic acids such as acetic acid, formic acid, phthalic acid, maleic acid, and oxalic acid, and salts thereof that can make the reaction solution acidic. The second step must be performed neutral or alkaline. The reaction pH is 8.
0 to 13.0 is desirable. As the catalyst, alkali metal compounds such as hydroxides and oxides of alkali metals, alkaline earth metal compounds such as hydroxides and oxides of alkaline earth metals, and amine compounds are used. For example, NaOH, KOH, Ca (O
H) ₂ , CaO, Mg (OH) ₂ , ammonia and the like.
The reaction time varies depending on the reaction temperature, the reaction pH and the like, and is not particularly limited. Thereafter, the second stage can be performed for a time sufficient for co-condensation and partial self-condensation to occur. The reaction temperature is preferably 100 ° C or lower.

Is from 1:10 to 10: 1 in molar ratio of phenols to amino compounds. In this case, the phenols include the phenols contained in the compound A. Similarly, amino compounds include those contained in compound B. If the amount of phenols is too large, the curability decreases, and if the amount of the amino compound is too large, the durability decreases. It is necessary that the total molar ratio of the aldehydes, the phenols, and the amino compounds contained therein is 1 to 5: 1.

During the reaction with the reaction components, and by the addition, a powdered co-condensation resin is obtained. Although the theoretical background is not clear, it is presumed that water-insoluble salts produced by the reaction with phenolic resin are appropriately aggregated to obtain fine powder.

The addition amount of the component is 0.1 to 7% by weight. 0.
If the amount is less than 1% by weight, the storage stability decreases, and if it exceeds 7% by weight, the strength of the cured powdery phenolic co-condensation resin decreases.

The addition amount of the component is preferably 1.0 to 3.0: 1 as a molar ratio of the alkali metal salt or ammonium salt therein to the alkaline earth metal salt therein.

The addition of the component may be performed at any stage in the reaction with, but is preferably added at the beginning of the second stage of the reaction with. The reaction product with is water-soluble, but the addition of produces a fine precipitate.

The reaction with the reaction component is desirably performed in an aqueous solvent, but may contain 1 to 20% of a water-soluble organic solvent such as methanol, ethanol, acetone, isopropyl alcohol, and dioxane. When reacted with and, light yellow or light brown diameter of 10-40
A 0 micron spherical phenolic resin is obtained as a precipitate. The spherical phenolic resin is filtered by a usual method, washed with water, and dried under normal pressure or reduced pressure to obtain a target powdery resin. Heating to 100 ° C. or more during drying is not preferred because the particles tend to fuse.

When the powdered phenolic resin of the present invention is actually used, it may be performed in substantially the same manner as the conventional alkali resole resin, but the heating time may be short because the curability is improved.

Although the main use of the powdered phenol co-condensation resin of the present invention is for molding materials, it can be used for all applications in which ordinary phenol resins can be used. Further, depending on the required water resistance and the like, a conventional urea formaldehyde resin, a phenol formaldehyde resin or the like may be used as a mixture.

If necessary, additives such as a thermoplastic resin, an antistatic agent, a filler, a bulking agent, a preservative, and a coloring agent can be added.

[Action]

A powdered phenol-based co-condensation resin was obtained by adding specific inorganic salts to the reaction step of the phenol-based co-condensation resin at a predetermined reaction ratio. This resin is a light-colored, smooth, non-fused powder that is easy to handle, and is an inexpensive, fast-curing resin with excellent durability, hydrolysis resistance, and storage stability that could not be achieved by conventional techniques. is there.

〔Example〕

The following examples are shown in order to more specifically illustrate the present invention, but the present invention is not limited to these examples.

Example 1 (Powder phenol urea co-condensation resin) 120 g of urea and 486 g of 37% formalin were charged and dissolved in a reaction flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel. After adjusting to 2.0, 90
The reaction was carried out at 30 ° C for 30 minutes. Add 190 g of phenol and 90
The reaction was carried out at 60 ° C for 60 minutes. Then, 25% sodium hydroxide was added to adjust the pH to 9.4, 15 g of calcium chloride and 6 g of sodium fluoride were added, reacted at 90 ° C. for 60 minutes, cooled, and then cooled to 1000 ml.
, And filtered, washed and dried under vacuum to obtain a pale yellow powdery phenolic resin. The co-condensation rate of this resin is 56%
was. Put this resin in a thermo-hygrostat at 35 ° C and 80% humidity.
It was stored for a period of 5 months, but there was no change without fusing.

Example 2 (Powder phenol thiourea co-condensation resin) 152 g of thiourea and 486 g of 37% formalin were charged and dissolved in a reaction flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel. After adjusting to 2.0, 9
The reaction was performed at 0 ° C. for 30 minutes. Add 80% phenol to 200
g, 9 g of calcium sulfate and 4 g of sodium fluoride at 90 ° C
For an additional 60 minutes. Then, the pH was adjusted to 9.4 by adding 25% sodium hydroxide, reacted at 90 ° C for 60 minutes, and cooled to 100
Poured into 0 ml of water, filtered, washed and dried under vacuum to obtain a pale yellow powdery phenolic resin. The co-condensation rate of this resin is
53%. This resin was stored in a thermo-hygrostat at a temperature of 35 ° C. and a humidity of 80% for 6 months, but there was no fusion and no change.

Example 3 (Powder phenol benzoguanamine co-condensation resin) In a reaction flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel, 152 g of benzoguanamine and 37% formalin 48 were added.
After 6 g and 150 g of water were charged and dissolved, 50% sulfuric acid was added to adjust the pH to 2.
After adjusting to 5, the reaction was carried out at 90 ° C. for 30 minutes. Further add 23g of strontium sulfate and 10g of ammonium fluoride to 80%
234 g of phenol was added and reacted at 90 ° C. for another 60 minutes.
Then, the pH was adjusted to 9.4 by adding 25% sodium hydroxide, and 90
The reaction was performed at 120 ° C. for 120 minutes. The resin solution was cooled, poured into 1000 ml of water, filtered, washed and vacuum dried to obtain a pale yellow powdery phenolic resin. The cocondensation rate of this resin was 45%. This resin was stored in a thermo-hygrostat at a temperature of 35 ° C. and a humidity of 80% for 6 months, but there was no change.

Reference Example 1 (Initial condensate A-1) In a reaction flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel, 188 g of phenol, 405 g of 37% formalin, 25
35.4 g of NaOH was dissolved while cooling, and then reacted at 75 ° C. for 4 hours, and then cooled to 35 ° C. This is designated as initial condensate A-1.

Reference Example 2 (Initial condensate A-2) In a reaction flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel, 220 g of resorcinol, 37% formalin 405 were added.
g, 25% NaOH (22.4 g)
After reacting at 35 ° C for 2 hours, it was cooled to 35 ° C. This is designated as initial condensate A-2.

Reference Example 3 (Initial condensate B-1) In a reaction flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel, 130 g of thiourea, 486 g of 37% formalin, and 50% of thiourea were added.
20.0 g of sulfuric acid was charged and dissolved, reacted at 70 ° C. for 1 hour, and cooled to 35 ° C. This is designated as an initial condensate B-1.

Reference Example 4 (Initial condensate B-2) A reaction flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel was charged with 191 g of guanidine hydrochloride and 486 of 37% formalin.
g and 50 g of sulfuric acid (7 g) were dissolved therein, reacted at 70 ° C. for 1 hour, and cooled to 40 ° C. This is referred to as an initial condensate B-2.

Reference Example 5 (Initial condensate B-3) Benzoguanamine, 374 g, 37% formalin was placed in a reaction flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel.
486 g and 22.0 g of 50% sulfuric acid were charged and dissolved while cooling. After reacting at 70 ° C. for 1 hour, the mixture was cooled to 35 ° C. This is referred to as an initial condensate B-3.

Example 4 A reaction flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel was charged with 30 g of the initial condensate A-1 and 100 g of phenol.
And initial condensate B-1, 350 g, 8 g of calcium nitrate and 3 g of sodium fluoride, 90 g and 6 g of urea were added, and 50% sulfuric acid was added.
After adjusting H to 2.0, the reaction was carried out at 90 ° C. for 30 minutes. Then 25
% Sodium hydroxide was added to adjust the pH to 9.4, and the mixture was reacted at 85 ° C. for 60 minutes. The mixture was cooled to 35 ° C., poured into 1000 ml of water, filtered, washed, and vacuum dried to obtain a pale yellow powdery phenolic resin. This resin was stored in a thermo-hygrostat at a temperature of 35 ° C. and a humidity of 80% for 6 months, but there was no change.

Example 5 30 g of initial condensate A-2 and 100 g of phenol were placed in a reaction flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel.
And initial condensate B-2, 350g guanidine hydrochloride 6g 50%
After adjusting the pH to 2.0 by adding sulfuric acid, the mixture was reacted at 90 ° C. for 30 minutes. Then add 25% sodium hydroxide and add calcium chloride
Adjust pH to 9.4 by adding 10 g and 5 g of sodium fluoride, and at 90 ° C
The reaction was performed for 60 minutes. The mixture was cooled to 35 ° C., poured into 1000 ml of water, filtered, washed, and vacuum dried to obtain a pale yellow powdery phenolic resin. This resin was stored in a thermo-hygrostat at a temperature of 35 ° C. and a humidity of 80% for 6 months, but there was no change.

Comparative Example 1 A conical flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel was charged with 200 g of phenol, 200 g of 37% formalin, and 10 g of water.
0 g, hexamethylenetetramine 20 g, calcium chloride 8.4
g, 40 g of a 7% sodium fluoride solution, reacted at 85 ° C. for 90 minutes, cooled to 35 ° C., poured into 1000 ml of water, filtered, washed, and vacuum dried to obtain a pale yellow powder phenol resin. This resin was stored in a thermo-hygrostat at a temperature of 35 ° C. and a humidity of 80% for 6 months, but there was no change.

Comparative Example 2 In a reaction flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel, 152 g of benzoguanamine and 35% of 37% formalin were added.
0 g and water 150 g were added and dissolved, and then 50% sulfuric acid was added to adjust the pH to 2.5.
Then, the reaction was carried out at 90 ° C. for 30 minutes. Further, 1 g of calcium chloride and 0.1 g of sodium fluoride were added, 334 g of 80% phenol was added, and the mixture was further reacted at 90 ° C. for 60 minutes. Then 25%
The pH was adjusted to 9.4 by adding sodium hydroxide, and the mixture was reacted at 90 ° C. for 120 minutes. The resin liquid was cooled to obtain a granular phenolic co-condensation resin. Poured into 1000 ml of water, filtered, washed and vacuum dried to obtain pale yellow granular phenolic resin. The cocondensation rate of this resin was 56%. This resin is heated to a temperature of 35 ° C and a humidity of 80
% For 1.5 months, but the granular resin was fused.

Comparative Example 3 A reaction flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel was charged with 200 g of phenol, 517 g of 37% formalin, and NaOH.
Was dissolved while cooling, and then reacted at 50 ° C. for 8 hours. After cooling to 45 ° C, add 127 g of melamine, 15 g of magnesium chloride and 7 g of potassium fluoride, and add 60 g at 85 ° C.
Allowed to react for 5 minutes and cooled. The obtained reaction product was red-brown and clay-like, and had a cocondensation rate of 1%. It could not be separated as a powdered resin.

Comparative Example 4 A reaction flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel was charged with 200 g of phenol, 517 g of 37% formalin,
After charging 11.8 g of (OH) ₂ and dissolving while cooling, 50
The reaction was performed at 8 ° C. for 8 hours. After cooling to 35 ° C, 50% sulfuric acid 30
g was dropped from the dropping funnel. At this time, the pH was 3.5.
Then, 127 g of melamine was added and reacted at 85 ° C. for 60 minutes. 12 g of calcium chloride and 4 g of sodium fluoride were added, and the mixture was cooled to 35 ° C., and 10% of NaOH was added, followed by further cooling. The resin solution obtained was reddish brown and the cocondensation was 35%. Put into 1000ml of water,
Filtration, washing and vacuum drying were performed to obtain a pale yellow phenolic resin having a diameter of several millimeters. The cocondensation rate of this resin was 56%. When this resin was stored in a thermo-hygrostat at a temperature of 35 ° C. and a humidity of 80% for one month, particles were fused.

(Measurement of curing speed) The curing behavior of the resin synthesized as described above was measured using TBA (Torsion
al Braid Analisis: manufactured by Toyo Seiki Co., Ltd., rheograph TBA). Table 1 shows the results.

(Flow characteristics) The flow characteristics of the resins obtained in Examples 1 to 5 and Comparative Examples 1 to 4 were measured according to JIS K-6911. Table 2 shows the results.

(Molding Test) Each of the obtained resins was heated at 150 ° C. in a mold for 30 minutes under a pressure of 50 kg / cm ² to prepare a 10 mm square test piece having a thickness of 3.5 mm. Each test piece was measured for compressive strength according to JIS K-6911. Table 2 shows the results.

(Effect of the Invention) As shown in Tables 1 and 2, the phenol-amino co-condensation resin obtained by the method of the present invention has a rapid curing property equal to or higher than that of the conventional amino resin, and a heat resistance equivalent to that of the conventional phenol resin. Shows sex. Furthermore, it has excellent storage stability and excellent flow characteristics. Also, the physical properties of the molded product are excellent.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-53-8695 (JP, A) JP-A-56-95918 (JP, A) JP-A-58-142907 (JP, A) JP-A-49-149 JP-A-49-34998 (JP, A) JP-A-3-95152 (JP, A) JP-A-3-243613 (JP, A) JP-A-3-265618 (JP, A) JP-A-61-51019 (JP, A) JP-A-61-127719 (JP, A) JP-B-43-28479 (JP, B1) US Patent 3,364,167 (US, A) UK Patent 1,057,400 (GB, B) ( 58) Field surveyed (Int.Cl. ⁷ , DB name) C08G 14/00-14/14 C08G 8/00-8/38 C08G 12/00-12/46 CA (STN) REGISTRY (STN)

Claims (11)

(57) [Claims] 1. A phenol, one or more compounds selected from the group consisting of compounds A obtained by reacting a phenol and an aldehyde, an amino compound (excluding melamine), and an amino compound (excluding melamine). One or two selected from the group consisting of compound B obtained by reacting aldehydes with melamine)
At least one kind is selected so as to always contain the compound B, and after reacting under acidic or neutral or alkaline conditions, the total molar ratio of aldehydes, phenols and amino compounds contained therein is At least one alkali metal salt or ammonium salt selected from the group consisting of sodium fluoride, potassium fluoride and ammonium fluoride, and a group consisting of calcium, magnesium and strontium. One or more selected from at least one salt of an alkaline earth metal selected from the group consisting of: and a reactive component is 0.1 to 7% by weight based on the weight of the phenol powder. Method of manufacturing resin. 2. The method according to claim 1, wherein the phenol is at least one member selected from the group consisting of phenol, resorcinol, catechol, phenylphenol and alkylphenol. 3. The method according to claim 1, wherein the amino compound is at least one member selected from the group consisting of urea, thiourea, guanidines, guanamines and hydantoins. . 4. The method according to claim 1, wherein the aldehyde is at least one selected from formaldehyde, acetaldehyde, n-butyraldehyde, paraformaldehyde and trioxane. 5. The method according to claim 1, wherein the compound B is a product obtained by reacting an amino compound with an aldehyde at a pH of 1.0 to 3.9. 6. The method according to claim 1, wherein the reaction molar ratio between the amino compound of compound B and the aldehyde is 1: 2 to 10.
A method for producing a powdered phenolic resin. 7. The method for producing a powdered phenolic resin according to claim 1, wherein an aldehyde is added at any stage of the reaction. 8. The method according to claim 1, wherein the molar ratio of the phenols to the amino compound contained in the reaction components is 10: 1 to 1:10.
A method for producing a powdered phenolic resin. 9. The molar ratio of the alkali metal salt or ammonium salt in the component to the alkaline earth metal salt in the component is 1.0 to 3.0: 1.
The method for producing a powdered phenolic resin according to claim (1). 10. The method for producing a powdery phenolic resin according to claim 1, wherein the components and / or the components are added and reacted. 11. The powdery phenolic resin is a condensate of a phenol, an amino compound and an aldehyde, and the proportion of methylene groups derived from co-condensation of the phenol-amino compound in all methylene groups is 20% or more. The method for producing a powdered phenolic resin according to claim 1, which is a product of an addition condensation reaction.