JP3314647B2 - Method for producing phenolic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a phenolic resin composition, and more specifically, to a phenolic resin composition used for producing a paper-based phenolic resin laminate used for electronic equipment and the like. The present invention relates to a method for manufacturing a product.

[0002]

2. Description of the Related Art Conventionally, a phenolic resin composition used for producing a paper-based phenolic resin laminate used for electronic equipment and the like is a resolving reaction of tung oil and phenols with aldehydes. It was common to manufacture. And, in order to impart flame retardancy to the paper-based phenolic resin laminate, a flame retardant such as a Br compound was added to the phenolic resin composition. In recent years, it has been required to reduce the use of halogen-based flame retardants in view of environmental problems and the like. Thus, a method of adding an aqueous solution of a methylolated melamine compound to the phenol resin after the resolation reaction, and then heating and dehydrating under reduced pressure to include a melamine component having flame retardancy in the phenol resin composition. Is being considered. However, when the amount of the melamine component is increased to improve the flame retardancy, the varnished phenolic resin composition for producing the paper-based phenolic resin laminate becomes turbid or precipitates, and the paper base having uniform performance is produced. There has been a problem that it is difficult to stably manufacture a phenolic resin laminate. Therefore, there is a need for a method of producing a varnished phenol resin composition that does not cause turbidity and that can increase the amount of a melamine component that can be contained in the phenol resin composition.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to react a tung oil and a phenol with a aldehyde with an aldehyde. A methylolated melamine compound aqueous solution is added to the phenolic resin, and then heated and dehydrated under reduced pressure,
A method for producing a phenolic resin composition containing a melamine component in a phenolic resin composition, wherein the phenolic resin composition varnished to produce a laminate does not become cloudy or precipitate, and the phenolic resin composition An object of the present invention is to provide a production method capable of increasing the amount of a melamine component contained in a product.

[0004]

According to a first aspect of the present invention, there is provided a method for producing a phenolic resin composition, comprising reacting a tung oil and a phenol with a aldehyde in the presence of an acidic catalyst as a primary reaction. After the reaction, a secondary reaction is a method for producing a phenolic resin composition produced by adding a tertiary amine as a basic catalyst and performing a resolving reaction, wherein the amount of ammonia added together with the tertiary amine during the resolving reaction is as follows: For a total amount of 100 parts by weight of tung oil and phenols, 0 to 0.35 parts by weight, and a methylolated melamine compound aqueous solution is added to a resin having a weight average molecular weight of 2,000 to 10,000 after the resolving reaction, Then, it is characterized by heating and dehydrating under reduced pressure.

[0005]

According to a second aspect of the present invention, there is provided a method for producing a phenolic resin composition according to the first aspect, wherein the aqueous solution of a methylolated melamine compound is an aqueous solution of a methylolated melamine compound modified with a phenol. It is characterized by.

[0007] manufacturing process of the phenol resin composition of the invention according to claim 3 is the method according to claim 1 or claim 2 wherein, characterized in that tertiary amines are triethylamine.

In the present invention, a resin having a weight average molecular weight of 2,000 to 10,000 obtained by adding a tertiary amine as a basic catalyst and subjecting to a resolving reaction after the novolak reaction is performed under the condition that the amount of ammonia is limited, An aqueous solution of a methylolated melamine compound is added. Therefore, even when the phenol resin to which the methylolated melamine compound aqueous solution is added is heated and dehydrated under reduced pressure, the varnished phenol resin composition becomes turbid to produce a laminate,
Precipitation hardly occurs. This is because the novolak reaction is followed by the resolation reaction, and furthermore, the amount of ammonia and the weight-average molecular weight are restricted. It is considered that it is suppressed. To elaborate further,
Conventionally, a phenol resin was produced by a resolation reaction without a novolak reaction, but in the case of only a resolation reaction, the reaction rate of the phenol resin composition was increased to increase the paper base. In order to be able to produce a phenolic resin laminate with good productivity, about 0.5 parts by weight based on 100 parts by weight of tung oil and phenols together with a tertiary amine as a basic catalyst in the resolving reaction. Amount of ammonia had to be added, but due to the presence of this considerable amount of ammonia, the polymerization reaction of the phenolic resin composition containing the methylolated melamine compound occurred in the heat dehydration step under reduced pressure. Was. Moreover, even when the amount of added ammonia was increased, the reaction rate was still insufficient. In the present invention, since the phenol resin is produced by the resolation reaction after the novolak reaction, the reaction rate of the phenol resin composition can be increased even if the amount of added ammonia is small. Therefore, by limiting the amount of ammonia to be added to a small amount, the polymerization reaction of the phenol resin composition containing the methylolated melamine compound in the heating and dehydrating step under reduced pressure can be suppressed. In the present invention, the timing of adding ammonia together with a tertiary amine as a basic catalyst does not need to be added at the same time. For example, after performing a resolving reaction in the presence of a tertiary amine, ammonia is added and A resolving reaction may be performed.

[0009]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, a reaction product of tung oil and phenols is used. The tung oil used in the present invention has a weight average molecular weight of about 870 and has a property of reacting with phenols. Examples of the phenol used in the present invention include phenol, cresol, resorcinol, and propylphenol. The reaction between paulownia oil and phenols is not particularly limited, but is preferably performed in the presence of methanol at a ratio of 8 to 25 mol of phenols to 1 mol of tung oil. The amount of methanol in the reaction between the tung oil and the phenols has an effect on the molecular weight of the obtained reaction product of the tung oil and the phenols, and the molecular weight of the reactant tends to decrease as the amount of methanol increases. When the ratio of phenols to 1 mol of tung oil is less than 8 mol, the problem of poor interlayer adhesion of the obtained paper-based phenolic resin laminate occurs, and when it exceeds 25 mol, the obtained paper base is reduced. Since a problem that the punching workability of the phenolic resin laminate is inferior occurs, the amount is preferably 8 to 25 mol. The ratio of phenols to 1 mol of tung oil may be in the range of 8 to 25 mol by adding phenols after the novolak reaction is completed. In addition, about 1 mol of tung oil, the weight average molecular weight can be determined by a method such as GPC (gel permeation chromatography).

In the present invention, a reaction product of tung oil and a phenol and an aldehyde are subjected to a novolak reaction as a primary reaction in the presence of an acidic catalyst. As aldehydes,
Examples include paraformaldehyde and aqueous formalin. Examples of the acidic catalyst include oxalic acid, succinic acid, maleic acid, fumaric acid, p-toluenesulfonic acid,
Examples include organic acids such as formic acid and acetic acid, and inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid. The acidic catalyst used in the reaction between tung oil and phenols may be used as a catalyst for the novolak reaction. In addition, it is desirable that the molar ratio of free phenols and aldehydes at the stage of performing the novolak reaction is 1: 0.3 to 1.3. If the aldehyde content is 0.3 or less, the novolak reaction product tends to polymerize. If the aldehyde content exceeds 1.3, unreacted aldehydes will remain excessively even if the aldehyde is added, resulting in waste. It is. The number of moles of free phenols is determined by measurement by GPC, a method of vaporizing free phenols and measuring the weight, or the like.

In the present invention, a phenolic resin composition is obtained by adding a basic catalyst as a secondary reaction after the novolak reaction and performing a resolation reaction. After the novolak reaction, the phenol resin composition is neutralized with triethanolamine or the like. It is preferable to perform a resolving reaction of a secondary reaction. As a basic catalyst used in the resolving reaction of the secondary reaction, a tertiary amine such as trimethylamine, triethylamine, triethanolamine or trimethanolamine is used as an essential component. And, if necessary, ammonia,
Organic bases such as dimethylamine, diethylamine, di-n-propylamine, i-propylamine, n-propylamine, dibenzylamine, benzylamine, or sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, An inorganic base such as lithium hydroxide can be used in combination as a basic catalyst. However, when using ammonia, the amount of ammonia added together with the tertiary amine is 100 parts by weight of the total amount of tung oil and phenols.
It is important that the amount is 0 to 0.35 parts by weight. 0.35
If the amount exceeds the weight part, a polymerization reaction of the phenol resin composition containing the methylolated melamine compound occurs in the heat dehydration step under reduced pressure in the subsequent step, and the varnished phenol resin composition becomes cloudy or precipitates I will. In the present invention, when the resolving reaction is performed, the reaction can be performed by adding an aldehyde.

In the present invention, an aqueous solution of a methylolated melamine compound is added to the resin that has undergone the resolving reaction, and then heated and dehydrated under reduced pressure. Here, the aqueous solution of a methylolated melamine compound is a solution containing water obtained by reacting melamine and aldehydes, and may be modified with phenols . It is important in the present invention that the weight-average molecular weight of the resin after the resolving reaction to which the aqueous solution of a methylolated melamine compound is to be added is 2,000 to 10,000. If it is less than 2,000, the solvent resistance (for example, methylene chloride resistance) of the paper-based phenolic resin laminate becomes poor. If it exceeds 10,000, the varnished phenolic resin composition becomes cloudy or precipitates. It is.

In the method for producing a phenolic resin composition of the present invention, various flame retardants, fillers, and denaturing resins such as epoxy resins can be appropriately compounded as required.

[0014]

【Example】

Example 1 To 130 parts by weight of melamine (hereinafter referred to as "parts"), 240 parts of 37% (37% by weight) formaldehyde was added, and 0.3 part of sodium hydroxide was further added.
After reacting at 8 ° C. for 70 minutes, 70 parts of water and 70 parts of methanol
The resulting mixture was diluted with an aqueous solution to obtain a methylolated melamine compound aqueous solution M-1.

Separately, 60 parts of phenol, 40 parts of tung oil, 5 parts of methanol, and 0.5 parts of acidic catalyst p-toluenesulfonic acid were added.
5 parts were reacted at 80 ° C for 90 minutes, tung oil phenol reactant T
-1 was obtained.

Tung oil phenol reactant T-1 has 37%
23 parts of formaldehyde was added and reacted at 90 ° C. for 30 minutes to obtain a novolak reaction product N-1. The reaction product N-1 was neutralized by adding 0.4 parts of triethanolamine and then 23 parts of 37% formaldehyde was added, and 2 parts of triethylamine was added as a basic catalyst.
After the reaction at 5 ° C for 60 minutes, 1 part of a 25% aqueous ammonia solution was further added, and the mixture was reacted at 85 ° C for 30 minutes to obtain a resol type phenolic resin R-1. To this, 29.4 parts of the above-mentioned aqueous solution of methylolated melamine compound M-1 was added, dehydrated under reduced pressure at 150 mmHg to 70 ° C., returned to normal pressure, and then added with 60 parts of methanol to add tung oil-modified phenol resin. I got a varnish. This resin varnish 60
Parts are cresyl diphenyl phosphate (4 parts), tetrabromobisphenol A diglycidyl ether (6 parts), tetrabromobisphenol A (1 part), 2,2-propane-bis [4- (3-polybromophenyloxy-2-hydroxypropyl) ) Oxy-3,5-dibromophenol] 0.5 part was added to obtain a phenol resin varnish S-1 for secondary impregnation.
Then, the phenolic resin varnish for secondary impregnation S-1 was used in the production of a laminate described below.

Hereinafter, the manufacturing process of the laminate will be described. Ma
The methylolated melamine compound solution M-1 was added to 2
20 parts, 50 parts of methanol and 50 parts of water
A resin varnish F-1 for impregnation was obtained. This resin for primary impregnation
Varnish F-1 was weighed 126 g / m ^TwoCoat on kraft paper
30 seconds after drying by impregnation at 135 ° C
And 160g / m^TwoWas obtained as a primary prepreg A. This one
Phenolic resin varnish for secondary impregnation on the next prepreg A
After impregnation with S-1, 100 seconds in a dryer at 155 ° C.
260g / m^TwoWas obtained. Next
Of the secondary prepregs, and the top layer has a thickness of 0.
A copper foil of 035 μm is disposed via an adhesive,
100kg / cm^TwoMolded at 160 ° C for 50 minutes
A 1.6 mm single-sided copper-clad laminate was obtained.

Comparative Example 1 A novolak reaction product N-1 was obtained in the same manner as in Example 1. Next, the reaction product N-1 was neutralized by adding 0.4 parts of triethanolamine, and then 23 parts of 37% formaldehyde was added.
85 parts of triethylamine as a basic catalyst
, And 2 parts of a 25% aqueous ammonia solution was further added, and the mixture was reacted at 85 ° C. for 30 minutes to obtain a resol type phenol resin R-2. To this, 29.4 parts of the above-mentioned aqueous solution of methylolated melamine compound M-1 was added, dehydrated under reduced pressure at 150 mmHg to 70 ° C., returned to normal pressure, and then added with 60 parts of methanol to add tung oil-modified phenol resin. I got a varnish. In 60 parts of this resin varnish,
As in Example 1, cresyl diphenyl phosphate 4
Parts, tetrabromobisphenol A diglycidyl ether 6 parts, tetrabromobisphenol A 1 part, 2,2-
Propane-bis [4- (3-polybromophenyloxy-2
-Hydroxypropyl) oxy-3,5-dibromophenol] was added to obtain a phenol resin varnish S-2 for secondary impregnation. Then, a single-sided copper-clad laminate having a thickness of 1.6 mm was obtained in the same manner as in Example 1 except that the phenol resin varnish for secondary impregnation S-2 was used.

(Comparative Example 2) A novolak reaction product N-1 was obtained in the same manner as in Example 1. Next, 0.4 part of triethanolamine was added to the reaction product N-1 to neutralize the mixture, 23 parts of 37% formaldehyde was added, and 2 parts of triethylamine was added as a basic catalyst. After reacting for 60 minutes, 1 part of 25% aqueous ammonia solution was further added,
After reacting for 0 minutes, resol type phenolic resin R-3
I got This resol type phenolic resin R-3
Single-sided copper having a thickness of 1.6 mm produced using phenolic resin varnishes for secondary impregnation S-3 and S-3 in the same manner as in Example 1 except that R-1 was used instead of R-1. A laminated laminate was obtained.

(Example 2) 20 parts of phenol and 300 parts of 37% formaldehyde were added to 130 parts by weight of melamine, and 0.3 part of sodium hydroxide was further added.
After reacting at 70 ° C. for 70 minutes, the mixture was diluted with 70 parts of water and 70 parts of methanol to obtain a methylolated melamine compound aqueous solution M-2.

In the same manner as in Example 1, a resol type phenolic resin R-1 was obtained. To this, 30 parts of the aqueous solution of methylolated melamine compound M-2 was added, and
After dehydration under reduced pressure at 0 mmHg to 70 ° C. and returning to normal pressure, 60 parts of methanol was added to obtain a tung oil-modified phenol resin varnish. To 60 parts of this resin varnish, 4 parts of cresyl diphenyl phosphate, 6 parts of tetrabromobisphenol A diglycidyl ether, 1 part of tetrabromobisphenol A, and 2,2-propane-bis [4- (3-polybromophenyloxy- 2-hydroxypropyl) oxy
[-3,5-dibromophenol] 0.5 part was added to obtain a phenol resin varnish S-4 for secondary impregnation. And this 2
A 1.6 mm thick single-sided copper-clad laminate was obtained in the same manner as in Example 1, except that the phenol resin varnish S-4 for the next impregnation was used.

Example 3 To the novolak reaction product N-1 obtained in Example 1 was added 23 parts of 37% formalin,
Then, 2 parts of triethylamine were added,
After reacting for 1 minute, a resol type phenolic resin R-4 was obtained. To this, 78 parts of the aqueous solution of methylolated melamine compound M-2 described in Example 2 was added, and 150 mmHg was added.
After dehydrating under reduced pressure to 70 ° C. and returning to normal pressure, 60 parts of methanol was added to obtain a tung oil-modified phenol resin varnish. To 60 parts of this resin varnish, 4 parts of cresyl diphenyl phosphate, 6 parts of tetrabromobisphenol A diglycidyl ether, and tetrabromobisphenol A
1 part and 0.5 part of 2,2-propane-bis [4- (3-polybromophenyloxy-2-hydroxypropyl) oxy-3,5-dibromophenol] are added, and phenol for secondary impregnation is added. A resin varnish S-5 was obtained. And except that this secondary impregnation phenolic resin varnish S-5 was used,
In the same manner as in Example 1, a single-sided copper-clad laminate having a thickness of 1.6 mm was obtained.

(Example 4) 60 parts of phenol and tung oil 40
Part of methanol, 10 parts of methanol and 0.5 part of an acidic catalyst p-toluenesulfonic acid at 80 ° C. for 90 minutes to obtain a tung oil phenol reactant T-2.

The tung oil phenol reactant T-2 contained 37%
23 parts of formaldehyde was added and reacted at 90 ° C. for 30 minutes to obtain a novolak reaction product N-2. Then, 0.4 parts of triethanolamine was added to the reaction product N-2 to neutralize the mixture, 23 parts of 37% formaldehyde was added, and 2 parts of triethylamine was further added as a basic catalyst. After the reaction, 1 part of a 25% aqueous ammonia solution was further added, and the mixture was reacted at 85 ° C. for 30 minutes to obtain a resol type phenol resin. to this,
78 parts of the aqueous methylolated melamine compound solution M-1 described in Example 1 was added, and the mixture was dehydrated under reduced pressure at 150 mmHg to 70 ° C., returned to normal pressure, and then 60 parts of methanol was added to remove the tung oil-modified phenol resin. Obtained. Then, in the same manner as in Example 1 except that the tung oil-modified phenol resin was used, a 1.6 mm thick single-sided copper produced using the secondary impregnation phenol resin varnishes S-6 and S-6. A laminated laminate was obtained.

Comparative Example 3 A tung oil phenol reactant T-2 and a novolak reactant N-2 were obtained in the same manner as in Example 4. Then, 0.4 parts of triethanolamine was added to the reaction product N-2 to neutralize the mixture, 23 parts of 37% formaldehyde was added, and 2 parts of triethylamine was further added as a basic catalyst. After reacting
Further, 2 parts of a 25% aqueous ammonia solution was added, and 85 ° C.
For 30 minutes to obtain a resol type phenol resin. To this, 78 parts of the aqueous solution of methylolated melamine compound M-1 described in Example 1 was added, and 150 mmHg was added.
After dehydrating under reduced pressure to 70 ° C. and returning to normal pressure, 60 parts of methanol was added to obtain a tung oil-modified phenol resin. Then, in the same manner as in Example 1 except that the tung oil-modified phenol resin was used, a 1.6 mm-thick single-sided copper prepared using the phenol resin varnish for secondary impregnation S-7 and S-7. A laminated laminate was obtained.

Example 5 In the same manner as in Example 4, a tung oil phenol reactant T-2 and a novolak reactant N-2 were obtained. Then, 0.4 parts of triethanolamine was added to the reaction product N-2 to neutralize it, 23 parts of 37% formaldehyde was added, and 2 parts of triethylamine was further added as a basic catalyst, and the mixture was heated at 85 ° C. for 90 minutes. The reaction was performed to obtain a resol type phenol resin. In addition, Example 1
94 parts of the aqueous solution of methylolated melamine compound M-1 described in (1) was added, and the mixture was dehydrated under reduced pressure at 150 mmHg to 70 ° C., returned to normal pressure, and then 60 parts of methanol was added to obtain a tung oil-modified phenol resin. Then, in the same manner as in Example 1 except that the tung oil-modified phenol resin was used, a 1.6 mm thick single-sided copper prepared using the phenol resin varnishes S-8 for secondary impregnation and S-8. A laminated laminate was obtained.

Comparative Example 4 A tung oil phenol reactant T-1 was obtained in the same manner as in Example 1. Then, 0.4 parts of triethanolamine was added to the tung oil phenol reactant T-1 to neutralize the same, and then 46 parts of 37% formaldehyde was added, and triethylamine was added as a basic catalyst in 2 parts.
And 2 parts of a 25% aqueous ammonia solution.
The reaction was performed for 0 minutes to obtain a resol type phenol resin.
To this, 6 parts of the aqueous solution of methylolated melamine compound M-1 described in Example 1 was added, and 70 ° C. at 150 mmHg.
After dehydration under reduced pressure to return to normal pressure, 60 parts of methanol was added to obtain a tung oil-modified phenol resin. Then, in the same manner as in Example 1 except that this tung oil-modified phenol resin was used, a phenol resin varnish for secondary impregnation S-9 and a thickness 1.6 produced using S-9.
mm single-sided copper-clad laminate was obtained. This comparative example is an example in which a resolving reaction was performed without performing a novolak reaction, and curing was insufficient under molding conditions of 160 ° C. and 50 minutes, and punching workability of the obtained copper-clad laminate was poor. It was not enough.

Comparative Example 5 A tung oil phenol reactant T-1 was obtained in the same manner as in Example 1. Next, 0.4 parts of triethanolamine was added to the tung oil phenol reactant T-1 to neutralize the same,
% Formaldehyde, 2 parts of triethylamine as a basic catalyst and 1 part of a 25% aqueous ammonia solution were added, and reacted at 85 ° C. for 90 minutes to obtain a resol type phenol resin. To this, the methylolated melamine compound aqueous solution M-1 described in Example 1 was mixed with 29.4.
The mixture was dehydrated under reduced pressure at 70 ° C. at 150 mmHg and returned to normal pressure. Then, 60 parts of methanol was added to obtain a tung oil-modified phenol resin. Then, except that this tung oil-modified phenol resin was used, in the same manner as in Example 1, the secondary impregnation phenol resin varnish S-10 and
A single-sided copper-clad laminate having a thickness of 1.6 mm manufactured using S-10 was obtained. This comparative example is an example in which a resolving reaction was performed without performing a novolak reaction.
Under the molding conditions of 0 minutes, the curing was insufficient, and the obtained copper-clad laminate was insufficient in punching workability.

In each of the above Examples and Comparative Examples, the production conditions such as the compounding amount for obtaining the tung oil-modified phenol resin and the phenol resin after the resolation reaction before adding the aqueous solution of the methylolated melamine compound were added. The weight-average molecular weights are summarized in Table 1, and the phenolic resin varnish for secondary impregnation obtained above and the quality of each single-sided copper-clad laminate were evaluated. The results are shown in Table 2. The results are shown in Table 2. The quality of the phenol resin varnish for secondary impregnation was visually evaluated for the presence or absence of turbidity in the varnish, and the quality of the single-sided copper-clad laminate was evaluated for flame retardancy and punching workability under the following conditions.

The flame retardancy was determined based on the UL test method by measuring the quenching time of five test pieces, calculating the average value and the maximum value. The average quenching time was 5 seconds or less, and the maximum quenching time was 5 seconds. In the case of 10 seconds or less, it was evaluated as passing the UL94V-0 level.

The punching workability was evaluated by the occurrence of cracks and bulges by punching at 50 ° C. If the number of cracks was 150 or less and the degree of bulge was 17 points or less, it was judged as acceptable. For cracks, 20 × 8 holes were punched with a hole diameter of 0.8 mm and a hole gap of 0.8 mm, and the number of cracks generated between the holes was evaluated (the smaller the number, the better), and the bulge was punched. Hole diameter 0.8m
The degree of bulge around the hole of m is evaluated by replacing the shade of white tone with a numerical value (the smaller the numerical value, the better). If both the crack and the bulge pass, the evaluation is ○. Table 2 is shown in Table 2 as x.

[0032]

[Table 1]

[0033]

[Table 2]

As is evident from the results in Table 2, the phenolic resin-based laminate of single-sided copper-clad paper according to the example of the present invention has the same Br content in the laminate as Comparative Example 4 (3% by weight).
However, since the content of the melamine component is larger than that of Comparative Example 4, good flame retardancy is obtained. In addition, the phenolic resin varnishes for secondary impregnation of the examples of the present invention all had good turbidity and good impregnation properties of the varnishes, but the phenolic resin varnishes for secondary impregnation of Comparative Examples 1 to 3 were varnishes. It was also confirmed that there was turbidity and impregnation was insufficient. Further, in Comparative Examples 4 and 5 in which the resolving reaction was performed without performing the novolak reaction, curing was insufficient under the molding conditions of 160 ° C. and 50 minutes, and the obtained copper-clad laminate was punched. Sex was inadequate.

[0035]

According to the method for producing a phenolic resin composition of the invention according to any one of claims 1 to 3 , after a novolak reaction, a tertiary amine is added as a basic catalyst under a condition in which the amount of ammonia is limited, to form a resol. An aqueous solution of a methylolated melamine compound is added to a resin having a weight average molecular weight of 2,000 to 10,000 obtained by the reaction.
Therefore, even if the phenol resin to which the aqueous solution of the methylolated melamine compound is added is heated and dehydrated under reduced pressure, the varnished phenol resin composition for producing a laminated board is less likely to become cloudy or precipitate.

Therefore, according to the method for producing a phenolic resin composition according to the first to third aspects of the present invention, a large amount of methylol is contained in the phenolic resin obtained by reacting a reaction product of tung oil and a phenol with an aldehyde. Melamine compound aqueous solution, and then heat dehydration under reduced pressure, even if the melamine component is contained in the phenolic resin composition, the varnished phenolic resin composition for producing a laminated board becomes cloudy. No precipitation occurs. That is, according to the method for producing a phenolic resin composition of the invention according to claims 1 to 3 , since the amount of the melamine component contained in the phenolic resin composition can be increased, a halogen for imparting a desired flame retardancy can be obtained. It is possible to reduce the amount of flame retardants used.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI C08L 61/28 C08L 61/28 (56) References JP-A-2-73820 (JP, A) JP-A 9-157414 (JP) JP-A-9-31146 (JP, A) JP-A-58-15521 (JP, A) JP-A-58-13617 (JP, A) JP-A-59-58020 (JP, A) 10-176024 (JP, A) JP-A-10-204140 (JP, A) JP-A-61-183325 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 61/00 -61/34 C08G 8/00-8/38 WPI / L (QUESTEL)

Claims (3)

(57) [Claims] 1. A novolak reaction between a reaction product of tung oil and phenols and an aldehyde in the presence of an acidic catalyst as a primary reaction, followed by a basic reaction as a basic catalyst.
A method for producing a phenolic resin composition produced by adding a tertiary amine and performing a resolving reaction, wherein the amount of ammonia added together with the tertiary amine during the resolving reaction is 100 parts by weight based on the total amount of tung oil and phenols. A phenol which is prepared by adding an aqueous solution of a methylolated melamine compound to a resin having a weight-average molecular weight of 2,000 to 10,000 after resolving reaction and then dehydrating by heating under reduced pressure. A method for producing a resin composition. 2. An aqueous solution of a methylolated melamine compound,
The method for producing a phenolic resin composition according to claim 1, which is an aqueous solution of a methylolated melamine compound modified with a phenol. 3. A process according to claim 1 or claim 2 Fe <br/> Nord resin composition according tertiary amine of the is characterized in that there <br/> with triethylamine.