JP3298369B2 - 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 particularly, to a method for producing a phenolic resin composition for a paper base laminate used for electronic equipment and the like.

[0002]

2. Description of the Related Art Conventionally, paper-based phenolic resin laminates used in electronic equipment are prepared by adjusting the viscosity of a resole-type phenolic resin modified with tung oil or the like with a solvent or the like, impregnating and drying the paper base material, and drying a plurality of phenolic resins. It is manufactured by laminating sheets, laminating a metal foil with an adhesive on one side or both sides depending on the application, and then heating and pressing.

A method for producing a phenolic resin composition is known in which after a novolak reaction is performed to improve impregnation properties and electrical properties, the resin is further subjected to a resolvation reaction (for example, Japanese Unexamined Patent Publication No. 2-73820).
However, the quality is not stable depending on the ratio of the novolak reaction to the resolation reaction, and when trying to shorten the molding time to improve productivity and save energy, the electrical characteristics such as heat resistance and insulation resistance are reduced. is there.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to provide a phenol resin composition which undergoes a novolak reaction and then a resolation reaction. The present invention provides a method for producing a phenol resin composition that can maintain good properties such as heat resistance and insulation resistance even if the molding time is shortened to improve productivity and save energy. is there.

[0005]

Method for producing a phenolic resin composition according to claim 1 of the present invention According to an aspect of the mark as the primary reaction
After reacting novolak the phenol and an aldehyde in an acidic catalyst, a method for producing a phenolic resin composition which reacts resole form by addition of a basic catalyst as a secondary reaction, before
The phenols react with aldehydes after reacting with tung oil.
The phenols modified with tung oil were excluded from the total novolak reaction and resolation reaction.
Free phenols and aldehydes have a molar ratio of
1: In a method for producing a phenolic resin composition for a paper base laminate having a ratio of 1.0 to 1.5, free phenols modified with tung oil are removed when a novolak reaction is performed. The molar ratio of phenols to aldehydes is 1: 0.8 to
1.3.

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 a basic compound is added and neutralized after the novolak reaction. After that, it is characterized by a resolving reaction.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the production method of the present invention, a phenol and an aldehyde are firstly subjected to a novolak reaction with an acidic catalyst as a primary reaction. Next, after neutralization, aldehydes and a basic catalyst are added as a secondary reaction to perform a resolation reaction, dehydrated under reduced pressure, and after adjusting the water content,
It is produced by appropriately mixing a solvent such as methanol.

Examples of the phenols constituting the phenolic resin composition of the present invention include those having a phenolic hydroxyl group, such as phenol, cresol, resorcinol, and propylphenol, alone or in combination.
Examples of the aldehyde include paraformaldehyde and aqueous formalin. The above phenols are tung oil
In After denaturation, so as to react with aldehydes. However, the molar ratio is calculated based on the number of moles of free phenols excluding modified phenols. As a method of analyzing free phenols, gel permeation chromatography (GPC), a method of vaporizing free phenols and measuring the weight thereof, or the like is used.

Examples of the acidic catalyst include oxalic acid, succinic acid, maleic acid, fumaric acid, p-toluenesulfonic acid,
Examples thereof include organic acids such as formic acid and acetic acid, and inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid. The catalyst was used to denature the phenols may also be used in common with tung oil. Further, as the basic catalyst, for example, ammonia, trimethylamine,
Triethylamine, dimethylamine, diethylamine,
Organic bases such as methylamine, hexamethylenetetramine, di-n-propylamine, i-propylamine, n-propylamine, triethanolamine, trimethanolamine, pyridine, dibenzylamine and benzylamine, or sodium hydroxide; Examples thereof include inorganic bases such as potassium hydroxide, calcium hydroxide, magnesium hydroxide, and lithium hydroxide, which are used alone or in combination.

It is important that the molar ratio of phenols to aldehydes in the novolak reaction is 0.8 to 1.3 moles of aldehyde per mole of phenol. If it exceeds 0.3 mol, the insulation resistance decreases, and if it is less than 0.8 mol, the heat resistance decreases.

When the resolation reaction is performed, an aldehyde is added to the novolak-type phenol resin composition obtained by the novolak reaction of the present invention, if necessary, and the reaction is performed.
In this case, the molar ratio of the phenols and aldehydes in the total novolak reaction and resolation reaction requires 1.0 to 1.5 mol of the aldehyde per 1 mol of the phenol.
If it exceeds 1.5 moles, unreacted aldehydes increase and the odor of the laminate becomes worse. If it is less than 1 mole, unreacted phenol increases and the odor of the laminate worsens, which is not practical. When the molar ratio of the phenols and aldehydes used in the novolak reaction is 1.0 to 1.3 moles of the aldehyde to 1 mole of phenol, and the novolak reaction is performed under the reaction conditions in which unreacted aldehyde remains,
It is not necessary to newly add aldehydes during the resolving reaction.

After the novolak reaction, a basic compound is added for neutralization. As the basic compound, a compound similar to the above basic catalyst can be used.

The phenolic resin composition may be modified, if necessary, with a flame retardant such as antimony, triphenyl phosphate, brominated bisphenol A, an inorganic or organic filler, or a phenolic resin such as an epoxy resin. May be appropriately compounded.

According to the method for producing a phenolic resin composition of the present invention, since the ratio of phenols to aldehydes is in a range where both unreacted monomers remaining in the resolving reaction are reduced, the same temperature, pressure and time are used. In the case of molding by the method, the residual unreacted monomer in the laminate decreases, and the heat resistance and the insulation resistance caused by the residual unreacted monomer hardly occur.

Therefore, in the method for producing a phenolic resin composition of the present invention, the fact that the molar ratio of phenols to aldehydes in the novolak reaction is in the range of 1: 0.8 to 1.3 means that the molding time Even if the length is shortened, there is an effect that a laminate having good properties such as heat resistance and insulation resistance can be obtained.
Therefore, the use of the above resin composition achieves improvement in productivity and energy saving, and enables cost reduction.

[0016]

【Example】

Example 1 As a primary reaction, 60 parts by weight of phenol (hereinafter referred to as "part"), 40 parts of tung oil and 0.5 part of an acidic catalyst p-toluenesulfonic acid were reacted at 100 ° C for 1 hour to obtain a tung oil phenol reactant A. By analyzing the tung oil phenol reactant A by gel permeation chromatography (GPC), it was confirmed that the tung oil phenol reactant A contained 44 parts of free phenol. Then
30 parts of 37% by weight formalin was added to the tung oil phenol reactant A, and reacted at 90 ° C. for 2 hours to synthesize a novolak type phenol resin composition. At this time, the molar ratio of phenol to formalin is 1: 0.8.

Next, as a secondary reaction, triethanolamine was added to the novolak-type phenol resin composition in an amount of 0.4%.
And neutralized by adding 37 parts by weight of formalin to 16 parts by weight.
And 2 parts of 25% ammonia and 2 parts of triethylamine as basic catalysts, and reacted at 80 ° C. for 3 hours. The reaction solution was dehydrated under reduced pressure of 150 mmHg and diluted with methanol to obtain a resin composition having a solid content of 50% by weight.
At this time, the molar ratio of phenol to formalin in the total novolak reaction and resolation reaction is 1: 1.2.

Next, the weight 1 previously impregnated by the following method
26 g / m ² kraft paper was secondarily impregnated with the above phenol resin composition to obtain a prepreg. The primary impregnation was performed as follows. A phenol resin product obtained by reacting 100 parts of phenol with 70 parts of formalin of 37% by weight and a melamine resin product obtained by reacting 100 parts of melamine with 100 parts of formalin of 37% by weight are mixed with an equal amount of resin. An aqueous methanol solution mixed with an equal amount of methanol was added to obtain a primary impregnated varnish having a solid content of 15%. The primary impregnated varnish was impregnated into kraft paper having a weight of 126 g / m ² ,
This was treated with a dryer at 5 ° C. for 30 seconds to obtain a primary prepreg A. After impregnating the primary prepreg A with the phenol resin composition, the primary prepreg A was treated with a dryer at 155 ° C. for 100 seconds,
Secondary prepreg B was obtained. The total content of the resin in this prepreg was 50%.

Next, eight prepregs B are stacked, and a copper foil having a thickness of 0.035 mm is provided on the uppermost layer via an adhesive, and is molded at a pressure of 100 kg / cm ^{2 at} a temperature of 160 ° C. for 50 minutes. A 1.6 mm insulating plate was obtained.

Example 2 Tungsten oil phenol reactant A as in Example 1 was 37% by weight
Was added and reacted to synthesize a novolak-type phenol resin composition. At this time, the molar ratio of phenol to formalin is 1: 1.2.

After neutralizing this novolak-type phenol resin composition with triethanolamine in the same manner as in Example 1, 2 parts of 25% ammonia and 2 parts of triethylamine were added as basic catalysts, and without adding formalin. By reacting, a phenol resin composition was obtained. At this time, the molar ratio of phenol to formalin in the total novolak reaction and resolation reaction is 1: 1.2. Next, a prepreg was overlaid and molded in the same manner as in Example 1 to obtain a 1.6 mm substrate.

Example 3 In the novolak reaction, 46 parts of 37% by weight of formalin were added to and reacted with tung oil phenol reactant A. In the resorlation reaction, 11 parts of 37% by weight of formalin were added and reacted. Except for the above, the reaction was carried out in the same manner as in Example 1 to obtain a phenol resin composition. The molar ratio of phenol to formalin in the novolak reaction at this time is 1: 1.2. In this case, the molar ratio of phenol to formalin in the total novolak reaction and resolation reaction is 1: 1.5. Next, a prepreg was overlaid and molded in the same manner as in Example 1 to obtain a 1.6 mm substrate.

Example 4 A phenol resin composition was obtained in the same manner as in Example 1, except that 3 parts of 25% ammonia and 2 parts of triethylamine were added and reacted as a basic catalyst. Next, a prepreg was overlaid and molded in the same manner as in Example 1 to obtain a 1.6 mm substrate.

Example 5 A reaction was carried out in the same manner as in Example 1 except that 0.5 part of oxalic acid was added as an acidic catalyst and reacted to obtain a phenol resin composition. Next, a prepreg was overlaid and molded in the same manner as in Example 1 to obtain a 1.6 mm substrate.

Comparative Example 1 In a novolak reaction, 15 parts of 37% by weight of formalin was added to and reacted with tung oil phenol reactant A. In a resorlation reaction, 31 parts of 37% by weight of formalin were added and reacted. Except for the above, the reaction was carried out in the same manner as in Example 1 to obtain a phenol resin composition. The molar ratio of phenol to formalin in the novolak reaction at this time is 1: 0.4. The molar ratio of phenol to formalin in the total novolak reaction and resolation reaction at this time is 1: 1.2.

Comparative Example 2 In the novolak reaction, 53 parts by weight of formalin of 37% by weight were added to the tung oil phenol reactant A and reacted, and in the resorlation reaction, 4 parts of 37% by weight of formalin were added and reacted. Except for the above, the reaction was carried out in the same manner as in Example 1 to obtain a phenol resin composition. At this time, the molar ratio of phenol to formalin is 1: 1.4.
At this time, the molar ratio of phenol to formalin in the total novolak reaction and resolation reaction is 1: 1.5. Next, the prepreg was overmolded in the same manner as in Example 1,
A 1.6 mm substrate was obtained.

Eight sheets of the obtained prepreg are laminated, and a copper foil having a thickness of 0.035 mm is disposed on the uppermost layer via an adhesive, and the copper foil is heated at a pressure of 100 kg / cm ² , a temperature of 160 ° C. and a temperature of 70 ° C.
After molding for a minute, a laminate was obtained.

The laminates of Examples 1 to 5 and Comparative Examples 1 and 2 were evaluated for solder heat resistance and insulation resistance. Solder heat resistance was measured by measuring the time required for the solder to float at 260 ° C. and for abnormalities such as peeling and swelling to occur. Insulation resistance is J
Based on IS-C-6481, C-96 / 20/65 +
It measured on the processing conditions of D-2 / 100. As shown in Table 1, the results of Examples 1 to 5 were shorter (16
(0 ° C., 50 minutes) and a long molding time (160 ° C., 70 minutes), as in Comparative Example 2, a laminate having excellent solder heat resistance and insulation resistance was obtained.

[0029]

[Table 1]

[0030]

When the phenolic resin composition obtained by the method for producing a phenolic resin composition according to claims 1 to 2 of the present invention is used, even if the molding time is shortened, good heat resistance and insulation properties are obtained. A laminate can be obtained. Therefore, it is possible to reduce costs by improving productivity and saving energy.

Continuation of the front page (56) References JP-A-53-46394 (JP, A) JP-A-61-181814 (JP, A) JP-A-3-103417 (JP, A) JP-A-59-58020 (JP) JP-A-58-13617 (JP, A) JP-A-2-73820 (JP, A) JP-A-59-176328 (JP, A) JP-A-53-143693 (JP, A) 35-17247 (JP, B1) JP-B 38-24248 (JP, B1) JP-B 40-17774 (JP, B1) JP-B 48-6950 (JP, B1) (58) Fields surveyed (Int. Cl ^7, DB name) C08G 8/00 -. 8/38 WPIDS ( STN)

Claims (2)

(57) [Claims] 1. A phenol and an aldehyde as a primary reaction.
A method for producing a phenolic resin composition, which comprises subjecting a compound to a novolak reaction with an acidic catalyst, and then adding a basic catalyst as a secondary reaction to cause a resolving reaction, wherein the phenol is tung oil
And then react with aldehydes
Both of the novolak reaction and resolation reaction , tung oil
The molar ratio of free phenols and aldehydes excluding phenols modified by the above is 1: 1.0 to 1.5
In a method for producing a phenolic resin composition for a paper base laminate, a resin modified with tung oil during a novolak reaction is used.
A method for producing a phenolic resin composition, wherein the molar ratio of free phenols and aldehydes excluding phenols is 1: 0.8 to 1.3. 2. The method for producing a phenolic resin composition according to claim 1, wherein after the novolak reaction, a basic compound is added and neutralized, and then a resolation reaction is performed.