JPH05320294A - Modified phenolic resin composition and production thereof - Google Patents

Abstract

PURPOSE:To obtain a modified phenolic resin compsn. capable of forming a cured product very excellent in flexibility, toughness and electrical properties, suitable for use in phenolic resin laminates, composite materials and coatings and as an industrial resin, and very useful in a phenolic resin laminate for use in a printed wiring board in particular, by using a highly modified resin having phenol and tung oil units sufficiently bonded to each other. CONSTITUTION:Tung oil having a phenol sufficiently added to the reactive double bonds thereof is reacted with a phenol and a formaldehyde in the presence of a basic catalyst to obtain a modified phenolic resin compsn.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resol type modified phenolic resin composition obtained by reacting tung oil sufficiently added with phenols, phenols and formaldehydes in the presence of a basic catalyst, and a method for producing the same. And a modified phenolic resin composition having excellent flexibility, mechanical properties, and electrical properties, which is suitable for a phenolic resin laminate for printed wiring boards, composite materials, paints, and the like, and a method for producing the same. .

[0002]

2. Description of the Related Art Phenolic resin has heat resistance, electrical characteristics,
It has excellent mechanical properties and is widely used for laminated boards for printed wiring boards, molding materials, composite materials, paints, etc. However, since the phenol resin generally has a defect that it is hard and brittle, it has a defect that the punching workability is poor when it is used for a laminated plate. As a method for improving this drawback, plant oils such as tung oil, dehydrated castor oil, cashew nut kernel oil and urushiols, and flexible phenol resins modified with alkylphenols are known. But recently
In the case of printed wiring boards, a laminated board with more excellent punching workability and toughness is required as the circuit becomes more dense, and a phenol resin that has both flexibility and toughness is needed. Therefore, it is difficult for conventional resins to satisfy these characteristics.

[0003]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention The present invention has been studied to obtain a phenol resin having excellent flexibility and high mechanical strength which cannot be obtained by the conventional method. As a result, the conventional tung oil-modified phenol resin is It was found that the flexibility and toughness are limited due to incomplete reaction with phenols, and tung oil with sufficient addition of phenols, phenols and formaldehydes in the presence of a basic catalyst. Resole-type modified phenolic resin made to react is flexible,
The present inventors have obtained the knowledge that they are extremely excellent in mechanical properties and electrical properties, and further advanced various studies based on this knowledge to complete the present invention. The object of the invention is to provide an extremely tough modified phenolic resin composition having excellent flexibility, mechanical properties and electrical properties, and a method for producing the same.

[0004]

The present invention relates to a resol type modified phenolic resin composition obtained by reacting tung oil sufficiently added with phenols, phenols and formaldehydes in the presence of a basic catalyst, Further, the weight ratio of phenols (A) and tung oil (B) is X <A / B <10 X = 0.024 x (fw-1) x M / fn (fn is the number average functional number of phenols, and fw is phenols. In the presence of an acidic catalyst to obtain a reaction composition consisting of tung oil and phenols to which phenols are sufficiently added. Further, a predetermined amount (C) of unreacted phenols is removed so that the weight ratio (AC) /B=0.4 to 1.3, and then the reaction is performed with formaldehydes in the presence of a basic catalyst. To a method of manufacturing le type modified phenolic resin composition.

The tung oil in the present invention refers to naturally occurring tung oil mainly composed of glycerin ester of eleostearic acid, which is a conjugated 3 atom in the eleostearic acid group.
The double bond of each has reactivity with phenols,
Up to two of these phenols can be added under normal reaction conditions. The tung oil with sufficient addition of phenols in the present invention means that most or all of the two double bonds among the double bonds having reactivity of the eleostearic acid group are in the ortho or para position of the phenols. It refers to a chemically bonded substance.

The phenols used in the present invention include phenol, cresol, xylenol, Pt-butylphenol, bisphenol A, resorcin and the like.
Of dihydric and dihydric phenols and their substitution products
Phenols containing at least 50 mol% of trifunctional or higher functional phenols are used.
Preferred phenols are phenol and cresol.

The formaldehydes used in the present invention are formaldehyde, paraformaldehyde and the like.

Examples of the basic catalyst in the present invention include catalysts such as ammonia, triethylamine, ethylenediamine, hexamethylenetetramine, triethanolamine and barium hydroxide.

In the present invention, the composition of the modified phenolic resin composition obtained by reacting tung oil sufficiently added with phenols, phenols and formaldehydes in the presence of a basic catalyst includes those added to tung oil. It is preferable that all phenols have a weight ratio of 0.4 to 1.3. The ratio is 1.
When it is 3 or more, the content of the tung oil component is small and the cured product of the resin composition is impaired in flexibility, and when it is 0.4 or less, the tung oil component is large and the strength of the cured product is lowered.

The ratio of phenols to tung oil in a modified phenolic resin composition obtained by reacting tung oil with sufficient addition of phenols, phenols and formaldehyde in the presence of a basic catalyst is 0.4 to 1.3 by weight ratio. To obtain a product, phenols are added to tung oil in a weight ratio of 0.
It is difficult to obtain it by a method of mixing and reacting with 4 to 1.3. In the reaction in the weight ratio within this range, the phenol gels before the sufficient addition to the double bond of the eleostearic acid group in tung oil, so the reaction is completed in an insufficient addition state. Has to be reacted with formaldehyde in the presence of a basic catalyst, and as a result, the resulting resin is incompletely bonded, which limits its flexibility and toughness.

In the present invention, the weight ratio of phenols (A) and tung oil (B) is X <A / B <10 X = 0.024 x (fw-1) x M / fn (fn is the number average of phenols. (Functional number, fw is the amount average functional number of phenols, M is the number average molecular weight of phenols) and reacted in the presence of an acidic catalyst, and a reaction composition comprising tung oil and phenols with sufficient addition of phenols From the reaction composition, a predetermined amount (C) of unreacted phenols is removed so that the weight ratio (AC) /B=0.4 to 1.3, and then the reaction is performed with formaldehydes in the presence of a basic catalyst. By doing so, the modified phenol resin composition of the present invention can be produced by reacting tung oil sufficiently added with phenols, phenols and formaldehydes in the presence of a basic catalyst.

The number average functionality of the phenols of the present invention means the reactive position of the phenols on the benzene nucleus (ie,
The total number of moles of phenolic functional groups) is divided by the total number of moles of phenols. The amount average functional number of phenols of the present invention means the number obtained by dividing the total product of the square of the number of functional groups of phenols and the number of moles of phenols by the total number of moles of functional groups of phenols. The number average molecular weight of the phenols of the present invention means the number obtained by dividing the total weight of the phenols by the total number of moles of the phenols.

In the present invention, the reaction ratio of the phenols (A) and tung oil (B) is (A) / (B) = X-by weight.
Is 10. When (A) / (B) is less than X, gelation occurs before the phenols are sufficiently added to the tung oil, or the viscosity is remarkably increased to obtain a reaction composition in which the phenols are sufficiently added to the tung oil. Becomes difficult. If it is 10 or more, the amount of unreacted phenols removed increases, which is economically disadvantageous. The preferred reaction ratio (A) / (B) is X-5. By the reaction, a reaction composition composed of tung oil sufficiently added with phenols and unreacted phenols is obtained.

In the present invention, the acidic catalyst used in the reaction of the phenols (A) and tung oil (B) includes paratoluenesulfonic acid, methanesulfonic acid, boron trifluoride, stannic chloride and stannic chloride. Friedel-Crafts type catalysts such as diiron, perfluoromethanesulfonic acid and the like can be mentioned. The amount of the acidic catalyst used is not particularly limited,
0.01 to 0.5% by weight, based on the total amount of reactants, is preferred.
The reaction is preferably carried out at a temperature of 50 to 120 ° C. 1
Above 20 ° C, ester bonds of tung oil are decomposed and cleaved, which is not preferable. If necessary, the reaction may be carried out in a solvent such as toluene.

In the present invention, a predetermined amount (C) of unreacted phenols in a reaction composition consisting of tung oil and phenols to which phenols are sufficiently added is expressed in a weight ratio of (AC) /B=0.4 to 1.3. And the ratio of the preferred phenols in the modified phenolic resin composition of the present invention is adjusted. Then, the amount of formaldehyde to be reacted in the presence of a basic catalyst is 0.6 to 1.5 as formaldehyde based on 1 mol of all phenols after removal of a predetermined amount of unreacted phenols.
It is a mole. The reaction was carried out under the basic catalyst at 60 to 100 ° C.
It is preferable to carry out at the temperature of. If necessary, the reaction may be carried out in a solvent such as toluene.

In the present invention, X, which represents the lower limit of the reaction ratio between the phenols (A) and tung oil (B), is represented by the following formula X = 0.024 × (fw-1) × M / fn, and the experimental value and Flory The gelling conditional expression of

In the present invention, up to 30% by weight of tung oil can be appropriately replaced with other drying oil such as dehydrated castor oil and linseed oil. Further, it can be appropriately modified within 20% with other modifiers such as rosin, aniline, and Kashnut kernel oil.

[0018]

The present invention will be illustrated by the following examples.

Example 1 Phenol (I) was prepared as a phenol. Phenol is a single component having a functional number of 3 and a molecular weight of 94. Therefore, its number average and number average functional number is 3, and number average molecular weight is 94.
X is 1.504. Charge a flask (5 liters) equipped with a stirrer with 2500 g of phenol (I) and 800 g of tung oil (II) (weight ratio (I) / (II) = 3.125), and use an appropriate amount of paratoluenesulfonic acid as a catalyst to tung oil at 100 ° C. The reaction was continued until the reaction of the functional group of 1 was completed. The time required for the reaction was 4 hours. The reaction state of functional groups of tung oil was traced by nuclear magnetic resonance spectroscopy. The reaction composition obtained contained 36% by weight of tung oil with sufficient addition of phenol and unreacted phenol.
It was 64% by weight. The reaction composition was neutralized with triethanolamine, and the unreacted phenol was removed by evaporation under vacuum until the unreacted phenol in the reaction composition became 34% by weight, and the bound phenol was also included in the charged tung oil. A mixture having a weight ratio of all phenol components of 1.25 was obtained. The average molecular weight of this mixture measured by the vapor pressure equilibrium method was 253.
Then, to this was added an appropriate amount of ammonia as a catalyst, 430 g of paraformaldehyde and 500 g of toluene, and
After reacting at 80 ° C until gelling time on a hot plate at 150 ° C reaches 6 minutes, dehydration and desolvation are performed under vacuum, and a 1/1 mixed solvent of toluene and methanol is added to cool. Then, a resole-type modified phenolic resin composition having a resin content of 52% by weight was obtained.

(Example 2) As a phenol, mixed cresol (III) consisting of 60% m-cresol and 40% p-cresol was prepared. The number average functionality of mixed cresol is
2.600, the number average functional number is 2.692, and the number average molecular weight is 108. X is 1.687. In a 5 liter flask equipped with a stirrer, 2500 g of mixed cresol (III) and 500 g of tung oil (II) were mixed.
g (weight ratio (III) / (II) = 5), and an appropriate amount of paratoluenesulfonic acid as a catalyst was reacted at 100 ° C. until the reaction of the functional group of tung oil was completed. The time required for the reaction was 4.5 hours. The reaction state of functional groups of tung oil was traced by nuclear magnetic resonance spectroscopy. The reaction composition thus obtained contained 26% by weight of tung oil with sufficient addition of cresol and 74% by weight of unreacted cresol. This reaction composition was neutralized with triethanolamine, the unreacted cresol in the reaction composition was removed by evaporation under vacuum until the unreacted cresol in the reaction composition became 22% by weight, and the added cresol was also included in the tung oil charged. A mixture with a weight ratio of all cresol components of 1.0 was obtained. The average molecular weight of this mixture measured by the vapor pressure equilibrium method was 390. Then, triethylamine as a catalyst, 400 g of paraformaldehyde and 500 g of toluene were added thereto, and the mixture was reacted at 80 ° C. until the gelation time of the resin on a hot plate at 150 ° C. reached 6 minutes, and then under vacuum. Was dehydrated and desolvented, and a 1/1 mixed solvent of toluene and methanol was added and cooled to obtain a resol-type modified phenolic resin composition having a resin content of 50% by weight.

(Comparative Example 1) 1000 g of phenol (I) and 800 g of tung oil (II) were placed in a 5-liter flask equipped with a stirrer.
Charged (weight ratio (I) / (II) = 1.25), and reacted at 100 ° C. using an appropriate amount of paratoluenesulfonic acid as a catalyst. After 1.5 hours from the start of the reaction, the viscosity suddenly increased and it became difficult to stir and gel. Under this condition, it was difficult to sufficiently add phenol to the functional group of tung oil.

(Comparative Example 2) As in Comparative Example 1, 1000 g of phenol (I) was added to a 5-liter flask equipped with a stirrer.
Charge 800g of tung oil (II) (weight ratio (I) / (II) = 1.2
5), using an appropriate amount of paratoluene sulfonic acid as a catalyst, 100
The reaction was carried out for 1 hour at a temperature shorter than the time at which gelation occurred, triethanolamine was added for neutralization, and the reaction was stopped by cooling. The reaction rate of functional groups of tung oil in this reaction mixture was 55% as measured by nuclear magnetic resonance spectrum. The reaction composition obtained was 57% by weight of tung oil with insufficient addition of phenol and 43% by weight of unreacted phenol. The average molecular weight of this reaction composition measured by the vapor pressure equilibrium method was 198. Then, a proper amount of ammonia as a catalyst, 430 g of paraformaldehyde and 500 g of toluene were added thereto, and the mixture was reacted at 80 ° C. until the gelation time of the resin on a hot plate at 150 ° C. reached 6 minutes, then under vacuum. Was dehydrated and desolvented, and a 1/1 mixed solvent of toluene and methanol was added and cooled to obtain a resole-type modified phenolic resin composition having a resin content of 52% by weight.

From Examples 1 and 2 and Comparative Examples 1 and 2, it is conventionally difficult to obtain a resin in which phenols are sufficiently added to or combined with tung oil, and according to the method for producing the modified phenol resin composition of the present invention. For the first time, it turns out that this is possible.

The modified phenolic resins obtained in Examples 1 and 2 and Comparative Example 2 were dropped on a hot plate at 150 ° C. to evaporate the solvent, and then the hot plate temperature was set to 165 ° C. to react and cure for 2 hours. A film having a thickness of about 0.3 mm was formed. Although the resin film of Comparative Example 2 was slightly cloudy, Examples 1 and 2
The resin film of was transparent. When the film was bent, the resin film of Comparative Example 2 was soft, but was brittle and easily ruptured. However, Examples 1 and 2
The resin film of 1 was tough and did not break despite being soft. As described above, the modified phenolic resin composition of the present invention is superior in flexibility and toughness as compared with the conventional resin having the same modification rate. In addition, the method for producing a modified phenolic resin composition of the present invention makes it possible to obtain an excellent modified phenolic resin composition for the first time.

[0025]

The cured product of the resol type modified phenolic resin composition of the present invention has extremely excellent flexibility, toughness and electrical characteristics, and is suitable for phenol resin laminates,
Suitable for composite materials, paints, industrial resins,
Particularly, it is extremely useful for a phenol resin laminated board used for a printed wiring board. Thus, the reason why the modified phenolic resin composition of the present invention is extremely excellent in flexibility and toughness is not clear, but in the phenolic resin composition of the present invention, the functional group of tung oil is sufficiently or completely phenolic. Because of the addition of the class, the cured product can be crosslinked more sufficiently,
Furthermore, it is considered that there is almost no unreacted tung oil or tung oil with insufficient bonding. Further, it has been difficult to obtain a resin having a high modification rate in which such tung oil and phenols are sufficiently bound, but the present invention made it possible for the first time.

Claims (2)

[Claims] 1. A modified phenolic resin composition obtained by reacting tung oil in which phenols are sufficiently added to a reactive double bond, phenols and formaldehydes in the presence of a basic catalyst. 2. A weight ratio of phenols (A) and tung oil (B): X <A / B <10 X = 0.024 × (fw-1) × M / fn (fn is the number average functional number of phenols, (fw is the number average functional number of phenols, M is the number average molecular weight of the phenols) and reacted in the presence of an acidic catalyst to obtain a reaction composition consisting of tung oil and phenols with sufficient addition of phenols, A predetermined amount (C) of unreacted phenols is removed from the reaction composition so that the weight ratio (AC) /B=0.4 to 1.3, and then reacted with formaldehyde in the presence of a basic catalyst. A method for producing a modified phenolic resin composition, which is characterized.