KR820001055B1 - Process for producing internally plasticized phenolic resins - Google Patents

Abstract

Internally plasticized phenolic resins useful as elec. insulators having good heat and solvent resistance are prepd. by treating a phenolic resin with an epoxidized vegitable oil in the presence of an amine. Thus, formaldehyde-phenol copolymer 500, epoxidized linseed oil 500, and Et3N 2g were heated 5hr at 160≰C. Then 221g 80% paraformaldehyde and 24g 25% aq. NH3 were added and the mixt. was heated 4.5h at 80≰C. The resulting resin had elec. resistance 9.2X1011Ω, heat resistance (200≰C air) > 60 min, and solvent resistance (trichloroethylene) > 60 min.

Description

Process for preparing internal plasticized phenolic resin

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an internally plasticized phenolic resin which is used for producing a laminated sheet having excellent electrical properties, heat resistance, solvent resistance, and extremely excellent punchability.

Background Art In recent years, laminated sheets used for insulating materials, particularly for communication and electronic devices, have been required to have excellent punching properties at room temperature or relatively low temperatures in view of automation and vitalization of processing equipment. Therefore, conventionally, a method of increasing the flexibility of the phenol resin by using a phenol and an alkylated phenol in combination or using a modifier such as dry oil or semi-dry oil of vegetable oil is used.

However, when the alkylated phenol is used, the cold punchability or the use of the vegetable oil is relatively slow in the reaction between the double bond of the vegetable oil and the phenol oil, so that the vegetable oil or the double bond remains unreacted in the resin as it is. There are drawbacks such as deterioration in heat resistance, a problem of workability during manufacture, such as gelation caused by double bond mutual polymerization reaction.

In order to improve these drawbacks, a method of using epoxidized vegetable oil (British patent No. 996,101, US Patent No. 36562222, West German Patent No. 2225458, etc.) has been proposed.

However, in these methods, not only in the case of phenol monomers but also in resol or novolak type phenol formaldehyde resins, the hydroxyl group of the unreacted phenol present in the resin preferentially reacts with the epoxy group of the epoxidized vegetable oil. Inactivated.

The reaction product of phenol and epoxidized vegetable oil produced in this way does not react with formarin and remains uncured in the resin. Therefore, only the punchability of the laminated board is excellent, but the properties such as heat resistance and solvent resistance are excellent. Cannot be satisfied.

An object of the present invention is to provide a method for producing an internally plasticized phenolic resin having an excellent punching property using an epoxidized vegetable oil and capable of producing a laminated sheet having excellent electrical properties, heat resistance, and solvent resistance.

This invention is characterized by heat-reacting formaldehydes with phenolformaldehyde resin and epoxidized vegetable oil which do not contain 4% or more of unreacted monovalent phenols.

In the present invention, the order of reacting phenol formaldehyde resin, epoxidized vegetable oil and formaldehyde is a method of reacting phenol formaldehyde resin, epoxidized vegetable oil and then reacting formaldehyde, epoxidized vegetable oil and formaldehyde. Although the reaction method, such as a method of reacting phenol formaldehyde resin and a reaction of phenol formaldehyde resin with epoxidized vegetable oil and formaldehyde at the same time, is not particularly specified, but preferably phenol formaldehyde resin and epoxy It is good to make the reacted plants react with formaldehyde.

Since the phenolformaldehyde resin used in the present invention does not contain 4% or more of unreacted monovalent phenols, there is no reactive inert substance with respect to formarin, such as a reactant between epoxidized vegetable oil and phenol, as described in the above patent. Therefore, it has a plasticizing effect and can prevent the fall of characteristics, such as heat resistance solvent resistance.

The use of phenol formaldehyde resins containing not more than 1% of unreacted monovalent phenols can prevent most of the deterioration in properties such as heat resistance and solvent resistance.

As a phenol formaldehyde resin which does not contain 4% or more of unreacted monovalent | monohydric phenols used for this invention, a phenol, m-cresol, o-cresol, p-cresol, t-butylphenol, octylphenol, nonylphenol, etc. And phenols are reacted with formaldehyde in the presence of a common acid catalyst such as hydrochloric acid, hydrochloric acid, p-toluene sulfonic acid, benzenesulfonic acid, phosphoric acid and the like, followed by removal under reduced pressure or washing with water to evaporate. The no-stick phenol formaldehyde resin 4,4'- dihydroxy diphenol propane 2,2 (bisphenol A), 4,4'- dihydroxy diphenyl meta (bisphenol F) which removed unreacted phenols 4,4'-dihydroxydiphenylcyclohexane, 4,4'-dihydroxydiphenylpentane-3,3,4,4'-dihydroxydiphenylbutane-2,2, 2- (4- Hydroxyphenyl).

Novolacs, such as (bisphenyl) novolac obtained by making 4-methyl and 4- (4-hydroxyphenyl) pentene-1 react with formaldehyde in the presence of a normal acid catalyst, are used. These may be used alone or in combination or co-condensation. The novolac itself is not cured but is flexible with a thermoplastic resin, thus providing flexibility and effective plasticization even after curing. Novolac (phenol) Novolac is rich in reactivity with epoxidized vegetable oil and contains less unreacted vegetable oil, and is good in terms of solvent resistance, heat resistance and size stability of the product using the obtained resin. (Bisphenols) Since novolac has no phenol mononuclear body at all, and there are few nucleolus again and novolak has an average number of hydroxyl groups per molecule, the probability that all phenolic hydroxyl groups in the novolak molecule react with epoxy groups is very high. It is less and the reaction activity with formaldehyde is large.

Therefore, it is excellent in solvent resistance, heat resistance, insulation resistance and size stability. When a mixture of (phenol) novolac and (bisphenols) novolac is used as the novolac, the solvent resistance, heat resistance and size stability are excellent due to the synergistic effect of the above effect.

Moreover, bisphenol can also be mixed and used for novolak.

In this invention, resol can also be used as a phenol formaldehyde resin which does not contain 4% or more of monovalent phenols.

Such a resol type phenol resin can be manufactured by the special mixing | blending and synthesis method demonstrated below. That is, in the present invention, about 1.02-3.0 mole of formaldehyde is used with respect to 1 mole of phenol, and about 0.02-0.03 mole of catalyst. In the present invention, at least 3.0 mole of formaldehyde is used with respect to 1 mole of phenol. The aldehyde is reacted using a large excess of 2-3 times or more of the compounding amount, which is generally known as a known example and put into practical use, and then neutralized and separated with an acid to obtain a resin.

As the phenol, phenol, cresol, xylenol, butyl phenol, nonyl phenol and the like are used.

The synthetic catalyst of the resin is one or a mixture of oxides or hydroxides of alkali metals such as sodium, carium, lithium, and trimethylamine. As the acid for neutralizing after synthesis, general acids such as inorganic acids such as lactic acid and hydrochloric acid, organic acids such as acetic acid, paratoluenesulfonic acid and benzenesulfonic acid can be used. As a proper pH value at the time of neutralization, below 4.5 is desirable 4.5-6.5.

That is, as the pH decreases, the precipitation production rate is good, and it is good at pH 6.5 or lower. However, if the pH value is too low, condensation reaction of methylol group occurs and polymerization proceeds. If the pH is 4.5 or more, condensation reaction of the methylol group is unlikely to occur. Thus, the resin used in the present invention can be obtained by selectively depositing the precipitated resin.

The phenol formaldehyde resin and the epoxidized vegetable oil are reacted by heating, but the reaction proceeds rapidly when reacted in the presence of a secondary and / or tertiary amine as a catalyst. The heating reaction is carried out at 80 ° C-160 ° C for 3-9 hours. Dimethylamine, diethylamine, dipropylamine, dibutylamine, diarylamine, diimylamine, and the like are trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine and dimethyl as tertiary amines. Amines, diethylamines, tribenzylamines, trephenylamines, benzyldimethylamines and the like are used, but are not particularly limited to these.

Epoxidized vegetable oils and phenolformaldehyde resins are preferably reacted so that the ratio of phenolic hydroxyl groups in the epoxy group is 1: 1-8. Below 1, the plasticizing effect is increased, but the properties such as solvent resistance, insulation resistance, heat resistance, etc. of the used product are lowered, and at 8 or higher, the deterioration of properties is hardly seen, but the plasticizing effect is lowered.

In addition, the epoxidized vegetable oil used in the present invention is internal epoxidized by oxidizing the double bond of fatty acids in unsaturated vegetable oil, and epoxidized flax oil epoxidized castor oil, epoxidized castor oil, epoxidized dehydrated castor oil, etc. The thing of 2-8% of oxygen oxirane content is used.

In addition, in the present invention, when novolak is used as the phenol formaldehyde resin, it cannot be cured as it is, so it is reacted with formaldehyde if necessary. The reaction catalyst in the case of reacting formaldehyde is not particularly specified, but inorganic substances such as hydroxides or oxides of ordinary alkali metals and alkali metals, and organic bases such as ammonia or trimethylamine can be used. As formaldehyde, formaldehyde formmarin, paraform, etc. are used.

Hereinafter, examples and comparative examples of the present invention will be described.

[Examples 1 and 2, Comparative Example 1]

Resin (A) (Epoxylated linseed oil, novolak-type phenol resin modified phenol resin) First, a novolak-type phenol resin was synthesized. To a 3-liter flask equipped with a reflux condenser, temperature, and stirrer, 1000 g of phenol, 430 g of 37% formarin, and 1.5 g of hydroxyl as a catalyst were added. The mixture is heated in an oil bath. When the temperature of the reaction mixture reaches 85 ° C., the heating is stopped, and the temperature is raised and heated to reflux by exothermic heat of reaction. Reheat where the severe reflux has settled and continue the reaction for 1 hour. After the reaction, the reactant in the flask is removed by moving the evaporation plate and tilting the water layer. The resin part of the evaporation plate is heated while stirring to remove water or unreacted phenol. When the resin temperature reaches 170-170 ° C The heating was stopped, the solids were allowed to flow out into the metal container, and solidification was confirmed by the absence of unreacted phenol, which was confirmed by high performance liquid chromatography (HLC).

500 g of said resin, 500 g of epoxidized flax oil, and 2 g of triethylamine are put into a 2 L three-necked flask equipped with a stirrer, a thermometer, and a cooler, and heated. The reaction was carried out at 160 ° C. for 5 hours to confirm that the peak of the epoxidized flax oil was almost lost by HLC. 24 g of 80% paraform 221 g 25% ammonia water was added to the reaction solution, and the reaction was carried out at 80 ° C. for 4 hours.

The gelling time on the hot plate (160 ° C.) was 203 seconds. This was dissolved in 400 g of methyl ethyl ketone. Let this varnish which mixed varnish 750g of late water-soluble phenol resins with this varnish 950g make resin (A).

Resin (B) (epoxylated soybean oil, novolak-type phenolic resin modified phenolic resin) 500 g of novolak-type phenolic resin used in resin (A) in a 2-liter flask equipped with a stirrer, a thermometer and a cooler, 300g, 80 of epoxidized soybean oil 221 g of% paraform and 19.2 g of 25% ammonia water were added thereto, and the reaction was carried out at 80 DEG C for 6 hours and a half.

The gelation time of the reaction product was 220 seconds at 160 ℃. Acetone and 350 g were added to the reaction product to dissolve completely to obtain a yellow transparent varnish. This varnish is referred to as resin (B).

Resin (C) (water-soluble phenol resin) 400 g of phenol, 600 g of 37% aqueous formarin solution, and 40 g of 30% trimethylamine were reacted at 60 ° C for 10 hours, dehydrated under reduced pressure, and methanol was added to adjust the water-soluble phenolic resin varnish with a nonvolatile content of 60%. .

Comparative resin (D) (paulown oil-modified phenolic resin) 800 g of m-cresol, paulownia oil, 450 g, and 1 g of p-toluenesulfonic acid were added thereto and reacted at 120 ° C for 2 hours. Next, the reaction solution was cooled to 70 ° C., and then 383 g of 80% paraform and 3 g of 25% ammonia water were added and reacted at 70 ° C. for 5 hours, during which time dehydration was performed under reduced pressure. The gelling time on the hot plate (160 ° C.) was 211 seconds. 400g MEK was added to this and the paulownia oil modified phenol resin resol varnish was obtained.

A water-soluble phenolic resin of Resin (C) was impregnated into lint cloth, and dried to prepare a resin impregnated paper in which the resin impregnation amount was adjusted to 15%. This resin impregnation was again impregnated with resin (A), (B) and comparative resin (D), and dried to prepare a resin impregnated paper in which the resin impregnation amount was adjusted to 48%.

Eight sheets of this resin impregnated paper and one sheet of copper foil with an adhesive were stacked and pressed for 50 minutes under conditions of 160-170 ° C. and 140 kg / cm 2 to obtain a red-filled plate coated with copper having a thickness of 1.6 mm.

Table 1 shows various properties of the obtained copper clad laminate.

TABLE 1

The alphabet of processing conditions conforms to Japanese JIS-C6481.

Example 3, Comparative Example 2

Resin (E) (epoxylated flax oil, bisphenol A novolak-type resin, modified phenol resin) 100 g of bisphenol A, 214 g of 37% formarin, catalyst p- in an agitator and a three-liter, two-liter flask equipped with a cooler at temperature. 2 g of toluenesulfonic acid is added and heated. When the temperature of the reaction mixture reaches 85 ° C., the heating is stopped and boiling is refluxed by exothermic heat of reaction. When the heated reflux subsides, it is heated again and the reaction is continued for 1 hour. After the reaction, the reactant in the flask is transferred to an evaporating plate, the water layer is obliquely removed, and a novolac bisphenol formarin resin is obtained. In this case, unreacted bisphenol A remained, but was used as it was in the following experiment.

500 g of said resin, 500 g of epoxidized flax oil, and 5 g of triethylamine are put into a 2 L three-necked flask equipped with a cooler at a stirrer, and heated. The mixture was reacted at 160 ° C for 4 hours to confirm that epoxidized linseed oil was almost lost by HLC.

Next, 148 g of 80% paraform and 24 g of ammonia were added to the reaction solution, and the mixture was reacted at 80 ° C for 4 hours. The gelling time on the hot plate (160 ° C.) was 234 seconds. 300 g of acetone was added to this and dissolved. This varnish is referred to as resin (E).

Resin (F) (water-soluble phenol resin) 400 g of phenol, 600 g of 37% formarin aqueous solution and 40 g of 30% trimethyl amine were reacted at 60 ° C. for 10 hours to dehydrate under reduced pressure, and methanol was added to adjust the water-soluble phenolic resin varnish with a nonvolatile content of 60%. .

Comparative resin (G) (paulownia oil-modified phenolic resin) m-cresol 800g, paulownia oil 450g, p-toluenesulfonic acid was added and reacted at 120 ° C for 2 hours-then the reaction solution was cooled to 70 ° C and then 80% para 383 g of form and 30 g of 25% ammonia water were added thereto, and the mixture was reacted at 70 DEG C for 5 hours. The gelling time on the hot plate (160 ° C.) was 211 seconds. 400g MEK was added to this and the paulownia oil-modified phenol resin resol varnish was obtained.

The water-soluble phenolic resin of resin (F) was impregnated with lint cloth and dried, and this resin impregnated paper which produced resin impregnated paper whose resin impregnation amount was adjusted to 15% was again impregnated with resin (E) and comparative resin (G) and dried. To prepare a resin impregnated paper in which the resin impregnation amount was adjusted to 48%. The eight resin-impregnated papers and one adhesive foil with adhesive were stacked together, and they were crimped for 50 minutes under conditions of 160-170 ° C. and 140 kg / cm 2 to obtain a laminated plate coated with 1.6 mm of thickness.

Table 2 shows various characteristics of the obtained copper clad laminate.

TABLE 2

Resin (J)

In the manufacturing method of resin (H), resin (I) was obtained by the same method using diethylamine instead of dimethylbenzyl amine.

Super Wall Resin (Water Soluble Phenolic Resin)

400 g of phenol, 800 g of 37% aqueous formarin solution, and 5 g of magnesium hydroxide were reacted at 55 ° C. for 8 hours, dehydrated under reduced pressure, and methanol was added to prepare a resin powder at 15%.

The resin for superwall coating was impregnated in a Konten printer, dried, and the resin impregnated paper which adjusted the resin impregnation amount to 15% was manufactured. Resin (H)-(J) was again impregnated to this resin impregnated paper, and the resin impregnated paper which adjusted 48% of resin impregnation amount was manufactured.

EXAMPLE 4, 5, COMPARATIVE EXAMPLE 3

Resin (H)

To a three-necked flask equipped with a stirrer, a thermometer, and a cooler, 1000g of phenol, 740g of 37% formarin, and 15g of 10% hydrochloric acid solution as a catalyst were added and reacted at 85 ° C for about 2 hours.The reaction was transferred to an evaporation plate, and the aqueous layer was removed by decantation. do. Next, the resin portion of the evaporating dish is heated while stirring to remove unreacted phenol. When the resin temperature reaches 170-175 ° C, the heating is stopped and spilled into a metal container to solidify. It was confirmed by high performance liquid chromatography (HLC) that no unreacted phenol remained. The hydroxyl equivalent of this novolak-type phenol resin was 105 g.

500 g of epoxidized soybean oil, 200 g of the novolak-type phenol resin synthesized above, 300 g of bisphenol A, and 30 g of dimethylbenzylamine were added thereto, and the mixture was reacted at 150 ° C. for 6 hours. After completion of the reaction, phenol 500g paraform 320g and ethylenediamine 6.8g were added and reacted at 80 ° C for 4 hours. The gelation time of the reaction product was 189 seconds on a hot plate at 160 ℃. Acetone was added to this and the resin content was adjusted to 52%.

Comparative resin (I) (paulin oil modified phenolic resin)

800 g of m-cresol, 400 g of paulownia oil, and 1 g of p-toluenesulfonic acid were added to a flask such as resin (H) and reacted at 120 ° C. for 2 hours. Next, the reaction solution was cooled to 70 ° C, and 333 g of 80% paraform and 28.8 g of 25% ammonia water were added thereto, followed by reaction at 80 ° C. for 3 hours, during which time dehydration was performed under reduced pressure. The gelation time of this reaction product was 203 seconds on a hotplate at 160 ° C. MEK was added to this and it prepared so that resin content might be 52%.

This resin impregnation was made by stacking eight sheets and one sheet of copper foil with adhesive, which was pressed for 50 minutes under conditions of 160-170 ° C and 140 kg / cm 2, to obtain a laminated plate coated with 1.6 mm of thickness.

Table 3 shows the characteristics of the obtained copper clad laminate.

TABLE 3

The alphabet of processing conditions conforms to JIS-C6481 of Japan.

Example 6-7 and Comparative Example 4

Resin (K)

940 g of phenol and 3250 g of 37% formarin were added to a four-necked flask equipped with a cooler and a stirring device, and 8 g of a 50% sodium hydroxide solution was added while stirring, followed by a water miscibility of 0.5 ml / g (30 ° C.) at a reaction temperature of 75 ° C. After the reaction, the mixture was cooled and adjusted to pH 5.0 with acetic acid to obtain a precipitate, which was separated and purified. 40 parts by weight of 5 parts by weight of epoxidized flax oil benzyl dimethylamine was added to 60 parts by weight of the resin, followed by reaction at 90 ° C. for 6 hours. The gelation time of this resin on a 160 ° C. hot plate was 188 seconds.

Resin (L)

Into a four-necked flask equipped with a cooler and a stirring device, 1080g of meracresol and 290g of 37% formarin were added thereto, and 8g of 50% sodium hydroxide was added while stirring. The reaction was then reacted at 60 ° C for 12 hours, cooled, and the pH was adjusted to 6.5 with hydrochloric acid. The precipitate was separated and purified by adjustment.

50 parts by weight of epoxidized soybean oil and 5 parts of benzyldimethylamine were added to 50 parts by weight of the resin, followed by reaction at 80 ° C for 10 hours. The gelation time of this resin on a 160 ° C. hot plate was 240 seconds.

The varnish of Example 6 was impregnated with a lint cloth preliminarily coated with an aqueous phenol formaldehyde varnish for ultrawall coating, and dried to prepare a resin impregnated base material having a resin content of 45% by weight. Eight sheets of this were polymerized and heated and pressed for 50 minutes under a lamination condition of 160-165 ° C. 80 kg / cm 2 to prepare a resin laminate having a thickness of 1.6 mm. The varnish of Example 7 was dissolved and mixed to 80 parts by weight as a solid with respect to 20 parts by weight of the varnish solids of the resol-type phenol formaldehyde varnish synthesized according to a conventional method using phenol paraformaldehyde, and previously prepared as a water-soluble phenol formaldehyde varnish for ultra-wall painting. The varnish was impregnated with the varnish on the ultra-walled, and a resin laminate was produced in the same manner as in Example 6.

As a comparative example, 873 g of paulownia oil 1142 g paratoluene sulfonic acid 1g was mixed and reacted at 110 ° C for 1 hour. Subsequently, 60 g of para tert-butylphenol 41 g paraform and 60 g of 25% ammonia water were placed in a reaction vessel and allowed to react at 80 ° C for 3 hours. Next, water was removed under reduced pressure and a solvent was added to prepare a resin varnish.

In order to compare the various characteristics of this resin laminated board which manufactured this resin laminated board by the method similar to Example 6 below using this resin varnish, it shows in Table 4. In addition, the paper base material which tries to impregnate the resin varnish shown in the comparative example mentioned above is not limited to lint cloth, Kraft paper and other paper base materials can also be used without exception.

TABLE 4

When the resin obtained in the present invention is used as a resin for laminated plates, as compared with vegetable oils having double bonds, such as paulownia oil, which are widely used in the past, as shown in Table 1, electrical properties such as insulation resistance and thermal stability such as soldering heat resistance are shown. Especially excellent. This is because the epoxidized vegetable oil used in the present invention does not have a double bond because it is reactive or active.

Again, the punchability is better than paulownia oil, the plasticizing effect is greater, and the epoxidized vegetable oil has excellent properties as a plasticizer of phenol resin.

Claims (1)

Characterized by heat-reacting formaldehydes with phenol-formaldehyde resins and epoxidized vegetable oils which do not contain 4% or more of unreacted free monovalent phenols (phenolic hydroxyl group is one phenol). Method for producing an internal plasticized phenolic resin.