JPS6017286B2 - Method for producing modified phenolic resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to isoprobenylphenol or isoprobenylphenol oligomers represented by the formula (b) or (m), alone or as a mixture, and a nonconjugated double phenol having an iodine value of 140 or more. After reacting with a drying oil having a bond under acidic catalyst or isoprobenylphenol or
) or isobrobenylphenol oligomers represented by formula (m) alone or as a mixture and an iodine value of 14
After reacting with a hostile oil having 0 or more non-conjugated double bonds using an acidic catalyst in the presence of phenols (first stage modification), further reacting the phenols with an acidic catalyst (second stage modification), The present invention relates to a method for producing a modified phenol resin, which is characterized in that the reaction product is then reacted with formaldehyde as part of the phenol component.

The purpose of the present invention is to produce highly effective drying oils having non-conjugated double bonds with an iodine value of 140 or more without losing the excellent properties of conventional phenolic resins mainly composed of phenols. Electrical insulating materials, laminates, and decorative materials that have significantly improved maneuverability without sacrificing their excellent electrical properties, heat resistance, chemical resistance, dimensional stability, warpage, etc. The present invention provides a method for producing a modified phenolic resin useful as a board.

Conventionally, a resol-type phenolic resin obtained by reacting phenols such as phenol, cresol, and xylenol with formaldehyde is impregnated with a base material and dried, and the resin-impregnated base material is used as a laminated material with a predetermined composition. It is well known that a laminate is then obtained by heating and pressing.

These laminates are widely used industrially as electrical insulating materials, structural materials, etc., but in recent years, with the development of electrical and electronic equipment, various laminates have been used for communication,
With the simplification, miniaturization, and higher performance of the mounting methods for components of consumer equipment, there is a demand for laminates with good electrical insulation, heat resistance, mechanical performance, and well-balanced properties such as machinability. has been increasing. Among them, there is a great demand for printed wiring materials, which are used after being punched into desired shapes in this field. However, since phenolic resins are generally hard and brittle, they must be heated to 100 to 150 degrees during punching, resulting in dimensional changes due to expansion and contraction, and warping due to changes in residual stress. However, the process of heating is complicated. For this reason, various methods have been proposed for producing phenolic resin laminates having these properties. In particular, it has long been proposed to use a drying oil containing a large amount of conjugated double bonds, such as tung oil, in order to maintain punching workability.

However, although modification by simply adding drying oil improves punching workability, other properties are significantly inferior, so methods have been proposed in which the drying oil is further modified.

For example, by reacting drying oil and phenols under an acidic catalyst and then reacting with formalin, the crosslinking density is increased while maintaining the punching workability of baggage oil, and the deterioration of other properties is prevented. It is.

Conventionally, drying oils with non-conjugated double bonds such as linseed oil and perilla oil have low chemical reactivity, so the proportion of phenols introduced into the drying oil is small, and sufficient crosslinking reaction does not proceed, resulting in internal hardening of the laminate. It was difficult to obtain a laminate due to the poor properties.

Even if a laminate can be manufactured under special conditions, it has the disadvantage that the layers may peel off during punching, or that the resin may dissolve when boiled for several minutes in a solvent such as trichloride, causing the layers to separate. Practical laminates with moisture and water resistance have rarely been seen.For these purposes, various electrical and mechanical properties as well as In order to produce a laminate with well-balanced workability, it was essential to use tung oil, which contains a large amount of conjugated double bonds and is highly chemically reactive with substances such as phenols.

An example of tung oil (fatty acid composition from China) is Q-ereostearic acid 81.5%, linoleic acid 6.7%, oleic acid 6%.
．． 4%, stearic acid 2.9%, palmitic acid 2.5%
It is.

Therefore, since tung oil has 80% or more conjugated double bonds in its main chain, it easily adds to phenols under acidic catalysts. However, even when phenol-modified tung oil is used, the interlayer adhesion of the laminate is still weak and delamination is likely to occur.

The reason for this is that the reaction between tung oil and phenols under an acidic catalyst is a Friedel-Crafts reaction, but under this reaction condition, tung oil tends to polymerize, and the impregnating effect of the resulting resin on the resin is poor. For these reasons, it cannot be said that it is satisfactory for miniaturized precision applications. In view of the above points,
As a result of intensive research, the present inventors discovered a method of extremely effectively modifying drying oil that has non-conjugated double bonds, which was previously thought to be unusable.
We have discovered a method for producing a phenolic resin for laminates that has excellent chemical and water resistance.

That is, isoprobenylphenol is a drying oil having an oligomer of isoprobenylphenol represented by formula (0) or formula (m) alone or as a mixture and a non-conjugated double bond having an iodine value of 140 or more. or isoprobenylphenol or isoprobenylphenol oligomers represented by formula (0) or formula (m) alone or in mixture with a non-conjugated dihydrogen having an iodine value of 140 or more. After reacting a drying oil having heavy bonds with an acidic catalyst in the presence of phenols (first stage modification), the phenols are further reacted with an acidic catalyst (second stage modification), and then the reaction product is By discovering a method for modifying drying oil by reacting it with formaldehyde as part of the phenolic component, and applying this method to the production method of phenolic resin, we have achieved various properties that are equal to or better than those of tung oil-modified phenolic resin. We succeeded in producing phenolic resin and arrived at the method of the present invention. The method of the present invention involves converting isoprobenylphenol or a single isoprobenylphenol oligomer represented by formula (b) or (m) into a drying oil having an iodine value of 140 or more and a non-conjugated double bond. Alternatively, after reacting the mixture under an acidic catalyst, the mixture is further reacted with a phenol, with or without adding an acidic catalyst as necessary, and then the reaction product is used as a part of the phenol component. The present invention provides a method for producing a modified phenol resin, which is characterized by reacting with formaldehyde.

A comparison of the phenolic modification of drying oil by conventional modification methods, the reactivity of the modified drying oil with formaldehyde, and the physical properties of the resulting resin and those obtained by the present invention is as follows. .

■ By the method of the present invention, drying oils with non-conjugated double bonds can be modified under relatively mild conditions, and by appropriately selecting reaction conditions, isoprobenyl can be modified even in the presence of phenols. Phenol or its oligomers can be preferentially introduced into the baggage oil. ■Isofu.

A large amount of oxyphenyl nuclei is introduced into the drying oil by the method of the present invention, in which a large amount of oxyphenyl nuclei is introduced into the drying oil (first stage modification) under an acidic catalyst (second stage modification). The crosslinking density of the resin can be increased. (2) The drying oil modified by the method of the present invention reacts rapidly with formaldehyde.

The reactivity of drying oils modified with isoprobenylphenol or isoprobenylphenol oligomers with formalin is higher than that of drying oils modified by conventional methods of modification with phenols. ■ The modified phenolic resin varnish obtained by the method of the present invention has uniformity and
It has excellent stability, and the laminate obtained by impregnating a base material with this resin varnish and heating and pressurizing it has improved interlayer bonding strength and increased moisture resistance, heat resistance, solvent resistance, and seismic pressure resistance.

However, the laminate obtained by impregnating the resin varnish obtained by converting the modified drying oil obtained by the modification method of the present invention into a sol as one of the phenol components has all the above advantages, and therefore has excellent electrical and mechanical properties. , moisture resistance, water resistance, heat resistance, dimensional stability, warpage, punching workability, etc. are significantly improved. Bag oils having non-conjugated double bonds with an iodine value of 140 or more that can be employed in the present invention include linseed oil, perilla oil, safflower oil, and hemp seed oil whose main components are triglycerides of linolenic acid and linoleic acid. , sardine oil, squid oil, etc.

Furthermore, esters of linolenic acid and linoleic acid, which are fatty components of oil, with monohydric alcohols or polyhydric alcohols are also broadly included. In the present invention, isoprobenylphenol or formula (0) or formula (m)
Reaction of oligomers of isoprobenylphenol expressed by Used in the reaction (first modification) of isoprobenylphenol oligomers represented by formula (0) or formula (m) alone or in a mixture with a drying oil having a non-conjugated double bond with an iodine value of 140 or more. Acidic catalysts include hydrogen acids such as sulfuric acid, phosphoric acid, and hydrochloric acid, p
-Organic acids such as toluenesulfonic acid and ayalic acid, as well as sulfonic acid type or carboxylic acid type cation exchange resins, and the amount used is 100 to 10,000, especially 500 to 500, per reactant. A range of is preferred.

The reaction conditions for the first stage modification are 65 to 150 qo for 1 to 3 hours, preferably 65 to 120°C for 1 to 2 hours. The reaction of bag oil with isoprobenylphenol and its oligomer gives very favorable results in the coexistence of the substance and other phenols having low reactivity.

This is because it is preferable in terms of dissolving isoprobenylphenol oligomers. The phenols in the present invention include (i) Isoph.

Phenols that are highly reactive with robenylphenol or its oligomers, such as phenol, cresol, xyler, cumylphenol, catechol, resorcinol, etc., and (ii) with isobrobenylphenol or its oligomers. Phenols with low reactivity such as butylphenol, aminophenol, hexylphenol, octylphenol, nonylphenol, dodecylphenol, phenylphenol, styrenated phenol, cumylphenol, bisphenol A, etc. can be used. In the present invention, the catalyst used for the reaction between the reaction product of bag oil and isoprobenylphenol or its oligomer and phenols (second stage modification) is p-toluenesulfonic acid, sulfuric acid, or hydrochloric acid. etc., and the amount of catalyst used is 300 to 10
00 blood, especially preferably in the range of 1000 to 500 blood vessels.

There are no particular restrictions on the reaction temperature and time, but 80-1
40oo for 0.5 to 3 hours, and conventional drying oil modification conditions with phenols (80 to 180oo for 1 hour).
6 hours), the reason is not clear, but the second
Step modification can also be carried out under relatively mild conditions. The following findings were made as a result of an investigation of the reaction of isoprobenylphenol or its oligomer with baggage oil and the products produced by the reaction of the reaction product with phenols.

For example, in the reaction of linolenic acid methyl ester, which is a component fatty acid of linseed oil, with isobrobenylphenol or its oligomer under an acidic catalyst, for example, the reaction was carried out at 100°C for 2 hours using a sulfuric acid catalyst. Gas chromatography revealed that the product was a reaction between linoleic acid methyl ester and two molecules of isoprobenylphenol or one molecule of isoprobenylphenol dimer.

Furthermore, as a result of analysis of the product using infrared absorption spectroscopy and nuclear magnetic resonance spectroscopy, it was found that unsaturated bonds remained as they were. That is, as a result of reacting the reactant with, for example, cresol at 100°C for 1 hour in the presence of a sulfuric acid catalyst, a modified product in which cresol was added to the double bond was obtained by gas chromatography and nuclear magnetic resonance spectroscopy. It became clear that On the other hand, the modified product obtained by the conventional method of modifying drying oil with phenols is a product of the so-called Friedel-Crafts reaction, as described in, for example, Japanese Patent Publication No. 45-135918.

0 Therefore, in the method of modifying baggage oil according to the method of the present invention, since unsaturated bonds still exist even after modification with isoprobenylphenol monomer or its oligomer, it is not possible to further introduce phenyl nuclei. can.

Therefore, the present invention can increase the ratio of phenyl nuclei introduced per molecule of drying oil compared to the conventional modification method. That is, according to the conventional method, the crosslinking reaction of the resin is achieved only by methylolization of the phenols added to the drying oil, whereas in the method of the present invention, the crosslinking reaction of the resin is achieved by methylolation of the phenols added to the drying oil, whereas in the method of the present invention, the crosslinking reaction of the resin is achieved by methylolation of the phenols added to the drying oil. Since this can also be achieved by using methylol compounds, its properties change during the curing stage of the resin. As is clear from the above description, the present invention is different from the conventional method of modifying baggage oil with phenols in the first stage inverting reaction of rare oil with isoprobenylphenol or its oligomer. It is based on the new discovery that substantially all unsaturated bonds in oil remain. The drying oil modified in the present invention has a high introduction rate of methylol groups through reaction with formalin, so the impregnation effect of the obtained phenolic resin on the laminate substrate is compared to that of the phenol resin obtained by the conventional modification method. It is assumed that this increases the crosslinking density after forming the laminate and contributes to improving the interlayer bonding strength. 5 As is clear from the above, the modification effects of the present invention include improved reactivity with formalin, improved impregnation effect of phenolic resin obtained by chemical characteristics such as increased introduction ratio of oxyphenyl nuclei, improved varnish properties, and An increase in crosslinking density occurs and the interlayer bond strength of the laminate improves.

Therefore, thermal, electrical and mechanical properties as well as chemical resistance are greatly improved. In order to effectively achieve the method of the present invention, it is necessary to add isoprobenylphenol or its oligomer to the drying oil in a weight ratio of 0.1 to 2 when modifying the drying oil.
Double amount, preferably 0.3-1. Use needle volume.

Isoprobenylphenol or its oligomer used in the method of the present invention is a compound represented by general formula 1, b, m, (in formula b, m, n is an integer of 0 to 18. In each of the above formulas, the hydroxyl group may be located at the ortho, meta or para position.

Monomers, dimers, and trimers can be synthesized as pure compounds, but oligomers of tetramer or higher coexist as a mixture. These monomers and oligomers can be used alone or in a mixture. In the method of the present invention, the phenolic resin is obtained by reacting it with formaldehyde under acidic or alkaline conditions after the modification reaction is completed.

A method to obtain a novolak type resin by reacting with formaldehyde under acidic conditions, a method to obtain a novolak type to resol type resin by partially reacting under acidic conditions, then making it alkaline and then reacting with formaldehyde, or after a modification reaction. Both methods of obtaining alkaline and pure resol type resins are possible.

In order to obtain a resol type resin, the acidic catalyst used is neutralized with ammonia, organic amines, etc., and then subjected to a reaction with formaldehyde. The formaldehyde/phenol (molar ratio) between the formaldehyde used in the reaction with all the phenols in the raw materials is generally 0.7 to 2. Preferably, the reaction is performed in the range of 0.8 to 1.6. The reaction temperature and time are also not limited, but are preferably in the range of 80 to 110 q○ for 1 to 5 hours. As a catalyst, hydrochloric acid, oxalic acid, p-toluenesulfonic acid, sulfuric acid, etc. are used when producing novolac type resin, and ammonia, methylamine, sulfuric acid, etc. are used when producing resol type resin.
Dimethylamine, triethylamine, ethylenediamine, diethylamine, caustic soda, caustic potash, etc. are used, but when 10 to 20 mol% of ethylenediamine is used in combination as an amine catalyst component containing ammonia, a laminate with good performance can be obtained, although the reason is not clear. A phenolic resin is obtained. The amount of drying oil used in order to exhibit excellent effects in the method of the present invention is 10 to 10% by weight, preferably 2% by weight, based on the phenol component in the phenolic resin raw material.
It ranges from 0 to 6% by weight.

As formaldehydes, formalin aqueous solution, paraformaldehyde, etc. are generally used. After completion of the reaction, the phenolic resin is dehydrated and dissolved in aromatic hydrocarbons, ketones, alcohols, or mixtures thereof to obtain a varnish. The method of the invention will be better understood by the following examples, but the invention is not limited to the scope of the examples.

Example 1 Weight % of p-isobrobenylphenol, 2nd base and 3
350 ml of p-isoprobenylphenol and 510 ml of linseed oil having a composition of 2% by weight were kept at 120°C in a pot, charged with 2.2 ml of 40% sulfuric acid, and stirred for 2 hours. .

After the reaction, cool and add 244 hours of synthetic cresol (60% m-body, 40% p-body) and 3.5 hours of 40% sulfuric acid to make 100q.
1 at o. I reacted for a while. Next, 550 g of phenol, 530 g of nonylphenol, 128 g of 37% formalin.
After adding 4.0 mol of 24.54% ammonia and 4.0 mol of ethylenediamine, the mixture was reacted at 98 to 100 oo for 5 hours. Water was removed under reduced pressure, and when the content reached 90 to 95 qC, dehydration was stopped and the mixture was cooled.

A varnish with a resin concentration of 50% was obtained by dissolving in a mixed solvent of methanol and toluene in a ratio of 2:1. Resin varnish with a thickness of 10 mm or more
Impregnated with Mills linter paper and dried to obtain a resin content of 45%.
prepreg was obtained.

Laminate 9 sheets of this prepreg (90kg/,
160 qo, 5 cm) to obtain a laminate. In addition, separately from this, a copper-clad laminate with a 35AC steel plate attached was obtained. The thickness was 1.6 ribs. Example 2 9 boxes of p-isoprobenylphenol with compositions of dimer and trimer, 2% by weight; p-isoprobenylphenol 350%, noel phenol, 266% and perilla oil, 650% 5. Keep the temperature at 100°C under normal conditions and add 20% sulfuric acid.
I charged 5 ta and let it fly for 2 hours.

After the reaction, 240 g of synthetic cresol and 5.2 g of 20% sulfuric acid were added.
The mixture was heated for 1 night and reacted at 100 oo for 1.5 hours.

Next, 560 phenol, 270 octylphenol
After adding 1280 g of 37% formalin, 41 g of 24.5% ammonia and 3.9 g of ethylenediamine, 98 ~
3 for 100q0. It reacted immediately. Water was removed under reduced pressure, and when the content reached 960%, dehydration was stopped and the mixture was cooled.
A varnish with a resin concentration of 50% was obtained by dissolving in a mixed solvent of methanol and toluene in a ratio of 2:1. Following the same treatment as in Example 1, a 1.6-wall thick laminate and a copper-clad laminate were obtained.

Example 3 9 boxes of p-isoprobenylphenol, 350% p-isoprobenylphenol, 300% phenol and 600% linseed oil with a composition of 2% dimeric and trimer by weight
2. Keep the water at 85 qo and add 40% sulfuric acid 3.1 qo in a bag. I worshiped insect time.

After the reaction, 230 g of synthetic cresol and 2.5 g of 40% sulfuric acid were added and reacted at 10,000 ml for 1.5 hours. Next, phenol 350 yen, nonylphenol 480 yen, 37%
1,400 tons of formalin, 50 tons of 24.5% ammonia, and 4.3 tons of ethylenediamine were added, and the mixture was reacted at 98 to 100 quarts for 4 hours.

Water was removed under reduced pressure, and when the content reached 95q0, dehydration was stopped and the mixture was cooled. A varnish with a resin concentration of 50% was obtained by dissolving in a mixed solvent of methanol and toluene in a ratio of 2:1. A willow laminate and a copper clad laminate having a thickness of 1.6 were obtained in the same manner as in Example 1.

Example 4 An oligomer of p-isoprobenylphenol having a composition of 9% by weight of p-isoprobenylphenol dimer, 1% by weight of trimer and tetramer, 17% by weight of p-isoprobenylphenol, 17% by weight of p-isoprobenylphenol.
0 yen and safflower oil 500 yen kept under 100 oo 4
3.2 hours of 0% sulfuric acid was charged and stirred for 2 hours.

After the reaction, 250 g of synthetic cresol and 2.5 g of 40% sulfuric acid were added and reacted at 100° C. for 1 hour. Next, phenol 300 times, nonylphenol 120 times, octylphenol 120 times, 37% formalin 700 times, 24.5%
25 minutes of ammonia and 2.0 hours of ethylenediamine were added, and the mixture was reacted at 97 to 98 degrees Celsius for 3 hours.

Water was removed under reduced pressure, and when the content reached 90-9y0, dehydration was stopped and the mixture was cooled. It was dissolved in a mixed solvent of methanol and toluene in a ratio of 2:1 to obtain a varnish with a resin concentration of 50%. A 1.6-thickness laminate and a copper-clad laminate were obtained in the same manner as in Example 1. Example 5 350 p-isoprobenylphenol oligomers with a composition of 9% by weight of p-isoprobenylphenol dimer, 1% by weight of trimer and tetramer, 2% by weight of nonylphenol
70 days of linseed oil and 500 times of linseed oil were kept under a rope at 140°C, and 2.5 days of 85% phosphoric acid was placed in a bag and roped for 2 hours.

After the reaction, cool and synthesize 250% of synthetic cresol and 40% sulfuric acid.
．． The mixture was reacted at 100° C. for 1 hour. Next, phenol 540 times, octylphenol 250 times, 37
% formalin 1300% and 24.5% ammonia 40%
．． 98 to 10 by adding 4.0 liters of ethylenediamine and 4.0 liters of ethylenediamine.
000 for 4 hours.

Water was removed under reduced pressure, and when the content reached 95 qo, dehydration was stopped and the mixture was cooled. A varnish with a resin concentration of 50% was obtained by dissolving it in a mixed solvent of methanol and toluene in a ratio of 2:1. Following the same treatment as in Example 1, a 1.6-thickness laminate and a copper-clad laminate were obtained.

Example 6 Oligomers of p-isoprobenylphenol with a composition of 9% by weight of p-isoprobenylphenol dimers, 1% by weight of trimers and 4-termers At 100:00 AM, the vessel was kept under the ground, charged with 2.2 hours of 85% phosphoric acid, and allowed to float for 2 hours.

After the reaction, 200 ml of synthetic cresol, 80 ml of xylenol, and 3.8 ml of 40% sulfuric acid were added and reacted at 100 ml for 1 hour. Next, 540 parts of phenol, 260 parts of octylphenol, 270 parts of nonylphenol, 1300 parts of 37% formalin, 41 parts of 24.5% ammonia and 4.0 parts of ethylenediamine were added and reacted at 98 to 10,000 for 4 hours. Water was removed under reduced pressure, and when the content reached 95 qo, dehydration was stopped and cooled, methanol and toluene 2:
1 to obtain a varnish with a resin concentration of 50%.
A 1.6-thickness laminate and a copper-clad laminate were obtained in the same manner as in Example 1.

Example 7 Oligomers of p-isoprobenylphenol with a composition of 9% by weight of p-isoprobenylphenol dimer, 1% by weight of trimers and tetramers - 340% and linseed oil 500%
I kept the temperature at 140 qo and put 2.2 qo of 85% phosphoric acid in a bag and roped it for 2 hours.

After the reaction, cool and add 130% phenol and 130% resorcinol.
After adding 3.6 g of sulfuric acid and 40% sulfuric acid, the mixture was reacted at 100 ml for 2 hours. Next, 500 parts of phenol, 250 parts of octylphenol, 280 parts of nonylphenol, 1278 parts of 37% formalin, 41 parts of 24.5% ammonia and 4.3 parts of ethylenediamine were added, and the mixture was reacted at 98 to 1000° for 4 hours. Water was removed under reduced pressure and the contents were reduced to 95q.
Dehydration was stopped and cooled when the temperature reached o. A varnish with a resin concentration of 50% was obtained by dissolving in a mixed solvent of methanol and toluene in a ratio of 2:1. A 1.6-thick willow laminate and a copper-clad laminate were obtained according to the same treatment as in Example 1. Comparative Example 1 Cresol 60M, linseed oil 350M and 40% sulfuric acid 1
The reaction was carried out for 3 hours at 12,000 pm for 4.3 pm.

After the reaction, cool and add 37% formalin for 760 hours, nonylphenol for 200 hours, octylphenol for 200 hours, and 24.
5% ammonia 29.0% and ethylenediamine 2.5%
98~100oo including evening 2. I reacted for a while.
Water was removed under reduced pressure, and when the content reached 95q0, dehydration was stopped and, after cooling, it was dissolved in a mixed solvent of methanol and toluene 2:1 to obtain a varnish with a resin concentration of 50%. A 1.6-thickness laminate and a copper-clad laminate were obtained in the same manner as in Example 1.

Comparative Example 2 Reaction was carried out at 120° C. for 4 hours using Fer/Fall 400 hours, linseed oil 230 hours, and 40% sulfuric acid 9.5 hours.

After the reaction, cool and add 530 ml of 37% formalin, 140 ml of octylphenol, 150 ml of nonylphenol, 24.
5% ammonia 21.0% and ethylenediamine 1.6
The reaction was carried out for 3 hours from 98 to 100 o'clock including evening. Water was removed under reduced pressure, and when the content reached 95%, dehydration was stopped and the mixture was cooled, and dissolved in a 2:1 mixed solvent of methanol and toluene to obtain a varnish with a resin concentration of 50%. A 1.6-thickness laminate and a copper-clad laminate were obtained according to the same process as in Example 1.

Comparative Example 3 Cresol 600g, squid oil 350g and 40% sulfuric acid 1
The reaction was carried out for 3 hours at 12,000 pm for 4.3 pm.

After the reaction, cool and add 760 hours of 37% formalin, 200 hours of nonylphenol, 200 hours of octylphenol, 24.
5% ammonia 29.0% and ethylenediamine 2.5%
98-10,000 including evening 2. I reacted for a while.
Water was removed under reduced pressure, and when the content reached 960%, dehydration was stopped and after cooling, it was dissolved in a mixed solvent of methanol and toluene in a ratio of 2:1 to obtain a varnish with a resin concentration of 50%. Following the same treatment as in Example 1, a 1.6-wall thick laminate and a copper-clad laminate were obtained.

Comparative Example 4 An oligomer of p-isoprobenylphenol having a composition of 9% by weight of p-isoprobenylphenol dimer, 1% by weight of trimer and tetramer, 300% of p-isoprobenylphenol, 264% of phenol
Yu and linseed oil 450 Yu to keep the loss at 8530, 4
2.9 tons of 0% sulfuric acid was placed in a bag and incubated for 2 hours.

Next, 380 g of synthetic cresol, 1 g of nonylphenol
After 10 minutes, 110 minutes of octylphenol, 630 minutes of 37% formalin, 23.0 hours of 24.5% ammonia and 2.0 hours of ethylene diamine were added and heated at 97 to 98°C for 2 hours. I reacted for a while. The content after removing water under reduced pressure is 90-9
Dehydration was stopped when the temperature reached 5qC. The obtained modified phenolic resin was in a non-uniform state in which the phenolic resin** and linseed oil were separated during gelation, and a laminate could not be obtained.

Table 1 shows the characteristics of the laminates obtained in Examples 1 to 7 and Comparative Examples 1 to 3 above.

Table 1 The method for the above characteristic test is as follows.

{1} Water absorption, insulation resistance, soldering heat resistance, and trichloride resistance were in accordance with JISC 6481.

'21 Punching workability conformed to ASTM D-614-44.

'31 Dimensional change rate was determined by heating a test piece of 140 skins x 13 ribs in length and inside for 2 hours at 100 minutes, then cooling it to room temperature.

■ For warping, test specimens of 14 mosquitoes x 13 ribs at 100qo.
After heating for a specific time, it was cooled to room temperature.

A straightedge was applied to the concave surface of the laminate, and the maximum distance was determined as the warpage of the test piece. Legs Only solder heat resistance was measured using copper-clad laminates.

Claims (1)

[Claims] 1. Isopropenylphenol or a non-conjugated isopropenylphenol oligomer represented by formula (II) or formula (III) alone or in a mixture with an iodine value of 140 or more in the presence or absence of phenols. After reacting with a drying oil having double bonds in the presence of an acidic catalyst, further reacting with phenols in the presence of an acidic catalyst, and then reacting the reaction product with formaldehyde as part of the phenol component. A method for producing a modified phenolic resin, characterized by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In formulas (II) and (III), n represents an integer from 0 to 18. ]