KR820001099B1 - Process for producing modified phenolic resin - Google Patents

Abstract

Modified phenolic resin was prepd. by reacting formaldehyde and reaction product (I) as one part of phenols. Thus, isopropenylphenal (or oligomer of isopropenylphenol) and drying oil (iodine number is 140, content of conjugated double bond is <= 50%) were reacted with phenols (or without phenols) in the presence of acid catalyst. The intermediate was reacted with phenols in the presence of acid catalyst to give compd (I).

Description

How to Prepare a Modified Phenolic Resin

The present invention relates to a method for producing a modified phenolic resin using dry oil having phenols introduced therein.

Conventionally, it is well known to obtain a laminate by impregnating and drying a resol-type phenolic resin obtained by reacting phenols such as phenol, cresol, and xylenol with formaldehyde, followed by laminating and heating and pressing them.

These laminated articles are widely used industrially as electrical insulation materials, structural materials, and the like. In particular, in recent years, the use as an electric device and an electronic device has increased significantly. Along with the simplification, miniaturization and high performance of the parts of these branches, the electrical insulation, heat resistance and alkali resistance are good, and the demand for laminated plates with balanced properties such as mechanical performance and punching characteristics is gradually increasing. I'm going.

Among them, the demand for printed wiring materials is extremely high, and in this field, the laminated board is punched out to a desired shape and used. However, since phenolic resins are generally hard and brittle, they should be heated and processed at 100 to 150 ° C during punching, resulting in dimensional changes due to expansion and contraction and warpage due to residual stress. The process of operation is complicated. For this reason, various methods are proposed in order to manufacture the phenol resin laminated board by which these faults were improved.

In particular, in order to maintain punchability, the use of modified phenol resins containing dry oils containing a large amount of conjugated double bonds such as copper oil has been proposed from the past.

However, the modification by simple addition of the drying oil improves the punchability, but the other performance is remarkably inferior. Therefore, a method of modifying and using the drying oil has been proposed. That is, a method has been proposed to improve the punchability and to increase the crosslinking density and to prevent the deterioration of other properties by reacting the dry oil containing a large amount of conjugated double bonds with phenols under an acidic catalyst and then reacting with formaldehyde. .

In this method, it is necessary to use kerosene containing a large amount of conjugated double bonds and having high chemical reactivity with phenols.

-엘레아 스테아르산(

-eleastearic acid) 81.5%(%는 중량 %를 나타냄, 이하 동일), 리놀산 6.7%, 올레인산 6.4%, 스테아르산 2.9%, 팔미트산 2.5%이다.One example of fatty acid composition of Chinese kerosene

Elea stearic acid

-eleastearic acid) 81.5% (% represents weight%, the same below), linoleic acid 6.7%, oleic acid 6.4%, stearic acid 2.9%, palmitic acid 2.5%.

Therefore, petroleum oil is easily added with phenols in the presence of an acidic catalyst because at least 80% of conjugated double bonds exist in the main chain thereof.

However, even in the case of using phenol-modified kinetics, the interlayer bonding force of the laminate is still weak and is likely to cause peeling. The reason for this is that the reaction between tungsten oil and phenol oil in the presence of an acidic catalyst is a pre-melk-kraft reaction, so the reaction is carried out under vigorous conditions, and therefore, the impregnation effect on the base material of the resin obtained by polymerizing tungsten oil is deteriorated. . Therefore, the resin thus obtained is not satisfactory for use in miniaturized precision parts.

It is extremely difficult to apply dry oil having a high content of non-conjugated double bonds such as isomerized linseed oil, dehydrated castor oil, toll oil and perilla oil and having a low content of conjugated double bonds to the above method. It is difficult.

For example, dehydrated castor oil is a glyceride of linoleic acid dehydrated with ricinoleic acid, the main component of castor oil, and examples of the fatty acid composition are 29% conjugated linoleic acid, 58% non-linoleic acid, 7.5% oleic acid, and ricinolein. 5.0% acid, 0.5% palmitic acid and stearic acid. As described above, the dry oil having a low content of the conjugated double bond has a poor chemical reactivity compared to the dry oil having a high content of the conjugated bond. Therefore, when these dry oils are used in the above method, the introduction of phenols into these dry oils is insufficient, and thus, sufficient crosslinking reaction does not proceed, so that laminates having excellent electrical performance, mechanical performance, chemical resistance, moisture resistance, and water resistance cannot be obtained. .

Japanese Patent Application Publication No. 45-35918 proposes a method for introducing phenol into dry oil having a low content of conjugated double defects with poor chemical reactivity. This method is a method of reacting dehydrated castor oil with phenol at high temperature in the presence of sulfuric acid catalyst, and a large amount of sulfuric acid must be used in the catalyst, and the moisture resistance, water resistance, and electrical properties of the retardable phenol resin produced by neutralization There is a difficult problem of damaging.

An object of the present invention is to provide a method for converting a dry oil having a low content of conjugated double bonds and a poorly reactive dry oil into phenol oils, which is effective for reforming a phenol resin by efficiently reacting with a phenol oil.

It is yet another object of the present invention to provide a method for producing a phenolic resin which enables a laminated plate having excellent punching property, electrical properties, moisture resistance, water resistance, chemical resistance, and mechanical properties using this modified dry oil. will be.

That is, the method of the present invention is a method for producing a modified phenolic resin using a dry oil incorporating phenols, wherein (a) a dry oil rule isopropenyl phenol having an iodine value of 140 or more and a conjugated double bond content of 50% or less. And / or introducing isopropenylphenol and / or its oligomers into the dry oil by reacting the oligomer with the presence or absence of phenols in the presence of an acidic catalyst, and (b) the isopropenol and / or The phenols are introduced by reacting the dry oil having the oligomer introduced therein with phenols and an acidic catalyst, and (c) isopropenylphenol and / or the dried oil having the oligomers and phenols obtained therein as part of the phenol component. It is a method characterized by reacting with formaldehyde.

Dry oil having an iodine value of 140 or more and a solid-liquid double bond content of 50% or less is unsaturated having an iodine value of 140 or more and having conjugated double bonds in various fatty acids constituting it. It means a synthetic dry oil obtained by separating and extracting vegetable and animal dry oils and vegetable oils and animal oils in which the amount of fatty acids is 50% or less of the amount of all-fat acid by isomerization, dehydration treatment or distillation and extraction.

Unsaturated fatty acids having conjugated double bonds are conjugated linoleic acid, isomerized conjugated linoleic acid, and isomerized conjugated linolenic acid.

Examples of dry oils having an iodine value of 140 or more and a conjugated double bond content of 50% or less (hereinafter referred to as "dry oils") include isomerized linseed oil, dehydrated castor oil, soil oil, linseed oil, forest oil, safflower oil and horse oil ( Iii) sardine oil, squid oil, etc.

Isomerized Amanine oil is a conjugated position of non-conjugated double bond by isomerization of linseed oil by alkali method, nickel method, sulfite method, iodine compound method, oxidation method, Tert-Butyl Hypochlorite method. It is a triglyceride of the conjugated linseed lactic acid obtained by moving to, and generally a conjugated double bond content is 10 to 40%.

For example, Nissei NC-101 (manufactured by Nissei Corporation, Japan). In the process of the present invention, linseed oil also broadly includes conjugated or unconjugated linolenic acid, a diester of ethylene glycol or monoester of monoalcohol of conjugated or unconjugated linolenic acid, which is a fatty acid component of isomerized linseed oil. It is.

Dehydrated castor oil is a triglyceride mainly composed of conjugated linoleic acid prepared by dehydrating castor oil in the presence of a catalyst or without catalyst. Generally, the conjugated double bond content is 20 to 50%. For example, the brand names "Heizen" (Japanese Soga Chemical Co., Ltd.), "DCO" (Japanese Itosei Company; Nippon Yujisha Co., Ltd., Japan) There is this. In the method of the present invention, dehydrated castor oil broadly includes esters of monohydric or dihydric alcohols of conjugated linoleic acid or a mixture with nonconjugated linoleic acid which is a fatty acid component of dehydrated castor oil.

The oils are oils of fatty acids, glycerides of tols, and oils of rosin. The properties of these materials vary depending on their history, usually with an iodine number of 150 or more and their conjugated double bond content of 15% or less.

Flaxseed oil, linseed oil, safflower oil, drink oil, sardine oil, and squid oil are mainly composed of triglycerides of linolenic acid and linoleic acid, and have an iodine value of 140 or more, but substantially no conjugated double bonds.

In the invention of the present invention, esters of linoleic acid, linoleic acid monohydric alcohol or dihydric alcohol which are fatty acid components of these oils are also broadly included.

Isopropenylphenol or its oligomer used in the present invention is a compound represented by the following formula (1) or (3) or (3).

In said Formula (1)-(3), n represents the integer of 0-18, and a hydroxyl group may be located in any of an ort, meta, or para position.

Among the oligomers, monomers, dimers and trimers can be synthesized as pure compounds, with oligomers of detramers or more coexisting as a mixture. These monomers and oligomers can be used individually or in the form of a mixture, respectively.

In the method of the present invention, the above-mentioned dry oil is first reacted with isopropenylphenol and / or with the above-mentioned dry oil by reacting the isopropenylphenol and / or its oligomer with an acidic catalyst in the presence or absence of phenols. Its oligomers are introduced (hereinafter referred to as "first stage denaturation").

The amount of isopropenylphenol and / or its oligomer used at this time is usually in the range of 0.1 to 2 weight times of the dry oil, and particularly preferably in the range of 0.3 to 1.5 weight times.

When using in more than 2 weight times, the improvement of the punching workability of the laminated board finally obtained becomes unsatisfactory.

In addition, when it is 0.1 weight times or more, the effect of denaturation is insufficient, and when the modified oil is provided for the production of the phenol resin, the dry oil is separated from the phenol resin to be uniform.

The acidic catalyst used in the first stage modification is an acid such as sulfuric acid, phosphoric acid, acetic acid, hydrochloric acid, boric acid, an organic acid such as p-toluenesulfonic acid, hydroxyl, or a sulfonic acid type or a carboxylic acid type cation exchange resin, and an acid having various strengths. You can use The amount used varies widely depending on the strength of the acid used, from 100 to 5000 ppm, in particular from 300 to the reactant, i.e. isopropenylphenol and / or its oligomers, and optionally mixtures of phenols and dry oils in combination. The range of 3000 ppm is preferable.

The first stage modification reaction is carried out by mixing isopropenylphenol and / or oligomers thereof, dry oils, phenols used in some cases, and acidic catalysts in the above ratios and holding them at 65 to 150 占 폚 for 0.5 to 3 hours.

A reaction at a lower temperature or shorter time than the above range is insufficient to introduce isopropenylphenol and / or its oligomers into the dry oil, and a reaction at a higher temperature or longer time than the above range causes polymerization of the dry oil. .

The completion of this modification reaction can be easily confirmed by finding out that the isopropenyl phenol component is substantially lost by the gas chromatography method.

Although the reaction of the first stage modification may be carried out without a solvent, extremely preferable results are obtained if the reaction is carried out in the presence of isopropenylphenol and / or various phenols other than the oligomers (hereinafter referred to as "phenols"). This is because these phenols are preferable in terms of dissolving isopropenylphenol oligomer to promote the modification reaction.

As these phenols, for example, butyl phenol, amyl phenol, hexyl phenol, octyl phenol, nonyl phenol, dodecyl phenol, phenyl phenol, styrenated phenol, cumyl phenol, bispetol A, phenol, cresol, xylenol, cadecool, Resorcin and the like.

It is sufficient to use these phenols up to 5 weight times of isopropenylphenol and / or the oligomer thereof, and no particular benefit is recognized even if the amount is higher than that.

The reaction product of the first stage modification obtained as described above is generally a brown liquid phase, and the modification product in the presence of the phenols is in a state in which the reaction product is uniformly dissolved in phenols.

In the method of the present invention, the reaction product of the first-stage modification obtained as described above is reacted again in the presence of phenols and an acidic catalyst to introduce phenol into dry oil into which isopropenylphenol and / or its oligomer is introduced. (Hereinafter referred to as "Second Stage Degeneration").

Phenol may coexist in the product of 1st stage modification, When using this product for reaction of 2nd stage modification, the said phenols may be previously removed from reaction product as needed, or it may be used as it is, without removing. Also good. In addition, it is not necessary to remove or neutralize the acidic catalyst used in the first stage modification reaction in advance.

As an example of the phenols used in a 2nd stage modification reaction, the thing similar to what was enumerated in description of a 1st stage modification reaction can be enumerated.

When phenols are used in the first stage modification, the phenols and the phenols used in the second stage modification may be the same kind or different kinds.

The amount of phenols used in the second stage modification reaction is related to the amount of phenols used in the first stage modification reaction. It is preferable that the sum total of the phenols normally used in 1st stage modification and 2nd stage modification is 0.1-5 times weight times, especially 0.5-2 weight times of dry oil. When less than 0.1 weight times, the mechanical strength and temperature-resistant water resistance of the laminated board obtained will become inadequate, and when more than 5 weight times, the punching workability improvement of the laminated board obtained will become inadequate.

The reaction product of the first modification contains an acidic catalyst used therein, and this catalyst alone is insufficient to perform the second stage modification reaction. Therefore, when performing 2nd stage modification | denaturation, it is necessary to add an acidic catalyst newly.

The acidic catalyst used herein is a strong acid such as p-toluenesulfonic acid, sulfuric acid, hydrochloric acid, etc., and its amount is 500 to 1000 ppm relative to the reactant, that is, the mixture of the reaction product of the first stage modification and the phenols added in the second stage modification. In particular, the range of 100-5000 ppm is preferable. If it is more than 100, the polymerization of dry oil is likely to occur, and if it is less than 100 ppm, the progress of the reaction becomes extremely difficult.

The reaction temperature and time for the second stage modification are preferably 0.5 to 3 hours at 80 to 140 ° C. This reaction condition is remarkably mild compared to the conditions of the modification of the conventional dry oil by phenols, that is, 1 to 6 hours at 80 to 180 ° C. The completion of the second stage modification reaction can be confirmed by finding out the reaction amount of phenols by gas chromatography and the like, and the termination of the reaction can be performed by neutralizing with ammonia or the like.

In this way, a reaction product of the second liquid phase modified in brown liquid is obtained.

As mentioned above, the structure of the reaction product at the time of performing reaction of a 1st stage and a 2nd stage modification is considered as follows.

In other words, sulfuric acid was used at a temperature of 100 ° C. in a reaction mixture in the presence of an acidic catalyst of 9,11-octadecaic acid, a fatty acid of dehydrated castor oil, and an acid catalyst of p-isopropenylphenol or an oligomer thereof. The reaction product in the case of reacting for 1 hour and performing the first stage modification is a structure in which 2 molecules of p-isopropenylphenol or 1 molecule of p-isopropenyl phenol dimer are added to 9,11-octadecadienoic acid methyl ester. It was found in gas chromatography and mass spectra. In addition, the analysis by infrared absorption spectrum and NMR spectrum of the product revealed that the conjugated diene of 9,11-octadecadienoic acid remained as it is. Therefore, the reaction product of the first stage modification of dehydrated castor oil is estimated to have the following chemical structure, for example.

Wherein R ₁ represents a glyceride residue,

를 나타내든지,R ₂ and R ₃ are all

Whether or not

Or R ₂ represents a hydrogen atom,

기를 나타낸다.R ₃ is

Group.

The reaction product described above was reacted with cresol and the reaction mixture containing cresol at 100 ° C. for 1 hour at 100 ° C. in the presence of 2800 ppm of sulfuric acid, followed by modification of the second stage to introduce two-molecule cresol. It is estimated to have the following chemical structure.

기를 나타낸다.Where R ₄ is

Group.

As described above, in the reaction of the first stage modification, when isopropenylphenol and / or its oligomer is reacted with dry oil, the unsaturated bond remains as it is.

This is a characteristic which is not seen when the dry oil is modified | denatured using phenols by a well-known method, and is seen only in modification | denaturation using isopropenyl phenol and / or its oligomers.

The modified product obtained by modifying dehydrated castor oil using phenols by a known method is a product of a so-called Friedel-Krafts reaction, as described in Japanese Patent Application Publication No. 45-35918, for example It is assumed that the following chemical structure.

기를 나타낸다.Where R ₆ is

Group.

In the method of this invention, the phenol resin is manufactured by making the reaction product of the 2nd stage modification obtained as mentioned above as a part of phenolic component, and reacting with formaldehyde.

In the production of this phenolic resin, the above-mentioned phenolic component is reacted under the diacidity of formaldehyde to obtain a novolak-type resin, partially acidic, and then alkalinized to continuously react with formaldehyde- Any method of obtaining a resol-type resin or obtaining a resol-type resin by making it alkaline after a modification reaction can be employ | adopted. In order to obtain a resol type resin, the acidic catalyst used for the modification remaining in the reaction product of the second stage modification is neutralized with ammonia, organic amines, and the like, followed by reaction with formaldehyde.

Regardless of any of the methods described above, when the phenol resin is produced by the method of the present invention, phenols are first added to the reaction product of the second stage modification as necessary to obtain a phenol component. The phenols added here are as having listed in description of reaction of a 1st stage and a 2nd stage modification.

However, the types of phenols used in the first and second stage modifications of the phenols added here may be mutually identical or different.

The ratio of the amount of phenols added to the reaction product of the second stage modification is the amount of total phenolic component (the amount of added phenols, isopropenylphenol used in the first and second stage modifications, and / or 10) to 100% by weight, preferably 20 to 60% by weight, based on the total amount of the oligomer and the amount of the phenols).

When dry oil is less than 10 weight%, the flexibility of the laminated board obtained is inadequate, and the improvement of punching workability is also not enough. If the amount is more than 100% by weight, the mechanical strength of the laminate becomes insufficient, which is not preferable. When the dry oil is in the range of 20 to 60% by weight, a resin is obtained that enables a laminated board having both punching workability, temperature resistance and water resistance.

As formaldehyde, formaldehyde aqueous solution, paraformaldehyde, etc. are generally used, and the amount thereof is generally in the range of 0.7 to 2.0 moles, preferably 0.8 to 1.6 moles, based on 1 mole of the entire phenol component. Outside of this range, when producing a laminated board, sufficient crosslinking density is not obtained, and mechanical strength, temperature resistance and water resistance become insufficient, which is not preferable.

As a catalyst for the reaction of the phenol component and formaldehyde, fumaric acid, hydroxyl acid, P-toluenesulfonic acid, sulfuric acid, and the like are used when preparing a novolak-type resin, and ammonia, methylamine, dimethylamine, tri Ethylamine, ethylenediamine, diethylamine, sodium hydroxide, potassium hydroxide and the like are used. In addition, a novolak-resol type resin can also be obtained by partially reacting in the presence of the above acid, followed by addition of the above-described base to react under basicity.

The amount of these catalysts varies greatly depending on their type, but is usually in the range of 0.1 to 2% for the total reaction system and 0.05 to 5% for the total reaction system for the base. In particular, when obtaining a resol type resin, using a mixture of ethylenediamine containing 10 to 20 mol% of ethylenediamine with ammonia and / or organic amines yields a resin which enables a laminate having excellent performance.

The phenolic component and formaldehyde are reacted in the presence of the above acid or base catalyst to produce a phenol resin. The reaction temperature and time at this time vary depending on the kind of phenols, the acid and the base, the amount and the like in the phenolic component. Generally, the range of 80 to 110 ° C and 1 to 5 hours is preferable. The end point of the reaction can be determined by measuring the gel time of the reaction mixture and confirming that the polyaddition condensation with the phenolic formaldehyde has reached the desired noon.

After the reaction reaches the end point, dehydration is continued to obtain a modified phenolic resin. The modified phenolic resin can be dissolved in aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol and ethanol, or a mixture thereof.

The varnish thus obtained is impregnated into a substrate made of paper, cloth, or the like, dried to form prepregs, polymerized, pressurized, and heated to obtain a laminate.

The features of the method according to the invention are described below.

Conventionally, dry oils which can be adapted to the production of modified phenolic resins are fixed to dry oils having a high content of conjugated double bonds, such as kerosene, for example, and even if the iodine value is 140 or more, dry oils having a conjugated double bond content of 50% or less are phenols. Because of its poor reactivity, it was extremely difficult to use for this purpose. However, according to the method of the present invention, isopropenylphenol and / or its oligomers and phenol oils can be efficiently introduced into dry oil having a low content of conjugated double bonds, and this can be used for producing modified phenol resins. That is, the present invention makes it possible to apply a dry oil having a low content of conjugated double bonds, which has been difficult to adapt to the production of a modified phenolic resin.

According to the method of the present invention, in the modification of the first stage, it is possible to introduce isopropenyl phenol and / or its oligomer into dry oil under relatively mild conditions, and the reaction product in this case is, for example, 4) As shown in the equation, the double bond of the dry oil is not lost and remains intact. This is a new fact that was never seen when modified using phenols by conventional methods, and is based on the specific reactivity of isopropenylphenol used in the present invention.

Since the double bond remains as it is in the reaction product of the first stage modification, an oxyphenyl group can be introduced again in the second stage modification by phenols. As described above, by modifying the dry oil in two stages, the amount of introduction of oxyphenyl nucleus per one molecule of the dry oil can be significantly increased compared to the conventional method, and the modification reaction can be made under mild conditions, thereby suppressing the synthesis of the dry oil. have.

In this way, when the reaction product of the second stage modification is reacted with formaldehyde as part of the phenolic component, the reactivity is good and methylolol is introduced at a high rate, and the obtained resin is easily uniform and stable varnish. You can do In the laminated board produced by superposing | polymerizing and prepress-heating the prepreg obtained using this varnish, the crosslinking density in resin increases, and the side bonding force of a laminated board also improves. As a result, the laminated sheet produced using the modified phenolic resin according to the present invention is a product which is rich in flexibility and excellent in punchability and excellent in electrical properties, temperature and water resistance, chemical resistance and mechanical properties.

Examples and Comparative Examples will be described below, where% is% by weight unless otherwise specified.

Example 1

270 g of a mixture of p-isopropenylphenol and its oligomer and 395 g of isomerized linseed oil having a composition of 3% p-isopropenylphenol 3%, dimer 87%, oligomer 10% or more of a trimer and 395 g of isomerized linseed oil were kept at 140 ° C. under stirring and 85% 1.7 g of phosphoric acid was added and stirred for 2 hours. After the reaction, the mixture was cooled and 193 g of synthetic cresol (m-form 60%, p-form 40%) and 5.5 g of 20% sulfuric acid were added, and the mixture was reacted at 100 ° C for 1 hour.

Subsequently, 430 g of phenol, 210 g of octyl phenol, 10 g of nonylphenol 210 g, 1010 g of 37% formalin, 32 g of 24.5% ammonia water, and 3.1 g of ethylenediamine were added and reacted at 98 to 100 ° C for 5 hours. Water was removed under reduced pressure, and after cooling, the mixture was dissolved in a mixed solvent of methol and toluene 2: 1 to obtain a varnish having a resin concentration of 50%.

The above resin varnish was impregnated into a 10 mils linter paper and dried to obtain a prepreg having a resin content of 45%. 9 sheets of this prepreg were polymerized and laminated molding (90 kg / cm <2>, 160 degreeC, 50 minutes) was obtained, and the laminated board was obtained. Moreover, the copper clad laminated board which fixed 35 micrometers copper foil was also produced separately from this. The thickness of all laminated boards was 1.6 mm.

Example 2

p-isopropenylphenol having a composition of 20% of p-isopropenylphenol, 69% of dimers, and 11% of oligomers of trimer and 11% thereof, and 270 g of nonylphenol 210g and 395 g of isomerized linseed oil were kept at 140 ° C under stirring. Then, 1.95 g of 40% p-toluenesulfonic acid was charged and stirred for 2 hours. After the reaction, the mixture was cooled and 190 g of synthetic cresol (m-form 60%, p-form 40%) and 4.0 g of 20% sulfuric acid were added and reacted at 100 ° C for 1 hour.

Subsequently, 430 g of phenol, 210 g of octylphenol, 1010 g of 37% formalin, 32 g of 24.5% ammonia water and 3.1 g of ethylenediamine were added thereto, and the mixture was reacted at 98 to 100 ° C for 4 hours. Water was removed under reduced pressure, and after cooling, the mixture was dissolved in a mixed solvent of methanol, toluene 2: 1 to obtain a varnish having a resin concentration of 50%.

According to the same treatment as in Example 1, a laminate having a thickness of 1.6 mm and a copper clad laminate were produced.

Example 3

200 g of isopropenylphenol having a composition of 10% p-isopropenylphenol, dimer 75%, oligomer 15% or more of a trimer and oligomer thereof, 177 g of phenol and 300 g of isomerized linseed oil were kept at 85 ° C. under stirring, 3.7 g of 20% sulfuric acid was added and stirred for 2 hours. After the reaction, the mixture was cooled and 150 g of synthetic cresol (m-form 60%, p-form 40%) and 3.0 g of 20% sulfuric acid were added thereto, and reacted at 100 ° C for 1 hour. Subsequently, 200 g of phenol, 289.6 g of nonylphenol, 845 g of 37% formalin, 30 g of 24.5% ammonia water, and 26 g of ethylenediamine were added and reacted at 98 to 100 ° C for 4 hours. Water was removed under reduced pressure, and after cooling, the mixture was dissolved in a mixed solvent of methanol, toluene 2: 1 to obtain a varnish having a resin concentration of 50%.

According to the same treatment as in Example 1, a laminate having a thickness of 1.6 mm and a copper clad laminate were produced.

Example 4

340 g of p-isopropenylphenol and 500 g of dehydrated castor oil were kept at 140 ° C under stirring, charged with 2.2 g of 85% phosphoric acid and stirred for 2 hours. After the reaction, the mixture was cooled and 244 g of synthetic cresol (m-form 60%, p-form 40%) and 7.0 g of 20% sulfuric acid were added, and the mixture was reacted at 100 ° C for 1 hour. Subsequently, 544 g of phenol, 266 g of octyphenol, 266 g of nonylphenol, 1278 g of 37% formalin, 41 g of 24.5% ammonia water, and 3.9 g of ethylenediamine were added and reacted at 98 to 100 ° C for 5 hours.

Water was removed under reduced pressure, and after cooling, it was dissolved in a mixed solvent of methanol and toluene 2: 1 to obtain a varnish having a resin concentration of 50%.

According to the same treatment as in Example 1, a laminate having a thickness of 1.6 mm and a copper clad laminate were produced.

Example 5

340 g of a mixture of p-isopropenylphenol and its oligomer having a composition of 3% p-isopropenylphenol 3%, dimer 87%, oligomer 10% of a trimer and oligomer thereof and 500 g dehydrated castor oil were kept at 140 ° C. under stirring, 85 Charge 2.2 g of% phosphoric acid and stir for 2 hours. After the reaction, the mixture was cooled, and then 127 g of phenol g resorcin and 7.2 g of 20% sulfuric acid were added thereto, and the mixture was reacted at 100 ° C for 1 hour.

Subsequently, 250 g of phenol, 2553 g of octylphenol, 260 g of nonylphenol, 1278 g of 37% formalin, 40.5 g of 24.5% ammonia water, and 4.3 g of ethylene diamine were added and reacted at 98 to 100 ° C for 4 hours. Water was removed under reduced pressure, and after cooling, it was dissolved in a mixed solvent of methanol and toluene 2: 1 to obtain a varnish having a resin concentration of 50%. According to the same treatment as in Example 1, a laminate having a thickness of 1.6 mm and a copper clad laminate were produced.

Example 6

350 g of p-isopropenylphenol having a composition of 98% isopropenylphenol, dimer and trimer 2%, and 510 g of linseed oil were kept at 120 DEG C under stirring, charged with 2.2 g of 40% sulfuric acid, and stirred for 2 hours. After the reaction, the mixture was cooled and reacted with 244 g of synthetic cresol (m-form 60%, p-form 40%) and 3.5 g of 40% sulfuric acid at 100 ° C for 1.5 hours.

Subsequently, 550 g of phenol, 530 g of nonylphenol, 1280 g of 37% formalin, 41 g of 24.5% ammonia and 4.0 g of ethyleneamine were added and reacted at 98 to 100 ° C for 5 hours.

Water was removed under reduced pressure, cooled, and dissolved in a mixed solvent of methanol, toluene 2: 1 to obtain a varnish having a resin concentration of 50%.

According to the same treatment as in Example 1, a laminate having a thickness of 1.6 mm and a copper clad laminate were produced.

Example 7

350 g of p-isopropenylphenol, 300 g of phenol and 600 g of linseed oil, each having a composition of 98% of p-isopropenylphenol, 75% of dimer and 2% of trimer, were stirred at 85 ° C and 3.1g of 40% sulfuric acid was added. Charged and stirred for 2.5 hours. After the reaction, 230 g of synthetic cresol (m-form 60%, p-form 40%) and 28 g of 40% sulfuric acid were added and reacted at 100 ° C. for 1.5 hours.

Subsequently, 350 g of phenol, 480 g of nonylphenol, 1400 g of 37% formalin, 50 g of 24.5% ammonia water and 4.3 g of ethylenediamine were added and reacted at 98 to 100 ° C for 4 hours.

Water was removed under reduced pressure, and after cooling, it was dissolved in a mixed solvent of methanol and toluene 2: 1 to obtain a varnish having a resin concentration of 50%.

Example 8

350 g of p-isopropenylphenol oligomers having a composition of 90% of p-isopropenylphenol dimers and 10% of oligomers of at least trimers, 270 g of nonylphenol and 500 g of linseed oil were kept at 140 ° C. with stirring and 2.5% of 85% phosphoric acid Was charged and stirred for 2 hours.

After the reaction, the mixture was cooled, and 250 g of synthetic cresol (m-form 60%, p-form 40%) and 2.3 g of 40% sulfuric acid were added, and the mixture was reacted at 100 ° C for 1 hour.

Subsequently, 540 g of phenol, 250 g of octylphenol, 1300 g of 37% formalin, 40.5 g of 24.5% ammonia water and 4.0 g of ethylenediamine were added and reacted at 98 to 100 ° C for 4 hours.

Water was removed under reduced pressure, cooled, and dissolved in a mixed solvent of methanol and toluene 2: 1 to obtain a varnish having a resin concentration of 50%. According to the same treatment as in Example 1, a laminate having a thickness of 1.6 mm and a copper clad laminate were produced.

Example 9

340 g of p-isopropenylphenol oligomer and 500 g of squid oil having a composition of 90% of p-isopropenyl phenol dimer, 10% of oligomer or more of trimer, and 500 g of squid oil were maintained under stirring at 100 ° C. Stirred for time. After the reaction, 200 g of synthetic cresol, 80 g of xylenol, and 3.8 g of 40% sulfuric acid were added thereto, and the mixture was reacted at 100 ° C for 1 hour.

Subsequently, 540g of phenol, 260g of octylphenol, 270g of nonylphenol, 1300g of 37% formalin, 41g of 24.5% ammonia water and 4.0g of ethylenediamine were added and reacted at 98 to 100 ° C for 4 hours. Water was removed under reduced pressure, and after cooling, the mixture was dissolved in a mixed solvent of methanol, toluene 2: 1 to obtain a varnish having a resin concentration of 50%.

According to the same treatment as in Example 1, a laminate having a thickness of 1.6 mm and a copper clad laminate were produced.

Example 10

350 g of p-isopropenylphenol, 266 g of nonylphenol and 650 g of toil oil glyceride having a composition of 98% of p-isopropenylphenol, dimer and trimer 2% were kept under stirring at 100 ° C., 5.5 g of 20% sulfuric acid. Was charged and stirred for 2 hours.

After the reaction, 240 g of synthetic cresol and 5.1 g of 20% sulfuric acid were added thereto, and the mixture was reacted at 100 ° C. for 1.3 hours. Subsequently, 560g of phenol, 270g of octylphenol, 1280g of 37% formalin, 41g of 24.5% ammonia water and 3.9g of ethylenediamine were added and reacted at 98 to 100 ° C for 3.5 hours. Water was removed under reduced pressure, and after cooling, it was dissolved in a mixed solvent of methanol, toluene 2: 1 to obtain a varnish having a resin concentration of 50%.

According to the same treatment as in Example 1, a laminate having a thickness of 1.6 mm and a copper clad laminate were produced.

Example 11

340 g of p-isopropenylphenol oligomer having a composition of 90% of p-isopropenylphenol dimer and 10% of oligomer of at least trimer and 500 g of toe oil glyceride were kept under stirring at 100 ° C., and 2.2 g of 85% phosphoric acid was charged. The mixture was stirred for 2 hours. After the reaction, the mixture was cooled, and 200 g of synthetic cresol, 80 g of xylenol, and 3.8 g of 40% sulfuric acid were added, and the mixture was reacted at 100 ° C. for 1 hour.

Subsequently, 540g of phenol, 260g of octylphenol, 270g of nonylphenol, 1300g of 37% formalin, 41g of 24.5% ammonia water and 4.0g of ethylenediamine were added and reacted at 98 to 100 ° C for 4 hours. Water was removed under reduced pressure, and after cooling, it was dissolved in a mixed solvent of methanol, toluene 2: 1 to obtain a varnish having a resin concentration of 50%.

According to the same treatment as in Example 1, a laminate having a thickness of 1.6 mm and a copper clad laminate were produced.

Example 12

340 g of p-isopropenylphenol oligomer having a composition of 90% of p-isopropenyl phenol dimer and 10% of oligomer of at least trimer and 500 g of tolu oil were kept at 140 ° C under stirring, and charged with 2.2 g of 85% phosphoric acid. Stirred for time. After the reaction, the mixture was cooled, and 130 g of phenol, 130 g of resorcin, and 3.6 g of 40% sulfuric acid were added thereto, and the mixture was reacted at 100 ° C. for 2 hours. Next, 500 g of phenol, 250 g of octylphenol, 280 g of nonylphenol, 1278 g of 37% formalin, 41 g of 24.5% ammonia water, and 4.3 g of ethylenediamine were added and reacted at 98 to 100 ° C for 4 hours. After the water was removed under reduced pressure and cooled, the resultant was dissolved in a mixed solvent of methanol, toluene 2: 1 to obtain a varnish having a resin concentration of 50%.

According to the same treatment as in Example 1, a laminate having a thickness of 1.6 mm and a copper clad laminate were produced.

Comparative Example 1

423 g of cresol, 210 g of isomerized oil and 13.7 g of 20% sulfuric acid were reacted at 120 ° C. for 3 hours.

After the reaction, the mixture was cooled, and 551 g of 37% formalin, 139 g of nonylphenol, 13.9 g of octylphenol, 20 g of 24.5% ammonia water and 1.6 g of ethylenediamine were added thereto, and the mixture was reacted at 97 to 98 ° C. for 2.5 hours.

Water was removed under reduced pressure, and after cooling, the mixture was dissolved in a mixed solvent of methanol, toluene 2: 1 to obtain a varnish having a resin concentration of 50%.

According to the same treatment as in Example 1, a laminate having a thickness of 1.6 mm and a copper clad laminate were produced.

Comparative Example 2

640 g of cresol, 300 g of dehydrated castor oil, and 19.5 g of 20% sulfuric acid were reacted at 120 ° C. for 3 hours. After the reaction, the mixture was cooled, and 757 g of 37% formalin, 200 g of nonylphenol, 200 g of octylphenol, 26.6 g of 24.5% ammonia water, and 2.3 g of ethylenediamine were added and reacted at 97 to 98 ° C. for 2.5 hours. Water was removed under reduced pressure, and after cooling, the mixture was dissolved in a mixed solvent of methanol, toluene 2: 1 to obtain a varnish having a resin concentration of 50%.

According to the same treatment as in Example 1, a laminate having a thickness of 1.6 mm and a copper clad laminate were produced.

Comparative Example 3

600 g of cresol, 350 g of linseed oil, and 14.3 g of 40% sulfuric acid were reacted at 120 ° C. for 3 hours. After the reaction, the mixture was cooled, and 760 g of 37% formalin, 200 g of nonylphenol, 200 g of octylphenol, 29.0 g of 24.5% ammonia water, and 2.5 g of ethylenediamine were added and reacted at 98 to 100 ° C. for 2.5 hours. Water was removed under reduced pressure, and after cooling, it was dissolved in a mixed solvent of methanol, toluene 2: 1 to obtain a varnish having a resin concentration of 50%.

According to the same treatment as in Example 1, a laminate having a thickness of 1.6 mm and a copper clad laminate were produced.

[Comparative Example 4]

300 g of p-isopropenylphenol oligomer having a composition of 90% of p-isopropenyl phenol dimer and 10% of oligomer of at least trimer, 264 g of phenol and 4450 g of linseed oil were maintained at 85 ° C. under stirring, and 2.9 g of 40% sulfuric acid was stirred. Charged and stirred for 2 hours. Subsequently, 380 g of synthetic cresol, 110 g of nonylphenyl 110 g octylphenol, 630 g of 37% formalin, 23.0% of 24.5% ammonia water and 2.0 g of ethylenediamine were added thereto and reacted at 97 to 98 ° C. for 2.5 hours to remove water under reduced pressure.

The modified phenolic resin thus obtained was in a heterogeneous state separated when the phenolic resin and linseed oil gelled, and thus a laminate could not be obtained.

[Comparative Example 5]

600 g of cresol, 350 g of toe oil glyceride, and 14.3 g of 40% sulfuric acid were reacted at 120 ° C. for 3 hours. After the reaction, the mixture was cooled, and 760 g of 37% formalin, 200 g of nonylphenol, 200 g of octylphenol, 29.0 g of 24.5% ammonia water, and 2.5 g of ethylenediamine were added and reacted at 98 to 100 ° C. for 2.5 hours.

Water was removed under reduced pressure, and after cooling, the mixture was dissolved in a mixed solvent of methanol, toluene 2: 1 to obtain a varnish having a resin concentration of 50%.

According to the same treatment as in Example 1, a laminate having a thickness of 1.6 mm and a copper clad laminate were produced.

Characteristic tests were carried out on the laminates produced in the above Examples and Comparative Examples, and the results are shown in the following table. This characteristic test was done by the following method.

(1) Absorption rate, insulation resistance, soldering heat resistance, and trichloroethylene according to JIS C 6481.

(2) Punchability was in accordance with ASTM D-614-44.

(3) The dimensional change rate was obtained by heating a test piece having a length and a width of 140 mm x 13 mm at 100 ° C. for 24 hours and cooling to room temperature to obtain a dimensional change.

(4) The warp was cooled to room temperature after heating the test piece of 140 mm x 13 mm at 100 degreeC for 24 hours. The straightest ruler was the maximum distance h with respect to the convex surface of the laminated board as follows:

Claims (1)

In the presence or absence of phenols, isopropenylphenol or a mixture of oligomers of isopropenylphenol and a dry oil having an oxo number of 140 or more and a conjugated double bond content of 50% or less in the presence of an acidic catalyst Thereafter, the phenols are reacted again in the presence of an acidic catalyst, and then the reaction product is reacted with formaldehyde as part of the phenol component.