JPH11217415A - Preparation of highly reactive modified-phen0l resin, and molding material, electric/electronic parts material, and semiconductor sealing material containing this highly reactive modified-phenol resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain by one process a low viscous resin for forming a molded article with excellent heat resistance, moisture resistance, corrosion resistance, adhesion, dimensional stability, and strengths, by mixing a heavy oil or a pitch, a phenol, and a formaldehyde compd. in the presence of an acid catalyst, then by stirring with heating them. SOLUTION: Mixing and stirring one mole of a heavy oil or a pitch having a true b. p. of 180-500 deg.C, and an aromatic hydrocarbon fraction value fa of 0.40-0.95, an aromatic hydrogen amt. value Ha of 20-80%; 0.3-10 moles of a phenol such as hydroxybenzene or hydroxynaphthalene; 0.2-9 moles in terms of formaldehyde of a formaldehyde; and 0.01-3 moles of an acid catalyst of a 15-50 mesh spherical, acidic cation-exchange resin at 50 deg.C or below, gives a mixture. This mixture is heated gradually up to 50-200 deg.C, then is subjected to polycondensation reaction for 15 min to 8 hr to give a highly reactive modified-phenol resin. This resin is used in combination with an epoxy resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention, when combined with an epoxy resin, improves the heat resistance, moisture resistance, corrosion resistance, adhesiveness, mechanical properties such as dimensional stability, strength, etc., in particular, moisture resistance and heat resistance. It is possible to easily produce a low-viscosity, highly reactive modified phenolic resin that becomes an excellent molded product in one step, and it is possible to use a polycondensation raw material that can be supplied stably and is cost-effective. The present invention relates to a method for producing a highly reactive modified phenol resin.

Further, the present invention relates to a modified phenol resin molding material containing a highly reactive modified phenol resin and an epoxy resin obtained by this method, a material for electric / electronic parts, and a semiconductor encapsulant.

[0003]

BACKGROUND OF THE INVENTION Phenolic resin molded products have excellent mechanical properties and have been widely used for a long time, either alone or in combination with other resins such as epoxy resins. In addition, there is a problem that the size and electric resistance are easily changed by absorbing moisture or alcohol, and the heat resistance, especially the oxidation resistance at high temperatures, is low.

[0004] In order to solve such a problem, various modifications of a phenol resin have been studied.
For example, many modified phenolic resins have been proposed which have improved resistance to deterioration or oxidation by light, chemicals or the like by modification using fats and oils, rosin or neutral aromatic compounds.

For example, Japanese Patent Application Laid-Open No. 61-235413 discloses that a phenolic resin having excellent heat resistance can be obtained by selecting a reaction component of a phenol-modified aromatic hydrocarbon resin. However, when a phenolic resin obtained by this method is used to produce a molded article, there is a disadvantage that the resin does not cure unless the resin is maintained at a high temperature for a long time.

JP-A-2-274714 discloses that conventional phenolic resins can be obtained by using inexpensive raw materials such as petroleum heavy oils or pitches as modifying materials and selecting special reaction conditions. It is disclosed that a modified phenol resin having no heat resistance, oxidation resistance and mechanical strength and useful as a molding material can be provided.

Further, Japanese Patent Application Laid-Open No. 4-145116 discloses that, when such a modified phenolic resin is produced, a crude modified phenolic resin obtained by polycondensing a starting compound is neutralized, washed and / or washed. It is disclosed that by performing an extraction treatment to neutralize and remove the acid remaining in the crude modified phenolic resin, it is possible to provide a modified phenolic resin that does not corrode metal members in contact with the resin. .

In this method for producing a modified phenol resin,
The acid remaining in the crude modified phenol resin is specifically neutralized and removed by a neutralization treatment using amines and a water washing treatment. However, the modified phenolic resin obtained in the purification step including such a neutralization treatment and a water-washing treatment is likely to have a neutralized substance remaining in the resin, and is used for products requiring severe heat resistance and corrosion resistance. Molding materials,
For example, it is still insufficient as a molding material for electric / electronic parts and a semiconductor sealing material.

JP-A-6-228257 teaches that a crude modified phenolic resin can be purified by a purification step including a special extraction treatment to provide a modified phenolic resin substantially containing no acid. . The modified phenol resin substantially free of acid obtained in such a purification step is combined with an epoxy resin,
A molding material having excellent heat resistance and moisture resistance and having no corrosiveness to metal can be provided.

[0010] However, these modified phenol resins have a high resin melt viscosity and are not suitable for rapidly and mass-producing molded articles having a complicated shape. There has been a demand for further improvements in mechanical properties such as properties and dimensional stability and strength.

Therefore, the present inventors have made it possible to react a petroleum heavy oil or a modified phenol resin obtained by polycondensing pitch, phenols and a formaldehyde polymer with phenols in the presence of an acid catalyst. A method for producing a highly reactive modified phenolic resin capable of producing a modified phenolic resin having a low resin melt viscosity and improved reactivity with an epoxy resin by reducing the molecular weight has been proposed (Japanese Patent Laid-Open No. 7-1995).
252339, Japanese Patent Application No. Hei 8-24173).

The highly reactive modified phenolic resin thus obtained has a high reactivity with the epoxy resin, a low resin melt viscosity and a good moldability. It is possible to provide a molding material having good moldability and excellent mechanical properties such as dimensional stability.

However, such a method for producing a modified phenol resin requires two steps, a polycondensation step and a low-molecular-weight step, so that the production step is complicated. By the way, in the soldering work generally performed at the time of the manufacture of electrical products, electricity, electronic components and semiconductors,
As a result, the modified phenol resin used as a resin material for electric and electronic parts or a semiconductor encapsulant is required to be further improved in terms of heat resistance.

Further, if the resin material has a high hygroscopicity, the water evaporates rapidly during the soldering operation, which may cause solder cracks and may corrode the composite metal material. Occurs.

[0015] In the field of electric, electronic parts or semiconductor encapsulants, the resin material is often compounded with a metal member, and the reliability of the product depends on the adhesiveness of the resin material to the metal member. Greatly affected.

Therefore, even with the modified phenolic resin, further improvement in hygroscopicity and improvement in adhesiveness have been demanded. In addition to the simplification of the production process described above and the improvement of the properties of the resulting modified phenolic resin, the raw oil is also reduced to the raw oil obtained by redistilling the bottom oil obtained in the conventional catalytic cracking process. In addition, there has been a high demand for feedstocks that can be obtained more efficiently and stably and are cost-effective.

The present inventors have conducted various studies and studies on a method for easily producing a highly reactive modified phenol resin having the above-mentioned excellent properties. By mixing the raw materials and performing polycondensation, in one step, having high reactivity with the epoxy resin,
Further, it has been found that a highly reactive modified phenol resin having a low viscosity can be obtained.

Further, the present inventors have found that a molding material obtained by combining this highly reactive modified phenolic resin and an epoxy resin has excellent moldability and excellent heat resistance, moisture resistance, corrosion resistance, adhesiveness and the like. It has been found that the molded article has particularly excellent heat resistance and moisture resistance, such as mechanical properties such as dimensional stability and strength.

The present invention has been made based on the findings of the inventors.

[0020]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and is intended to provide a highly reactive modified phenol resin having a low melt viscosity and a high reactivity with an epoxy resin. It is an object of the present invention to provide a method for producing a highly reactive modified phenol resin which can be produced and supplied easily and stably in one step.

Furthermore, the present invention comprises a highly reactive modified phenolic resin obtained by the above method and an epoxy resin,
Molding materials that can produce molded articles with particularly excellent heat resistance and moisture resistance, such as moldability, heat resistance, moisture resistance, corrosion resistance, adhesive strength, and mechanical strength such as dimensional stability, especially materials for electrical and electronic parts And a semiconductor sealing material.

[0022]

SUMMARY OF THE INVENTION In the method for producing a highly reactive modified phenolic resin according to the present invention, a specific amount of a heavy oil or pitch, a phenol, a formaldehyde compound, and an acid catalyst are mixed and then obtained. The mixture is heated and stirred to polycondensate these heavy oils or pitches, phenols and formaldehyde compounds.

In the present invention, the total polycondensation raw material (including the catalyst)
May be heated and stirred to carry out a polycondensation reaction (first method), or a polycondensation raw material (including a catalyst)
Heat and stir the mixture obtained by mixing specific ones of
At this time, the polycondensation may be performed while sequentially adding the remaining polycondensation raw materials (or catalysts) (second to sixth methods).

In the first to sixth methods for producing a highly reactive modified phenolic resin according to the present invention, petroleum and coal-based heavy oils or pitches, particularly a catalytic cracking step in a petroleum refining process or A specific distillate obtained in the pyrolysis step can be used, and an aromatic hydrocarbon compound can be further added as a raw material.

In the first to sixth methods for producing a highly reactive modified phenolic resin according to the present invention, a Bronsted acid selected from the group consisting of organic acids, inorganic acids and solid acids is used as the acid catalyst. Is desirable.

In the first to sixth methods for producing a highly reactive modified phenolic resin according to the present invention, the heavy oils or pitches are subjected to a treatment for removing a paraffin fraction as a low-reactive component. May be used.

Further, in the production method of the present invention, the highly reactive modified phenol resin obtained by the polycondensation reaction is subjected to (i) a step of removing unreacted components from the reaction mixture, and (ii) a catalyst residue. It is desirable to purify in at least one step selected from the group consisting of a step and (iii) a step of removing residual phenols and use it for various uses.

The modified phenolic resin molding material according to the present invention is characterized by containing a highly reactive modified phenolic resin obtained by the above-mentioned method and an epoxy resin.
This modified phenolic resin material may further contain an inorganic filler in addition to these resin components.

The material for electric / electronic parts according to the present invention is characterized by being obtained by molding the highly reactive modified phenolic resin molding material. Furthermore, a semiconductor encapsulant according to the present invention is characterized by being made of the above-mentioned highly reactive modified phenolic resin molding material.

[0030]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the present invention will be described more specifically. In the method for producing a highly reactive modified phenolic resin according to the present invention, a polycondensation reaction is performed by heating and stirring a mixture containing a specific amount of heavy oils or pitches, a formaldehyde compound, a phenol and an acid catalyst. Manufactures modified phenolic resins.

As the heavy oils or pitches used as a raw material in the polycondensation reaction of the present invention, any of petroleum-based and coal-based raw materials may be used. Examples of petroleum heavy oils or pitches include crude oil distillation residue, hydrogenolysis residue, catalytic cracking residue, naphtha or LPG pyrolysis residue, and vacuum distillation of these residues, and extras obtained by solvent extraction. And a specific distillate obtained in a cracking step such as thermal cracking and catalytic cracking in a petroleum refining process. Examples of the coal-based heavy oils or pitches include a specific fractionated component obtained by distilling coal tar in coal dry distillation, heavy oil in coal liquefaction, and the like.

In the case of petroleum heavy oils or pitches, it is preferable to select and use an appropriate aromatic hydrocarbon fraction fa value and aromatic ring hydrogen amount Ha value. For example, petroleum heavy oils or pitches are 0.40 to 0.95, preferably 0.5 to 0.8, more preferably 0.55 to 0.8.
A fa value of 0.75 and 20-80%, preferably 25-6
It is desirable to have a Ha value of 0%, more preferably 25-50%.

The fa value and the Ha value are calculated from the data obtained by ¹³ C-NMR measurement and the data obtained by ¹ H-NMR of petroleum heavy oils or pitches based on the following formulas.

[0034]

(Equation 1)

F of raw petroleum heavy oils or pitches
When the a value is less than 0.4, the aromatic component is reduced, and thus the effect of modifying the performance of the obtained modified phenolic resin is improved.
In particular, the effect of improving the heat resistance and oxidation resistance tends to decrease.

In the case of petroleum heavy oils or pitches having a fa value larger than 0.95, the reactivity between aromatic carbon and formaldehyde tends to be low. If the Ha value of the petroleum heavy oils or pitches as the raw material is less than 20%, the aromatic ring hydrogen content that reacts with formaldehyde decreases and the reactivity decreases, so the effect of modifying the performance of the phenol resin decreases. Tend to.

When a petroleum heavy oil or pitch having a Ha value of more than 80% is used as a raw material, the strength of the modified phenol resin tends to decrease. As such petroleum heavy oils or pitches, the use of distillate oil obtained in cracking processes such as thermal cracking and catalytic cracking in a petroleum refining process can be used to ensure stable supply of raw materials and reduction of pretreatment. From the viewpoint, it is particularly preferable.

In the petroleum refining process, the raw materials used in such a cracking step include, for example, tar sands, straight-run heavy gas oil obtained in the distillation step, atmospheric distillation residue oil and vacuum distillation residue, and desulfurization. Residual oil such as desulfurized reduced pressure heavy gas oil and desulfurized heavy oil obtained in the process, refined oil or intermediate refined oil can be exemplified. Of these residual oils, refined oils and intermediate refined oils, tar sands, atmospheric distillation residual oils and vacuum distillation residual oils are usually used in thermal cracking, and straight-run heavy gas oils and ordinary oils are used in catalytic cracking. Pressure distillation residue oil, desulfurized vacuum heavy gas oil, desulfurized heavy oil, and the like are used.

The catalytic cracking method and the thermal cracking method applied to the production of such a distillate are not particularly limited as long as a distillate having the desired physical properties described above can be obtained. Any method applied in the field may be used. Therefore, for example, catalytic cracking methods include moving bed catalytic cracking, airlift / thermophor catalytic cracking, food reflow catalytic cracking, fluidized bed catalytic cracking (FC
C) method, UOP catalytic cracking method, shell catalytic cracking method, Esso IV
Type catalytic cracking method and ortho-flow catalytic cracking method. The pyrolysis methods include delayed coking, fluid coking, flexi caulking, bisbreak, ureka, CHERY-P, and ACTIV.
Method, KKI method, coke fluidized bed coking method and ACR method.

In the cracking step, the catalytic cracked product and the thermal cracked product obtained by such a method are separated into fractions having various true boiling points and various compound compositions, and among them, the fractions suitable for the present invention are included. The distillate used has the above-mentioned aromatic hydrocarbon fraction fa value and aromatic ring hydrogen content Ha value, and has a true boiling point of 180 ° C or higher and 500 ° C or lower, preferably 180 or higher and 490 ° C or lower, and Preferably it is 190 or more and 490 ° C or less.

When a distillate having a true boiling point of less than 180 ° C. is used, the amount of the condensed polycyclic aromatic component contained in the raw material oil is small, and the reactivity is reduced. Such a distillate is a relatively heavy fraction extracted from the middle stage of the column other than the top and bottom of the distillate in the cracking step. Therefore, by using such a column middle distillate as a polycondensation raw material, in the catalytic cracking unit and the thermal cracking unit conventionally used in the cracking step of the petroleum refining process, the oil is extracted from the reaction tower and is sent to the rectification tower. The fraction obtained by the supply, that is, the intermediate refined oil and the circulating oil can be used as a raw material, and there is no need to distill the bottom oil again, so that the raw material can be supplied stably and at low cost. .

The fractionated fraction obtained by distillation of coal tar described above as a coal-based raw material is a fractionated fraction having a boiling point exceeding 200 ° C., preferably from 200 to 360 ° C.
Coal carbonization is an essential process in the coal chemical industry,
It is carried out to produce gas, coal tar and coke from coal.

The coal tar produced by such coal dry distillation can be classified into coke oven tar, horizontal retort tar, upright retort tar, generator furnace tar, water gas tar and the like according to the carbonization method.

Coal tar is classified into a high-temperature tar (900 to 1200 ° C.) and a low-temperature tar (450 to 700 ° C.) depending on the level of the carbonization temperature, and has different compositions and properties.

In the present invention, the fractionated component used as the coal-based heavy oils or pitches may be any coal tar distilled as long as it has the above-mentioned boiling point. From the viewpoint of a large amount, a high-temperature tar such as a coke oven tar is particularly suitable.

By distilling such coal tar, various fractionated components can be obtained. For example, when distilling coke oven tar obtained during coke production, tar gas oil (boiling point of about 94 to 178 ° C.), carbol gas oil (Carbonated oil: boiling point about 168-200 ° C), naphthalene oil (medium oil)
And absorption oil (boiling point about 202-223 ° C), heavy oil (boiling point about 218-314 ° C), anthracene oil (boiling point about 296 ° C).
To 360 ° C.) and pitch (residue: boiling point of about 450 ° C. or higher) and the like are obtained as fractionation components.

Among these, the fractional components having a boiling point exceeding 200 ° C. are naphthalene oil, absorbent oil, heavy oil, anthracene oil and pitch. As the heavy coal oils or pitches used in the present invention, such fractionated components having the above-mentioned boiling points may be used alone or in combination of two or more. Further, a specific component may be separated and recovered from the mixture of these fractionated components, and may be a mixture of, for example, a mixture of fractions having a boiling point higher than that of naphthalene oil, such as naphthalene, anthracene, tar acids and tar bases. Can be used.

However, coal-based (coal-tar) heavy oils or pitches generally have higher fa and Ha values than petroleum-based heavy oils, but do not react with formaldehyde compounds. From the progress, it is presumed that the coal-based feedstock has a fundamental difference in reactivity with the formaldehyde compound based on the molecular structure.

When a fractionated component having a boiling point of 200 ° C. or lower is used, the amount of the condensed polycyclic aromatic component contained in the feedstock oil is small, and the reactivity is reduced. In addition, coal liquefaction is performed to produce gasoline and the like from coal, and the coal is liquefied at a high temperature of about 500 ° C. and high-pressure hydrogen (200 to 700 atm).
This is a process in which a lower hydrocarbon is produced by various reactions such as coal structure cleavage, deoxygenation, sulfur removal, denitrification, and hydrogenation.

In the present invention, heavy oil produced by such coal liquefaction can also be used as the heavy coal oil or pitch, and this heavy oil can be used alone. It may be used by mixing with one or more of the above-mentioned coal tar fractionation components.

The coal-based heavy oils or pitches described above are products that are stably produced in a general process in the coal chemical industry. Therefore, by using these, stable and low-cost raw materials can be obtained. Can be supplied.

In the present invention, coal-based heavy oils or pitches may be used as they are, but acidic compounds such as phenols and carboxylic acids, and carbazoles, pyridines, anilines and quinolines. It is possible that some basic compounds, such as compounds, may be contained, and it is desirable to remove them.

The removal of such acidic compounds and basic compounds can be performed by, for example, extraction with sulfuric acid or caustic soda. The petroleum-based and coal-based heavy oils or pitches described above are not particularly limited in the number of condensed aromatic hydrocarbons constituting the heavy oils or pitches, but are mainly composed of 2 to 4 condensed polycyclic aromatic hydrocarbons. It is preferred to be constituted.
When the heavy oils or pitches contain a large amount of condensed polycyclic aromatic hydrocarbons having 5 or more rings, the condensed polycyclic aromatic hydrocarbons generally have a high boiling point, for example, a boiling point exceeding 450 ° C. Therefore, the boiling point of the raw material varies greatly, making it difficult to collect those having a narrow boiling point range, and as a result, it is difficult to stabilize the quality of the product. When the heavy oils or pitches are mainly monocyclic aromatic hydrocarbons, the reactivity with formaldehyde is low, and the effect of modifying the obtained phenol resin tends to be small.

These heavy oils or pitches are:
This may be used as it is in the polycondensation reaction, but a low-reactivity paraffin fraction, that is, having 15 to 4 carbon atoms including normal paraffin, isoparaffin, cycloparaffin and the like.
It may be used after performing the treatment for removing the saturated hydrocarbon fraction of 0.

The removal treatment of the paraffin fraction is as follows.
For example, by column chromatography according to a conventional method,
The reaction can be performed at 80 ° C to 120 ° C using furfural.

Examples of the filler to be packed in the column used in such column chromatography include activated alumina gel and silica gel. These fillers may be used alone or in combination of two or more.

The developing agents used in such chromatography include aliphatic saturated hydrocarbon compounds having 5 to 8 carbon atoms, such as n-pentane, n-hexane, n-heptane and n-octane; Ethers such as ethers,
Examples thereof include halogenated hydrocarbons such as chloroform and carbon tetrachloride, and alcohols such as methyl alcohol and ethyl alcohol. It is desirable to use two or more of these developing agents as appropriate.

By performing such a paraffin fraction removal treatment, the effect of modifying the performance of the modified phenolic resin can be improved, and the amount of unreacted components contained in the reaction mixture after the polycondensation reaction is reduced. To facilitate the purification process.

Examples of the phenol used as a raw material together with the heavy oils or pitches in the present invention include a hydroxybenzene compound and a hydroxynaphthalene compound. Examples of hydroxybenzene compounds include phenol, cresol, xylenol,
Resorcin, hydroquinone, catechol, phenylphenol, vinylphenol, nonylphenol, p-tert
-Butylphenol, bisphenol A, bisphenol F and the like. Examples of the hydroxynaphthalene compound include monohydroxynaphthalene compounds such as α-naphthol and β-naphthol, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene,
4-dihydroxynaphthalene and 2,3-dihydroxynaphthalene, 3,6-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,
Dihydroxynaphthalene compounds such as 7-dihydroxynaphthalene, and the above-mentioned mono- or dihydroxynaphthalene compounds having a substituent such as an alkyl group, an aromatic group, and a halogen atom, for example, 2-methyl-1-naphthol, 4-phenyl-1-naphthol, Examples thereof include 1-bromo-2-naphthol and 6-bromo-2-naphthol. These phenols may be used alone or in combination of two or more.

In the method for producing a highly reactive modified phenolic resin according to the present invention, such phenols are used in an amount of 0.3 mol or more based on 1 mol of heavy oils or pitches calculated from the average molecular weight, and 10 mol or less, preferably 9
It is desirable that the compound be used in an amount of not more than mol, more preferably not more than 8 mol.

When the phenols are used in an amount of less than 0.3 mol, the reactivity between heavy oils or pitches and formaldehyde is inferior to the reactivity between phenols and formaldehyde. Therefore, the crosslink density may not be sufficient, and the strength of the cured product may be lower than that of a general phenol resin. In particular, it has a low impact resistance and tends to exhibit a brittle defect. On the other hand, when the amount of the phenol exceeds 10 mol, the modifying effect by the modification of the phenol resin tends to be small.

The aromatic hydrocarbon compound used in the polycondensation reaction in the present invention is an aromatic hydrocarbon compound consisting only of a hydrocarbon group and an aromatic ring and a halide thereof, and has an effect of improving the moisture absorption resistance and adhesiveness of the resin. It has the effect of improving.

In the aromatic hydrocarbon compound used in the present invention, the aromatic ring may be a single ring or a condensed ring, and two or more identical or different aromatic rings may have a bond or a hydrocarbon. It may be linked by a linking group.

Examples of the hydrocarbon group which is a substituent of the aromatic ring include an alkyl group such as a methyl group and an ethyl group. Examples of the halogen atom contained in the halogenated aromatic hydrocarbon compound include fluorine, chlorine, bromine, and iodine.

Examples of the aromatic hydrocarbon compound include compounds having a non-condensed aromatic ring, specifically, benzene compounds substituted with an alkyl group such as toluene, o-xylene, m-xylene and p-xylene, and chlorobenzene. And halogenated benzene compounds such as o-chlorotoluene, m-chlorotoluene and p-chlorotoluene (the alkyl substituents of which may be substituted), and the like.

In the first to sixth methods for producing a highly reactive modified phenolic resin according to the present invention, such an aromatic hydrocarbon compound is added to one mole of heavy oils or pitches calculated from the average molecular weight. Thus, it is desirable to use 0.1 to 5 mol, preferably 0.5 to 3 mol, more preferably 0.5 to 2 mol.

When the aromatic hydrocarbon compound is used in an amount of less than 0.1 mol, the desired effect of improving the hygroscopicity and adhesiveness may not be obtained. on the other hand,
When the amount of the aromatic hydrocarbon compound exceeds 5 mol,
In some cases, a desired improvement effect in heat resistance may not be obtained.

The formaldehyde compound used in the polycondensation reaction of the present invention includes, in addition to formaldehyde,
Examples thereof include linear polymers such as paraformaldehyde and polyoxymethylene (especially oligomers), and cyclic polymers such as trioxane.

[0069] Such a formaldehyde compound acts as a crosslinking agent, and paraformaldehyde and formaldehyde are particularly preferred. The formaldehyde compound may be used by dissolving in a suitable solvent such as water. Therefore, formaldehyde may be used as an aqueous solution having an appropriate concentration, and is particularly preferably used as formalin (concentration of 35% or more).

In the method for producing a highly reactive modified phenolic resin according to the present invention, such a formaldehyde compound contains heavy oils or pitches 1 calculated from the average molecular weight.
It is used in an amount of not less than 0.2 mol, preferably not less than 0.5 mol, and not more than 9 mol, preferably not more than 7 mol, more preferably not more than 6 mol, in terms of formaldehyde, based on the mol. Is desirable.

When the amount of the formaldehyde compound is less than 0.2 mol per 1 mol of the heavy oils or pitches, the yield of the resin is lowered and the strength of the cured product of the modified phenol resin obtained is low, so that it is preferable. Absent. On the other hand, if it is more than 9 moles, the resulting modified phenolic resin is polymerized, and not only cannot obtain the desired viscosity, but also the reaction mixture may solidify extremely.

In the second to sixth methods for producing a phenolic resin according to the present invention, such a formaldehyde compound is not more than 1 mol, preferably not more than 0.1 mol, in terms of formaldehyde, per mol of phenol. 9 mol or less,
More preferably, it is used in an amount of 0.8 mol or less.

When the amount of the formaldehyde compound is more than 1 mol per 1 mol of the phenol, not only the resulting modified phenol resin is polymerized and the desired viscosity cannot be obtained but also the reaction mixture becomes solidified. Sometimes.

In the polycondensation reaction in the present invention, an acid catalyst is used for polycondensing heavy oils or pitches, formaldehyde compounds and phenols.
As such an acid catalyst, a Bronsted acid or a Lewis acid can be used, but a Bronsted acid is preferably used. Examples of Bronsted acids include oxalic acid,
Examples thereof include organic acids such as toluenesulfonic acid, xylenesulfonic acid and formic acid, inorganic acids such as hydrochloric acid and sulfuric acid, and solid acids such as acidic cation exchange resins.

Among such Bronsted acids, oxalic acid and sulfuric acid are preferable as the organic acid and the inorganic acid. The acidic cation exchange resin used as the solid acid is a resin in which a cation exchange group is covalently bonded to a base resin having a three-dimensional network structure.

Examples of the base resin include polystyrene, styrene / divinylbenzene copolymer, poly (meth) acrylic acid and polyacrylonitrile. Examples of the cation exchange group include a strongly acidic group such as a sulfonic acid group and a weakly acidic group such as a carboxyl group.

The acidic cation exchange resin as an acid catalyst is
Usually, it is desirable to use as a spherical body having a particle size of 15 to 50 mesh. Specific examples of such an acidic cation exchange resin include Diaion SKIB and PK21.
6, SK104 and PK208 (Mitsubishi Chemical Corp .: trade name), Amberlite IR-120B and IR-1
12 (manufactured by Organo: trade name), Dowex 50w
x8, HCR and HGR (manufactured by Dow Chemical Company, trade name), strong acidic cation exchange resins such as Duolite C-20 and C-25 (manufactured by Sumitomo Chemical Co., Ltd.), and Diaion WK10 (Mitsubishi Chemical Corporation) Weak acid cation exchange resins such as Amberlite IRc-50 (manufactured by Organo: trade name) and Duolite CS-101 (manufactured by Sumitomo Chemical Co., Ltd.).

When such a solid acid is used as an acid catalyst, the acid is not contained in a free state in the reaction mixture. Therefore, the solid acid is removed from the polycondensation reaction product by a simple method such as filtration. Thus, there is an advantage that a low-viscosity, high-reactivity modified phenol resin containing substantially no acid can be obtained.

In the first production method according to the present invention, such an acid catalyst is used in an amount of 0.01 mol or more, preferably 0.05 mol or more, per 1 mol of heavy oils or pitches calculated from the average molecular weight. It is used in an amount of not less than 3 mol and not more than 3 mol, preferably not more than 2 mol. In the second to sixth production methods, the acid catalyst is used in an amount of 0.01 mol or more and 3 mol or less, preferably 2.5 mol or less, based on 1 mol of the heavy oils or pitches calculated from the average molecular weight. , More preferably 2
It is desirable to use it in an amount of not more than mol. In addition,
When using an acidic cation exchange resin as the acid catalyst,
The amount of the acid catalyst is an amount in terms of a cation exchange group.

When the amount of the acid catalyst used is small, the reaction time tends to be long, and when the reaction temperature is not increased, the reaction tends to be insufficient. On the other hand, even if the amount of the acid catalyst used is large, the reaction speed is not so high, which may be disadvantageous in cost.

In the first method for producing a highly reactive modified phenolic resin according to the present invention, the specific amounts of the raw materials and the acid catalyst described above are mixed in advance, and the resulting mixture is heated and stirred to carry out the polycondensation reaction. I do.

In such a polycondensation reaction of heavy oils or pitches, phenols and formaldehyde compounds in the presence of an acid catalyst, the mixing temperature and mixing time of the raw materials are adjusted according to the raw material composition and the properties of the obtained resin. Also, the polycondensation reaction temperature and the reaction time are controlled. It goes without saying that the reaction temperature and the reaction time also affect each other.

Such a polycondensation reaction can be carried out, for example, by the following method. That is, first, the specific amount of heavy oils or pitches, phenols, formaldehyde compounds and acid catalysts are stirred at a temperature at which the polycondensation reaction does not proceed, for example, at a temperature of 50 ° C. or less, preferably 40 to 50 ° C. Mix evenly.

Next, the obtained mixture was mixed with 50 to 200
° C, preferably 80 to 200 ° C, more preferably 80 to 200 ° C.
Gradually raise the temperature to 180 ° C, 15 minutes to 8 hours,
The polycondensation reaction is preferably performed for 30 minutes to 6 hours.

The mixing of the raw materials for polymerization is not particularly limited as long as a uniform mixture can be obtained before the polycondensation reaction proceeds. For example, the mixing may be performed while the temperature is gradually raised to the polycondensation reaction temperature. In the second to sixth methods for producing a highly reactive modified phenolic resin according to the present invention, in the polycondensation reaction using the raw material and the acid catalyst described above, heavy oils or pitches,
At least one of an acid catalyst and a formaldehyde compound is added sequentially.

That is, in the second method for producing a highly reactive modified phenolic resin according to the present invention, first, heavy oils or pitches and phenols are mixed and heated and stirred. Are sequentially added with a formaldehyde compound and an acid catalyst. In this production method, the acid catalyst and the total amount of the formaldehyde compound may be sequentially added. When a part of the formaldehyde compound is mixed with the mixture under heating and stirring, the remaining formaldehyde compound is sequentially added together with the acid catalyst.

In the third method for producing a highly reactive modified phenol resin according to the present invention, first, a heavy oil or pitch, a phenol, and a formaldehyde compound are mixed, heated and stirred, and then heated. Only the acid catalyst was sequentially added to the stirring mixture.

In the fourth method for producing a highly reactive modified phenolic resin according to the present invention, first, petroleum heavy oils or pitches, phenols, and an acid catalyst are mixed, heated and stirred, and then mixed. Only the formaldehyde compound is sequentially added to the heated and stirred mixture.

In the fifth method for producing a highly reactive modified phenolic resin according to the present invention, first, heavy oils or pitches and an acid catalyst are mixed and heated with stirring, and then the mixture during heating and stirring is mixed. Phenols and a formaldehyde compound are successively added.

In the sixth method for producing a highly reactive modified phenol resin according to the present invention, first, a formaldehyde compound and an acid catalyst are mixed and heated and stirred. Oils or pitches and phenols are added sequentially.

In the second to sixth methods for producing a highly reactive modified phenolic resin according to the present invention, the sequential addition of heavy oils or pitches, an acid catalyst and / or a formaldehyde compound may be carried out by a method such as dropping. It is desirable to carry out for 10 to 120 minutes, preferably for 20 to 80 minutes.

[0092] If the addition time is less than 10 minutes, the reaction proceeds rapidly and the heat generation becomes intense, making it difficult to control the temperature. On the other hand, when the rate of addition exceeds 120 minutes, the addition takes a long time and the reaction time tends to be long.

In the polycondensation reaction of the present invention, the sequential addition to the mixture under heating and stirring is not particularly limited at the start time, and the mixture under heating and stirring is uniformly mixed and the temperature is stabilized. Just start.

In the second method for producing a modified phenolic resin according to the present invention, the formaldehyde compound is sequentially added together with the acid catalyst. However, the sequential addition of the formaldehyde compound is synchronized with the sequential addition of the acid catalyst. It may start and end, and it is desirable to mix both at this time. Also, the sequential addition of a formaldehyde compound
It may be carried out separately from the acid catalyst. In this case, it may be synchronized with the sequential addition of the acid catalyst, or may be started, for example, by being shifted earlier than the acid catalyst.

The polycondensation reaction of heavy oils or pitches, phenols and formaldehyde compounds in the presence of an acid catalyst, which is carried out by adding a raw material and an acid catalyst in this order, comprises the steps of: The reaction temperature and reaction time are controlled according to the speed, the properties of the obtained resin, and the like. It goes without saying that the reaction temperature and the reaction time also affect each other.

In the second to fourth methods for producing a highly reactive modified phenolic resin according to the present invention, such a polycondensation reaction can be carried out, for example, by the following method.
That is, first, a raw material containing heavy oils or pitches and phenols and, if desired, at least a part of a formaldehyde compound or an acid catalyst, is added at 30 to 120 ° C., preferably at 30 to 120 ° C. before the addition of the formaldehyde compound and / or the acid catalyst. Heat and stir at a temperature of 40-80 ° C to mix uniformly.

Next, a formaldehyde compound and / or
Alternatively, the acid catalyst is added sequentially, noting the sharp rise in temperature of the reaction mixture. After the addition of the formaldehyde compound and / or the acid catalyst is completed, the reaction mixture is added to the mixture for 50 minutes.
To 200 ° C., preferably 80 to 200 ° C., more preferably 80 to 180 ° C., for 15 minutes to 8 hours,
The reaction is preferably performed for 30 minutes to 6 hours. The fifth and sixth manufacturing methods can be performed under the same conditions.

In the first to sixth production methods of the present invention, such polycondensation reaction of heavy oils or pitches, formaldehyde compounds and phenols can be carried out without using a solvent. The viscosity of the reaction mixture (reaction system) may be reduced by using an appropriate solvent so that a uniform reaction occurs.

Examples of such a solvent include nitrated aromatic hydrocarbons such as nitrobenzene; nitrated aliphatic hydrocarbons such as nitroethane and nitropropane;
Halogenated aliphatic hydrocarbons such as perchrene, trichlene and carbon tetrachloride can be mentioned.

The method for producing a highly reactive modified phenolic resin according to the present invention described above has a lower molecular weight than the method for producing a highly reactive modified phenolic resin disclosed in JP-A-7-252339. No steps are required, and the number of steps is significantly reduced.

The highly reactive modified phenolic resin according to the present invention is excellent in moldability due to low resin melt viscosity, has high reactivity with epoxy resin, and has high reactivity as disclosed in JP-A-7-252339. It has better heat resistance than reactive modified phenolic resin. In addition, the highly reactive modified phenolic resin of the present invention has excellent adhesiveness and low hygroscopicity when an aromatic hydrocarbon compound is contained in the raw material. A modified phenolic resin molding material having excellent mechanical properties such as dimensional stability and strength, moisture resistance and heat resistance, and exhibiting excellent adhesiveness and low moisture absorption can be provided.

The highly reactive modified phenolic resin thus produced can be used for various applications. However, since there is a possibility that unreacted components, acid catalysts and the like remain in the resin, the high reactive modified phenolic resin is appropriately used. It is desirable to remove the unreacted components, low molecular components, acid catalyst, reaction solvent and the like by performing a purification treatment.

As a method for purifying a reaction mixture, ie, a crude highly reactive modified phenol resin containing an acid catalyst, unreacted substances, low molecular components and a reaction solvent, for example, (i) removing unreacted components from the reaction mixture A purification treatment, (ii) a purification treatment for removing a catalyst residue from the reaction mixture, and (ii)
i) Purification treatment for removing residual phenols by any of steam distillation, nitrogen gas blowing and vacuum distillation.

In the above-mentioned refining treatment (i), of the components contained in heavy oils or pitches used as a raw material,
Components that have low reactivity and remain in the reaction product in an unreacted state or in an insufficiently reacted state and a reaction solvent appropriately used in the reaction are removed.

In the first treatment for removing the unreacted components from the reaction mixture, the polycondensation reaction product obtained by the first to sixth polycondensation methods and a specific extraction solvent are mixed with each other so that the reaction mixture is in a fluid state. Unreacted substances contained in the reaction mixture upon contact at a certain temperature, such as low-reactive substances contained in heavy oils or pitches, or low-molecular components remaining in an insufficiently reacted state in addition thereto Is removed.

Here, the temperature at which the reaction mixture enters a fluid state is a temperature at which the reaction mixture forms a liquid-liquid two-phase with the extraction solvent and can maintain the liquid state, or the temperature at which the reaction mixture is dissolved in the extraction solvent and becomes liquid. This is the temperature at which the state can be maintained. By heating the reaction mixture to a temperature at which a fluid state can be maintained and bringing it into contact with the extraction solvent, the rate of elution of unreacted substances contained in the reaction mixture into the extraction solvent and the elution efficiency can be increased.

The extraction solvent used in the first treatment is as follows:
Form a liquid-liquid two-phase system or solution with the reaction mixture based on the modified phenolic resin at the above-mentioned temperature, and form a liquid-liquid two-phase system or a liquid-solid two-phase system at a lower temperature. A solvent, specifically selected from aliphatic hydrocarbons having 6 to 20 carbon atoms, alicyclic hydrocarbons having 6 to 20 carbon atoms, aromatic hydrocarbons having 6 to 20 carbon atoms, and aliphatic petroleum fractions You.

Examples of the aliphatic hydrocarbon include hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane and the like.

The alicyclic hydrocarbon includes, for example, cyclohexane, cycloheptane, cyclooctane and the like. Examples of the aromatic hydrocarbon include benzene, toluene, xylene, and the like.

Examples of the aliphatic petroleum fraction include kerosene and naphtha. These compounds may be used alone or in combination of two or more as an extraction solvent. Of these, n-heptane, n-octane and naphtha are particularly preferred.

In the present invention, such contact between the extraction solvent and the reaction mixture can be carried out by introducing both into the same vessel and then heating the mixture to a temperature at which the reaction mixture becomes fluid. Incidentally, the contact between the extraction solvent and the reaction mixture may be started by pouring the extraction solvent at the same temperature into the reaction mixture after heating to a desired temperature, and furthermore, by starting by charging the former into the latter. Is also good.

In addition, when the reaction mixture and the extraction solvent are brought into contact with each other, by stirring and mixing both, the extraction efficiency of unreacted substances can be improved. In particular, when the reaction mixture and the extraction solvent form a liquid-liquid two-layer, an increase in the contact area between the two by stirring promotes rapid and efficient extraction of unreacted substances.

The first treatment may be performed while refluxing, or may be performed in a closed system without reflux in order to prevent the amount of the extraction solvent from being reduced by evaporation.
In the first treatment, the contact between the reaction mixture and the extraction solvent is carried out, for example, at 50 to 200 ° C., preferably 70 to 130 ° C.
C., more preferably at 80 to 120.degree.

The amount of the extraction solvent used in the first treatment can be appropriately selected depending on the amount of unreacted substances contained in the reaction mixture, the amount of unreacted substances to be removed by one purification treatment, and the like. For example, for 1 g of the weight of the reaction mixture,
It is desirable to use 0.5 to 4 ml, preferably 1 to 2 ml.

In the first treatment, the contact time is not particularly limited, but is usually 10 to 60 minutes, particularly 20 to 30 minutes.
It can be done quickly in minutes. After completion of the contact operation described above, the reaction mixture and the extraction solvent are allowed to stand while cooling or cooling to form a liquid-liquid two-phase system or a liquid-solid two-phase system. Then, by separating the extraction solvent by decantation or the like, unreacted substances dissolved in this solvent can be easily removed from the reaction mixture.

In the first treatment, such a contacting operation and a separating operation are performed in this order. However, the number of times of this operation is not particularly limited, and it may be once, and the extraction solvent is renewed. It may be repeated several times.

According to such a first treatment, since the extraction operation is performed while the reaction mixture is in a fluid state, unreacted substances can be efficiently removed with a small amount of solvent, and the liquid mixture can be removed during the contact operation. Since it is not necessary to maintain a solid two-phase system, the setting of the contact temperature becomes easy.

In another treatment (second treatment) that can be applied in the purification step (i), first, the reaction mixture obtained by the polycondensation reaction or the crude highly reactive modified phenol resin is mixed with a soluble mixture of the reaction mixture. Dissolve in solvent.

As such a soluble solvent, for example,
Toluene; a mixed solvent of toluene and an alcohol such as ethyl alcohol; and a mixed solvent of toluene and a ketone such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and ethers such as toluene and tetrahydrofuran, diethyl ether and methyl tertiary butyl ether And a mixed solvent thereof.

The solution obtained by dissolving the crude highly reactive modified phenolic resin in these soluble solvents has a low viscosity and good operability, so that the purification operation is facilitated. Next, the solution thus obtained contains at least one compound selected from the group consisting of aliphatic hydrocarbons having 10 or less carbon atoms, alicyclic hydrocarbons having 10 or less carbon atoms, and aliphatic petroleum fractions. Is charged into a solvent containing As a result, the resin main component is precipitated, and components soluble in the solvent, that is, unreacted and low-reacted components, a reaction solvent during the polycondensation reaction, and the like are removed.

Examples of such a hydrocarbon solvent include aliphatic or alicyclic hydrocarbons such as pentane, hexane, heptane and cyclohexane, and aliphatic petroleum fractions such as naphtha. Particularly, n-hexane And naphtha are preferred. The highly reactive modified phenolic resin obtained in the second treatment of the purification step (i) is in a powder form.

In still another treatment (third treatment) of the purification step (i), first, the reaction mixture obtained by the polycondensation reaction or the crude highly reactive modified phenol resin is dissolved in a solvent soluble in the reaction mixture. .

Examples of such a reaction mixture soluble solvent include acetonitrile, methanol, dimethyl sulfoxide and the like. Next, the obtained solution is separated from the solution containing the highly reactive modified phenol resin to form a liquid-liquid two-layer solvent system, and is brought into contact with an extraction solvent that dissolves unreacted components. Insoluble components, that is, unreacted components, components remaining after a low reaction, and a reaction solvent during the polycondensation reaction are extracted and removed.

[0124] Such an extraction solvent can be appropriately selected according to the soluble solvent. For example, when acetonitrile, methanol or dimethyl sulfoxide is used as the soluble solvent, aliphatic hydrocarbons having 10 or less carbon atoms, carbon Solvent containing at least one compound selected from the group consisting of alicyclic hydrocarbons having a number of 10 or less and an aliphatic petroleum fraction: n-hexane, heavy naphtha (boiling point 80 to
150 ° C.).

The volume ratio (extraction solvent / solution) of the extraction solvent to the crude highly reactive modified phenol resin solution is not particularly limited, but is usually 10/90 to 90/10, preferably 2/90.
0/80 to 80/20.

According to the third treatment, the efficiency of removing unreacted components and the like is increased, and the extraction solvent can be easily separated and removed after the extraction. In another treatment (fourth treatment) of the purification step (i), first, the reaction mixture obtained by the polycondensation reaction or the crude highly reactive modified phenolic resin is allowed to stand while being heated and melted.

By allowing the crude highly reactive modified phenol resin to stand in a heated state, unreacted components, components remaining after a low reaction, and the reaction solvent during the polycondensation reaction are separated from the modified phenol resin as a supernatant liquid. It will be.

In the fourth treatment, the crude high-reactivity modified phenolic resin is usually used at 70 to 200 ° C., preferably at 80 to 200 ° C.
The composition is heated and melted at a temperature of 80 ° C., more preferably 80 to 150 ° C., and is usually allowed to stand for 15 minutes to 4 hours, preferably 20 minutes to 4 hours.

According to the fourth treatment, the supernatant containing unreacted components and the like can be easily separated and removed from the highly reactive modified phenol resin by decantation. There is an advantage that it is no longer necessary to use.

In still another treatment (fifth treatment) of the purification step (i), the reaction mixture obtained by the polycondensation reaction or the crude high-reactivity modified phenol resin is directly used in the form of 10 ^-7 to 1-7.
The molecular distillation is performed under a high vacuum of 0 ^-4 mmHg to remove unreacted components, components remaining after a low reaction, a reaction solvent during the polycondensation reaction, and the like.

In the fifth treatment, since a highly reactive modified phenol resin in a dry state containing no unreacted components or the like can be directly obtained, it is necessary to separate the solvent containing the unreacted components or the like. It has the advantage of not being.

In the last example (sixth treatment) applicable in the purification step (i), first, a crude high-reactivity modified phenol resin is dissolved in a soluble solvent to prepare a reaction mixture solution. Examples of such a soluble solvent include the organic solvents exemplified in the first treatment, and a mixed solvent of toluene and ketones, particularly a mixed solvent of toluene and methyl isobutyl ketone, is suitably used.

Next, the obtained solution was mixed with water and allowed to stand to form a three-layer solvent system consisting of a highly reactive modified phenol resin solution layer, an aqueous layer, and an unreacted oil layer in order from the bottom. The unreacted oil layer and aqueous layer are removed.

According to the sixth treatment, since the unreacted oil layer completely separates the highly reactive modified phenol resin layer via water, the unreacted oil layer can be surely and easily removed. Since the catalyst is extracted into the aqueous layer, there is an advantage that the subsequent purification step (ii) is facilitated.

In the sixth treatment, the amount of the soluble solvent is adjusted so that the specific gravity of the highly reactive modified phenol resin solution layer is heavier than that of water. If the amount of the soluble solvent is too large, the specific gravity of the highly reactive modified phenol resin layer becomes too light, and
And water becomes the lowermost layer, which is not preferable.

The first to sixth treatments in the purification step (i) may be performed alone or in combination of two or more. The modified phenolic resin from which unreacted substances have been removed to a high degree in this manner has the advantage that the weight does not decrease when heated and the reactivity with the epoxy resin is improved.

When the second process is not performed,
In the first and third to sixth treatments, the crude high-reactivity modified phenolic resin is a group consisting of an aliphatic hydrocarbon having 10 or less carbon atoms, an alicyclic hydrocarbon having 10 or less carbon atoms, and an aliphatic petroleum fraction. May be combined with a process of charging a solvent containing at least one compound selected from the group consisting of:

Further, the first to the first steps applied to the purification step (i)
According to the first treatment of the sixth treatment, the polycondensation reaction mixture and a specific extraction solvent are brought into contact with each other at a temperature at which the polycondensation reaction mixture is in a fluidized state, and the uncondensed polycondensation reaction is carried out. Since the reaction product is extracted and removed with the extraction solvent, the unreacted product extraction conditions can be easily set, for example, as compared with the second process in which the polycondensation reaction product is put into the extraction solvent and precipitated as a solid. In addition, since the efficiency of removing unreacted substances is high and no solvent is used, the operation of extracting unreacted substances can be simplified and the cost of purifying the modified phenol resin can be reduced.

In the above-mentioned purification treatment (ii), the acid catalyst remaining in the reaction mixture is removed, and a highly reactive modified phenol resin containing substantially no acid is obtained. In such a purification treatment (ii), when an organic acid and an inorganic acid are used as the acid catalyst, the reaction mixture may be used as it is or dissolved in a specific solvent and washed with water or washed with an aqueous alkali solution to remove the catalyst residue. Is carried out. In addition, according to the washing using the alkaline aqueous solution, together with the acid catalyst,
There is an advantage that unreacted phenols can be removed.

Solvents for dissolving the reaction mixture are not particularly limited, for example, alcohols such as methyl alcohol and ethyl alcohol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; tetrahydrofuran, diethyl ether and methyl tertiary Ethers such as butyl ether; aromatic compounds such as toluene and xylene; and mixed solvents thereof.

Examples of the alkali used for preparing the aqueous alkali solution include sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, and sodium hydrogen carbonate.

In the purification treatment (ii), when a solid acid is used as the acid catalyst, the catalyst residue can be easily removed by filtering the reaction mixture. This purification treatment (ii)
Also, in order to improve work operability such as filtration,
The reaction mixture may be dissolved in the above solvent.

In the purification treatment (ii), when oxalic acid is used as the acid catalyst, oxalic acid can be decomposed and removed by heating the reaction mixture to a temperature of 180 ° C. or higher.

The above purification treatments (i) and (ii)
It can be done in any order. Further purification (ii
In (i), the reaction mixture is subjected to steam distillation, nitrogen blowing, vacuum distillation, or the like as it is, or after removing unreacted components and acid catalysts in purification treatment (i) and / or purification treatment (ii). Removes the remaining unreacted phenols. Unreacted phenols may be removed by any one of these methods or a combination of these methods.

By performing such a purification treatment to remove an acid catalyst, unreacted substances, a reaction solvent and the like which may remain in the resin, the resin is substantially free of acid and therefore has no corrosiveness to metals. In addition, since the reactivity with the epoxy resin is improved, a highly reactive modified phenol resin having improved heat resistance and dimensional stability can be obtained. In the present specification, “substantially contains no acid” means that no acid or the like remains at all, or even if a very small amount remains, it does not show significant corrosiveness to metals.

The modified phenolic resin molding material according to the present invention contains an epoxy resin together with the highly reactive modified phenolic resin obtained by the method for producing a highly reactive modified phenolic resin according to the present invention. The epoxy resin has a small molding shrinkage, and is excellent in heat resistance, abrasion resistance, chemical resistance, and electrical insulation, and is used in combination with a curing agent and / or a curing accelerator, if necessary.

Examples of such epoxy resins include glycidyl ether type, glycidyl ester type, glycidylamine type, mixed type and alicyclic type epoxy resins.

More specifically, the glycidyl ether type (phenol type) includes bisphenol A type epoxy resin, biphenyl type epoxy resin, bisphenol F
Type epoxy resin, tetrabromobisphenol A type epoxy resin, tetraphenylolethane type epoxy resin,
Phenol novolak type epoxy resin, o-cresol novolak type epoxy resin, etc .; glycidyl ether type (alcohol type) includes polypropylene glycol type epoxy resin, hydrogenated bisphenol A type epoxy resin, etc .; Phthalic acid type epoxy resin, dimer acid type epoxy resin, etc .; as glycidylamine type, diaminodiphenylmethane type epoxy resin, isocyanuric acid type epoxy resin, hydantoic acid type epoxy resin, etc .; as mixed type, p-aminophenol type Epoxy resins, p-oxybenzoic acid type epoxy resins and the like can be mentioned. Among the above epoxy resins, a bisphenol A type epoxy resin, a biphenyl type epoxy resin, a glycidylamine type epoxy resin, and a phenol novolak type epoxy resin are preferable. A combination of two or more of the above epoxy resins can also be used.

In the present invention, the mixing ratio of the highly reactive modified phenol resin and the epoxy resin is not particularly limited, but the total ratio of the highly reactive modified phenol resin and the epoxy resin is 100 parts by weight, and (Parts by weight), more preferably 20/80.
８０80/20 (parts by weight).

When the weight ratio of the modified phenolic resin is less than 10 parts by weight, the effect of improving the heat resistance and moisture resistance of the obtained molded article is not sufficient, and when it exceeds 90 parts by weight, the molding temperature tends to increase.

As the curing agent and / or curing accelerator used in the modified phenolic resin molding material of the present invention, various curing agents and curing accelerators used for curing epoxy resins can be used. Examples of the curing agent include cyclic amines, aliphatic amines, polyamides, aromatic polyamines, and acid anhydrides.

Specifically, for example, cyclic amines include hexamethylenetetramine and the like; aliphatic amines include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperamine, Examples include isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, and menthanediamine.

Examples of polyamides include vegetable oil fatty acids (dimer or trimer acid), aliphatic polyamine condensates, and the like;
As aromatic polyamines, m-phenylenediamine,
4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, m-xylylenediamine and the like can be mentioned.

The acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, chlorendic anhydride,
Dodecinyl succinic anhydride, methyltetrahydrophthalic anhydride, methylendmethylenetetrahydrophthalic anhydride and the like can be mentioned.

As a curing accelerator, 1,8-diazabicyclo
Diazabicycloalkenes such as (5,4,0) undecene-7 and derivatives thereof, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol and tris (dimethylaminomethyl) phenol; 2 -Methylimidazole, 2-ethyl-4
Imidazoles such as -methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, tributylphosphine,
Organic phosphines such as methyldiphenylphosphine and triphenylphosphine, tetra-substituted phosphonium and tetra-substituted borates such as tetraphenylphosphonium and tetraphenylborate, 2-ethyl-4-methylimidazole and tetraphenylborate, and N-methylmorpholine.
Examples thereof include tetraphenylboron salts such as tetraphenylborate, Lewis acids such as boron trifluoride-amine complex, Lewis bases such as dicyandiamide and adipic dihydrazide, and other polymercaptans and polysulfides. These curing agents and curing accelerators may be used alone or in combination of two or more.

The modified phenolic resin molding material may further contain an inorganic filler in addition to the highly reactive modified phenolic resin, epoxy resin, and a curing agent and / or a curing accelerator used as required. .

By adding an inorganic filler to the resin molding material, the strength, dimensional stability and the like of the obtained molded article can be further improved. As such an inorganic filler, various inorganic fillers that can be used as an inorganic filler or a reinforcing material in a plastic material can be used, for example, glass fiber, carbon fiber, phosphor fiber,
Reinforcing fibers such as boron fibers; hydrated metal oxides such as aluminum hydroxide and magnesium hydroxide; metal carbonates such as magnesium carbonate and calcium carbonate; metal borates such as magnesium borate; silica, mica and fused silica Examples include inorganic fillers.

The amount of the inorganic filler is not particularly limited. For example, the amount is usually 20 to 2,000 parts by weight, preferably 20 to 2,000 parts by weight, based on 100 parts by weight of a resin component obtained by adding an epoxy resin to a highly reactive modified phenol resin. 20-80
0 parts by weight, more preferably 50 to 600 parts by weight.

The above-mentioned modified phenolic resin molding material may further contain an additive, if necessary.
Examples of such additives include internal release agents such as silicones and waxes, coupling agents, flame retardants, light stabilizers, antioxidants, pigments, extenders, and the like.

The modified phenolic resin molding material according to the present invention described above is obtained by mixing a highly reactive modified phenolic resin and an epoxy resin with, if necessary, a curing agent and / or a curing accelerator, an inorganic filler and various additives. And applied to the production of molded articles.

In the present invention, the order of mixing the highly reactive modified phenolic resin and epoxy resin with optional components such as a curing agent is not particularly limited. For example, the highly reactive modified phenolic resin and the epoxy resin are kneaded. Then, after a curing agent (curing accelerator) is added and further mixed well, an inorganic filler and other additives are added and mixed as needed to obtain a fine powdery molding powder (compound).

Specifically, such a compound is:
It can be prepared by the following procedure. The highly reactive modified phenol resin and epoxy resin are mixed and stirred at room temperature using an automatic mortar.

Other additives such as a curing agent and / or a curing accelerator and wax are added to the stirring mixture and mixed. Add and mix the inorganic filler.

Further, after mixing for 3 to 10 minutes with a hot roll machine adjusted to 80 ° C. to 90 ° C., the mixture is returned to room temperature and pulverized to obtain a compound. In this case, the addition of the inorganic filler and other additives is separately performed after mixing the highly reactive modified phenol resin and the epoxy resin, but may be performed at any time.

Such a modified phenolic resin molding material according to the present invention can be formed into a molded article by various conventionally known resin molding means. Examples of such molding means include compression molding, injection molding, and injection molding. Extrusion molding, transfer molding, cast molding and the like can be mentioned.

More specifically, when a molded article is produced by transfer molding using the modified phenolic resin molding material of the present invention, the molding temperature is 120 to 200.
° C, injection pressure 5 to 300 kgf / cm ² , preferably 20
~ 300 kgf / cm ² , mold clamping pressure 50 ~ 250 kgf /
Molding conditions of cm ² and a molding time of 1 to 10 minutes are desirable.

[0167] The molded product may have a size of 150 to 30.
By heating at a temperature of 0 ° C. for 0.5 to 24 hours,
It is desirable to perform post cure. By applying post cure to the molded body, the heat resistance of the molded body can be further improved.

The modified phenolic resin molding material according to the present invention has a low melt viscosity, a high reactivity with an epoxy resin, and in particular, a highly reactive modified phenolic resin having improved heat resistance, adhesion and low moisture absorption. Is used, the moldability is good, and the mechanical properties such as dimensional stability of the obtained molded article, moisture resistance, heat resistance, adhesiveness and moisture absorption are improved. Further, in the modified phenolic resin molding material according to the present invention, if a modified phenolic resin containing substantially no acid is used, corrosiveness to a metal member can be reduced,
By adding an inorganic filler, the mechanical strength, electrical insulation and the like of the molded article can be further improved.

Therefore, this modified phenolic resin molded article is useful as a material for electric / electronic parts such as printed circuit boards, insulating materials, sealing materials, etc., which require extremely strict standards for dimensional stability, heat resistance, moldability, and the like. It is also useful as a semiconductor encapsulant that requires improved heat resistance, dimensional stability and moisture absorption as measures against stress damage due to high integration.

[0170]

According to the first to sixth methods for producing a highly reactive modified phenolic resin according to the present invention, it is possible to reduce the step of lowering the molecular weight, which is indispensable in the conventional method, and to further reduce the melt viscosity of the resin. Low, high reactivity with epoxy resin, high reactivity modified phenolic resin showing excellent adhesion and low moisture absorption especially when aromatic hydrocarbon compounds are added to the raw material,
It can be manufactured in one step.

In the first to sixth methods for producing a highly reactive modified phenolic resin according to the present invention, a polycondensation raw material oil which can be efficiently and stably supplied and is advantageous in terms of cost, ie, a petroleum refining process. By using the distillate oil of specific physical properties obtained in the catalytic cracking step or the thermal cracking step, particularly without using a treatment such as distillation under reduced pressure, the highly reactive modified phenol resin having the above excellent characteristics can be stably obtained. And it can be supplied economically.

Further, according to the method for producing a highly reactive modified phenol resin according to the present invention, the highly reactive modified phenol resin obtained by the polycondensation reaction is further purified to remove unreacted components and acid catalysts. By removing it, the resin melt viscosity is low, the reactivity with epoxy resin is high, and it shows excellent heat resistance, adhesiveness and low moisture absorption, and has corrosiveness because it contains substantially no acid It is possible to produce highly reactive modified phenolic resins.

The modified phenolic resin molding material according to the present invention contains the highly reactive modified phenolic resin obtained by the method of the present invention and an epoxy resin, has good moldability, and has good mechanical properties such as dimensional stability. It is possible to provide a molding material that can produce a molded article having excellent characteristics and excellent moisture resistance and heat resistance, particularly a material for electric / electronic parts and a semiconductor encapsulant.

[0174]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which do not limit the scope of the present invention.

In the following examples, all parts are by weight unless otherwise specified. The properties of the feedstock oil used as the reaction feedstock are shown in Tables 1 to 3 below.
Shown in

[0176]

[Table 1]

[0177]

[Table 2]

[0178]

[Table 3]

The number average molecular weight, reactivity with the epoxy resin (determined by the gelation time; the shorter the reactivity, the higher the reactivity), the melt viscosity of the resin and the hydroxyl equivalent weight, etc., measured in the following examples, were determined by the following apparatus. Or it measured by the measuring method.

<Number-average molecular weight> Measuring apparatus: GPC apparatus HLC-8020 manufactured by Tosoh Corporation (column: TSK gel 3000HXL + TSK gel 2500HXL × 3, standard substance: polystyrene) From the obtained data, the molecular weight was determined using polystyrene as a standard substance. Converted. <Glass transition temperature> Measurement method: dynamic viscoelasticity measurement device: Rheology Co., Ltd., DVE RHEOSPECTOLER DVE-
4V type Load method: Tensile method Measurement frequency: 10 Hz Heating rate: 5 ° C./min Dynamic measurement displacement: ± 5 × 10 ⁻⁴ cm Test piece: width 4 mm × thickness 1 mm × span 30 mm <hydroxyl equivalent> acetyl chloride It was measured by the method.

<ICI Viscosity> The ICI viscosity was measured using an ICI cone plate viscometer manufactured by ICI. <Geling time> 170 ° C. according to JIS K 6910
Was measured.

<Heating Weight Reduction Rate> 10 g of the weighed sample was placed in a thermostat maintained at a predetermined temperature and kept for 2 hours, and the weight ratio before and after the high temperature treatment was determined to be the heating weight reduction rate.

<Shore hardness immediately after molding> It was measured using a Shore hardness tester. <Bending strength and elastic modulus> Measured in accordance with JIS K 6911.

<Peel strength> Measured in accordance with JIS K6481. <Hygroscopicity> A molded article was prepared in accordance with JIS K 7209, and the weight difference between the molded article before and after treatment under predetermined conditions was measured and determined.

[0185]

Example 1 100 g of raw oil X and 150 g of phenol were charged into a 1-liter glass reaction vessel,
It was kept at 40 ° C. while stirring at a speed of rpm. After the temperature of the mixture during the stabilization was stabilized, a mixture of 116.2 g of formalin (37% aqueous solution) and 53.1 g of sulfuric acid (97%) was added dropwise over 20 minutes while paying attention to the temperature rise. Keep the temperature at 100 ° C for 100 minutes to continue the reaction,
A reaction product was obtained.

The above reaction product was dissolved in 450 ml of a mixed solvent of toluene / methyl isobutyl ketone (mixing ratio: 2/1), and the obtained resin mixed solution was washed with distilled water to remove the acid. The mixed solvent was removed with an evaporator. Thereafter, unreacted phenol is removed by steam distillation, and water is removed by blowing nitrogen to remove 242.
g of a crude highly reactive modified phenolic resin was obtained.

Next, the crude highly reactive modified phenol resin in a molten state by heating was poured into 4800 ml of n-hexane to remove unreacted raw material oil, precipitate the resin, and filtered and dried to obtain 203 g of the highly reactive modified phenol resin. A phenolic resin was obtained.

The number-average molecular weight, melt viscosity at 150 ° C., and hydroxyl equivalent of the obtained highly reactive modified phenol resin were measured. The results are shown in Table 4 together with the reaction conditions.

[0189]

Examples 2 to 5 The same operation as in Example 1 was carried out except that the reaction conditions were changed as shown in Table 4, and high-reactivity modified phenol resins were obtained in the yields shown in Table 4.

The number-average molecular weight, melt viscosity at 150 ° C., and hydroxyl equivalent weight of the obtained highly reactive modified phenol resin were measured. The results are shown in Table 4 together with the reaction conditions.

[0191]

Example 6 100 g of feedstock oil X, 150 g of phenol and 80 g of formalin (37% by weight aqueous solution) were charged into a 1 liter glass reaction vessel and kept at 40 ° C. while stirring at a speed of 250 to 350 rpm. When the temperature stabilizes, add 37 g of sulfuric acid (97% by weight) while paying attention to
The mixture was added dropwise over 4 minutes, and after completion of the addition, the reaction was continued at 95 ° C. for 106 minutes while maintaining the temperature to obtain a reaction product.

The above reaction product was poured into 450 ml of a mixed solvent of toluene / methyl isobutyl ketone (mixing ratio: 2/1) to dissolve the resin, and the resulting resin mixed solution was washed with distilled water to remove the acid. The mixed solvent and unreacted phenol were removed by an evaporator to obtain 197 g of a crude highly reactive modified phenol resin.

Next, the crude highly reactive modified phenol resin in a heated and melted state was poured into 5200 ml of n-hexane to remove unreacted raw oil and precipitate the resin, followed by filtration and drying to obtain 173 g of highly reactive modified phenol resin. A phenolic resin was obtained.

The physical properties of the resulting highly reactive modified phenolic resin are shown in Table 4 together with the reaction conditions.

[0195]

Example 7 The same operation as in Example 1 was carried out except that the reaction conditions were changed as shown in Table 4, and each highly reactive modified phenol resin was obtained in the yield shown in Table 4.

The physical properties of the resulting highly reactive modified phenolic resin are shown in Table 4 together with the reaction conditions.

[0197]

Example 8 9.58 parts by weight of the highly reactive modified phenolic resin obtained in Example 1 and a biphenyl type epoxy resin (YX-4000H, manufactured by Yuka Shell Epoxy Co., Ltd.)
After mixing and stirring 14.48 parts by weight at room temperature using an automatic mortar, 0.49 parts by weight of triphenylphosphine (TPP) as a curing catalyst was mixed with the stirred mixture to obtain a resin mixture containing a curing accelerator.

The gelation time of the resin mixture containing the curing accelerator was measured and is shown in Table 5. Further, 0.25 parts by weight of carnauba wax was further added to the obtained compound and mixed, and then 0.20 of carbon black was used as an inorganic filler.
Parts by weight and fused silica (CRS1102, manufactured by Tatsumori Co., Ltd.)
-GT200T) 75 parts by weight. The obtained mixture was heated to a temperature of 3 to 1 with a hot roll machine adjusted to 80 to 90 ° C.
After further mixing for 0 minutes, the mixture was cooled to room temperature and pulverized to obtain a compound (molding material). Table 5 shows the composition of this compound.

The obtained compound was heated at 175 ° C., 90
Transfer molding was performed under the conditions of seconds, and post-curing was further performed at 175 ° C. for 6 hours to obtain a molded body. The Shore hardness, glass transition point, bending properties, and moisture absorption of the obtained molded body immediately after molding were measured. The results are shown in Table 5.

[0200]

Examples 9 to 14 Instead of the highly reactive modified phenolic resin obtained in Example 1, the highly reactive modified phenolic resins obtained in Examples 2 to 7 were used. A curing accelerator-containing resin mixture, a compound and a molded body were produced in the same manner as in Example 8, except that the mixing ratio of the epoxy resin and the epoxy resin was set to the value shown in Table 5.

Table 5 shows the gelation time of the obtained curing accelerator-containing resin mixture, the physical properties of the molded product, and the like.

[0202]

[Table 4]

[0203]

[Table 5]

[0204]

Example 15 Raw material oil X 100 g, phenol 263
g, 164 g of formalin (37% by weight aqueous solution) and 11 g of sulfuric acid (97% by weight) were charged into a 1-liter glass reactor, and stirred at a speed of 250 to 350 rpm.
The temperature was raised to 95 ° C. over a period of minutes, and the reaction was maintained at 95 ° C. for 100 minutes to obtain a reaction product.

The purified product was purified in the same manner as in Example 1. However, the unreacted phenol was removed by blowing nitrogen at 160 ° C. to obtain 290 g of the crude phenol resin, and the crude phenol resin in the heat-melted state was poured into 6000 ml of n-hexane.

The properties of the resulting highly reactive modified phenolic resin are shown in Table 6 together with the reaction conditions.

[0207]

Example 16 Raw material oil 100 g, phenol 206
g, formalin (37% by weight aqueous solution) and 116 g of acidic ion exchange resin Diaion SK1B (manufactured by Mitsubishi Chemical Corporation) are charged into a 1-liter glass reactor, and stirred for 20 minutes at a speed of 250 to 350 rpm. Then, the temperature was raised to 120 ° C., and the reaction was held at 120 ° C. for 280 minutes to obtain a reaction product.

The reaction product was filtered through a 60-mesh wire net to remove Diaion SK1B. After unreacted phenol was removed by subjecting the obtained resin to steam distillation at 160 ° C., water was removed by blowing nitrogen to obtain 234 g of a crude highly reactive modified phenol resin.

Next, the highly reactive modified phenol resin in a heated and melted state was poured into 4800 ml of n-hexane to remove unreacted raw material oil, precipitate the resin, and filtered and dried to obtain 215 g of highly reactive modified phenol resin. A modified phenolic resin was obtained.

The physical properties of the resulting highly reactive modified phenolic resin are shown in Table 6 together with the reaction conditions.

[0211]

Example 17 AST was prepared from 120 g of feedstock oil X shown in Table 1.
Paraffin and low-reactive components were removed according to MD-2549. The column used was activated alumina gel (Wako Pure Chemical Industries, Ltd.) and silica gel (Fuji Dewison Co., Ltd.), and the developing agents used were n-pentane, diethyl ether, chloroform, and ethyl alcohol.

100 g of the raw oil obtained above, 263 g of phenol, 181 g of formalin (37% by weight aqueous solution)
And 11 g of sulfuric acid (97% by weight) were charged into a 1-liter glass reactor, heated to 95 ° C. over 20 minutes while stirring at a speed of 250 to 350 rpm, and held at 95 ° C. for 100 minutes to carry out a reaction product. I got

The above reaction product was dissolved in 450 ml of a mixed solvent of toluene / methyl isobutyl ketone (mixing ratio: 2/1), and the obtained resin mixed solution was washed with distilled water to remove the acid, and then the evaporator was removed. To remove the mixed solvent. Further, unreacted phenol was removed by blowing nitrogen at 160 ° C. to obtain 267 g of a highly reactive modified phenol resin.

The physical properties of the resulting highly reactive modified phenolic resin are shown in Table 6 together with the reaction conditions.

[0215]

Examples 18 to 20 Except that the highly reactive modified phenolic resin obtained in Examples 15 to 17 was used, a resin mixture containing a curing accelerator, a compound and a molded product were produced in the same manner as in Example 8. did.

Table 7 shows the mixing ratio, physical properties and the like.

[0219]

[Table 6]

[0218]

[Table 7]

[0219]

Example 21 Raw material oil X 100 g, phenol 263 g
And 100 g of m-xylene were charged into a 1 liter glass reactor, and stirred at a speed of 250 to 350 rpm.
It was kept at 0 ° C. When the temperature was stabilized, a mixture of 164 g of formalin (37% by weight aqueous solution) and 74 g of sulfuric acid (97% by weight) was added dropwise over 20 minutes while paying attention to the temperature rise. The product was obtained.

The above reaction product was purified by the same operation as in Example 15. However, after nitrogen blowing, 342 g of crude phenol resin was obtained,
Poured into 00 ml of n-hexane.

The physical properties of the resulting highly reactive modified phenolic resin are shown in Table 8 together with the reaction conditions.

[0222]

Example 22 Raw material X 100 g, phenol 206
g, 100 g of m-xylene and 70 g of Diaion SK1B (manufactured by Mitsubishi Chemical Corporation) were charged into a 1 liter glass reactor, and stirred at a speed of 250 to 350 rpm.
It was kept at 0 ° C. When the temperature was stabilized, 136 g of formalin (37% by weight aqueous solution) was added dropwise over 20 minutes while paying attention to the temperature rise, and after completion of the addition, a reaction was carried out at 120 ° C. for 280 minutes to obtain a reaction product.

The above reaction product was filtered with a 60-mesh wire net to remove Diaion SK1B. The resulting resin was blown with nitrogen at 160 ° C. to remove unreacted phenol to obtain 282 g of a crude highly reactive modified phenol resin.

Next, the crude highly reactive modified phenol resin in a heated and molten state was poured into 7000 ml of n-hexane to remove unreacted oil and precipitate the resin, followed by filtration and drying.
256 g of a highly reactive modified phenolic resin was obtained.

Table 8 shows the physical properties of the resulting highly reactive modified phenolic resin together with the reaction conditions.

[0226]

Example 23 In the same manner as in Example 17, 100 g of raw oil X, 263 g of phenol and 100 g of m-xylene from which paraffin components and components having low reactivity were removed were charged into a 1-liter glass reactor, and the speed was 250 to 350 rpm. It was kept at 40 ° C. with stirring. When the temperature was stabilized, a mixture of 181 g of formalin (37% by weight aqueous solution) and 85 g of sulfuric acid (97% by weight) was added dropwise over 20 minutes while paying attention to the temperature rise. The product was obtained.

The above reaction product was purified in the same manner as in Example 17 to obtain 314 g of a highly reactive modified phenol resin. Table 8 shows the physical properties of the resulting highly reactive modified phenolic resin together with the reaction conditions.

[0228]

Examples 24 to 26 In the same manner as in Example 24 except that the highly reactive modified phenolic resin obtained in Examples 21 to 23 was used, a resin mixture containing a curing accelerator, a compound and a molded article were produced. .

Table 9 shows the mixing ratio, physical properties and the like.

[0230]

[Table 8]

[0231]

[Table 9]

[0232]

Example 27 100 g of feed oil X and 206 g of phenol
Is charged into a 1-liter glass reaction vessel, and 250 to 35
It was kept at 40 ° C. while stirring at a speed of 0 rpm. When the temperature stabilizes, formalin (37% by weight aqueous solution) 136.
A mixture of 4 g and 62.3 g of sulfuric acid (97% by weight) was added dropwise over 20 minutes while paying attention to the temperature rise.
A reaction was performed at 100 ° C. for 100 minutes to obtain a reaction product.

The above reaction product was poured into 450 ml of a mixed solvent of toluene / methyl isobutyl ketone (mixing ratio: 2/1) to dissolve the resin, and the obtained resin mixed solution was washed with distilled water to remove the acid. The mixture was concentrated by an evaporator until the solvent concentration became 10% by weight to obtain a resin varnish.

The resin varnish was poured into 5800 ml of n-hexane to remove unreacted raw material oil, precipitate the resin, and filtered to obtain 273 g of a crude highly reactive modified phenol resin.

Further, the crude highly reactive modified phenol resin obtained was subjected to steam distillation at 160 ° C. to remove unreacted phenol, and then water was removed by blowing nitrogen to obtain 236 g of the highly reactive modified phenol resin. A phenolic resin was obtained.

The physical properties of the resulting highly reactive modified phenolic resin are shown in Table 10 together with the reaction conditions.

[0237]

Example 28 Raw material oil X 100 g, phenol 263 g
And 73 g of an acidic ion-exchange resin Diaion SK1B (manufactured by Mitsubishi Chemical Corporation) are charged into a 1-liter glass reaction vessel, and stirred while stirring at a speed of 250 to 350 rpm.
C. was maintained.

When the temperature becomes stable, formalin (37% by weight)
Aqueous solution (164.8 g) was added dropwise over 20 minutes while paying attention to temperature rise, and after completion of the addition, a reaction was carried out at 120 ° C. for 280 minutes to obtain a reaction product.

The above reaction product was put into 450 ml of dimethyl sulfoxide to dissolve it, and the resin exchange solution was filtered through a 60-mesh wire net to remove the used ion exchange resin. The resin mixture was mixed with 350 ml of heavy naphtha (boiling point 80
Liquid-liquid extraction using a separatory funnel at -150 ° C) to remove unreacted feedstock oil to obtain a crude highly reactive modified phenolic resin.

The resulting crude highly reactive modified phenol resin was subjected to steam distillation at 160 ° C. to remove dimethyl sulfoxide and unreacted phenol, and then water was removed by blowing nitrogen to obtain 203 g of highly reactive phenol resin. A modified phenolic resin was obtained.

The properties of the resulting highly reactive modified phenolic resin are shown in Table 10 together with the reaction conditions.

[0242]

Example 29 The crude highly reactive modified phenol resin obtained in the same manner as in Example 6 was subjected to steam distillation at 160 ° C. to remove unreacted phenol, and nitrogen was blown at the same temperature to remove water. Thus, 197 g of a crude highly reactive modified phenol resin was obtained.

Next, the crude highly reactive modified phenol resin in the heat-melted state was cooled to 120 ° C., and left undisturbed at that temperature to remove unreacted raw material oil separated in the upper layer to obtain 178 g of highly reactive modified phenol resin. A phenolic resin was obtained.

The properties of the resulting highly reactive modified phenolic resin are shown in Table 10 together with the reaction conditions.

[0245]

Example 30 Raw oil X10 obtained in the same manner as in Example 17 and from which paraffin components and components having low reactivity were removed.
0 g and 263 g of phenol were charged into a 1-liter glass reaction vessel and maintained at 40 ° C. while stirring at a speed of 250 to 350 rpm. When the temperature stabilizes, formalin (3
165 g of a 7% by weight aqueous solution and sulfuric acid (97% by weight) 73.
7 g of the mixture was added dropwise over 20 minutes while paying attention to the temperature rise, and after completion of the addition, a reaction was carried out at 95 ° C. for 100 minutes to obtain a reaction product.

The above reaction product was dissolved in 450 ml of a mixed solvent of toluene / methyl isobutyl ketone (mixing ratio: 2/1), and the resulting resin mixed solution was washed with distilled water to remove the acid. The mixed solvent and unreacted phenol were removed by an evaporator to obtain 242 g of a highly reactive modified phenol resin.

Next, the crude high-reactivity modified phenol resin thus obtained was subjected to molecular distillation to remove unreacted raw material oil.
12 g of a highly reactive modified phenolic resin was obtained. Table 10 shows the physical properties of the resulting highly reactive modified phenolic resin together with the reaction conditions.

[0248]

Example 31 Raw material oil X 100 g and phenol 263 g
Is charged into a 1-liter glass reaction vessel, and 250 to 35
It was kept at 40 ° C. while stirring at a speed of 0 rpm. When the temperature stabilizes, formalin (37% by weight aqueous solution) 164.
A mixture of 8 g and 73.74 g of sulfuric acid (97% by weight) was added dropwise over 20 minutes while paying attention to the temperature rise.
A reaction was carried out at 5 ° C. for 100 minutes to obtain a reaction product.

The above reaction product was dissolved in 450 ml of a mixed solvent of toluene / methyl isobutyl ketone (mixing ratio: 2/1), and the obtained resin mixed solution was washed with a 0.3% by weight aqueous sodium hydroxide solution. After removing the acid and unreacted phenol with an evaporator, the mixture was concentrated to a resin concentration of 10% by weight to obtain a resin varnish.

The resin varnish was poured into 5800 ml of n-hexane to remove unreacted raw material oil, precipitate the resin, and filtered and dried to obtain 190 g of a highly reactive modified phenol resin.

The physical properties of the resulting highly reactive modified phenolic resin are shown in Table 10 together with the reaction conditions.

[0252]

Example 32 Raw material X 100 g and phenol 263
g into a 1 liter glass reactor, 250-35
It was kept at 40 ° C. while stirring at a speed of 0 rpm. When the temperature is stabilized, formalin (37% by weight aqueous solution) 164
g and 74 g of sulfuric acid (97% by weight) were added dropwise over 20 minutes while paying attention to the temperature rise, and after the completion of the addition, a reaction was carried out at 95 ° C. for 100 minutes to obtain a reaction product.

The above reaction product was dissolved in 300 ml of a mixed solvent of toluene / methyl isobutyl ketone (mixing ratio: 2/1), and the aqueous sulfuric acid was removed. After transferring the obtained resin mixed solution to a separating funnel, 333 ml of distilled water was added and shaken.
An organic layer containing unreacted oil, a resin solution layer and an aqueous layer were separated, and the organic layer containing unreacted oil and the aqueous layer were removed.

The resulting resin solution layer was washed with distilled water to remove the acid, and then the mixed solvent and unreacted phenol were removed with an evaporator to obtain 335 g of a highly reactive modified phenol resin.

Table 10 shows the physical properties of the resulting highly reactive modified phenolic resin together with the reaction conditions.

[0256]

Examples 33 to 38 Example 8 was repeated except that the highly reactive modified phenolic resin obtained in Examples 27 to 32 and the phenol novolak type epoxy resin (trade name EOCN-1020, manufactured by Nippon Kayaku) were used. Similarly, a hardening accelerator-containing resin mixture, a compound and a molded article were produced.

Table 11 shows the mixing ratio, physical properties and the like.

[0258]

[Table 10]

[0259]

[Table 11]

[0260]

Example 39 Raw material A10 obtained in the same manner as in Example 17 and from which paraffin components and components having low reactivity were removed.
0 g, 114.4 g of phenol, and 26.4 g of paraformaldehyde were charged into a 1-liter glass reaction vessel, and stirred at a speed of 250 to 350 rpm at 40 ° C.
Held. When the temperature stabilizes, add 10 g of oxalic acid,
The temperature was raised to 140 ° C. in 30 minutes. After heating to 140 ° C,
The reaction was performed while stirring at the same temperature for 90 minutes to obtain a reaction product.

To the above reaction product, 7 parts of toluene and acetone were added.
190 ml of a mixed solvent mixed at a ratio of 3: 3 was added and dissolved, and 140 ml of distilled water was added to the obtained resin mixed solution, followed by washing with water to remove the acid remaining in the resin mixed solution. The mixed solvent was removed from the resulting acid-removed resin mixed solution using an evaporator to obtain a crude highly reactive modified phenol resin.

Further, nitrogen was blown into the above resin at 155 ° C. for 30 minutes to remove unreacted phenol remaining in the resin to obtain 158.3 g of a highly reactive modified phenol resin. Table 12 shows the physical properties of the resulting highly reactive modified phenolic resin together with the reaction conditions.

[0263]

Example 40: 100 g of feed oil A, 16.3 of phenol
g, 2.6 g of paraformaldehyde and 1.4 oxalic acid
g into a 1 liter glass reaction vessel,
The temperature was raised to 140 ° C. in 30 minutes while stirring at a speed of 50 rpm. After the temperature was raised to 140 ° C., the reaction was performed while stirring at the same temperature for 90 minutes to obtain a reaction product.

Next, the reaction product was allowed to stand and cooled to room temperature, and the unreacted raw material oil separated in the upper layer was removed by decantation to obtain a crude highly reactive modified phenol resin. 3 at 155 ° C on the crude highly reactive modified phenolic resin
Nitrogen was blown for 0 minutes to remove unreacted phenol remaining in the resin. Thereafter, the temperature is further reduced to 1 under a nitrogen atmosphere.
The temperature was raised to 80 ° C., held for 1 hour, and then lowered to room temperature.
g of a highly reactive modified phenolic resin was obtained.

The physical properties of the resulting highly reactive modified phenolic resin are shown in Table 12 together with the reaction conditions.

[0266]

Example 41 100 g of feed oil A, phenol 114.
4 g and 18.5 g of paraformaldehyde were charged into a 1 liter glass reaction vessel and kept at 40 ° C. while stirring at a speed of 250 to 350 rpm. When the temperature was stabilized, 1.4 g of oxalic acid was added, and the temperature was raised to 100 ° C. in 15 minutes. After the temperature was raised to 100 ° C, 1.4 g of oxalic acid was further added, the temperature was raised to 140 ° C over 15 minutes, and the reaction was performed for 90 minutes to obtain a reaction product.

The above reaction product was charged into heavy naphtha,
Unreacted feedstock was removed. The crude highly reactive modified phenol resin thus obtained was subjected to steam distillation at 155 ° C. to remove unreacted phenol remaining on the resin. Thereafter, the temperature was further raised to 180 ° C. in a nitrogen atmosphere, and after holding for 1 hour, the temperature was lowered to room temperature to obtain 72 g of a highly reactive modified phenol resin.

The physical properties of the resulting highly reactive modified phenolic resin are shown in Table 12 together with the reaction conditions.

[0269]

Example 42: 100 g of feed oil A, 62.4 of phenol
g and 12 g of paraformaldehyde were charged into a 1-liter glass reaction vessel and kept at 40 ° C. while stirring at a speed of 250 to 350 rpm. When the temperature was stabilized, 1.4 g of oxalic acid was added, and the temperature was raised to 140 ° C. in 30 minutes.
After the temperature was raised to 140 ° C., the reaction was performed while stirring at the same temperature for 90 minutes to obtain a reaction product.

The above reaction product was purified in the same manner as in Example 40 to obtain 35 g of a highly reactive modified phenol resin.
Table 12 shows the physical properties of the resulting highly reactive modified phenolic resin together with the reaction conditions.

[0271]

Example 43 Raw material B (100 g), phenol (100)
g, paraformaldehyde 19.7 g, and oxalic acid 1.
3 g was charged into a 1-liter glass reaction vessel, and 250 to
140 ° C. in 30 minutes while stirring at a speed of 350 rpm
Heat up to After the temperature was raised to 140 ° C., the reaction was performed while stirring at the same temperature for 90 minutes to obtain a reaction product.

The above reaction product was allowed to stand, the temperature was lowered to 50 ° C., and the unreacted raw material oil separated in the upper layer was removed by decantation to obtain a crude highly reactive modified phenol resin.
The crude highly reactive modified phenol resin was subjected to distillation under reduced pressure until phenol no longer distills out, and then unreacted phenol was removed by further blowing nitrogen at 155 ° C.

To the resin thus obtained, 100 ml of heavy naphtha was added, and the mixture was stirred under reflux at 100 ° C. for 30 minutes to extract unreacted raw oil remaining in the resin, and decanted to remove heavy naphtha containing unreacted raw oil. After removing unreacted raw material oil remaining in the resin, the temperature is further raised to 180 ° C. in a nitrogen atmosphere, kept for 1 hour, and then lowered to room temperature to remove 71 g of the highly reactive modified phenol resin. Obtained.

The physical properties of the resulting highly reactive modified phenolic resin are shown in Table 12 together with the reaction conditions.

[0275]

Example 44 100 g of feed oil B and 100 g of phenol
And 1.4 g of oxalic acid in a 1 liter glass reaction vessel, and stirring at a speed of 250 to 350 rpm.
Hold at 40 ° C. When the temperature is stabilized, add 7 g of paraformaldehyde and start raising the temperature. When the temperature reached 70 ° C., another 7 g of paraformaldehyde was added, and 90
Heat to ° C. When the temperature reached 90 ° C., 5.7 g of paraformaldehyde and 1.3 g of oxalic acid were added, the temperature was raised to 100 ° C., and the reaction was carried out with stirring at the same temperature for 100 minutes to obtain a reaction product.

After the above reaction product was distilled under reduced pressure at 40 mmHg until almost no phenol was distilled off, unreacted phenol was removed by further blowing nitrogen at 155 ° C.

The resin thus obtained was treated with heavy naphtha to remove unreacted raw material oil remaining in the resin, and the temperature was further raised to 180 ° C. in a nitrogen atmosphere to reduce the temperature.
After keeping for a time, the temperature was lowered to room temperature to obtain 76 g of a highly reactive modified phenol resin.

The physical properties of the resulting highly reactive modified phenolic resin are shown in Table 12 together with the reaction conditions.

[0279]

Example 45 100 g of feed oil C, 121.
6 g, 29.3 g of paraformaldehyde, and 1.3 g of oxalic acid were charged into a 1-liter glass reaction vessel,
While stirring at a speed of 0 to 350 rpm, 10 minutes in 20 minutes
Heat to 0 ° C. After heating to 100 ° C,
The reaction was carried out with stirring for 0 minutes to obtain a reaction product.

The above reaction product was dissolved by adding 190 ml of acetonitrile, and 190 ml of heavy naphtha was added to the obtained resin mixed solution to extract and remove unreacted oil remaining in the resin mixed solution.

Acetonitrile was removed from the resulting acid-removed resin mixed solution using an evaporator to obtain a crude highly reactive modified phenol resin. The crude highly reactive modified phenolic resin was distilled at 185 ° C. under reduced pressure to remove unreacted phenol, and then held at the same temperature for 1 hour while blowing with nitrogen.
Then, the temperature was lowered to room temperature to obtain 98 g of a highly reactive modified phenol resin.

The physical properties of the resulting highly reactive modified phenolic resin are shown in Table 12 together with the reaction conditions.

[0283]

Example 46 Raw material oil C, 100 g, o-cresol 12
1.6 g, 29.7 g of paraformaldehyde and 1.33 g of paratoluenesulfonic acid were charged into a 1-liter glass reaction vessel, and heated to 100 ° C. in 20 minutes while stirring at a speed of 250 to 350 rpm. After the temperature was raised to 100 ° C., the reaction was carried out with stirring at the same temperature for 100 minutes to obtain a reaction product.

The above reaction product was dissolved by adding 190 ml of methyl isobutyl ketone, and 140 ml of distilled water was added to the obtained resin mixed solution, followed by washing with water to remove the acid remaining in the resin mixed solution.

The obtained acid-removed resin mixed solution was concentrated using an evaporator until the resin concentration reached 60 wt%, and the obtained resin solution was charged into heavy naphtha to remove unreacted raw material oil remaining in the resin. .

[0286] 15
Nitrogen was blown at 5 ° C. for 30 minutes to remove unreacted o-cresol remaining in the resin to obtain 123 g of a highly reactive modified phenol resin.

The physical properties of the resulting highly reactive modified phenolic resin are shown in Table 12 together with the reaction conditions.

[0288]

Example 47: 100 g of feedstock oil D, phenol 126.
4 g, paraformaldehyde (20.4 g), and oxalic acid (11.2 g) were charged into a 1-liter glass reaction vessel.
While stirring at a speed of 50 to 350 rpm, 1 minute in 30 minutes
The temperature was raised to 60 ° C. After heating to 160 ° C, 9
The reaction was carried out with stirring for 0 minutes to obtain a reaction product.

The above reaction product was treated in the same manner as in Example 46 to obtain 88 g of a highly reactive modified phenol resin. Table 12 shows the physical properties of the resulting highly reactive modified phenolic resin together with the reaction conditions.

[0290]

Example 48 100 g of feedstock oil E, α-naphthol 28
3.0 g, paraformaldehyde 79.0 g, and acidic ion exchange resin Diaion SK1B (Mitsubishi Chemical Corporation)
Into a 1-liter glass reaction vessel and stirring at a speed of 250 to 350 rpm.
The temperature was raised to 100 ° C. in minutes. After the temperature was raised to 100 ° C., the reaction was carried out with stirring at the same temperature for 100 minutes to obtain a reaction product.

The reaction product was filtered through a 60-mesh wire net to remove the used ion-exchange resin, allowed to stand still, cooled to room temperature, and the unreacted raw material oil separated in the upper layer was removed by decantation. Thus, a crude highly reactive modified phenol resin was obtained.

The above crude highly reactive modified phenolic resin was added to 15
After steam distillation at 5 ° C. for 30 minutes, nitrogen was further blown at the same temperature for 10 minutes to remove unreacted α-naphthol remaining in the resin to obtain 224 g of a highly reactive modified phenol resin.

The physical properties of the resulting highly reactive modified phenolic resin are shown in Table 12 together with the reaction conditions.

[0294]

Examples 49-58 The highly reactive modified phenolic resins obtained in Examples 38-48 were used, and ortho-cresol novolak type epoxy resin (trade name EOCN1020, manufactured by Nippon Kayaku) or bisphenol type epoxy resin (YX- 4000
Except that H) was used, a curing accelerator-containing resin mixture, a compound and a molded article were produced in the same manner as in Example 8.

Table 13 shows the mixing ratio, physical properties and the like.

[0296]

[Table 12]

[0297]

[Table 13]

[0298]

Example 59: 100 g of feed oil B, 94 g of phenol,
18.5 g of paraformaldehyde and 2.5 g of oxalic acid were charged into a 1-liter glass reaction vessel, and 250 to 350
After maintaining the temperature at 40 ° C. while stirring at a speed of rpm, the temperature was raised to 140 ° C. over 30 minutes, and the reaction was maintained for 90 minutes to obtain a reaction product.

The above reaction product was poured into 161 ml of methyl isobutyl ketone to dissolve the resin mixture, and the resulting resin mixed solution was washed with distilled water to remove the acid. Modified phenolic resin 160
g was obtained.

160 ml of heavy naphtha was added to the resulting crude highly reactive modified phenol resin, and the mixture was heated to about 98 ° C. and stirred for 30 minutes. Thereafter, the mixture was cooled to room temperature, and the heavy naphtha layer containing the unreacted oil separated in the upper layer was removed by decantation. A series of unreacted oil extraction and removal operations using heavy naphtha was performed once more under the same conditions.

Next, after dissolving the lower resin layer at 150 ° C., unreacted phenol was removed by blowing in nitrogen to obtain 65 g of a highly reactive modified phenol resin. Table 14 shows the physical properties of the resulting highly reactive modified phenolic resin together with the reaction conditions.

[0302]

Example 60 A highly reactive modified phenol resin was obtained in the same manner as in Example 59. However, the reaction conditions were changed as shown in Table 14, and the reaction product was dissolved in 182 ml of methyl isobutyl ketone to obtain 167 g of a crude highly reactive modified phenol resin.

The properties of the resulting highly reactive modified phenolic resin are shown in Table 14 together with the reaction conditions.

[0304]

Example 61: 100 g of feed oil B, phenol 114
g, paraformaldehyde 18.5 g and oxalic acid 2.8
g into a 1 liter glass reaction vessel,
After maintaining at 40 ° C. while stirring at a speed of 50 rpm, 30
The temperature was raised to 140 ° C. over a period of 90 minutes, and the reaction was held for 90 minutes to obtain a reaction product.

The above reaction product was introduced into 182 ml of a mixed solvent of methyl isobutyl ketone and toluene (7: 1) to dissolve the resin, and the resulting resin mixed solution was washed with distilled water to remove the acid, and then evaporated. The mixed solvent was removed by using to obtain 175 g of a crude highly reactive modified phenol resin.

The resulting crude highly reactive modified phenolic resin
350 ml of n-heptane was added, and the temperature was raised to about 85 ° C., followed by stirring for 30 minutes. Thereafter, the mixture was cooled to room temperature, and the n-heptane layer containing the unreacted oil separated in the upper layer was removed by decantation.

Next, after dissolving the lower resin layer at about 150 ° C., unreacted phenol was removed by steam distillation to obtain 77 g of a highly reactive modified phenol resin. Table 14 shows the physical properties of the resulting highly reactive modified phenolic resin together with the reaction conditions.

[0308]

Example 62 A highly reactive modified phenol resin was obtained in the same manner as in Example 59. However, the reaction conditions were changed as shown in Table 14, the resulting heated mixture of 160 g of crude phenol resin and heavy naphtha was cooled to 80 ° C., and unreacted phenol was removed by steam distillation.

The physical properties of the resulting highly reactive modified phenolic resin are shown in Table 14 together with the reaction conditions.

[0310]

Example 63 Petroleum-based feedstock X 100 g, phenol 1
22 g, 25.4 g of paraformaldehyde and 1.3 g of oxalic acid were charged into a 1-liter glass reaction vessel,
After maintaining the temperature at 40 ° C. while stirring at a speed of 0 to 350 rpm, the temperature was raised to 100 ° C. over 30 minutes, and the reaction was maintained for 90 minutes to obtain a reaction product.

The above reaction product was added to and dissolved in 180 ml of a mixed solvent of methyl isobutyl ketone and toluene (7: 3), and the resulting resin mixed solution was washed with distilled water to remove the acid, and then evaporated. The mixed solvent was removed to obtain 200 g of a crude highly reactive modified phenol resin.

The resulting crude highly reactive modified phenolic resin
400 ml of n-octane was added, and the temperature was raised to about 90 ° C., followed by stirring for 30 minutes. Thereafter, the mixture was cooled to 80 ° C., and the n-octane layer containing unreacted oil separated into an upper layer by standing at this temperature was removed by decantation.

Next, after dissolving the lower resin layer at about 150 ° C., unreacted phenol is removed by blowing nitrogen, whereby 9% of the highly reactive modified phenol resin is removed.
2 g were obtained.

The properties of the resulting highly reactive modified phenolic resin are shown in Table 14 together with the reaction conditions.

[0315]

Example 64 Coal-based feedstock S100g, phenol 1
00 g, 19.7 g of paraformaldehyde and 1.3 g of oxalic acid were placed in a 1-liter glass reaction vessel,
After maintaining the temperature at 40 ° C. while stirring at a speed of 0 to 350 rpm, the temperature was raised to 140 ° C. over 30 minutes, and the reaction was maintained for 90 minutes to obtain a reaction product.

The above reaction product was added to and dissolved in 161 ml of methyl isobutyl ketone, and the resulting resin mixed solution was washed with distilled water to remove the acid. Modified phenolic resin 160
g was obtained.

To the obtained crude highly reactive modified phenol resin was added 320 ml of heavy naphtha, and the mixture was heated to about 98 ° C. and stirred for 30 minutes. Then, cool down to 80 ° C,
The heavy naphtha layer containing the unreacted oil separated by standing at this temperature and separated into an upper layer was removed by decantation.

Next, after dissolving the lower resin layer at about 150 ° C., unreacted phenol was removed by performing steam distillation to obtain 51 g of a highly reactive modified phenol resin. Table 14 shows the physical properties of the resulting highly reactive modified phenolic resin together with the reaction conditions.

[0319]

Example 65 A highly reactive modified phenol resin was obtained in the same manner as in Example 59. However, the reaction conditions were changed as shown in Table 14, and the reaction mixture was dissolved in 170 ml of methyl isobutyl ketone to obtain 169 g of a crude phenol resin.
Cooled to 0 ° C.

Table 14 shows the physical properties of the resulting highly reactive modified phenolic resin together with the reaction conditions.

[0321]

Example 66 100 g of petroleum heavy oil B, 114 g of o-cresol, 18.5 g of paraformaldehyde and 2.8 g of oxalic acid were charged into a 1-liter glass reaction vessel, and
After maintaining the temperature at 40 ° C. while stirring at a speed of 50 to 350 rpm, the temperature was raised to 140 ° C. over 30 minutes, and the reaction was maintained for 90 minutes to obtain a reaction product.

The above reaction product was dissolved in 190 ml of a mixed solvent of toluene and acetone (7: 3), and the resulting resin mixed solution was washed with distilled water to remove the acid and mixed with an evaporator. The solvent was removed to obtain 174 g of a crude highly reactive modified phenol resin.

To the resulting crude highly reactive modified phenol resin was added 350 ml of heavy naphtha, and the mixture was heated to about 98 ° C. and stirred for 30 minutes. Then, cool down to 80 ° C,
The heavy naphtha layer containing the unreacted oil separated by standing at this temperature and separated into an upper layer was removed by decantation.

Next, after dissolving the lower resin layer at about 150 ° C., unreacted o-cresol was removed by performing steam distillation to obtain 79 g of a highly reactive modified phenol resin.

Table 14 shows the physical properties of the resulting highly reactive modified phenolic resin together with the reaction conditions.

[0326]

Example 67 In the same manner as in Example 66, a highly reactive modified phenol resin was obtained. However, the reaction conditions were changed as shown in Table 14, and the reaction mixture was dissolved in 200 ml of a mixed solvent to obtain 197 g of a crude phenol resin.

The properties of the resulting highly reactive modified phenolic resin are shown in Table 14 together with the reaction conditions.

[0328]

Comparative Example 1 100 g of feedstock B, 94 g of phenol, 18.5 g of paraformaldehyde and 2.5 g of oxalic acid
250-350 rp in a 1 liter glass reaction vessel
After maintaining the temperature at 40 ° C. while stirring at a speed of m, the temperature was increased to 140 ° C. over 30 minutes, and the reaction was maintained for 90 minutes to obtain a reaction product.

The above reaction product was added to and dissolved in 161 ml of methyl isobutyl ketone. The obtained resin mixed solution was washed with distilled water to remove the acid, and the mixed solvent was removed with an evaporator. Thereafter, unreacted phenol was removed by steam distillation, and water was removed by blowing nitrogen to obtain 148 g of a crude highly reactive modified phenol resin.

Next, 3200 ml of heavy naphtha at a temperature of about 10 ° C.
And unreacted oil and the like were dissolved in heavy naphtha to precipitate a resin. The obtained resin was filtered and dried to obtain 78 g of a modified phenol resin.

Table 14 shows the physical properties of the resulting highly reactive modified phenolic resin together with the reaction conditions.

[0332]

[Table 14]

[0333]

EXAMPLE 68 100 g (0.72 mol) of the raw material oil P, 38.2 g (0.41 mol) of phenol, and 9.1 g (0.30 mol) of paraformaldehyde were charged into a 1-liter glass reaction vessel. It was kept at 40 ° C. while stirring at a speed of 350 rpm. After the temperature was stabilized, 1.5 g (0.012 mol) of oxalic acid was added, the temperature was raised to 140 ° C. over 30 minutes, and the reaction was continued with stirring at the same temperature for 90 minutes to obtain a polycondensation reaction mixture. Was.

To the reaction mixture, 120 ml of methyl isobutyl ketone was added to obtain a resin mixed solution. The obtained resin mixed solution was washed with 82 ml of distilled water to remove the acid remaining in the resin mixed solution.

The obtained acid-removed resin mixed solution was concentrated by an evaporator until the resin concentration became 60% by weight, and then charged into heavy naphtha to remove unreacted raw material oil remaining in the resin solution.

Distillation under reduced pressure was carried out until no phenol was distilled off from the resulting crude highly reactive modified phenol resin, and then nitrogen was blown into the crude highly reactive modified phenol resin at 155 ° C. to remove 55% of the phenol. .3g
Was obtained.

The properties of the resulting highly reactive modified phenolic resin are shown in Table 15 together with the reaction conditions.

[0338]

EXAMPLE 69 100 g (0.72 mol) of feed oil P, 115.1 g (1.22 mol) of phenol, 18.9 g (0.63 mol) of paraformaldehyde and 1.5 of oxalic acid
g (0.012 mol) was charged into a 1-liter glass reaction vessel, and the temperature was maintained at 40 ° C. while stirring at a rate of 250 to 350 rpm. After the temperature was stabilized, 1.5 g (0.012 mol) of oxalic acid was further added, and 1 hour was added over 20 minutes.
The temperature was raised to 00 ° C., and the reaction was continued while stirring at the same temperature for 220 minutes to obtain a polycondensation reaction mixture.

Next, the above reaction mixture was charged into heavy naphtha, and unreacted raw materials were removed to obtain a crude highly reactive modified phenol resin. This crude highly reactive modified phenolic resin
Unreacted phenol remaining in the resin was removed by blowing nitrogen at 55 ° C. for 30 minutes.

Next, the temperature of the crude highly reactive modified phenol resin from which phenol was removed was raised to 180 ° C. in a nitrogen atmosphere, maintained for 1 hour, and then lowered to room temperature to obtain 83 g of the highly reactive modified phenol resin. Obtained.

The physical properties of the resulting highly reactive modified phenolic resin are shown in Table 15 together with the reaction conditions.

[0342]

EXAMPLE 70 100 g (0.72 mol) of raw material oil P, 62.4 g (0.66 mol) of phenol, and 12.0 g (0.63 mol) of paraformaldehyde were charged into a 1-liter glass reaction vessel, and the mixture was heated at 250 to 350 rpm. The temperature was maintained at 40 ° C. while stirring at a speed of. After the temperature was stabilized, 0.75 g (0.006 mol) of oxalic acid was added, and the temperature was raised to 90 ° C. over 20 minutes. Then, 0.75 g of oxalic acid
(0.006 mol), the temperature was raised to 100 ° C. over 10 minutes, and the reaction was continued with stirring at the same temperature for 90 minutes to obtain a polycondensation reaction mixture.

The reaction mixture was charged into heavy naphtha,
Unreacted raw materials were removed by heating and stirring to obtain a crude highly reactive modified phenol resin. The resulting crude highly reactive modified phenol resin was subjected to steam distillation at 155 ° C. to remove unreacted phenol remaining in the resin.

Next, the crude highly reactive modified phenol resin from which phenol has been removed is heated to 180 ° C. in a nitrogen atmosphere, kept at the same temperature for 1 hour, and then cooled to room temperature to obtain 8%.
1.2 g of a highly reactive modified phenolic resin was obtained.

The properties of the resulting highly reactive modified phenolic resin are shown in Table 15 together with the reaction conditions.

[0346]

EXAMPLE 71 100 g (0.68 mol) of the starting oil Q, 102.2 g (1.09 mol) of phenol and 19.6 g (0.65 mol) of paraformaldehyde were charged into a 1-liter glass reaction vessel, and the mixture was heated at 250 to 350 rpm. The temperature was maintained at 40 ° C. while stirring at a speed of. After the temperature stabilizes,
1.6 g (0.013 mol) of oxalic acid was added, the temperature was raised to 100 ° C. over 20 minutes, and the reaction was continued with stirring at the same temperature for 100 minutes to obtain a polycondensation reaction mixture.

To this reaction mixture, 170 ml of methanol was added to prepare a resin mixed solution. 170 ml of heavy naphtha was added to the obtained resin mixed solution to remove unreacted raw materials remaining in the resin mixed solution.

Next, methanol was distilled off from the resin mixed solution using an evaporator to obtain a crude highly reactive modified phenol resin. Nitrogen was blown into the resulting crude highly reactive modified phenol resin at 155 ° C. for 30 minutes to remove unreacted phenol remaining in the resin.

Then, the crude highly reactive modified phenol resin from which phenol was removed was heated to 180 ° C. in a nitrogen atmosphere, kept at the same temperature for 1 hour, and then cooled to room temperature for 12 hours.
5.6 g of a highly reactive modified phenolic resin was obtained.

Table 15 shows the physical properties of the obtained highly reactive modified phenolic resin together with the reaction conditions.

[0351]

Example 72 100 g (0.68 mol) of feed oil Q, 102.2 g (1.09 mol) of phenol, 19.6 g (0.65 mol) of paraformaldehyde, and 3.2 oxalic acid
g (0.025 mol) was charged into a 1-liter glass reaction vessel, and stirred at a speed of 250 to 350 rpm.
The temperature was raised to 100 ° C. over 0 minutes, and the mixture was stirred at the same temperature for 100 minutes, and the reaction was continued to obtain a polycondensation reaction mixture.

To this reaction mixture, 120 ml of methyl isobutyl ketone was added to obtain a resin mixed solution. The obtained resin mixed solution was washed with 82 ml of distilled water to remove the acid remaining in the resin mixed solution.

From the obtained acid-removed resin mixed solution, methyl isobutyl ketone was distilled off using an evaporator, and then 170 ml of acetonitrile was added to obtain a resin mixed solution again. 170 ml of heavy naphtha was added to the obtained resin mixed solution.
Was added to remove unreacted raw materials remaining in the resin mixed solution.

After removing acetonitrile from the resin mixed solution by using an evaporator, distillation was performed under reduced pressure until no more phenol was distilled off, thereby obtaining a crude highly reactive modified phenol resin.

The resulting crude high-reactivity modified phenol resin was blown with nitrogen at 55 ° C. to remove the remaining phenol to obtain 131.0 g of a high-reactivity modified phenol resin.

The physical properties of the resulting highly reactive modified phenolic resin are shown in Table 15 together with the reaction conditions.

[0357]

Example 73 100 g (0.68 mol) of feed oil Q, 110.5 g (1.18 mol) of phenol and 0.4 ml of oxalic acid
8 g (0.06 mol) was charged into a 1-liter glass reaction vessel, and stirred at a speed of 250 to 350 rpm.
It was kept at 0 ° C. After the temperature was stabilized, 8.5 g (0.28 mol) of paraformaldehyde was added and the temperature was raised,
When the temperature reaches 70 ° C., the mixture further contains 8.0 of paraformaldehyde.
g (0.27 mol) was added. Subsequently, the temperature was further increased, and when the temperature reached 90 ° C., paraformaldehyde 8.0 was added.
g and oxalic acid 0.8 g (0.06 mol)
The temperature was raised to 00 ° C., and the reaction was continued while stirring at the same temperature for 100 minutes to obtain a reaction mixture.

The reaction mixture was distilled under reduced pressure until almost no phenol was distilled off, and nitrogen was further blown at 155 ° C. to remove unreacted phenol to obtain a crude highly reactive modified phenol resin.

The resulting crude highly reactive modified phenol resin was charged into heavy naphtha to remove unreacted raw materials remaining in the resin. Next, the crude highly reactive modified phenol resin after removing the unreacted raw materials was heated to 180 ° C. under a nitrogen atmosphere,
After holding at the same temperature for 1 hour, the temperature was lowered to room temperature and 121 g
Was obtained.

The properties of the resulting highly reactive modified phenolic resin are shown in Table 15 together with the reaction conditions.

[0361]

Example 74 100 g (0.61 mol) of feedstock R, 108.6 g (1.16 mol) of phenol, 15.6 g (0.52 mol) of paraformaldehyde and 1.6 of oxalic acid
g (0.013 mol) was charged into a 1-liter glass reaction vessel, and stirred at a speed of 250 to 350 rpm.
The temperature was raised to 100 ° C. over 0 minutes, and the reaction was continued while stirring at the same temperature for 100 minutes to obtain a polycondensation reaction mixture.

To the reaction mixture was added 170 ml of acetonitrile to prepare a resin mixed solution, and 170 ml of heavy naphtha was added to the obtained resin mixed solution to remove unreacted raw materials remaining in the resin mixed solution.

Acetonitrile was distilled off from the obtained resin mixed solution using an evaporator to obtain a crude highly reactive modified phenol resin. 1 for crude highly reactive modified phenolic resin
Nitrogen was blown at 55 ° C. for 30 minutes to remove unreacted phenol remaining in the resin.

Next, the crude highly reactive modified phenol resin from which phenol has been removed is heated to 180 ° C. in a nitrogen atmosphere, kept at the same temperature for 1 hour, and then cooled to room temperature to obtain 12%.
1 g of a highly reactive modified phenolic resin was obtained.

The properties of the resulting highly reactive modified phenolic resin are shown in Table 15 together with the reaction conditions.

[0366]

Example 75 Raw oil R (100 g, 0.61 mol), phenol 125.4 g (1.33 mol), paraformaldehyde 24 g (0.80 mol), m-xylene 70.7
g and 1.6 g (0.008 mol) of paratoluenesulfonic acid in a 1-liter glass reaction vessel,
While stirring at a speed of 350 rpm, 10
The temperature was raised to 0 ° C., and the reaction was continued while stirring at the same temperature for 100 minutes to obtain a polycondensation reaction mixture.

To the reaction mixture, 180 ml of methyl isobutyl ketone was added to make a resin mixed solution, and the obtained resin mixed solution was washed with 120 ml of distilled water to remove residual acid in the resin.

The obtained acid-removed resin mixed solution was distilled under reduced pressure until almost no distilling of methyl isobutyl ketone and residual unreacted phenol in the resin was completed.
To give a crude highly reactive modified phenolic resin.

The highly reactive modified phenol resin from which phenol was removed was charged into heavy naphtha, and the mixture was heated and stirred to remove unreacted raw materials remaining in the resin to obtain 108 g of a highly reactive modified phenol resin.

Table 15 shows the physical properties of the obtained highly reactive modified phenolic resin together with the reaction conditions.

[0371]

Example 76 100 g (0.61 mol) of feedstock R, 45 g (0.48 mol) of phenol, 10 g (0.33 mol) of paraformaldehyde, and 10 g of oxalic acid (0.1 g).
063 mol) in a 1 liter glass reaction vessel,
The temperature was raised to 100 ° C. over 20 minutes while stirring at a speed of 250 to 350 rpm, and the reaction was continued while stirring at the same temperature for 100 minutes to obtain a polycondensation reaction mixture.

The reaction mixture was blown with nitrogen at 155 ° C. for 30 minutes to remove unreacted phenol remaining in the resin to obtain a crude highly reactive modified phenol resin. Add 170ml to the crude highly reactive modified phenol resin after removing phenol.
Was added to obtain a resin mixed solution.
170 ml of heavy naphtha was added to the obtained resin mixed solution to remove unreacted raw materials remaining in the resin mixed solution.

Next, the resin mixed solution was distilled under reduced pressure until the distillation of dimethyl sulfoxide almost disappeared. Then, the temperature was further raised to 180 ° C. in a nitrogen atmosphere, kept at the same temperature for 1 hour, and cooled to room temperature to obtain 55 g of A highly reactive modified phenolic resin was obtained.

The properties of the resulting highly reactive modified phenolic resin are shown in Table 15 together with the reaction conditions.

[0375]

Example 77 100 g (0.61 mol) of raw material oil R, 263 g (2.80 mol) of phenol, 63 g (2.10 mol) of paraformaldehyde, and an acidic ion exchange resin Diaion SK1B (manufactured by Mitsubishi Chemical Corporation) 18.8g
Is charged into a 1-liter glass reaction vessel, and 250 to 35
The temperature was raised to 100 ° C. over 20 minutes while stirring at a speed of 0 rpm, and the reaction was continued while stirring at the same temperature for 100 minutes to obtain a polycondensation reaction mixture.

To the above reaction mixture, 340 ml of methyl isobutyl ketone was added to obtain a resin mixed solution. The obtained resin mixed solution was filtered using a 60-mesh wire net to remove the used ion exchange resin.

The obtained acid-removed resin mixed solution was concentrated using an evaporator until the resin concentration reached 60% by weight, and then charged into heavy naphtha to remove unreacted raw materials remaining in the resin.

After the resulting crude highly reactive modified phenol resin was distilled under reduced pressure until almost no unreacted phenol was distilled off, 143 g of the highly reactive modified phenol resin was further blown with nitrogen at 155 ° C. Obtained.

The physical properties of the resulting highly reactive modified phenolic resin are shown in Table 15 together with the reaction conditions.

[0380]

Examples 78-87 The highly reactive modified phenolic resins obtained in Examples 68-77 were used, and epoxy resins (YX
-4000H), except that a curing accelerator-containing resin mixture, a compound and a molded article were produced in the same manner as in Example 8.

Table 16 shows the mixing ratio, physical properties and the like.

[0382]

[Table 15]

[0383]

[Table 16]

Continued on the front page (31) Priority claim number Japanese Patent Application No. Hei 9-264142 (32) Priority date Hei 9 (1997) September 29 (33) Priority claim country Japan (JP) (31) Priority claim number Special 9-328199 Ganpei (32) Priority Date Heisei 9 (1997) November 28 (33) Country of priority claim Japan (JP) (72) Inventor Tomoaki Fujii 4 Kazashi-cho, Kasu-gun, Kashima-gun, Ibaraki Pref. Inside the Kashima Refinery of Oil Co., Ltd. Oil Company Kashima Refinery

Claims (11)

[Claims] 1. A method for producing a highly reactive modified phenolic resin by polycondensing heavy oils or pitches, phenols and formaldehyde compounds, comprising the following methods: 1) heavy oils or pitches; 0.3 mol per 1 mol of the heavy oils or pitches calculated from the average molecular weight.
10 to 10 moles of phenols, 0.2 to 9 moles of formaldehyde compounds in terms of formaldehyde,
After mixing with 0.1 to 3.0 moles of an acid catalyst, the resulting mixture is heated and stirred: 2) Heavy oils or pitches and phenols are mixed and heated and stirred, while heating and stirring. , The acid catalyst and the phenol 1
Method of sequentially adding a formaldehyde compound of not more than 1 mol in terms of formaldehyde to mol: 3) Heavy oils or pitches, phenols, and not more than 1 mol of formaldehyde in terms of 1 mol of the phenols. A method in which a formaldehyde compound is mixed and heated and stirred, and an acid catalyst is sequentially added to the mixture being heated and stirred: 4) Heavy oils or pitches, phenols, and an acid catalyst are mixed and heated and stirred. Then, a method of sequentially adding 1 mol or less of a formaldehyde compound in terms of formaldehyde to 1 mol of the phenol to the mixture under heating and stirring: 5) mixing heavy oils or pitches with an acid catalyst; Heat and stir, and add phenols and phenols 1 to the mixture while heating and stirring.
A method of sequentially adding a formaldehyde compound of not more than 1 mol in terms of formaldehyde to mol: and 6) mixing and heating and stirring an acid catalyst of not more than 1 mol of formaldehyde compound in terms of formaldehyde per 1 mol of phenols. Then, heavy oils or pitches and phenols are successively added to the mixture under heating and stirring: 7) heavy oil or pitches, phenols, and 1 mol of the phenols in terms of formaldehyde. A part of a formaldehyde compound of 1 mol or less is mixed and heated and stirred, and a polycondensation reaction is carried out by one of the following methods: a method of sequentially adding an acid catalyst and the remaining formaldehyde compound to the heated and stirred mixture. A method for producing a highly reactive modified phenolic resin, characterized in that: 2. The method for producing a highly reactive modified phenolic resin according to claim 1, wherein the heavy oils or pitches are petroleum heavy oils or pitches. 3. The heavy oils or pitches are obtained in a catalytic cracking step or a thermal cracking step in a petroleum refining process, have a true boiling point of 180 ° C. or more and 500 ° C. or less, and have an aromatic hydrocarbon fraction fa 3. A distillate having a value of 0.40 to 0.95 and an aromatic ring hydrogen content Ha value of 20 to 80%. A method for producing a reactive modified phenolic resin. 4. The highly reactive modified phenolic resin according to claim 1, wherein an aromatic hydrocarbon compound is used as a raw material in addition to the heavy oils or pitches. Production method. 5. The high-reaction according to claim 1, wherein the acid catalyst is a Bronsted acid selected from the group consisting of an organic acid, an inorganic acid, and a solid acid. Method for producing a modified phenolic resin. 6. The process for producing a highly reactive modified phenolic resin according to claim 1, wherein the acid catalyst is an acidic cation exchange resin. 7. The highly reactive modified phenol according to any one of claims 1 to 6, wherein the heavy oils or pitches are used after being subjected to a paraffin fraction removal treatment. Method of manufacturing resin. 8. The highly reactive modified phenolic resin obtained by the polycondensation reaction comprises (i) a reaction mixture containing the highly reactive modified phenolic resin, an aliphatic hydrocarbon, an alicyclic hydrocarbon and an aliphatic hydrocarbon. A treatment in which an extraction solvent containing at least one compound selected from the group consisting of petroleum fractions is brought into contact with the polycondensation reaction mixture at a temperature at which the mixture is in a fluidized state; And a solvent containing at least one compound selected from the group consisting of aliphatic hydrocarbons having 10 or less carbon atoms, alicyclic hydrocarbons having 10 or less carbon atoms, and aliphatic petroleum fractions. A solution is prepared by diluting the reaction mixture with a soluble solvent, and the obtained solution is separated from the solution containing the highly reactive modified phenol resin to form a liquid-liquid two-layer solution. After standing the reaction mixture heated molten state, the process to remove the supernatant by decantation; to form a medium system and process of contacting an extraction solvent which dissolves the unreacted components of the reaction mixture ^{10-7 -4} mmH
g of a molecular distillation under a high vacuum; and a solution is prepared by diluting the reaction mixture with a soluble solvent, and the resulting solution and water are mixed and allowed to stand. 3 consisting of resin solution layer, water layer and unreacted oil layer
Removing the unreacted components from the reaction mixture, by forming at least one treatment selected from the group consisting of: removing the aqueous layer and the unreacted oil layer after forming the layer solvent system; (ii) the catalyst Removing the residue, and (ii)
i) Purification in at least one step selected from the group consisting of: a step of removing residual phenols by any of steam distillation, nitrogen gas blowing and vacuum distillation. The method for producing a highly reactive modified phenolic resin according to any one of the above. 9. A modified phenolic resin molding material comprising a highly reactive modified phenolic resin obtained by the method according to claim 1 and an epoxy resin. 10. A material for electric / electronic parts obtained by molding the modified phenolic resin molding material according to claim 9. 11. A semiconductor encapsulant comprising the modified phenolic resin molding material according to claim 9.