JP2001064341A - Production of modified phenolic resin and molding material, electrical and electronic component material, semiconductor sealing material, and flame-retardant resin composition all containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a modified phenolic resin having a low melt viscosity and high reactivity with an epoxy resin simply and stably in one step by mixing a heavy oil or a pitch with a specified concentration of a phenol and a specified concentration of a formaldehyde compound and an acid catalyst and polycondensing the mixture by heating under agitation. SOLUTION: A heavy oil or a pitch (1 mol) is condensed with above 10 to 50 mol of a phenol and 1.0-40 mol (in terms of formaldehyde) of a formaldehyde compound. It is also possible that a mixture obtained by mixing all the condensible materials including a catalyst is polycondensed by heating under agitation or that a mixture obtained by mixing specified materials is polycondensed by heating under agitation while the remaining condensible materials are gradually added to the condensation system. When the heavy oil or the pitch is derived from petroleum, it is desirably a selected one having an aromatic hydrocarbon fraction fa of 0.40-0.95 and an aromatic ring hydrogen content Ha value of 0.20-0.80.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a combination of an epoxy resin and an epoxy resin to improve heat resistance, moisture resistance, corrosion resistance, adhesiveness, and mechanical properties such as dimensional stability and strength. A modified phenol that can easily produce a low-viscosity modified phenol resin that becomes an excellent molded product in one step, can be supplied stably, and can use a cost effective polycondensation raw material. The present invention relates to a method for producing a resin.

Further, the present invention relates to a modified phenol resin molding material containing a modified phenol resin and an epoxy resin obtained by this method, a material for electric and electronic parts, a semiconductor encapsulant, and a new and useful modified phenol resin. The present invention relates to a composition for a flame-retardant urethane resin used.

[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. 61-23541
No. 3 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.

Japanese Patent Application Laid-Open No. 2-274714 discloses that a conventional phenol resin can be obtained by using petroleum heavy oils or pitches, which are inexpensive raw materials, as a modifying material 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 phenol resin is produced, a crude modified phenol resin obtained by polycondensing a raw material compound is subjected to a neutralization treatment, a water washing treatment and / or an extraction treatment. It is disclosed that a modified phenol resin that does not corrode a metal member in contact with the resin can be provided by neutralizing and removing the acid remaining in the crude modified phenol 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 phenol resin can be provided in a purification step including a special extraction treatment to provide a modified phenol 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.

However, these modified phenolic resins have a high resin melt viscosity and are not suitable for rapidly and mass-producing molded articles having complicated shapes, and also have a heat resistance when combined with epoxy resins. There has been a demand for further improvements in mechanical properties such as properties and dimensional stability and strength. Therefore, the present inventors have developed a method of reducing the molecular weight by reacting 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. Thus, a method for producing a modified phenol resin capable of producing a modified phenol resin having a low resin melt viscosity and improved reactivity with an epoxy resin has been proposed (JP-A-7-2523).
39, JP-A-9-216927).

The modified phenolic resin thus obtained has high reactivity with the epoxy resin, low resin melt viscosity and good moldability. When combined with the epoxy resin, heat resistance and moldability are improved. It is possible to provide a molding material which is good and excellent in mechanical properties such as dimensional stability. However, such a method for producing a modified phenol resin requires two steps of 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 in the production of electric products, electric, electronic parts and semiconductors are exposed to high temperatures, and from this viewpoint, electric, electronic parts and semiconductor encapsulants are used. There is a demand for further improvement in heat resistance of the modified phenol resin used as a resin material. Further, if the resin material has a high hygroscopicity, there is a problem in that the water evaporates rapidly during the soldering operation, which may cause solder cracks and may corrode the composite metal material.

[0011] In the fields of electric, electronic parts and 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 phenol resin, further improvement in hygroscopicity and improvement in adhesiveness have been demanded.

Urethane resins generally have good toughness, abrasion resistance, aging resistance, heat resistance and the like, and are easy to process as foams. Is widely used in applications such as vibration damping materials, building materials, and structural materials. However, urethane resin is not only easily melted and softened by heat when exposed to a flame, but also easily ignited depending on the type.

Further, since a large amount of smoke is generated at the time of combustion and highly toxic cyan gas and carbon monoxide are generated, it is strongly desired to impart high flame retardancy for fire prevention measures. Conventionally, in order to impart flame retardancy to urethane resins, it has been common to use chlorine-containing phosphate esters, bromine-based polyols and bromine-containing phosphate esters as flame retardants.

[0014] However, although the flame retardancy of these conventional urethane resins to which a flame retardant is added is improved, there is a problem that harmful halogen compounds represented by dioxin and the like are generated during combustion. 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 obtained by redistilling the bottom oil obtained in the conventional catalytic cracking step. 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 studied and studied various methods for producing a modified phenol resin having the above-mentioned excellent properties more easily, and as a result, have found that a specific raw material containing a catalyst at a specific quantitative ratio can be obtained. It has been found that by mixing and performing polycondensation, a modified phenol resin having high reactivity with an epoxy resin and low viscosity can be obtained in a single step in a high yield.

Further, the present inventors have found that a molding material obtained by combining the modified phenol resin and the epoxy resin has excellent moldability and excellent heat resistance, moisture resistance, corrosion resistance, adhesiveness and dimensional stability. It has been found that molded articles having particularly excellent heat resistance and moisture resistance, such as mechanical properties such as strength, and that the urethane resin produced using the modified phenol resin has high flame retardancy. Was.

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

[0018]

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

Further, the present invention comprises a modified phenolic resin and an epoxy resin obtained by the above method, and has a mechanical strength such as moldability, heat resistance, moisture resistance, corrosion resistance, adhesiveness and dimensional stability. In particular, it is an object of the present invention to provide a molding material capable of producing a molded article excellent in heat resistance and moisture resistance, in particular, a material for electric / electronic parts and a semiconductor encapsulant, and a flame-retardant urethane resin composition containing the modified phenol resin. The purpose is.

[0020]

SUMMARY OF THE INVENTION In the method for producing a modified phenolic resin according to the present invention, a specific amount of heavy oils or pitches, a phenol, a formaldehyde compound, and an acid catalyst are mixed, and the resulting mixture is mixed. It is characterized in that these heavy oils or pitches, phenols and formaldehyde compounds are polycondensed by heating and stirring.

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 catalyst) (second to seventh methods). In the first to seventh modified phenolic resin production methods according to the present invention, as heavy oils or pitches, petroleum or coal-based ones, particularly a catalytic cracking step, a thermal cracking step or a catalytic reforming step in a petroleum refining process. It is possible to use a specific distillate or residual oil obtained in the refining process, and it is possible to further add an aromatic hydrocarbon compound as a raw material.

In the first to seventh modified phenolic resin production methods according to the present invention, it is desirable to use a Bronsted acid selected from the group consisting of organic acids, inorganic acids and solid acids as the acid catalyst. In the first to seventh modified phenol resin production methods according to the present invention, the heavy oils or pitches may be used after the paraffin fraction which is a low-reactive component is removed.

Further, in the production method of the present invention, the modified phenol resin obtained by the polycondensation reaction is subjected to (i) a step of removing unreacted components from the reaction mixture, (ii) a step of removing catalyst residues, and (iii) It is desirable to purify in at least one step selected from the group consisting of the step of removing residual phenols and use it for various applications. The modified phenolic resin molding material according to the present invention is characterized by containing the modified phenolic resin obtained by the above-described method and an epoxy resin. The modified phenolic resin molding 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 obtained by molding the above modified phenolic resin molding material. Furthermore, a semiconductor encapsulant according to the present invention is characterized by being made of the above modified phenolic resin molding material. Further, the flame-retardant resin composition according to the present invention is characterized by comprising the modified phenolic resin obtained by the above-mentioned method, a polyol, an isocyanate, a blowing agent and a catalyst.

[0025]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the present invention will be described more specifically. In the method for producing a 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 to produce a modified phenolic resin. ing.

As the heavy oils or pitches used as raw materials in the polycondensation reaction of the present invention, any of petroleum-based and coal-based raw oils may be used. Petroleum heavy oils or pitches include crude oil distillation residue, hydrogenolysis residue, catalytic cracking residue, catalytic reforming residue, naphtha or LPG pyrolysis residue, and vacuum distillation of these residues. Extract, heat-extracted product by solvent extraction, specific distillate oil or residual oil obtained in cracking process such as thermal cracking and catalytic cracking in petroleum refining process, and residual oil in catalytic reforming of naphtha etc. A reduced-pressure distillate can be exemplified. As coal-based heavy oils or pitches,
Specific fraction components obtained by distilling coal tar in coal dry distillation and heavy oil in coal liquefaction can be exemplified.

In the case of petroleum heavy oils or pitches, it is preferable to select and use appropriate aromatic hydrocarbon fraction fa values and aromatic ring hydrogen content Ha values. 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, respectively, based on the following equations.

[0029]

(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.

H of raw petroleum heavy oils or pitches
If the a value is less than 20%, the amount of aromatic ring hydrogen that reacts with formaldehyde decreases and the reactivity decreases, so that the effect of modifying the performance of the phenol resin tends to decrease. 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, distillate oil and residue oil obtained in cracking or reforming processes such as thermal cracking, catalytic cracking and catalytic reforming in a petroleum refining process are used. Is particularly preferable from the viewpoint of stable supply of the raw material and the like. In the petroleum refining process, the raw materials used in such a cracking or reforming step include, for example, tar sands, straight-run naphtha obtained in the distillation step, straight-run heavy gas oil, atmospheric distillation residue, and vacuum distillation residue. And a residual oil such as a desulfurized vacuum heavy gas oil and a desulfurized heavy oil obtained in the desulfurization step, a refined oil or an intermediate refined oil. 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, and straight-run naphtha is used in catalytic reforming.

The catalytic cracking method, the thermal cracking method and the catalytic reforming method applied to the production of such distillate oil and residual oil are not particularly limited as long as the distillate oil and residual oil having the desired physical properties described above can be obtained. However, any method conventionally used in the field of petroleum refining may be used. Thus, for example, catalytic cracking methods include moving bed catalytic cracking, airlift / thermophor catalytic cracking, food reflow catalytic cracking, fluidized bed catalytic cracking (FCC), UOP catalytic cracking, shell catalytic cracking, Esso IV type catalytic cracking method, ortho flow catalytic cracking method and the like can be mentioned. Examples of the pyrolysis method include delayed coking method, fluid coking method, flexi coking method, visbreak method, Yurika method, CHERY-P method, ACTIV method, KKI method, coke fluidized bed coking method and ACR method. be able to. Further, examples of the contact reforming method include a platform forming method, a power forming method, a cat forming method, a food reforming method, a reni forming method, a hydroforming method, and a hyperforming method.

In the cracking or reforming step, the catalytic cracking product, the thermal cracking product and the catalytic reforming product obtained by such a method are separated into fractions having various boiling points and various compound compositions. Among them, the distillate oil and the residual oil suitably used in the present invention are the above-mentioned aromatic hydrocarbon fraction f
It has an a value and an aromatic ring hydrogen content Ha value, and has a lower limit of boiling point (distillation starting temperature) of 170 ° C. or higher, preferably 180 ° C. or higher, more preferably 190 ° C. or higher.

The lower limit of the boiling point (distillation starting temperature) is 170
When a distillate oil having a temperature lower than 0 ° C. is used, the amount of the condensed polycyclic aromatic component contained in the feedstock oil is small, and the reactivity decreases. The distillation fraction of coal tar described above as a coal-based raw material has a boiling point of 200 ° C. or higher, preferably 200 to 360 °.
It is a fractionation component having a boiling point of ° C. Coal carbonization is an essential step in the coal chemical industry, and is performed to produce gas, coal tar, coke, and the like from coal.

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 coal distillation method. In addition, coal tar has a high-temperature tar (900 to 1200 ° C) and a low-temperature tar (450 to
700 ° C), each having a different composition and properties.

In the present invention, the fractionated component used as the coal-based heavy oils or pitches may be obtained by distilling any coal tar 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 at the time of coke production, tar gas oil (boiling point of about 94 to
178 ° C), carbol gas oil (calcium carbonate: boiling point about 168-
200 ° C), naphthalene oil (medium oil) and absorbent oil (boiling point about 202-223 ° C), heavy oil (boiling point about 218-314)
° C), anthracene oil (boiling point about 296 to 360 ° C) and pitch (residue: boiling point about 450 ° C or more) are obtained as fractional components.

Among these, the fractionated components having a boiling point of 200 ° C. or higher 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 less than 200 ° C. is used, the amount of the condensed polycyclic aromatic component contained in the feedstock oil is small, and the reactivity is reduced.

Coal liquefaction is carried out to produce gasoline and the like from coal. The coal is made to react with high-pressure hydrogen (200 to 700 atm) at a high temperature of about 500 ° C. to cleave the coal structure, deoxygenate and desorb sulfur. This is a step of converting into lower hydrocarbons by various reactions such as denitrification and hydrogenation. In the present invention, as the coal-based heavy oils or pitches, heavy oil produced by such coal liquefaction can also be used. You may mix and use with one or more types of 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 phenols, acidic compounds such as carboxylic acids, and carbazoles,
Basic compounds such as pyridines, anilines, and quinolines may be contained, and it is desirable to remove these.

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 two or more condensed polycyclic aromatic hydrocarbons. Preferably, it is configured.
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.

Also, 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. Such a removal treatment of the paraffin fraction can be performed, for example, by column chromatography according to a conventional method.

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. Further, as the developing agent used in such chromatography, n-pentane, n-hexane, n-heptane, aliphatic saturated hydrocarbon compounds having 5 to 8 carbon atoms such as n-octane, diethyl ether and the like Examples include halogenated hydrocarbons such as ether, 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 the hydroxybenzene compound 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, 1,4-dihydroxynaphthalene and 2,3-dihydroxynaphthalene, 3 , 6-dihydroxynaphthalene, 1,
Dihydroxynaphthalene compounds such as 5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene; and alkyl groups, aromatic groups, halogen atoms, and the like. The mono or dihydroxy naphthalene compound having a substituent, for example, 2-methyl-1-naphthol, 4-
Examples thereof include phenyl-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol and the like. These phenols may be used alone or in combination of two or more.

In the method for producing a modified phenolic resin according to the present invention, such phenols are used in an amount of more than 10 mol and not more than 50 mol per mol of heavy oils or pitches calculated from the average molecular weight. Preferably, it is used in an amount of 40 mol or less, more preferably 35 mol or less. When this phenol is used in an amount of 10 mol or less, the resin yield does not improve,
It may be disadvantageous in terms of cost, and when used for producing a urethane resin, it may not be possible to impart high flame retardancy. On the other hand, when the amount of the phenol exceeds 50 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 are bonded by a bond or a hydrocarbon bonding group. They may be combined.

Examples of the hydrocarbon group serving as 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. As such an aromatic hydrocarbon compound, a compound having a non-condensed aromatic ring, specifically, an alkyl-substituted benzene compound such as toluene, o-xylene, m-xylene and p-xylene, chlorobenzene, o- Chlorotoluene, m-chlorotoluene and p-
Examples thereof include a halogenated benzene compound such as chlorotoluene (an alkyl substituent may be substituted).

In the first to seventh modified phenolic resin production methods according to the present invention, the aromatic hydrocarbon compound is selected from heavy oils or pitches 1 calculated from the average molecular weight.
0.1 to 5 mol, preferably 0.5 to 3 mol, per mol
Mole, more preferably 0.5 to 2 mole. When the aromatic hydrocarbon compound has a content of 0.
If used in an amount of less than 1 mol, the desired improvement in hygroscopicity and adhesiveness may not be obtained. On the other hand, when the amount of the aromatic hydrocarbon compound exceeds 5 mol, 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. 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 modified phenolic resin according to the present invention, such a formaldehyde compound is used in an amount of 1.0 mol or more in terms of formaldehyde with respect to 1 mol of heavy oils or pitches calculated from the average molecular weight. Preferably, it is used in an amount of 2.0 mol or more and 40 mol or less, preferably 35 mol or less, more preferably 30 mol or less.

When the amount of the formaldehyde compound is less than 1.0 mol per 1 mol of the heavy oils or pitches, the yield of the resin decreases 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 40 mol, the resulting modified phenolic resin is polymerized to not only obtain a desired viscosity but also extremely harden the reaction mixture.

In the second to seventh 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 the 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 obtained modified phenol resin is polymerized and the desired viscosity cannot be obtained, but also the reaction mixture may solidify extremely. is there.

In the polycondensation reaction of 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 preferred as organic acids and inorganic acids. 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. As the base resin,
Polystyrene, styrene / divinylbenzene copolymer,
Examples thereof include 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 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, based on 1 mol of heavy oils or pitches calculated from the average molecular weight. It is used in an amount of 3 mol or less, preferably 2 mol or less. In the second to seventh 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 heavy oils or pitches calculated from the average molecular weight. It is more preferable that the amount is 2 mol or less. When an acidic cation exchange resin is used 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 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 then the resulting mixture is heated and stirred to perform a polycondensation reaction.

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 lower, preferably 40 to 50 ° C. Mix evenly. Then, the obtained mixture is gradually heated to a temperature of 50 to 200 ° C, preferably 80 to 200 ° C, more preferably 80 to 180 ° C,
The polycondensation reaction is carried out for 5 minutes to 8 hours, preferably for 30 minutes to 6 hours.

The mixing of the polycondensation raw materials 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 seventh modified phenolic resin production methods according to the present invention, in the polycondensation reaction using the raw material and the acid catalyst described above, at least one of heavy oils or pitches, an acid catalyst and a formaldehyde compound Are sequentially added.

That is, in the second method for producing a modified phenolic resin according to the present invention, first, heavy oils or pitches and phenols are mixed and heated and stirred. A formaldehyde compound and an acid catalyst are sequentially added. 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 into the mixture under heating and stirring (seventh production method),
The remaining formaldehyde compound is added sequentially with the acid catalyst.

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

In the fifth method for producing a 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 under heating and stirring is mixed with phenol. And the formaldehyde compound are added sequentially. And the sixth method for producing a modified phenolic resin according to the present invention comprises the steps of first mixing a formaldehyde compound and an acid catalyst and heating and stirring the mixture, and then mixing the mixture under heating and stirring with heavy oils or pitches. Phenols are added sequentially.

In the second to seventh modified phenolic resin production methods according to the present invention, the sequential addition of heavy oils or pitches, an acid catalyst and / or a formaldehyde compound is carried out by a method such as dropping and the like. Minutes, preferably 20 to 80 minutes. If the addition time is less than 10 minutes, the reaction proceeds abruptly 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 according to the present invention, the sequential addition to the mixture during heating and stirring is not particularly limited at the start time, and the mixture during 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, but the sequential addition of the formaldehyde compound starts and ends in synchronization with the sequential addition of the acid catalyst. At this time, it is desirable to mix both. Further, the sequential addition of the formaldehyde compound may be performed separately from the acid catalyst, and in this case, even when synchronized with the sequential addition of the acid catalyst,
For example, it may be started 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 the raw material and the 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 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 to seventh manufacturing methods can be performed under the same conditions.

In the first to seventh 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. Such solvents include, for example, nitrated aromatic hydrocarbons such as nitrobenzene;
Examples include nitrated aliphatic hydrocarbons such as nitroethane and nitropropane; and halogenated aliphatic hydrocarbons such as perchrene, trichlene and carbon tetrachloride.

The method for producing a modified phenol resin according to the present invention described above is different from the method for producing a modified phenol resin disclosed in JP-A-7-252339 and the like.
There is no need for a low molecular weight step, and the number of steps is significantly reduced. The modified phenolic resin according to the present invention is excellent in moldability due to a low resin melt viscosity, has high reactivity with an epoxy resin, and is compared with a modified phenolic resin disclosed in JP-A-7-252339. Further, it has excellent heat resistance. The modified phenolic resin of the present invention has excellent adhesiveness and low hygroscopicity when it contains an aromatic hydrocarbon compound as a raw material. It is possible to provide a modified phenolic resin molding material which is excellent in mechanical properties such as strength, moisture resistance and heat resistance, and exhibits excellent adhesiveness and low moisture absorption.

The modified phenolic resin thus produced can be used for various purposes. However, since unreacted components and acid catalysts may remain in the resin, the modified phenolic resin may be appropriately purified. It is desirable to remove unreacted components, low molecular components, acid catalysts, reaction solvents and the like. Examples of a method for purifying a reaction mixture, that is, a crude modified phenol resin containing an acid catalyst, an unreacted substance, a low-molecular component, and a reaction solvent include (i) a purification treatment for removing an unreacted component from the reaction mixture, and (ii) A purification treatment for removing a catalyst residue from the reaction mixture, and (iii) a purification treatment for removing residual phenols by any of steam distillation, nitrogen gas blowing, and reduced pressure distillation can be given.

In the refining treatment (i), of the components contained in the heavy oils or pitches used as the 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 unreacted components from the reaction mixture, the polycondensation reaction product obtained by the first to seventh polycondensation methods and a specific extraction solvent are mixed at a temperature at which the reaction mixture becomes a fluid state. Contacting to remove unreacted substances contained in the reaction mixture, for example, low-reactive substances contained in heavy oils or pitches, or low-molecular components remaining in an insufficiently reacted state in addition thereto .

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
Form a liquid-liquid two-phase system or solution with the reaction mixture based on the modified phenolic resin at the above-mentioned temperatures, 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. Examples of the alicyclic hydrocarbon include 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 a fluid state. 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.

Further, when the reaction mixture and the extraction solvent are brought into contact with each other, by stirring and mixing them, 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, the increase in the contact area between the two by stirring promotes rapid and efficient extraction of unreacted substances. Such a first treatment may be performed while refluxing, or may be performed in a closed system without refluxing, in order to prevent a reduction in the amount of extraction solvent due to evaporation.

In the first treatment, the reaction mixture is brought into contact with the extraction solvent at, for example, 50 to 200 ° C., preferably 70 to 200 ° C.
To 130 ° C, more preferably 80 to 120 ° C. 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. It is desirable to use 0.5 to 4 ml, preferably 1 to 2 ml, based on 1 g of the weight.

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 process, 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 may be one, and the extraction solvent may be renewed. It may be repeated several times. According to such a first treatment, the extraction operation is performed while the reaction mixture is in a fluid state, so that unreacted substances can be efficiently removed with a small amount of solvent, and the liquid-solid two-phase is used during the contact operation. Since there is no need to maintain the system, the setting of the contact temperature becomes easy.

In another treatment (second treatment) applicable in the purification step (i), first, the reaction mixture obtained by the polycondensation reaction or the crude modified phenol resin is dissolved in a solvent soluble in the reaction mixture. I do. Examples of such a soluble solvent include 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, toluene and tetrahydrofuran, and diethyl. Examples of the solvent include a mixed solvent with ethers such as ether and methyl tertiary butyl ether.

The solution obtained by dissolving the crude modified phenolic resin in these soluble solvents has a low viscosity and good operability, so that the purification operation becomes easy. 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 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 or the crude modified phenol resin obtained by the polycondensation reaction 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 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. Components, that is, unreacted components, components remaining after a low reaction, and a reaction solvent during the polycondensation reaction are extracted and removed.

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 solvents having 10 or less carbon atoms, 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 of the extraction solvent to the crude modified phenol resin solution (extraction solvent / solution) is not particularly limited, but is usually 10/90 to 90/10, preferably 20/8.
0 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.

Another treatment of purification step (i) (fourth treatment)
First, the reaction mixture or the crude modified phenolic resin obtained by the polycondensation reaction is allowed to stand while being heated and melted. By allowing the crude modified phenol resin to stand in a heated state, unreacted components, components remaining after a low reaction, a reaction solvent during the polycondensation reaction, and the like are separated from the modified phenol resin as a supernatant.

In the fourth treatment, the crude modified phenolic resin is usually treated at 70 to 200 ° C., preferably at 80 to 180 ° C.
More preferably, it is maintained in a heated and melted state at a temperature of 80 to 150 ° C., and usually 15 minutes to 4 hours, preferably 20 minutes to
Let stand for 4 hours. According to the fourth treatment, the supernatant containing the unreacted components and the like can be easily separated and removed from the modified phenol resin by decantation, so that it is not necessary to use a solvent or the like in removing the unreacted components. There are advantages.

In still another treatment (fifth treatment) in the purification step (i), the reaction mixture obtained by the polycondensation reaction or the crude modified phenol resin is directly used for 10 ^-7 to 10 ^-4 mm
The molecular distillation is performed under a high vacuum of Hg to remove unreacted components, components remaining after a low reaction, a reaction solvent during the polycondensation reaction, and the like. Such a fifth treatment has an advantage in that a modified phenolic resin in a dry state containing no unreacted components or the like can be directly obtained, so that a separation operation of a solvent or the like containing unreacted components or the like is not required. ing.

In the last example (sixth treatment) applicable in the purification step (i), first, a crude 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,
In particular, a mixed solvent of toluene and methyl isobutyl ketone is preferably used.

Next, the resulting solution was mixed with water and allowed to stand to form a three-layer solvent system consisting of a modified phenol resin solution layer, an aqueous layer and an unreacted oil layer in this order from the bottom. And the aqueous layer. According to the sixth treatment, since the unreacted oil layer completely separates the modified phenol resin layer via water, it can be reliably and easily removed, and the acid catalyst is extracted into the aqueous layer. To be
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 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 modified phenol resin layer becomes too light and becomes less than 1, 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. In the case where the second treatment is not performed, the first and third to sixth treatments are carried out by directly treating the crude modified phenolic resin with an aliphatic hydrocarbon having 10 or less carbon atoms or an alicyclic carbon having 10 or less carbon atoms. It may be combined with a process of charging a solvent containing at least one compound selected from the group consisting of hydrogen and an aliphatic petroleum fraction.

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 is brought into contact with a specific extraction solvent at a temperature at which the polycondensation reaction mixture is in a fluidized state, so that the polycondensation reaction mixture is not mixed. Since the reaction product is extracted and removed with the extraction solvent, for example, the unreacted product extraction conditions can be easily set 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 modified phenol resin substantially containing no acid is obtained. Such a purification treatment (i
i) In the case where an organic acid and an inorganic acid are used as the acid catalyst, the reaction mixture is used as it is or by dissolving it in a specific solvent and washing with water or washing with an aqueous alkali solution to remove catalyst residues. It is. Note that washing with an alkaline aqueous solution has an advantage that unreacted phenols can be removed together with the acid catalyst.

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. Also in this purification treatment (ii), the reaction mixture may be dissolved in the above solvent in order to improve workability such as filtration.

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 purification processes (i) and (ii) described above can be performed in any order. Further purification treatment (iii)
In the above, by removing the unreacted components and the acid catalyst and the like in the reaction mixture as it is or in the purification treatment (i) and / or the purification treatment (ii), steam distillation, blowing of nitrogen, or distillation under reduced pressure is performed. The remaining unreacted phenols are removed. 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 substantially contains no acid and thus has no corrosiveness to metals. In addition, since the reactivity with the epoxy resin is improved, a 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 modified phenolic resin obtained by the method for producing a 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, dicyclopentadiene type epoxy resin, etc .; as glycidyl ether type (alcohol type), polypropylene glycol type epoxy resin, hydrogenated bisphenol A type epoxy resin, etc .; Phthalic anhydride 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 resin, p-oxybenzoic acid type epoxy resin and the like. 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 modified phenol resin and the epoxy resin is not particularly limited, but is 10/90 to 90/10 (parts by weight) with the total of the modified phenol resin and the epoxy resin being 100 parts by weight. It is preferably 20/80 to 80/20 (parts by weight). If 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 if 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, hexamethylenetetramine and the like as cyclic amines; diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperamine and the like as aliphatic amines Examples include isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, and menthanediamine.

Polyamides include vegetable oil fatty acid (dimer or trimer acid) polyamides, aliphatic polyamine condensates, etc .; Aromatic polyamines include m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'- Examples thereof include diaminodiphenyl sulfone and m-xylylenediamine.

Examples of 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 the 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 polymercaptan and polysulfide. These curing agents and curing accelerators may be used alone or in combination of two or more.

The above-mentioned modified phenolic resin molding material contains, in addition to the above-mentioned modified phenolic resin, epoxy resin and, if necessary, a curing agent and / or a curing accelerator,
Further, an inorganic filler may be contained. By adding an inorganic filler to the resin molding material, the strength, dimensional stability, and the like of the obtained molded body 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, reinforcing materials such as glass fiber, carbon fiber, phosphor fiber, and boron fiber can be used. 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; inorganic fillers such as silica, mica and fused silica; Can be mentioned.

The amount of such an inorganic filler is not particularly limited. For example, the amount is usually 2 parts per 100 parts by weight of a resin component obtained by adding an epoxy resin to a modified phenol resin.
0 to 2000 parts by weight, preferably 20 to 800 parts by weight,
More preferably, it is used in an amount of 50 to 600 parts by weight. Further, the above-mentioned modified phenolic resin molding material may further contain additives, if necessary. Examples of such additives include silicone, internal mold release agents such as waxes, and coupling agents. , Flame retardant, light stabilizer,
Examples include antioxidants, pigments, extenders, and the like.

The modified phenolic resin molding material according to the present invention described above comprises a modified phenolic resin and an epoxy resin, and if necessary, a curing agent and / or a curing accelerator,
Prepared by mixing inorganic fillers and various additives,
Applied to manufacture of molded articles. In the present invention, the order of mixing the modified phenolic resin and the epoxy resin with an optional component such as a curing agent is not particularly limited. For example, the modified phenolic resin and the epoxy resin are kneaded, and a curing agent (curing accelerator) is used. , And further mixed well, and if necessary, an inorganic filler and other additives are added and mixed to obtain a fine powdery molding powder (compound).

Specifically, such a compound is
It can be prepared by the following procedure. The modified phenol resin and the 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.

[0115] The inorganic filler is added and mixed. Furthermore, 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 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 manufactured by transfer molding using the modified phenolic resin molding material according to the present invention, a molding temperature of 120 to 200 ° C. and an injection pressure of 5
３００300 kgf / cm ² , preferably 20-300 kg
Molding conditions of f / cm ² , a mold clamping pressure of 50 to 250 kgf / cm ^2, and a molding time of 1 to 10 minutes are desirable.

[0117] 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. In the modified phenolic resin molding material according to the present invention, the melt viscosity is low, the reactivity with the epoxy resin is high, and particularly, the modified phenolic resin which is improved in heat resistance, adhesiveness and low hygroscopicity is used, The moldability is good, and the mechanical properties such as dimensional stability of the obtained molded article, moisture resistance, heat resistance, adhesion 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.

The composition for a flame-retardant urethane resin according to the present invention is used particularly for producing a foam, and contains the modified phenol resin of the present invention, a polyol, an isocyanate, a blowing agent and a catalyst. Examples of polyols include aliphatic diols such as glycol; aromatic diols such as bisphenol A; triols such as glycerol; tetraols such as pentaerythritol; polyalkylene glycols; Polyether polyols such as alkylene glycols and sugar alcohols, or addition polymers of alkylene oxides with compounds having two or more active hydrogens such as ethylenediamine; and the above-mentioned diols, triols, tetraols, polyalkylene glycols and sugar alcohols Polyesters such as esters of a compound having two or more hydroxyl groups and an acid having two or more carboxyl groups such as adipic acid, phthalic acid and 1,4-cyclohexanedicarboxylic acid And which may or may not be reall. These polyols may be used alone or in combination of two or more.

As the isocyanates, generally used aromatic polyisocyanates, alicyclic polyisocyanates or aliphatic polyisocyanates can be employed. Specific examples of the isocyanates include 2,4- and 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,2'-diphenylmethane diisocyanate, and polymethylene polyphenyl polyisocyanate. These isocyanates may be used alone or in combination of two or more.

The amount of such isocyanates used is as follows:
Equivalent ratio of isocyanate group to hydroxyl group (NCO / OH)
It is desirable to use it in a ratio of 1.0 to 1.3. In the composition for a flame-retardant urethane resin according to the present invention, the amount of the modified phenolic resin is not particularly limited, but is preferably 1 to 60 parts by weight, more preferably 2 to 60 parts by weight, per 100 parts by weight of polyols. 30 parts by weight. 1
If the amount is less than 60 parts by weight, no improvement in flame retardancy is observed. If the amount exceeds 60 parts by weight, the improvement in flame retardancy not only reaches a peak, but also the physical properties of the foam in the case of urethane foam tend to be remarkably reduced.

As the catalyst, various compounds conventionally used in the production of polyurethane can be used. For example, dimethylethanolamine, dimethylaminoethoxyethanol, triethylenediamine, bis (2-dimethylaminoethyl) ether , N, N,
N ', N'-tetramethylhexamethylenediamine,
N, N ', N', N "-pentamethyldiethylenetriamine, 2,4,6-tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol, 2,6-di-t-butyl Examples thereof include -4-dimethylaminotrimethylsilanephenol, triethylaminediazabicycloundecene, lead naphthenate, lead octenoate, iron octenoate, iron naphthenate, and organotin compounds (such as dibutyltin dilaurate and tin octylate).

Such a catalyst varies depending on the activity of the catalyst, but is usually 0.1 to 100 parts by weight of polyols.
It is used in an amount of from 0.01 to 2.0 parts by weight. As the foaming agent, an organic liquid or water that is easily evaporated at a low boiling point is generally used, and the type thereof is not particularly limited. Such foaming agents include, for example, petroleum ether, naphtha, pentane,
Volatile oils such as hexane; low molecular weight fatty acid esters such as ethyl acetate; ketones such as methyl ethyl ketone and acetone; lower aliphatic monohydric alcohols such as methyl alcohol and ethyl alcohol; methylene chloride, carbon tetrachloride, trichlorofluoromethane; Trichlorotrifluoroethane, dichloromethane, trichloroethane, dichloromethylene, low boiling point halogenated hydrocarbons such as trifluorotrichloromethane, or water and the like, and these can be used alone or in combination of two or more. May be used.

The amount of these foaming agents is not particularly limited.
For example, it is appropriately adjusted according to the desired density (expansion ratio) of the foam to be produced. However, the addition amount of a general foaming agent is 1 to 4 with respect to 100 parts by weight of polyols.
0 parts by weight, preferably 10 to 30 parts by weight. These are reacted by stirring to obtain a flame-retardant urethane resin.

The composition for a flame-retardant urethane resin according to the present invention may contain a foam stabilizer in addition to the resin composition, the catalyst and the foaming agent. Such foam stabilizers include, for example, various polyoxyethylene alkyl phenyl ethers acting as foam stabilizers, nonionic surfactants such as castor oil ethylene oxide adducts, or anionic surfactants such as metal soaps Or an amphoteric surfactant such as lecithin and a silicone-based foam stabilizer can be mentioned, and the use of a silicone-based foam stabilizer is particularly desirable.

[0126]

According to the first to seventh methods for producing a modified phenolic resin according to the present invention, it is possible to reduce the number of steps for lowering the molecular weight, which is indispensable in the conventional method, to achieve a higher yield. In addition to having a low resin melt viscosity and a high reactivity with an epoxy resin, a modified phenol resin useful as a flame-retardant urethane resin raw material can be produced in one step.

In the first to seventh modified phenol resin production processes according to the present invention, a polycondensation feedstock which can be efficiently and stably supplied and is advantageous in cost, that is, a catalytic cracking step in a petroleum refining process By using the distillate oil or residual oil of specific physical properties obtained in the pyrolysis step or the catalytic reforming step without performing treatment such as distillation under reduced pressure, the modified phenol resin having the above-mentioned excellent properties can be stabilized. And can be supplied economically.

Further, according to the method for producing a modified phenol resin according to the present invention, the modified phenol resin obtained by the polycondensation reaction is further purified to remove unreacted components, acid catalysts and the like. Manufactures modified phenolic resin with low melt viscosity, high reactivity with epoxy resin, excellent heat resistance, adhesiveness and low hygroscopicity, and substantially non-acidic and non-corrosive It is possible to

The modified phenolic resin molding material according to the present invention contains the modified phenolic resin obtained by the method of the present invention and an epoxy resin, has good moldability, and has excellent mechanical properties such as dimensional stability. In addition, it is possible to provide a molding material capable of producing a molded article excellent in moisture resistance and heat resistance, particularly a material for electric / electronic parts and a semiconductor encapsulant.

Further, the composition for a flame-retardant urethane resin according to the present invention can provide a molded article which is hardly flammable and does not generate harmful halogen compounds typified by dioxin even when burned.

[0131]

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. Table 1 below shows the properties of the feedstock oil used as the reaction feedstock.

[0132]

[Table 1]

In the following examples, the number average molecular weight, the reactivity with the epoxy resin (determined by the gel time; the shorter the reactivity, the higher the reactivity), the melt viscosity of the resin, the hydroxyl equivalent, etc. Measured by the method. <Number average molecular weight> Measuring apparatus: GPC apparatus HLC-8020 manufactured by Tosoh Corporation (column: TSK gel 3000HXL + TSK gel 2500HXL x 3, standard substance: polystyrene) From the obtained data, the molecular weight was converted using polystyrene as a standard substance.

<Hydroxy group equivalent> It was measured by the acetylation chloride method. <ICI viscosity> Measured using an ICI cone plate viscometer manufactured by ICI. <Geling time> 170 according to JIS K 6901
Measured in ° C.

<Shore hardness immediately after molding> It was measured using a Shore hardness tester. <Glass transition temperature> Determined from the transition point of the linear expansion curve using TMA. <Bending strength and elastic modulus> Measured in accordance with JIS K 6911.

<Moisture Absorption> 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. <Evaluation of Flame Retardancy> Measured in accordance with JIS A 9514 (6.9 burning test of rigid urethane foam heat insulating material).

[0137]

Example 1 230 g (0.7 mol) of feedstock oil and phenol 1
464 g (15.6 mol), 266 g of paraformaldehyde
(8.9 mol) and 12 g (0.1 mol) of oxalic acid were charged into a 2 liter glass reaction vessel, and the temperature was raised to 100 ° C. over 20 minutes while stirring at a speed of 200 to 300 rpm, and further maintained at the same temperature for 100 minutes. The reaction was continued 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 modified phenol resin. Next, the crudely modified phenol resin was distilled under reduced pressure until the distillation of phenol disappeared, and then phenol was completely removed by blowing nitrogen at a temperature of 185 ° C.

To the obtained resin, 500 ml of heavy naphtha was added, and the mixture was stirred under reflux at 100 ° C. for 30 minutes to extract unreacted oil remaining in the resin. Then, heavy naphtha containing unreacted raw oil was removed by decantation. Thereafter, the temperature was raised to 160 ° C. in a nitrogen atmosphere, and the temperature was maintained for 1 hour to remove the remaining heavy naphtha, thereby obtaining 1159 g of a modified phenol resin.

The hydroxyl equivalent, the softening point, the viscosity at 150 ° C. and the number average molecular weight of the resulting modified phenol resin were measured, and the results are shown in Table 2 together with the reaction conditions.

[0141]

Examples 2 to 5 A modified phenol resin was produced in the same manner as in Example 1 except that the reaction conditions were changed as shown in Table 2. Hydroxyl equivalent of the resulting modified phenolic resin,
The softening point, the viscosity at 150 ° C., and the number average molecular weight were measured, and the results are shown in Table 2 together with the reaction conditions.

[0142]

[Table 2]

[0143]

Example 6 9.35 parts by weight of the modified phenol resin obtained in Example 1 and a biphenyl type epoxy resin (YX-4000H, manufactured by Yuka Shell Epoxy Co., Ltd.)
After mixing and stirring 94 parts by weight at room temperature using an automatic mortar,
The stirring mixture was mixed with 0.25 parts by weight of triphenylphosphine (TPP) as a curing catalyst to obtain a curing accelerator-containing resin mixture.

The gelation time of the resin mixture containing the curing accelerator was measured and is shown in Table 3. 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.)
-GP200T) in an amount of 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 3 shows the compounding 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 characteristics, and moisture absorption of the obtained molded body immediately after molding were measured. The results are shown in Table 3.

[0146]

Example 7 In Example 6, instead of using the modified phenol resin obtained in Example 1, 9.76 parts by weight of the modified phenol resin obtained in Example 2 was used, and a biphenyl type epoxy resin (oiled oil) was used. A curing accelerator-containing resin mixture, a compound and a molded product were obtained in the same manner as in Example 6, except that the amount of use was 14.99 parts by weight (trade name: YX-4000H, manufactured by Shell Epoxy Co., Ltd.).

Table 3 shows the gelation time, the compounding composition of the compound, the Shore hardness immediately after molding of the molded article, the glass transition point, the bending properties, and the moisture absorption of the obtained curing accelerator-containing resin mixture.

[0148]

Example 8 In Example 6, instead of using the modified phenolic resin obtained in Example 1, 9.48 parts by weight of the modified phenolic resin obtained in Example 3 was used, and a biphenyl-type epoxy resin (oiled oil) was used. A curing accelerator-containing resin mixture, a compound, and a molded product were obtained in the same manner as in Example 6, except that the amount of use was 14.82 parts by weight (trade name: YX-4000H, manufactured by Shell Epoxy Co., Ltd.).

Table 3 shows the gelation time, the compounding composition of the compound, the Shore hardness immediately after molding of the molded article, the glass transition point, the bending properties, and the moisture absorption of the obtained curing accelerator-containing resin mixture.

[0150]

Example 9 In Example 6, instead of using the modified phenolic resin obtained in Example 1, 9.35 parts by weight of the modified phenolic resin obtained in Example 4 was used, and a biphenyl type epoxy resin (oiled oil) was used. A curing accelerator-containing resin mixture, a compound, and a molded article were obtained in the same manner as in Example 6, except that the amount of use was 14.95 parts by weight (trade name, manufactured by Shell Epoxy Co., Ltd., trade name: YX-4000H).

Table 3 shows the gelation time, the compounding composition of the compound, the Shore hardness immediately after molding of the molded article, the glass transition point, the bending properties, and the moisture absorption of the obtained curing accelerator-containing resin mixture.

[0152]

Example 10 In Example 6, instead of using the modified phenol resin obtained in Example 1, 9.85 parts by weight of the modified phenol resin obtained in Example 5 was used, and a biphenyl-type epoxy resin (oiled oil) was used. A curing accelerator-containing resin mixture, a compound and a molded product were obtained in the same manner as in Example 6, except that the amount of use was 14.45 parts by weight (trade name: YX-4000H, manufactured by Shell Epoxy Co., Ltd.).

Table 3 shows the gelation time, the compounding composition of the compound, the Shore hardness immediately after molding of the molded article, the glass transition point, the bending characteristics, and the moisture absorption of the obtained curing accelerator-containing resin mixture.

[0154]

Comparative Example 1 In Example 6, instead of using the modified phenolic resin obtained in Example 1, 8.72 parts by weight of a phenol novolak resin was used, and a biphenyl type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd.) Product name YX-40
00H) Except that the amount used was 16.03 parts by weight,
In the same manner as in Example 6, a curing accelerator-containing resin mixture, a compound, and a molded product were obtained.

Table 3 shows the gelation time, the compounding composition of the compound, the Shore hardness immediately after molding of the molded article, the glass transition point, the bending properties, and the moisture absorption of the obtained curing accelerator-containing resin mixture.

[0156]

[Table 3]

[0157]

Example 11 12.3 parts by weight of the modified phenolic resin obtained in Example 1 and 70 parts by weight of a polyester polyol were placed in a four-necked round-bottomed flask, and stirred at 120 ° C. for 20 minutes (100 rpm) for compatibilization. did. Next, the obtained mixture is
Transfer to a 1L polypropylene beaker and add a foam stabilizer (SH
193; Toray Tow Corning Silicone) 1.1 parts by weight, water 2.1
Parts by weight, 17.5 parts by weight of a foaming agent (HCFC141b) and 0.7 parts by weight of a catalyst (Polycat 8; manufactured by Air Products) are added.
The temperature was adjusted to ° C. Next, 121 parts by weight of 4,4′-diphenylmethane diisocyanate adjusted to 20 ° C. was added, and the mixture was vigorously stirred (3000 rpm) for 20 to 30 seconds with a small mixer, and the resulting mixture was molded into a 300 mm × 200 mm × 50 mm stainless steel mold. It was introduced into the frame and foamed, and after 15 minutes from the start of the reaction, it was demolded to obtain a rigid polyurethane foam.

For the obtained rigid polyurethane foam, measurement of foam density and evaluation of flame retardancy (JIS A9514)
Compliant). Table 4 shows the results.

[0159]

Example 12 The procedure of Example 11 was repeated, except that the modified phenolic resin obtained in Example 1 was used instead of the modified phenolic resin obtained in Example 1 to obtain a hard resin. A polyurethane foam was obtained. For the obtained rigid polyurethane foam, the foam density was measured and the flame retardancy was evaluated (based on JIS A9514). Table 4 shows the results.

[0160]

Example 13 The procedure of Example 11 was repeated, except that the modified phenolic resin obtained in Example 3 was used instead of the modified phenolic resin obtained in Example 1. A polyurethane foam was obtained. For the obtained rigid polyurethane foam, the foam density was measured and the flame retardancy was evaluated (based on JIS A9514). Table 4 shows the results.

[0161]

Example 14 The procedure of Example 11 was repeated, except that the modified phenol resin obtained in Example 4 was used instead of the modified phenol resin obtained in Example 1. A polyurethane foam was obtained. For the obtained rigid polyurethane foam, the foam density was measured and the flame retardancy was evaluated (based on JIS A9514). Table 4 shows the results.

[0162]

Example 15 The procedure of Example 11 was repeated, except that the modified phenolic resin obtained in Example 5 was used instead of the modified phenolic resin obtained in Example 1. A polyurethane foam was obtained. For the obtained rigid polyurethane foam, the foam density was measured and the flame retardancy was evaluated (based on JIS A9514). Table 4 shows the results.

[0163]

Comparative Example 2 1 L of 70 parts by weight of polyester polyol
After placing in a polypropylene beaker, add a foam stabilizer (SH
193; Toray Tow Corning Silicone) 1.1 parts by weight, water 2.1
Parts by weight, 17.5 parts by weight of a foaming agent (HCFC141b) and 0.7 parts by weight of a catalyst (Polycat 8; manufactured by Air Products) were added, and the temperature was adjusted to 20 ° C. Next, 121 parts by weight of 4,4′-diphenylmethane diisocyanate adjusted to 20 ° C. was added, and the mixture was vigorously stirred (3000 rpm) for 20 to 30 seconds with a small mixer, and the resulting mixture was molded into a 300 mm × 200 mm × 50 mm stainless steel mold. The foam was foamed in a frame, and after 15 minutes had passed from the start of the reaction, the mold was released to obtain a rigid polyurethane foam.

For the obtained rigid polyurethane foam, measurement of foam density and evaluation of flame retardancy (JIS A9514)
Compliant). Table 4 shows the results.

[0165]

[Table 4]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08G 18/40 C08G 18/40 59/62 59/62 H01L 23/29 H01L 23/30 R 23/31 / / (C08G 18/40 101: 00) (72) Inventor Haruhiko Takeda 4 Towada, Kasu-gun, Kashima-gun, Ibaraki Pref. Kashima Stone Oil Co., Ltd. No.4 Wada Kashima Stone Oil Kashima Refinery F-term (reference) 4J033 CA01 CA02 CA03 CA11 CA12 CA13 CA14 CA18 CA19 CA22 CA26 CA42 CB01 CB11 CB25 CC03 CC08 CC09 CD02 CD03 CD05 FA01 FA08 HB01 HB06 4J034 CA04 CA24 CC02 CB02 CB02 CB02 DJ08 HA01 HA07 HC12 HC22 HC52 HC67 HC71 NA01 QC01 4J036 AA01 DB15 DC02 FB08 4M109 AA01 BA01 CA21 EA02 EA11 EB03 EB04 EB07 EB12 EB18 EC05 EC20

Claims (12)

[Claims] 1. A heavy oil or pitch and 1 mol of the heavy oil or pitch calculated from the average molecular weight, more than 10 mol and not more than 50 mol of phenols and 1.0 mol in terms of formaldehyde. A method for producing a modified phenol resin by polycondensing 〜40 mol of a formaldehyde compound, comprising: 1) mixing a heavy oil or pitch with a phenol, a formaldehyde compound, and an acid catalyst, 2) mixing heavy oils or pitches with phenols and stirring under heating, and adding the acid catalyst and 1 mole of the phenols to formaldehyde equivalent to 1 mol of the phenols. At 1
Method of sequentially adding less than 1 mol of formaldehyde compound: 3) Mix heavy oils or pitches, phenols, and 1 mol or less of formaldehyde compound in terms of formaldehyde with respect to 1 mol of the phenols, and heat and stir. Then, a method of sequentially adding an acid catalyst to the mixture under heating and stirring: 4) mixing heavy oils or pitches, phenols, and an acid catalyst, heating and stirring, and adding the mixture under heating and stirring to: Method of sequentially adding 1 mol or less of a formaldehyde compound in terms of formaldehyde to 1 mol of the phenols: 5) Mix heavy oils or pitches with an acid catalyst, heat and stir, and heat and stir the mixture. , A method of sequentially adding phenols and 1 mol or less of formaldehyde compound in terms of formaldehyde to 1 mol of phenols: 1 mol or less of formaldehyde compound per 1 mol of phenols and an acid catalyst are mixed and heated with stirring, and heavy oils or pitches and phenols are sequentially added to the mixture under heating and stirring. how to:
And 7) mixing heavy oil or pitches, phenols, and a part of a formaldehyde compound in an amount of 1 mol or less in terms of formaldehyde with respect to 1 mol of the phenols, and heating and stirring the mixture, A method for producing a modified phenol resin, wherein the polycondensation reaction is carried out by any one of the following methods: a method of sequentially adding an acid catalyst and the remaining formaldehyde compound. 2. The method 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, a thermal cracking step or a catalytic reforming step in a petroleum refining process, and the lower limit of the boiling point (distillation starting temperature) is 170 ° C. or more. And an aromatic hydrocarbon fraction fa value of 0.40-0.
The method for producing a modified phenol resin according to any one of claims 1 to 2, wherein the distillate oil or the residual oil has an aromatic ring hydrogen content Ha value of 20 to 80%. . 4. The method for producing a modified phenol resin according to claim 1, wherein an aromatic hydrocarbon compound is used as a raw material in addition to the heavy oils or pitches. 5. The modified phenol 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 of manufacturing resin. 6. The method for producing a modified phenol resin according to claim 1, wherein the acid catalyst is an acidic cation exchange resin. 7. The modified phenolic resin according to claim 1, wherein the heavy oils or pitches are used after a paraffin fraction removal treatment. Method. 8. The modified phenolic resin obtained by the polycondensation reaction is selected from the group consisting of (i) a reaction mixture containing the modified phenolic resin, an aliphatic hydrocarbon, an alicyclic hydrocarbon and an aliphatic petroleum fraction. An extraction solvent containing at least one compound selected is brought into contact with the polycondensation reaction mixture at a temperature at which the polycondensation reaction mixture is in a fluid state; a solution is prepared by diluting the reaction mixture containing the modified phenol resin with a soluble solvent, In addition, aliphatic hydrocarbons having 10 or less carbon atoms, 1 carbon atoms
A process of introducing the solvent into a solvent containing at least one compound selected from the group consisting of an alicyclic hydrocarbon and an aliphatic petroleum fraction of 0 or less; diluting the reaction mixture with a soluble solvent to prepare a solution; Separating the solution containing the modified phenolic resin from the solution containing the modified phenolic resin to form a liquid-liquid two-layer solvent system and contacting it with an extraction solvent that dissolves unreacted components; leaving the reaction mixture in a heated molten state After that, a process of removing the supernatant by decantation; a process of subjecting the reaction mixture to molecular distillation under a high vacuum of 10 ⁻⁷ to 10 ⁻⁴ mmHg; and diluting the reaction mixture with a soluble solvent to prepare a solution; The obtained solution and water are mixed and allowed to stand to form a three-layer solvent system composed of a modified phenol resin solution layer, an aqueous layer and an unreacted oil layer in order from the bottom, and then the aqueous layer and the unreacted oil layer are removed. place , By at least any one treatment selected from the group consisting of, removing unreacted components from the reaction mixture, removing the (ii) catalyst residue,
And (iii) at least one step selected from the group consisting of steam distillation, nitrogen gas blowing and vacuum distillation to remove residual phenols. 8. The method for producing the modified phenolic resin according to any one of items 7 to 7. 9. A modified phenolic resin molding material comprising a 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. 12. A composition for a flame-retardant resin comprising a modified phenolic resin obtained by the method according to claim 1 and a resin comprising a polyol, an isocyanate, a foaming agent and a catalyst. .