JP2000086741A - Method for producing epoxy resin, epoxy resin, epoxy resin composition, cured product obtained by molding and curing the resin composition, and laminate - Google Patents

Abstract

(57) [Summary] A low-grade phenol resin obtained by the polycondensation of petroleum heavy oils or pitches, a formaldehyde polymer and a phenol with a phenol in the presence of an acid catalyst. A method for producing an epoxy resin in which a highly reactive modified phenol resin is prepared by molecular polymerization and the obtained highly reactive modified phenol resin is reacted with epihalohydrin in the presence of an alkali metal hydroxide. According to the method for producing an epoxy resin, an epoxy resin having a low melt viscosity and a high reactivity with a curing agent can be produced. This epoxy resin is excellent in heat resistance, water resistance and mechanical strength, has improved dimensional stability, and is a tough cured product.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is capable of producing a cured product having excellent heat resistance, water resistance and mechanical strength, improved dimensional stability, and toughness. Laminated materials, composite materials, paints, adhesives and adhesives, and a method for producing an epoxy resin that can provide an epoxy resin that is extremely useful for a wide range of applications, an epoxy resin obtained by this method, an epoxy resin molding material using the same, The present invention relates to a cured product and a laminate obtained by molding and curing this molding material.

[0002]

BACKGROUND OF THE INVENTION Epoxy resins are generally hardened with various hardeners to provide mechanical properties, water resistance,
It has excellent cured properties such as chemical resistance, heat resistance and electrical properties, and is used in a wide range of fields such as adhesives, paints, laminates, molding materials and casting materials. Among such epoxy resins, liquid and solid bisphenol A epoxy resins obtained by reacting bisphenol A with epichlorohydrin are most widely used industrially as general-purpose epoxy resins. Examples of other general-purpose epoxy resins include a flame-retardant solid epoxy resin obtained by reacting tetrabromobisphenol A with a liquid bisphenol A-type epoxy resin.

[0003] However, cured products obtained using such general-purpose epoxy resins have the drawback that, although the toughness increases as the molecular weight of the epoxy resin increases, the heat resistance decreases.

In order to compensate for such a decrease in heat resistance, a cured product obtained by mixing a general-purpose epoxy resin with a polyfunctional epoxy resin such as cresol novolak epoxy resin has high heat resistance, but has low toughness. And the water absorption is also high. Therefore, such a general-purpose epoxy resin composition is an insulating material in the electric / electronic field, which has particularly strict requirements for heat resistance, water resistance, mechanical strength, and the like.
For example, there is room for improvement as a molding material applied to a semiconductor sealing material or a laminate for a circuit board.

In order to solve such problems, a modified phenol resin obtained by polycondensing a heavy petroleum oil or pitches, a formaldehyde polymer and a phenol in the presence of an acid catalyst is converted into an alkali metal. An epoxy resin obtained by reacting with an epihalohydrin in the presence of a hydroxide has been proposed (JP-A-7-19676).
No. 6).

According to this epoxy resin, a cured product having excellent heat resistance, water resistance and mechanical strength can be provided as compared with the above-mentioned general-purpose epoxy resin or its composition. However, this epoxy resin has a problem that the resin melt viscosity is high and the reactivity with the curing agent is poor.

The present inventors have conducted various studies and studies in view of such a situation. As a result, the reaction product obtained by the polycondensation reaction is used as it is or after purifying the reaction product to formaldehyde polymer and other crosslinking agent. By epoxidizing the highly reactive modified phenol resin obtained by reacting with phenols to reduce the molecular weight in the absence and in the presence of an acid catalyst, the resin melt viscosity is low and the reactivity with the curing agent is low. The inventors have found that a significantly improved epoxy resin can be obtained, and have completed the present invention.

[0008]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and has a low resin melt viscosity, a remarkably improved reactivity with a curing agent, and therefore an excellent performance. A method for producing an epoxy resin having heat resistance, water resistance, mechanical strength and dimensional stability, and capable of producing a tough cured product, an epoxy resin obtained by this method, an epoxy resin composition using the same, and It is an object of the present invention to provide a cured product and a laminate obtained by molding and curing a resin composition.

[0009]

SUMMARY OF THE INVENTION A method for producing an epoxy resin according to the present invention is a modified phenol resin obtained by polycondensing a heavy petroleum oil or pitch, a formaldehyde polymer, and a phenol in the presence of an acid catalyst. To prepare a highly reactive modified phenolic resin by reacting the modified phenolic resin with phenols to reduce the molecular weight in the presence of an acid catalyst,
The highly reactive modified phenol resin is reacted with epihalohydrin in the presence of an alkali metal hydroxide.

In the method for producing an epoxy resin according to the present invention, it is preferable that the reaction temperature in the depolymerization step is usually 50 ° C. or more and 200 ° C. or less. Further, in the polycondensation step, the petroleum heavy oils or pitches and the formaldehyde in which the number of moles of formaldehyde is 1 to 15 per 1 mol of the petroleum heavy oils or pitches. The mixture containing the polymer and the mixture is heated and stirred in the presence of an acid catalyst, and the phenols are added to the mixture under heating and stirring, and the number of moles of the phenols is reduced to 1 mole of the petroleum heavy oils or pitches. It is preferable to add the phenol resin in an amount of 0.3 to 5 in order, and to subject them to polycondensation to prepare a modified phenol resin.

In the present invention, the modified phenolic resin obtained in the polycondensation step is selected from the group consisting of (i) an aliphatic hydrocarbon having 10 or less carbon atoms and an alicyclic hydrocarbon having 10 or less carbon atoms. Treated with a solvent containing at least one compound to be purified to remove the solvent-soluble components including unreacted components, and / or (ii) the acid catalyst used in the polycondensation step has a solubility of 0.1 It is the following, and after treating with an extraction solvent capable of dissolving most of the modified phenol resin, extracting and removing the catalyst residue and purifying, the obtained purified modified phenol resin may be used in the depolymerization step. desirable.

The epoxy resin according to the present invention is characterized by being an epoxy resin obtained by such a method for producing an epoxy resin. The epoxy resin composition according to the present invention comprises (A) an epoxy resin obtained by such a method for producing an epoxy resin, (B) a curing agent, and if necessary, (C) a curing accelerator. I have. The epoxy resin composition according to the present invention further comprises (D)
An inorganic filler may be contained.

The cured product and the laminate according to the present invention are obtained by molding and curing such an epoxy resin composition.

[0014]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the present invention will be described more specifically. The production method of the epoxy resin according to the present invention, the modified phenolic resin obtained in a specific polycondensation step, a low-molecularization step in a low-molecularization step under specific conditions to a highly reactive modified phenolic resin, this is epoxidized Manufactures epoxy resins.

In the polycondensation step in the present invention, more specifically, heavy petroleum oils or pitches, a formaldehyde polymer and phenols are polycondensed in the presence of an acid catalyst.

The petroleum heavy oils or pitches used as a raw material in the polycondensation reaction include crude oil distillation residue, hydrogenolysis residue, catalytic cracking residue, catalytic reforming oil, naphtha or L.
It is obtained as a pyrolysis residual oil of PG, a distillate of these residual oil under reduced pressure, an extract by solvent extraction or a heat-treated product. It is preferable to select and use appropriate ones of the fa value and the Ha value from these.

For example, petroleum heavy oils or pitches have an aromatic hydrocarbon fraction fa value of 0.40 to 0.95, preferably 0.5 to 0.8, and a value of 20 to 80%, preferably 20 to 80%. It is desirable to have an aromatic ring hydrogen content Ha value of 25 to 60%.

The aromatic hydrocarbon fraction fa value and the aromatic ring hydrogen content Ha value are the values obtained by ¹³ C-NMR measurement of petroleum heavy oils or pitches, and ¹ H-NM, respectively.
It is calculated from the data by R based on the following equation.

[0019]

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

When a petroleum heavy oil or pitch having a Ha value of more than 80% is used as a raw material, the strength of the modified phenol resin tends to decrease. Further, the petroleum heavy oils or pitches used in the present invention are not particularly limited in the number of condensed rings of aromatic hydrocarbons constituting the heavy oils or pitches.
It is preferred to be mainly composed of a condensed polycyclic aromatic hydrocarbon having 4 to 4 rings. When the petroleum heavy oils or pitches contain a large amount of condensed polycyclic aromatic hydrocarbons having 5 or more rings, the condensed polycyclic aromatic hydrocarbons generally have a high boiling point, for example, 45
Since the boiling point may exceed 0 ° C., the variation in the boiling point of the raw materials is large, and it is difficult to collect those having a narrow boiling point range. As a result, it is difficult to stabilize the quality of the product. In addition, when the petroleum heavy oils or pitches are mainly monocyclic aromatic hydrocarbons, since the reactivity with formaldehyde is low, the effect of modifying the obtained phenolic resin tends to be small. is there.

The formaldehyde polymer used as a raw material together with petroleum heavy oils or pitches in the present invention acts as a crosslinking agent. Specific examples of such a formaldehyde polymer include a linear polymer such as paraformaldehyde and polyoxymethylene (particularly an oligomer) and a cyclic polymer such as trioxane.

In the polycondensation step of the present invention, such petroleum heavy oils or pitches and the formaldehyde polymer are such that the number of moles of formaldehyde polymer in terms of formaldehyde is less than that of the petroleum heavy oil or pitch. Are mixed at a ratio of 1 to 15, preferably 2 to 12, and more preferably 3 to 11, with respect to 1 mol of the value calculated from the average molecular weight of the above.

When the mixing ratio of the formaldehyde polymer to the petroleum heavy oils or pitches is less than 1,
It is not preferable because the strength of the cured product of the modified phenol resin obtained is low. On the other hand, when it is larger than 15, both the performance and yield of the obtained cured product hardly change.
It is considered wasteful to use more formaldehyde polymer. Further, the excess formaldehyde polymer may hinder the lowering of the molecular weight of the modified phenol resin in the lowering step of the molecular weight described below.

The phenols used as a raw material in the polycondensation step include, specifically, phenol, cresol, xylenol, resorcin, catechol, hydroquinone, α-naphthol, β-naphthol, bisphenol A, bisphenol F and the like. Phenolic compounds can be mentioned. These may be used alone or 2
A combination of more than one species may be used.

Such phenols have a mole number of phenols of 0.3 to 5, preferably 0.1 to 5 per mole of a value calculated from the average molecular weight of the petroleum heavy oils or pitches. A quantity of 5 to 3 is added to the raw material mixture.

If the amount is less than 0.3, the reactivity between petroleum heavy oils or pitches and formaldehyde is inferior to the reactivity between phenols and formaldehyde. And the strength of the cured product may be lower than that of a general phenol resin.
In particular, it has a low impact resistance and tends to exhibit a brittle defect. On the other hand, when the addition amount of phenols exceeds 5, the modifying effect due to the modification of the phenol resin tends to decrease.

In the polycondensation step of the present invention, an acid catalyst is used for polycondensing heavy petroleum oils or pitches, formaldehyde polymer and phenols. As such an acid catalyst, a Bronsted acid or a Lewis acid can be used, but a Bronsted acid is preferably used. As the Bronsted acid, toluenesulfonic acid, xylenesulfonic acid, hydrochloric acid, sulfuric acid, formic acid and the like can be used, and p-toluenesulfonic acid and hydrochloric acid are particularly preferable.

The acid catalyst is used in an amount of 0.1 to 30% by weight, preferably 1 to 20% by weight, based on the total weight of petroleum heavy oils or pitches, formaldehyde polymer and phenols. Is preferred.

When the amount of the acid catalyst used is small, the reaction time tends to be prolonged, and the reaction tends to be insufficient unless the reaction temperature is raised. 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 polycondensation step using the raw material and the acid catalyst described above, for example, a mixture containing petroleum heavy oils or pitches and a formaldehyde polymer in the above-described ratio in the presence of an acid catalyst is used. It is preferred that phenols are sequentially added to the mixture under heating and stirring to the above-mentioned ratio to cause the amount to become the above-mentioned ratio, and then these materials are subjected to polycondensation.

The phenols are prepared by a method such as dropping.
It is desirable to add sequentially at a rate of 0.05 to 5% by weight / minute, preferably 0.1 to 2% by weight / minute based on the total amount of the reaction mixture.

If the rate of addition is less than 0.05% by weight / minute, the time required for the addition is too long and the cost increases. On the other hand, if the rate of addition exceeds 5% by weight / minute, the added phenol rapidly reacts with free formaldehyde, making it difficult to form a uniform mixture or co-condensate.

The reason why such non-uniformity occurs is that the reactivity of phenols with formaldehyde is significantly higher than that of petroleum heavy oils or pitches. If not maintained, it is presumed that formaldehyde may selectively react with phenols or a condensate of phenols formed by the reaction with formaldehyde and become insoluble.

In the polycondensation step of the present invention, the timing of addition of the phenol to the mixture of the petroleum heavy oils or pitches and the formaldehyde polymer is not particularly limited. From the state where the rate is substantially 0%,
It is desirable to start the sequential addition of phenols at the time of 70% or less, preferably 50% or less.

If the formaldehyde conversion exceeds 70%, the amount of formaldehyde which reacts with the added phenols decreases, and the performance of the resulting modified phenol resin tends to decrease.

In the heating and stirring of a mixture of petroleum heavy oils or pitches and a formaldehyde polymer in the presence of an acid catalyst, the mixture depends on the raw material composition, the addition rate of the phenols, the properties of the obtained resin, and the like. The reaction temperature and reaction time are selected. In addition, the reaction temperature and the reaction time also
It goes without saying that the conditions affect each other. Heating and stirring of such a raw material mixture in the presence of an acid catalyst,
For example, it is desirable to carry out at a temperature of 50 to 160 ° C., preferably 60 to 120 ° C. for 0.5 to 10 hours, preferably 1 to 5 hours.

In the production of the modified phenolic resin of the present invention, when the reaction is carried out batchwise, it can be carried out in one step, and it is preferable to carry out the reaction in one step. In the case of performing a continuous method, the conventional modified phenol resin is used,
It is not necessary to use a device that is difficult to control, such as continuously mixing two or more reaction products by a fixed amount at a time. You only have to send it. Such devices are relatively inexpensive and have good operability.

In the present invention, such polycondensation reaction of petroleum heavy oils or pitches, formaldehyde polymer, and phenols can be carried out without using a solvent. Reaction mixture (reaction system)
May be reduced so that a uniform reaction occurs.

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

In the present invention, the modified phenol resin obtained by the above-described polycondensation reaction is used in the below-mentioned molecular weight reduction step. In the molecular weight reduction step, the modified phenolic resin is reacted with a phenol under a specific temperature condition in the absence of a formaldehyde polymer and other crosslinking agents and in the presence of an acid catalyst to reduce the molecular weight. In such a depolymerization step, other reaction conditions, amounts of raw materials and catalysts may be set so that the modified phenol resin has desired properties by the reaction between the modified phenol resin and phenols.

Incidentally, in the reaction mixture of the above-mentioned polycondensation reaction, in addition to the modified phenol resin, there is a possibility that an acid catalyst, unreacted substances, low molecular components, a reaction solvent and the like may remain. It affects the reaction conditions during the reaction and the amounts of raw materials, catalysts, etc. involved in the reaction. For example,
When the modified phenol resin used in the depolymerization step contains an acid catalyst, it affects the amount of the acid catalyst added in the step. In particular, when the modified phenolic resin contains a large amount of a formaldehyde polymer as a cross-linking agent as an unreacted component, a polycondensation reaction between the modified phenolic resin, the formaldehyde polymer, and phenols occurs, and lower molecular weight is inhibited. May be done.

Therefore, in order to suitably set the reaction conditions in the molecular weight reduction step so that the molecular weight of the modified phenolic resin is efficiently reduced by the reaction between the modified phenolic resin and phenols, it is necessary to use The modified phenolic resin is an amount of an acid catalyst that inhibits the lowering reaction,
It is preferable not to contain an unreacted substance or a reaction solvent or the like, and it is particularly preferable not to contain an acid catalyst or a formaldehyde polymer.

Such a modified phenolic resin can be prepared by adding an unreacted component, acid catalyst And by removing the unreacted components, low-molecular components, acid catalysts, reaction solvents, and the like by preventing the reaction solvent and the like from remaining or by appropriately purifying the reaction mixture obtained by the polycondensation reaction. Can be.

As a method for purifying a reaction mixture, that is, a crude modified phenol resin containing an acid catalyst, unreacted substances, low molecular components and a reaction solvent, for example, (i) treating the reaction mixture with a specific solvent, A purification treatment for precipitating the resin and removing solvent-soluble components including unreacted components, (i
i) A purification treatment in which the reaction mixture is treated with a specific solvent to extract and remove catalyst residues.

In the refining treatment (i), among the components contained in the petroleum heavy oils or pitches used as the raw material, the reactivity is low and the reaction product is in an unreacted state or in the reaction product. The components remaining in an insufficient state and the reaction solvent appropriately used during the reaction are removed.

In such a purification treatment (i), the reaction mixture obtained in the polycondensation step is prepared at any time from an aliphatic hydrocarbon having 10 or less carbon atoms and an alicyclic hydrocarbon having 10 or less carbon atoms. Poured into a solvent containing at least one compound selected from the group consisting of, to precipitate the resin main component, components soluble in the solvent, that is, components that remain unreacted and low reaction,
And by removing the reaction solvent and the like during the polycondensation reaction.

Examples of such a hydrocarbon solvent include aliphatic or alicyclic hydrocarbons such as pentane, hexane, heptane and cyclohexane, and n-hexane is particularly preferred.

In the above purification treatment (ii), a catalyst residue such as an acid remaining in the reaction mixture and a formaldehyde polymer as a cross-linking agent are removed, and the modified phenol resin substantially containing no acid and the cross-linking agent is removed. Is obtained. If such a catalyst remains in the modified phenol resin, it is necessary to set the amount of the acid catalyst used in the depolymerization step in consideration of the acid catalyst residue, which makes it difficult to control the reaction conditions.

In the purification treatment (ii), the reaction mixture is prepared by using an extraction solvent in which the solubility of the acid catalyst used in the polycondensation step is 0.1 or less and which can dissolve most of the modified phenol resin. It is carried out by treating and extracting the catalyst residue.

The solvent is not particularly limited as long as it has the above-mentioned properties, but preferred examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene. Of these, toluene is particularly preferred.

In the present invention, the purification treatment (ii) is not particularly limited in terms of the temperature and the like, and may be carried out under conditions where the above-mentioned properties of the solvent are sufficiently exhibited. Further, the purification treatment (ii) may be carried out easily and simply, by adding the reaction mixture to a solvent or adding a solvent to the reaction mixture.

The modified phenol resin substantially free of acid after such purification treatment (ii) is usually in the form of a varnish dissolved in a solvent. If this is a final purified product, the varnish-like modified phenol resin may be used as it is as a raw material in the next stage of the low-molecular-weight reduction step. Alternatively, it may be precipitated and used as a powdery modified phenol resin.

Although the purification treatment (ii) removes most of the catalyst residue remaining in the reaction product, if necessary, the modified phenol resin after the purification treatment (ii) may be neutralized and / or treated. The catalyst residue such as acid in the resin may be further removed by washing with water.

Examples of the neutralization treatment include addition of a basic substance to the modified phenol resin after the purification treatment (ii). Examples of such a basic substance include sodium hydroxide, potassium hydroxide, Hydroxides of alkali metals and alkaline earth metals such as calcium hydroxide and magnesium hydroxide; and ammonia, diethylenetriamine, triethylenetetramine, aniline and phenylenediamine.

In the purification step applicable in the present invention, such purification treatments (i) and (ii) can be performed in any order. However, since the modified phenol resin after the purification treatment (ii) is in a varnish form, the modified phenol resin is poured into a solvent in which the modified phenol resin is insoluble, for example, n-hexane to cause re-precipitation, and the powdered modified phenol resin is collected. This is desirable from the viewpoint of operability when used in the low molecular weight process.

In the case where the purification treatment (ii) is performed after the purification treatment (i), the resulting varnish-like modified phenol resin can be used as it is as a raw material in the next step of depolymerization. This method is preferable from the viewpoint of manufacturing cost.

In the present invention, such a modified phenol resin, that is, the reaction product obtained in the polycondensation step, is used as it is or after purification, in the absence of a formaldehyde polymer and other crosslinking agents. In the presence, it is reacted with phenols to reduce the molecular weight.

The reaction conditions such as the reaction temperature in the depolymerization step, or the amounts, types and combinations of the raw materials and the acid catalyst used can reduce the viscosity of the modified phenolic resin. There is no particular limitation as long as the moldability of the epoxy resin obtained by use can be improved.

Examples of the acid catalyst and phenol used in the depolymerization step of the present invention include the compounds exemplified in the above-mentioned polycondensation step. In particular,
Examples of phenols used in the depolymerization step include phenol, cresol, xylenol, resorcin, catechol, hydroquinone, α-naphthol, β-naphthol, bisphenol A, bisphenol F and the like.

In the depolymerization step of the present invention, the acid catalyst is used in an amount of 0.1 to 100 parts by weight of the modified phenol resin.
It is desirable to use 15 parts by weight, preferably 0.2 to 10 parts by weight.

The phenol is used in an amount of 100 parts by weight or more, preferably 100 to 250 parts by weight, more preferably 100 to 200 parts by weight, based on 100 parts by weight of the modified phenol resin.
It is desirable to use parts by weight. The depolymerization reaction is
When the amount of phenols is 100 parts by weight or more, the reaction proceeds to an extent sufficient to obtain the desired effect. However, if an excessive amount of phenol is used, a large amount of unreacted phenol remains, which increases the cost required for the post-treatment.

In the depolymerization step using an acid catalyst and a phenol, the modified phenol resin is mixed with the phenol in the presence of the acid catalyst in a temperature range of 50 ° C. to 200 ° C. for 15 minutes to 2.0 hours. Time, preferably 30 minutes to 2.
It is desirable to react for 0 hours.

In the reaction for lowering the molecular weight in the above temperature range, in a relatively low temperature range, specifically, at 50 ° C. or more and 120 ° C. or less, cleavage of acetal bond and / or methylene ether bond present in the modified phenol resin molecule is performed. -It is considered that dissociation occurs and phenols bind to the dissociation terminal. Such a low-molecular-weight reduction reaction in a low temperature range is more preferably performed at a temperature of 80 ° C or more and 120 ° C or less.

Further, a relatively high temperature range, specifically, 120 ° C.
Above 200 ° C. or lower, the cleavage of the methylene bond in addition to the acetal bond and / or methylene ether bond present in the modified phenol resin molecule.
It is believed that dissociation occurs. The depolymerization step in such a high temperature range is more preferably performed at 140 ° C. or more and 180 ° C. or less.

In the depolymerization step of the present invention, a reaction solvent may or may not be used. The reaction solvent used is not particularly limited as long as it does not inhibit the above-mentioned low-molecular-weight reduction reaction.For example, the solvent used during the polycondensation reaction, and alcohols, specifically, butyl alcohol, ethyl alcohol, methyl alcohol, hexyl Alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol and the like can be mentioned. Such a solvent is preferably used in an amount of 0 to 300 parts by weight based on 100 parts by weight of the modified phenol resin.

The highly reactive modified phenolic resin obtained in the above-described process can be subjected to the epoxidation process as it is, but there is a possibility that unreacted components, acid catalysts and the like remain in the resin. . Therefore, the modified phenol resin is purified by the same method using the solvents mentioned in the above purification treatments (i) and (ii) or by using another solvent to remove unreacted components and acid catalysts. It is desirable to remove it. Solvents preferably used for the purification of such highly reactive modified phenolic resins include, for example, methyl isobutyl ketone; toluene; a mixed solvent of toluene and alcohols such as ethyl alcohol and methyl alcohol; and ethers such as toluene and tetrahydrofuran. And a mixed solvent of toluene and ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone.

The highly reactive modified phenol resin is obtained by extracting unreacted components, acid catalysts and the like using such a solvent, and then, if necessary, using distilled water and / or a mixed solution of distilled water and isopropyl alcohol. It is desirable to wash with water.

If unreacted substances remain, steam-distillation is carried out, if necessary, to produce a highly reactive modified phenol resin having higher purity. Also,
Unreacted substances can also be removed by blowing nitrogen under heating instead of steam distillation. Further, these methods may be combined.

Further, the highly reactive modified phenolic resin is
After removing unreacted components, acid catalysts, etc., it is preferable to remove the solvent of the extraction solvent or to treat with an aliphatic or alicyclic hydrocarbon having 10 or less carbon atoms or a mixed solvent thereof to precipitate the resin. . Examples of such a hydrocarbon solvent include the solvents described in the purification treatment (i) of the modified phenol resin, and n-hexane is particularly preferred.

By carrying out such a purification treatment to remove the acid catalyst, unreacted substances, reaction solvent and the like which may remain in the resin, in addition to the above-mentioned characteristics, a high reactivity containing substantially no acid is obtained. It can be a modified phenolic resin. Even if the highly reactive modified phenolic resin obtained in the above-described process remains as it is, the number average molecular weight is reduced to 300 to 800, the reactivity with the epoxy resin is improved, and the resin melt viscosity is reduced. 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.

In the method for producing an epoxy resin according to the present invention, the highly reactive modified phenolic resin thus obtained is reacted with epihalohydrin in the presence of an alkali metal hydroxide to epoxidize it, thereby producing an epoxy resin. I do.

Examples of such an epihalohydrin include epichlorohydrin, epibromhydrin, epiiodohydrin and β-methylepichlorohydrin.

Further, examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide. For example, an epoxy resin is obtained by adding an alkali metal hydroxide to a mixture containing the above-mentioned highly reactive modified phenol resin and preferably an excess of epihalohydrin,
Alternatively, it can be produced by reacting at a temperature of usually 20 to 120 ° C., preferably 50 to 80 ° C. while adding.

In such an epoxidation step, the alkali metal hydroxide may be added to the reaction system as an aqueous solution. In this case, the aqueous alkali metal hydroxide solution is continuously added to the reaction system, and water and epihalohydrin are continuously flown out under reduced pressure or normal pressure as a mixed effluent, and the effluent is further combined with water and epihalohydrin. , Water may be removed, and epihalohydrin may be continuously returned to the reaction system.

The epoxy resin is prepared by adding the following catalyst to a dissolved mixture of a highly reactive modified phenol resin and epihalohydrin and reacting at a temperature of 50 to 150 ° C. to prepare a halohydrin ether. This halohydrin etherified product is subjected to a reaction at 20 to 120 ° C., preferably 50 to 120 ° C. in the presence of an alkali metal hydroxide (solid or aqueous solution).
It can also be produced by reacting at a temperature of 80 ° C. and dehydrohalogenating (ring closed).

Examples of such a catalyst include quaternary ammonium salts such as tetramethylammonium chloride and tetraethylammonium bromide; tertiary amines such as benzyldimethylamine and 2,4,6- (trisdimethylaminomethyl) phenol; 2-ethyl-4-methylimidazole, 2-
Imidazoles such as phenylimidazole; phosphonium salts such as ethyltriphenylphosphonium iodide;
And phosphines such as triphenylphosphine.

In the epoxidation reaction of these highly reactive modified phenol resins, it is desirable that epihalohydrin is used in an amount of usually 1 to 20 mol, preferably 2 to 15 mol, per 1 equivalent of the hydroxyl group of the phenol resin. It is desirable that the alkali metal hydroxide is used in an amount of 0.8 to 3 mol, preferably 1 to 2 mol, per equivalent of the hydroxyl group of the phenol resin.

In the above-mentioned epoxidation reaction, the reaction solvent is not necessarily used, but is desirably used in order to carry out the reaction smoothly. Examples of such a reaction solvent include alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, ethers such as dioxane and ethylene glycol dimethyl ether, aprotic polar solvents such as dimethyl sulfone and dimethyl sulfoxide, and the like. Examples can be given.

The reaction solvent is used in an amount of 2 to 100 parts by weight, preferably 10 to 9 parts by weight, per 100 parts by weight of epihalohydrin.
Preferably, it is used in an amount of 0 parts by weight. The reaction product of such an epoxidation reaction is removed after washing with water or without washing with water, while removing epihalohydrin and other additional solvents under reduced pressure under heating, for example, at a temperature of 150 to 250 ° C. and a pressure of 10 mmHg or less.

Further, the purified product thus obtained is
Furthermore, in order to obtain an epoxy resin having a small amount of hydrolyzable halogen, it can be dissolved again in the solvent used above, and an aqueous solution of an alkali metal hydroxide can be added to carry out a reaction to ensure ring closure. In this case, the amount of the alkali metal hydroxide used is preferably from 0.01 to 1 equivalent to 1 equivalent of the hydroxyl group of the highly reactive modified phenol resin used for the epoxidation.
The amount is 0.2 mol, particularly preferably 0.05 to 0.1 mol. This reaction can be performed, for example, at a reaction temperature of 50 to 120 ° C and a reaction time of 0.5 to 2 hours.

After completion of the reaction, the formed salt is removed by filtration, washing with water, and the like, and the solvent is distilled off under reduced pressure under heating to obtain an epoxy resin having a small hydrolyzable halogen.

The epoxy resin obtained by the above-described method for producing an epoxy resin of the present invention, that is, the epoxy resin of the present invention has a low resin melt viscosity and a high reactivity with a curing agent, so that it can be used in various fields. It is suitable as a material of a cured resin used in the above.

The epoxy resin composition of the present invention is a composition for obtaining such a cured resin, and comprises the epoxy resin (A) and the curing agent (B) of the present invention and, if necessary, a curing accelerator. (C).

The curing agent (B) applied to the epoxy resin composition of the present invention includes amine compounds, acid anhydride compounds, amide compounds and phenol compounds. More specifically, amine compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, and isophoronediamine; amide compounds such as polyamide resins synthesized from dimer of dicyandiamide and linolenic acid and ethylenediamine; Phthalic anhydride,
Acid anhydride compounds such as trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride; and In addition to phenolic compounds such as phenol novolak and modified products thereof,
It is also possible to use imidazole; BF ₃ -amine complexes and guanidine derivatives. Further, a modified phenol resin or a highly reactive modified phenol resin used as a raw material of the epoxy resin of the present invention can also be used as a curing agent. These curing agents may be used alone or in combination of two or more.

These curing agents (B) are desirably used in an amount of 0.7 to 1.2 equivalents relative to 1 equivalent of the epoxy group of the epoxy resin. 0.1 equivalent of epoxy group.
When the amount is less than 7 equivalents or when the amount exceeds 1.2 equivalents, the curing tends to be incomplete, and good cured physical properties may not be obtained.

The curing accelerator (C) applicable in the present invention
Examples include diazabicycloalkenes such as 1,8-diazabicyclo (5,4,0) undecene-7 and derivatives thereof, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol Tertiary amines such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2
Imidazoles such as -phenylimidazole, 2-phenyl-4-methylimidazole, and 2-heptadecylimidazole; organic phosphines such as tributylphosphine, methyldiphenylphosphine and triphenylphosphine;
Tetra-substituted phosphonium / tetra-substituted borate such as tetraphenyl phosphonium / tetraphenyl borate,
2-ethyl-4-methylimidazole / tetraphenylborate, tetraphenylboron salts such as N-methylmorpholine / tetraphenylborate, Lewis acids such as boron trifluoride-amine complex, dicyandiamide, Lewis bases such as adipic dihydrazide, Other polymer captans,
Polysulfide and the like can be exemplified. These curing agents and curing accelerators may be used alone or in combination of two or more.

The curing accelerator (C) is preferably used in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the epoxy resin. Further, by adding an inorganic filler (D) to the epoxy resin composition of the present invention, the strength, dimensional stability and the like of the obtained molded article can be further improved.

As the inorganic filler (D),
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 fibers such as glass fiber, carbon fiber, phosphor fiber, and boron fiber; aluminum hydroxide, magnesium hydroxide, and the like. Hydrated metal oxides; metal carbonates such as magnesium carbonate and calcium carbonate; metal borates such as magnesium borate; and inorganic fillers such as silica, alumina, talc, mica, fused silica and crystalline silica. it can.

In the case where the epoxy resin composition of the present invention is used as a semiconductor encapsulant, among the above-mentioned inorganic fillers, crushed or granular fused silica or crystalline silica is preferred. The blending amount of the inorganic filler (D) is not particularly limited, but is preferably, for example, 30 to 95% by weight, preferably 70 to 93% by weight of the whole composition.

Further, the epoxy resin composition according to the present invention may further contain an additive, if necessary.
Examples of such additives include silicone, internal release agents such as waxes, silane coupling agents, flame retardants, light stabilizers, antioxidants, pigments such as carbon black, and extenders. it can.

Furthermore, in the epoxy resin composition of the present invention, an epoxy resin other than the epoxy resin of the present invention can be used in combination. Such epoxy resins include, for example, phenolic compounds such as bisphenol A, bisphenol F, bisphenol AD, hydroquinone, methylhydroquinone, dimethylhydroquinone, dibutylhydroquinone, resorcinol, methylresorcinol, biphenol, tetramethylbiphenol,
Phenols such as dihydroxynaphthalene, dihydroxydiphenyl ether, phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, dicyclopentadiene phenol resin, phenol aralkyl resin, naphthol novolak resin, and terpene phenol resin; An epoxy resin produced from a polyhydric phenol resin obtained by a condensation reaction with aldehydes such as benzaldehyde, crotonaldehyde, gluoxal and the like and epihalohydrin; an amine compound such as diaminodiphenylmethane, aminophenol, xylene diamine and the like; epihalohydrin And carboxylic acids such as methyl hexahydrophthalic acid, And the like mer acid, and epoxy resins produced from an epihalohydrin it can be exemplified.

A part of the epoxy resin used for making the cured product flame-retardant may be a brominated epoxy resin. As such a brominated epoxy resin, for example,
Epoxy resin produced from brominated bisphenol A or brominated phenol novolak resin and epihalohydrin, low molecular weight epoxy resin and brominated bisphenol A
And an epoxy resin produced by the reaction with

It is preferable that such other epoxy resin accounts for 50% by weight or less based on the total amount of the epoxy resin component. If the use ratio of the other epoxy resin exceeds this range, the effect of the present invention may not be sufficiently exhibited. The epoxy resin composition of the present invention in which the epoxy resin (A) and the curing agent (B) of the present invention and, if necessary, the curing accelerator (C) and the filler (D) are blended, the components are uniformly mixed. Obtained by mixing. Such an epoxy resin composition of the present invention can be easily made into a cured product, that is, a cured product according to the present invention, by a method similar to a conventionally known method.

For example, the cured product according to the present invention comprises an epoxy resin (A) and a curing agent (B) according to the present invention, an optional curing accelerator (C), a filler (D) and other additives. And, for example, an extruder, a kneader and a kneading device such as a roll, and sufficiently mixed until uniform to obtain an epoxy resin composition, and then melt the epoxy resin composition, and then use a casting or transfer molding machine or the like. And heating at 80 to 200 ° C. for 2 to 10 hours.

The laminate according to the present invention is prepared, for example, by dissolving the resin composition of the present invention in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, or methyl isobutyl ketone to prepare a varnish. A base material such as woven fabric, nonwoven fabric or paper made of carbon fiber, polyester fiber, polyamide fiber, alumina fiber or natural fiber is impregnated, dried by heating to produce a prepreg, and a plurality of obtained prepregs are laminated and hot-pressed. It can be manufactured by molding.

[0098]

According to the method for producing an epoxy resin of the present invention, the epoxy resin is produced by epoxidizing the highly reactive modified phenol resin obtained by the above-mentioned polycondensation step and low-molecular-weight step. An epoxy that has low melt viscosity, is easy to mold, has high reactivity with the curing agent, and therefore has excellent heat resistance, water resistance and mechanical strength, has improved dimensional stability, and can produce a tough cured product. It is possible to provide resin and epoxy resin compositions.

The cured product according to the present invention is excellent in heat resistance, water resistance and mechanical strength, is improved in dimensional stability and is tough, so that it can be used in general fields known as general-purpose epoxy resins. It can be suitably used for molded articles such as cast molding, laminated boards, sealing materials, adhesives, composite materials or paints.

[0100]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

In the following examples, all parts are by weight unless otherwise specified. Table 1 shows the properties of the feedstock oil used as the reaction feedstock. These feedstocks are obtained by distilling the bottom oil obtained by fluid catalytic cracking (FCC) of vacuum gas oil.

[0102]

[Table 1]

Further, the hydroxyl equivalent, the softening point, the number average molecular weight, the melt viscosity, the epoxy equivalent, the gel time, the hardness at the time of molding and demolding, the glass transition temperature,
The moisture absorption, adhesive strength, and solder crack resistance were measured by the following apparatus or measuring method.

<Hydroxy group equivalent> Measured according to the acetyl chloride method. <Softening point> Measured according to JIS K 2207, ring and ball method. <Number average molecular weight> Measuring device: GPC device HLC-8020 manufactured by Tosoh Corporation (column: TSK gel 3000HX)
L + TSK gel 2500HXL * 3, standard substance: polystyrene) From the obtained data, the molecular weight was converted using polystyrene as a standard substance. <Melt viscosity> Measured using an ICI cone plate viscometer manufactured by ICI. <Epoxy equivalent> Measured according to the hydrochloric acid-dioxo acid method. <Gelling time> Curing time when mixing epoxy resin, epoxy resin curing agent and curing accelerator at 175 ° C. The shorter the time, the higher the reactivity. <Hardness at the time of mold release> ShoreD hardness at the time of mold release <Glass transition temperature> Determined from the transition point of the thermal expansion curve using TMA. <Hygroscopic rate> Moisture absorption when the sample is held at 85 ° C and 85% RH for 168 hours to absorb moisture. <Adhesive force> 4mm width aluminum peel test. <Solder crack resistance> 80-pin QFP: 16 test pieces at 85 ° C
After being kept at 85% RH for 168 hours to absorb moisture, it was immersed in a 260 ° C. solder bath for 30 seconds to determine the number of cracks.

[0105]

Production Example 1 Production of highly reactive modified phenol resin (polycondensation step) 334 g of raw oil, 370 g of paraformaldehyde, 137 g of p-toluenesulfonic acid monohydrate and 678.5 g of p-xylene were charged into a glass reactor. The temperature was raised to 95 ° C. while stirring, and maintained at this temperature for 1 hour. To the reaction mixture was added 209 g of phenol (1.3 g).
After dropping at a dropping rate of g / min, the mixture was further stirred for 15 minutes.

The reaction mixture was poured into 3,300 g of n-hexane to precipitate a reaction product, and then filtered to remove unreacted components and reaction solvent. 1,600 g of precipitate
After washing with n-hexane, vacuum drying was performed to obtain a crude modified phenol resin containing acid. This resin was dissolved in 10 times the weight of toluene, and the insolubles mainly composed of p-toluenesulfonic acid monohydrate were removed by filtration. The obtained resin toluene solution is concentrated until the resin concentration becomes 50% by weight,
A varnish-like modified phenolic resin was obtained.

The resulting modified phenolic resin varnish was neutralized by adding a small amount of triethylenetetramine, poured into 3.3 times the weight of n-hexane to precipitate the resin, and filtered. Then, it was vacuum dried to obtain 580 g of a powdery modified phenol resin. (Low-molecularization step) Obtained modified phenolic resin 100
g, phenol 200 g and p-toluenesulfonic acid 1
5 g of hydrate was charged into a 1-liter glass reactor,
While stirring at a speed of 0 to 350 rpm, 9
The temperature was raised to 5 ° C. and kept at this temperature for 90 minutes.

The obtained reaction mixture was dissolved in 400 ml of a mixed solvent of toluene / methyl isobutyl ketone (7/3) to prepare a resin mixed solution, which was washed with distilled water to remove acid and unreacted phenol by extraction. did. The solvent was removed from the resin solution after the extraction with an evaporator to obtain a crude highly reactive modified phenol resin. Unreacted phenol was removed by blowing nitrogen into the crude highly reactive modified phenol resin at 160 to 170 ° C. to finally obtain a powdery highly reactive modified phenol resin.

Table 2 shows the hydroxyl equivalents and softening points of the resulting highly reactive modified phenolic resin. The number average molecular weight of this highly reactive modified phenol resin was 810, and the melt viscosity at 150 ° C. was 6 ps.

[0110]

Production Examples 2-3 Preparation of highly reactive modified phenolic resin The reaction temperature in the depolymerization step was changed to the value shown in Table 2 (Production Example 2), or orthocresol was used instead of phenol (Production Example) A highly reactive modified phenolic resin was produced in the same manner as in Example except for 3).

The hydroxyl equivalent and the softening point of the resulting highly reactive modified phenolic resin are shown in Table 2. The number average molecular weight and the melt viscosity at 150 ° C. of this highly reactive modified phenol resin were 650 and 1 ps in Production Example 2, and 780 and 4 ps in Production Example 3, respectively.

[0112]

Example 1 Production of Epoxy Resin 290 g of the highly reactive modified phenolic resin obtained in Production Example 1, 1295 g of epichlorohydrin and isopropyl alcohol were placed in a 3 L three-necked flask equipped with a thermometer, a stirrer, and a condenser. After charging 585 g, the mixture was heated to 35 ° C. and uniformly dissolved, and 190 g of a 48.5% by weight aqueous sodium hydroxide solution was added dropwise over 1 hour. During this period, the temperature was gradually raised so that the temperature in the system reached 65 ° C. at the end of the dropping. Thereafter, the reaction mixture was reacted at 65 ° C. for 30 minutes.

Next, the reaction mixture was washed with water to remove by-product salts and excess sodium hydroxide, and further, excess epichlorohydrin and isopropyl alcohol were distilled off under reduced pressure to obtain a crude epoxy resin. This crude epoxy resin was dissolved in 580 to 1040 g of methyl isobutyl ketone, and a 48.5% by weight aqueous solution of sodium hydroxide 6-1 was dissolved.
0 g was added and reacted at a temperature of 65 ° C. for 1 hour. After the completion of the reaction, sodium phosphate monobasic was added to neutralize the excess sodium hydroxide, and washed with water to remove by-product salts. Next, methyl isobutyl ketone was completely removed from the neutralized epoxy resin under reduced pressure to obtain a purified epoxy resin. Table 3 shows the epoxy equivalent and the softening point of the obtained epoxy resin.

[0114]

Examples 2-3 Production of an epoxy resin An epoxy resin was produced in the same manner as in Example 1 except that the highly reactive modified phenol resin used and the amount used were changed as shown in Table 3. Table 3 shows the epoxy equivalent and the softening point of the obtained epoxy resin.

[0115]

Example 4 Production of Epoxy Resin Composition for Semiconductor Encapsulation In the amounts shown in Table 4, the epoxy resin produced in Example 1 and a brominated bisphenol A type epoxy resin (Epicoat, trade name of Yuka Shell Epoxy Co., Ltd.) 5050, epoxy equivalent: 385, bromine content: 49%), phenol novolak resin as an epoxy resin curing agent (manufactured by Gunei Chemical Co., Ltd., hydroxyl equivalent: 103, softening point: 85 ° C, indicated by “C” in the table) , Fused silica powder (Tatsumori Co., Ltd. RD-8) as an inorganic filler and triphenylphosphine as a curing accelerator, antimony trioxide as a flame retardant aid, and epoxysilane as a filler surface treatment agent (Shin-Etsu Chemical Co., Ltd. product name KBM403), carnauba wax was added as a release agent to produce an epoxy resin composition for semiconductor encapsulation.

Then, the obtained composition was melt-mixed at a temperature of 70 to 130 ° C. for 5 minutes using a mixing roll. Each of the obtained molten mixtures was taken out in a sheet shape and pulverized to obtain a molding material. Using this molding material, each test piece was molded by a transfer molding machine at a mold temperature of 180 ° C. and a molding time of 180 seconds, and was post-cured at 180 ° C. for 8 hours. Table 4 shows the results of testing the glass transition temperature, moisture absorption, and solder crack resistance of the test pieces after post-curing.

[0117]

Examples 5 to 7 Production of Epoxy Resin Composition for Semiconductor Encapsulation
One of the epoxy resins and epoxy resin curing agent granulated using modified as shown in Table 4, and except that the amount of the epoxy resin curing agent and an inorganic filler and the amount shown in Table 4, Example 4 Similarly, an epoxy resin composition and a test piece were produced. Table 4 shows the results of testing the glass transition temperature, moisture absorption, and solder crack resistance of each test piece after post cure.

[0118]

Comparative Examples 1-3 Preparation of Epoxy Resin Composition for Semiconductor Encapsulation
The epoxy resin to be used is a tetramethyl biphenol type epoxy resin (Yuika Shell Epoxy Co., Ltd. Epicoat
YX4000H, epoxy equivalent: 193, indicated by "A" in the table) or orthogresol type epoxy resin (Yuka Kasper Epoxy Co., Ltd., Epicoat 180S65, epoxy equivalent: 213,
In the same manner as in Example 4, except that the composition was changed to "B" in the table) and the types and amounts of the epoxy resin curing agent and the inorganic filler were changed as shown in Table 4, the epoxy resin composition and the test were performed in the same manner as in Example 4. Pieces were produced.

Table 4 shows the results of testing the glass transition temperature, moisture absorption, and solder crack resistance of each test piece after post-curing. As shown in Table 4, the compositions of Examples 4 to 7 can provide molding materials excellent in reactivity and moldability as compared with the compositions of Comparative Examples 1 to 3, and further, the test pieces are
The balance between the moisture absorption and the adhesion was excellent, and as a result, the solder crack resistance was excellent.

[0120]

[Table 2]

[0121]

[Table 3]

[0122]

[Table 4]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) // C08J 5/24 CFC C08J 5/24 CFC (72) Inventor Hiromi Miyashita Higashi Kamisu-cho, Kashima-gun, Ibaraki Pref. No. 4 Wada Kashima Refinery Co., Ltd. Kashima Refinery (72) Inventor Shin Hasegawa No. 4 Higashiwada, Kamisu-cho, Kashima-gun, Ibaraki Pref. Kashima Refinery Co., Ltd. Kashima Refinery F-term (reference) AE03 AE04 AE06 AE07 AE09 AE10 AE11 AF02 AF03 AF04 AF06 AG03 AG16 AH02 AH21 AJ04 AL09 AL12 4J002 CC042 CD041 CD061 CL032 DA018 DE078 DE148 DE238 DJ018 DJ048 DJ058 DK008 DL008 EL136 EN037 EN046 EU076 EU0727 EU117 007 EU076 EU0727 FD142 FD146 FD157 GQ00 4J033 CA01 CA02 CA03 CA11 CA12 CA14 CA19 CA22 CA34 CA37 CB01 CB12 CB 18 CC03 CC08 CD03 FA01 FA08 HB01 HB03 HB08 HB09 4J036 AF06 BA01 BA06 DB21 DB22 DC03 DC06 DC10 DC31 DC41 DC46 DD07 FA05 FB07 FB13 GA04 GA20 JA08

Claims (9)

[Claims] 1. A modified phenol resin is prepared by polycondensing a petroleum heavy oil or pitches, a formaldehyde polymer, and a phenol in the presence of an acid catalyst. A high-reactivity modified phenol resin is prepared by reacting with phenols to reduce the molecular weight in the presence of a catalyst, and the high-reactivity modified phenol resin is reacted with epihalohydrin in the presence of an alkali metal hydroxide. A method for producing an epoxy resin. 2. The method for producing an epoxy resin according to claim 1, wherein the reaction temperature in the depolymerization step is a temperature of 50 ° C. or more and 200 ° C. or less. 3. In the polycondensation step, the number of moles of the petroleum heavy oil or pitch and the formaldehyde equivalent is 1 to 1 mol of the petroleum heavy oil or pitch.
And a mixture containing the above-mentioned formaldehyde polymer in a ratio of 15 to 15 is heated and stirred in the presence of an acid catalyst, and the mixture is heated and stirred, and the phenols are added to the mixture. 3. The modified phenolic resin according to claim 1 or 2, wherein the modified phenolic resin is prepared by sequentially adding an amount of 0.3 to 5 with respect to 1 mol of oils or pitches and subjecting them to polycondensation. Production method of epoxy resin. 4. The modified phenolic resin obtained in the polycondensation step is at least one selected from the group consisting of (i) an aliphatic hydrocarbon having 10 or less carbon atoms and an alicyclic hydrocarbon having 10 or less carbon atoms. And purifying by removing the solvent-soluble components including unreacted components, and / or
Or (ii) the acid catalyst used in the polycondensation step has a solubility of 0.1 or less, and is treated with an extraction solvent capable of dissolving the modified phenolic resin, and the catalyst residue is extracted and purified, and then obtained. The method for producing an epoxy resin according to any one of claims 1 to 3, wherein the purified modified phenol resin is used in the low-molecularization step. 5. An epoxy resin obtained by the method according to claim 1. 6. An epoxy resin obtained by the method according to any one of claims 1 to 4, and (B) a curing agent,
An epoxy resin composition comprising, if necessary, (C) a curing accelerator. 7. The epoxy resin composition according to claim 6, further comprising (D) an inorganic filler. 8. A cured product obtained by molding and curing the epoxy resin composition according to claim 6 or 7. 9. A laminate obtained by molding and curing the epoxy resin composition according to claim 6 or 7.