JPH10120869A - Production of highly reactive modified phenol resin, and molding material, material for electric and electronic parts, and semiconductor-sealing material containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for producing a highly reactive modified phenol resin which has not only a low melt viscosity but also a high reactivity with an epoxy resin and which, when combined with an epoxy resin, can give a molding material having a good moldability, a high heat resistance, and a very low moisture absorption. SOLUTION: This process contains a polycondensation step for preparing a modified phenol resin by polycondensing a petroleum-derived heavy oil or pitch, a formaldehyde polymer, and a phenol in the presence of an acid catalyst and a mol.wt. reduction step for reducing the mol.wt. of the modified phenol resin by reacting the resin with a hydroxynaphthalene compd. at 50-200 deg.C in the absence of a cross-linker such as a formaldehyde polymer and is the presence of an acid catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention provides excellent moldability due to low melt viscosity, and high reactivity with epoxy resin. Therefore, the present invention can provide corrosion resistance or mechanical properties such as dimensional stability by combining with epoxy resin. The present invention relates to a method for producing a highly reactive modified phenolic resin which can provide a modified phenolic resin which is excellent in heat resistance and strength, and particularly excellent in heat resistance and moisture resistance. Furthermore, the present invention relates to a modified phenolic resin molding material containing a highly reactive modified phenolic resin and an epoxy resin obtained by this method, a material for electric / electronic parts, and a semiconductor encapsulant.

[0002]

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.

[0003] In order to solve such a problem, various modifications of a phenol resin have been studied.
For example, many modified phenolic resins have been proposed which have improved resistance to deterioration or oxidation by light, chemicals or the like by modification using fats and oils, rosin or neutral aromatic compounds.

For example, Japanese Patent Application Laid-Open No. 61-235413 discloses that a phenol 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 phenolic resin is produced, a crude modified phenolic resin obtained by polycondensing a starting compound is neutralized, washed with water and / or washed. It is disclosed that by performing an extraction treatment to neutralize and remove the acid remaining in the crude modified phenolic resin, it is possible to provide a modified phenolic resin that does not corrode metal members in contact with the resin. .

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

Japanese Patent Application Laid-Open No. 6-228157 teaches that a crude modified phenol resin can be purified by a purification step including a special extraction treatment to provide a modified phenol resin containing substantially no acid. I have. The modified phenol resin substantially free of acid obtained in such a purification step has excellent heat resistance and moisture resistance by being combined with an epoxy resin, and provides a molding material having no corrosiveness to metals. Can be provided.

[0009] However, these modified phenolic resins have a high resin melt viscosity and are not suitable for rapidly and mass-producing molded articles having a complicated shape. There has been a demand for further improvements in mechanical properties such as properties and dimensional stability and strength.

Accordingly, the present inventors have made the modified phenolic resin lower in molecular weight by reacting it with phenols in the presence of an acid catalyst, thereby lowering the resin melt viscosity and improving the reactivity with the epoxy resin. A method for producing a highly reactive modified phenol resin capable of producing a modified phenol resin has been proposed (Japanese Patent Application Laid-Open No. 7-252339, Japanese Patent Application No. 8-241).
No. 73).

[0011] In the process for producing a modified phenolic resin, the molecular weight reduction step is performed at a relatively low temperature (50 ° C or higher and 1 ° C or lower).
The molecular weight of the modified phenolic resin is reduced (at 20 ° C. or lower) (JP-A-7-252339), or the molecular weight of the modified phenolic resin is reduced at a relatively high temperature (over 120 ° C. and 200 ° C. or lower). At a relatively low temperature, such a low-molecular-weight reaction cuts and dissociates an acetal bond and / or a methylene ether bond present in a modified phenol resin molecule, and binds a phenol to a dissociation terminal to form a modified phenol resin. Is believed to increase the phenolic content of At a relatively high temperature, in addition to the acetal bond and / or methylene ether bond present in the modified phenol resin molecule, the methylene bond is also cleaved and dissociated, so that particularly low resin melt viscosity and hygroscopicity are realized. Have been.

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

However, these highly reactive modified phenolic resins are excellent in moisture resistance and heat resistance as compared with conventional modified phenolic resins, but are not yet sufficiently excellent. In the field of (1), further improvement in moisture resistance and heat resistance has been demanded from the viewpoint of solder crack resistance.

The present inventors have conducted various studies and examinations in view of the current situation. As a result, the reaction product obtained by the polycondensation reaction is used as it is or after purifying the product to formaldehyde polymer and other crosslinking agent. By reacting with a hydroxynaphthalene compound to reduce the molecular weight in the absence and in the presence of an acid catalyst, a modified phenol resin having high reactivity with an epoxy resin and having a low viscosity is obtained, and The present inventors have found that a molding material obtained by combining a modified phenol resin and an epoxy resin exhibits high heat resistance and low moisture absorption, and completed the present invention.

[0015]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and has excellent moldability due to low viscosity of a molten resin and high reactivity with an epoxy resin. In combination with an epoxy resin, it is possible to produce a modified phenol resin which is a molding material having excellent corrosion resistance or mechanical properties such as dimensional stability and strength, and also having excellent heat resistance and moisture resistance. It is an object of the present invention to provide a method for producing a highly reactive modified phenol resin.

Further, the present invention provides a method for producing a highly reactive modified phenolic resin capable of producing a modified phenolic resin having substantially no acid and having no corrosive property in addition to the above-mentioned properties. It is intended to provide.

Furthermore, the present invention provides a molded article containing the highly reactive modified phenolic resin obtained by the method of the present invention and an epoxy resin, having good moldability, exhibiting high heat resistance and low moisture absorption. It is an object of the present invention to provide a molding material that can be used, particularly a material for electric / electronic parts and a semiconductor encapsulant.

[0018]

SUMMARY OF THE INVENTION The process for producing a highly reactive modified phenolic resin according to the present invention comprises polycondensing a petroleum heavy oil or pitches, a formaldehyde polymer, and a phenol in the presence of an acid catalyst. A polycondensation step of preparing a modified phenolic resin, and reacting the resulting modified phenolic resin with a hydroxynaphthalene compound in the presence of an acid catalyst under conditions substantially free of formaldehyde polymer as a cross-linking agent. And a step of lowering the molecular weight.

In the method for producing a highly reactive modified phenolic resin according to the present invention, the depolymerization step is usually performed at a temperature of 50 ° C. or more and 200 ° C. or less. When the depolymerization reaction is performed at a relatively low temperature, that is, at a temperature of 50 ° C. or more and 120 ° C. or less, cleavage and dissociation of an acetal bond and / or a methylene ether bond existing in the modified phenol resin molecule occur. When the depolymerization reaction is carried out at a relatively high temperature, that is, at a temperature exceeding 120 ° C. and not more than 200 ° C., a methylene bond is added in addition to the acetal bond and / or methylene ether bond present in the modified phenol resin molecule. It is thought that the cleavage and dissociation of.

In the method for producing a highly reactive modified phenolic resin according to the present invention, in the polycondensation step, the petroleum heavy oils or pitches and the formaldehyde polymer are converted into formaldehyde equivalent moles of the formaldehyde polymer. The mixture was heated and stirred in the presence of an acid catalyst so that the number thereof was 1 to 15 with respect to 1 mole of the petroleum heavy oils or pitches. Are preferably added sequentially until the molar number of the phenols becomes a ratio of 0.3 to 5 with respect to 1 mol of the petroleum heavy oils or pitches, and the raw materials are subjected to polycondensation. .

In the present invention, the modified phenol 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. And / or (ii) extraction 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 phenolic resin. The solvent treatment includes a solvent-soluble component including unreacted components and / or a catalyst residue and a formaldehyde polymer as a cross-linking agent. It is possible to effectively prevent the acid catalyst residue and the formaldehyde polymer from being entrained in the depolymerization step.

The modified phenolic resin molding material according to the present invention is characterized by containing (A) a highly reactive modified phenolic resin obtained by the above method and (B) an epoxy resin. The modified phenolic resin material may further contain (C) a curing agent and / or a curing accelerator, and (D) an inorganic filler, in addition to the resin components (A) and (B).

The modified phenolic resin molding material according to the present invention contains the highly reactive modified phenolic resin (A) and the epoxy resin (B) in a ratio of 10/90 to 90/10 (parts by weight). Is preferred.

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

[0025]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the present invention will be described more specifically. The method for producing a highly reactive modified phenolic resin according to the present invention is a method for producing a highly reactive modified phenolic resin by depolymerizing a modified phenolic resin obtained in a specific polycondensation step in a low-molecularization step under specific conditions. doing.

In the polycondensation step of 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 this polycondensation reaction include crude oil distillation residue, hydrogenated residue, catalytic cracked residue, naphtha or LPG pyrolysis residue, and the like. It is obtained as a vacuum distillation product of the residual oil, 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 amount Ha value are 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.

[0030]

(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 the 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 phenolic 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 a petroleum heavy oil or pitch and a formaldehyde polymer are obtained by converting the formaldehyde polymer into a formaldehyde-equivalent mole in terms of the formaldehyde polymer or the pitch. The components are mixed at a ratio of 1 to 15, preferably 2 to 12, more preferably 3 to 11, with respect to 1 mol calculated from the average molecular weight of the class.

For heavy petroleum oils or pitches,
When the mixing ratio of the formaldehyde polymer is less than 1, it is not preferable because the strength of the cured product of the modified phenolic resin obtained is low. On the other hand, when it is larger than 15, both the performance and the yield of the obtained cured product hardly change, and it is considered useless 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.

When the addition 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 the petroleum heavy oils or pitches, the formaldehyde polymer and the phenols.
It is preferably used in an amount of% by weight.

When the amount of the acid catalyst used is small, the reaction time tends to be long, and the reaction tends to be insufficient unless the reaction temperature is increased. 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 above-described raw materials and an acid catalyst, 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 cause of such non-uniformity is that phenols are much more reactive to formaldehyde than petroleum heavy oils or pitches, and the initial concentration of phenols is kept low. If not, it is presumed that formaldehyde selectively reacts with phenols or a condensate of phenols formed by the reaction with formaldehyde and becomes insoluble in the system.

In the polycondensation step of the present invention, the timing of adding the phenol to the mixture of the petroleum heavy oils or pitches and the formaldehyde polymer is not particularly limited, but the formaldehyde reaction estimated from the amount of the remaining free formaldehyde is not 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.

When 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.

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

In the production of the modified phenolic resin of the present invention, when the reaction is carried out batchwise, it is possible to carry out the reaction 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. A complete mixing type reaction vessel is placed in the middle part, and the phenols to be added are placed in 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 a 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 method for producing a highly reactive modified phenolic resin according to the present invention, the modified phenolic resin obtained by the above-described polycondensation reaction is used in the below-described molecular weight reduction step. In the molecular weight reduction step, the modified phenolic resin is reacted with a hydroxynaphthalene compound under specific temperature conditions 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 low molecular weight reduction step, other reaction conditions and the amounts of the raw materials and the catalyst are set so that the modified phenol resin has a desired viscosity by a reaction between the modified phenol resin and the hydroxynaphthalene compound. .

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, reaction solvents 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. Particularly, when the modified phenol resin contains a large amount of a formaldehyde polymer as a cross-linking agent as an unreacted component, the polycondensation reaction of the modified phenol resin, the formaldehyde polymer and the hydroxynaphthalene compound leads to a reduction in molecular weight. May be hindered.

Therefore, in order to appropriately set the reaction conditions in the low-molecular-weight reduction step so that the modified phenolic resin is efficiently reduced in molecular weight by the reaction between the modified phenolic resin and the hydroxynaphthalene compound, the low-molecular-weight reduction step is required. The modified phenolic resin used in the above should not contain an acid catalyst and an unreacted substance or a reaction solvent in such an amount as to inhibit a low-molecular-weight reaction, particularly, an acid catalyst and a formaldehyde polymer. Is preferable.

Such a modified phenolic resin can be prepared by adding an unreacted component, an acid catalyst, or the like in the reaction mixture by appropriately selecting the raw materials, the amount of the acid catalyst and the reaction solvent used in the polycondensation reaction, or the conditions of the polycondensation reaction. And by removing the unreacted components, low molecular components, acid catalysts, reaction solvents, etc. by preventing the reaction solvent and the like from remaining or by appropriately purifying the reaction mixture obtained by the polycondensation reaction. be able to.

As a method for purifying a reaction mixture, ie, a crude modified phenolic 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 to precipitate A purification treatment for removing solvent-soluble components including unreacted components, (ii) the reaction mixture,
Purification treatment in which the catalyst residue is extracted and removed by dissolving in a specific solvent can be exemplified.

In the above refining treatment (i), of the components contained in the petroleum heavy oils or pitches used as the raw materials, 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 no cross-linking agent. 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 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.

Such a solvent is not particularly limited as long as it has the above-mentioned properties. For example, aromatic hydrocarbons such as benzene, toluene and xylene can be mentioned as preferable examples, and among them, toluene is particularly preferable.

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 a 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 depolymerization step, and is again charged into a solvent in which the modified phenol resin is insoluble, such as n-hexane. Alternatively, it may be precipitated and used as a powdery modified phenol resin.

The purification treatment (ii) removes most of the catalyst residue remaining in the reaction product, but if desired, the modified phenol resin after the purification treatment (ii) may be subjected to a neutralization treatment and / or 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, and the like. 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.

When the purification treatment (ii) is performed after the purification treatment (i), the obtained varnish-like modified phenolic 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 method for producing a highly reactive modified phenolic resin according to the present invention, such a modified phenolic resin, that is, the reaction product obtained in the polycondensation step is used as it is or after purification, to formaldehyde polymer and other products. Is reacted with a hydroxynaphthalene compound in the absence of a crosslinking agent 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 to be used are determined by reducing the viscosity of the modified phenolic resin and the reaction with the epoxy resin. There is no particular limitation as long as the reactivity can be improved.

Examples of the acid catalyst used in the depolymerization step of the present invention include the compounds exemplified in the above-mentioned polycondensation step. 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, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxynaphthalene compounds such as 2,7-dihydroxynaphthalene, and alkyl Group, aromatic group, mono- or dihydroxynaphthalene compound having a substituent such as a halogen atom, for example, 2-methyl-1-naphthol, 4-phenyl-1-naphthol, 1-bromo-2-naphthol, 6-bromo- Examples thereof include 2-naphthol.

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 hydroxynaphthalene compound is preferably used in an amount of 100 parts by weight or more, preferably 100 to 300 parts by weight, more preferably 100 to 250 parts by weight, based on 100 parts by weight of the modified phenol resin. If the hydroxynaphthalene compound is 100 parts by weight or more, the depolymerization reaction proceeds to an extent sufficient to obtain the desired effect. However, if an excessive amount of the hydroxynaphthalene compound is used, a large amount of the unreacted hydroxynaphthalene compound remains, thereby increasing the cost required for the post-treatment.

In the depolymerization step using such an acid catalyst and a hydroxy compound, the modified phenol resin is mixed with a hydroxynaphthalene compound at 50 ° C. in the presence of an acid catalyst.
It is desirable that the reaction be performed at a temperature in the range of 200 to 200 ° C for 15 minutes to 2.0 hours, preferably 30 minutes to 2.0 hours.

In the lower molecular weight reaction 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 existing in the modified phenol resin molecule is performed. It is considered that dissociation occurs and the hydroxynaphthalene compound is bonded to the dissociation terminal to increase the hydroxynaphthyl group content of the modified phenol resin. 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 high-reactivity modified phenol resin obtained in the above-described low-molecular-weight-reduction step has (a) a lower number average molecular weight than the modified phenol resin obtained in the polycondensation step, and (b) The reactivity with the epoxy resin (determined by the gelation time: the shorter the reactivity, the higher the reactivity) is further improved, and (c) the melt viscosity of the resin is reduced.

Specifically, according to the method of the present invention, the resin has a number average molecular weight of 350 to 650, particularly 350 to 600, and a resin melt viscosity measured at a temperature of 150 ° C. of 1.0 to 1.0.
A highly reactive modified phenolic resin of 8.5 poise, especially 1.0 to 8.0 poise can be obtained.

The highly reactive phenolic resin obtained by the depolymerization reaction in a high temperature range has a lower resin melt viscosity (for example, a resin melt viscosity measured at a temperature of 150 ° C. of 1.0 to 1.0).
-4.5 poise, especially 1.0-4.0 poise).

Such a highly reactive modified phenolic resin is excellent in moldability due to a low resin melt viscosity, and has high reactivity with an epoxy resin. It is possible to provide a resin molding material having excellent mechanical properties such as excellent heat resistance and moisture absorption resistance.

Further, it has been found that a highly reactive phenol resin obtained by a depolymerization reaction particularly in a high temperature range exhibits particularly low hygroscopicity when used as a molding material in combination with an epoxy resin. Such a molding material can be suitably used for a product which does not like corrosion of a metal portion due to moisture absorption of a resin portion, deterioration of dimensional stability, and the like.

Although the highly reactive modified phenolic resin obtained in the above-described steps can be used as it is for various uses, 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 an alcohol such as ethyl alcohol and methyl alcohol;
A mixed solvent of toluene and tetrahydrofuran; a mixed solvent of toluene and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone;

The highly reactive modified phenolic resin is obtained by extracting unreacted components such as hydroxynaphthalene compound or an acid catalyst using such a solvent, and then, if necessary, using distilled water and / or distilled water. It is desirable to carry out a water washing treatment with a mixed solution of isopropyl alcohol.

If unreacted hydroxynaphthalene compound remains, the unreacted hydroxynaphthalene compound can be removed by steam distillation if necessary.

Also, unreacted hydroxynaphthalene compound can 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 performing such a purification treatment to remove an acid catalyst, unreacted substances, a reaction solvent, and the like which may remain in the resin, in addition to the above-described characteristics, since it contains substantially no acid, A highly reactive modified phenol resin having no corrosiveness 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 (B) an epoxy resin together with the highly reactive modified phenolic resin (A) obtained by the method according to the present invention. Further, the modified phenolic resin molding material according to the present invention may be added to the highly reactive modified phenolic resin (A) within a range not contrary to the object of the present invention by JP-A-7-252339 and / or JP-A-8-24173. Highly reactive modified phenolic resin disclosed in the specification may be blended.
The epoxy resin has a small molding shrinkage and is excellent in heat resistance, abrasion resistance, chemical resistance, and electric insulation, and is used in combination with (C) a curing agent and / or a curing accelerator as needed.

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

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

In the present invention, the mixing ratio (A) / (B) of the highly reactive modified phenol resin and the epoxy resin is, for example, 10 times the total of the modified phenol resin and the epoxy resin.
The 0 parts by weight is preferably 10/90 to 90/10 (parts by weight), but is not particularly limited and can be set as appropriate.

As the (C) 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. . As the curing agent, for example, cyclic amines, aliphatic amines,
Examples include polyamides, aromatic polyamines, and acid anhydrides.

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

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

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

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

A molding material containing such a highly reactive modified phenol resin (A) and epoxy resin (B) exhibits high heat resistance and low moisture absorption. This has higher heat resistance and lower moisture absorption as compared with a conventional highly reactive modified phenol resin.
Such a molding material is a product which dislikes corrosion of a metal part due to moisture absorption of a resin part, deterioration of dimensional stability or generation of cracks when subjected to a heat history, for example, electric / electronic parts,
It can be suitably used as a semiconductor sealing material and the like.

The modified phenolic resin molding material according to the present invention may further comprise (A) a highly reactive modified phenolic resin, (B) an epoxy resin, and (C) a curing agent and / or a curing accelerator used as required. Further, (D) an inorganic filler may be further contained.

By adding the inorganic filler (D) to the resin molding material, 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 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 the inorganic filler (D) is not particularly limited, but may be, for example, 20 to 800 parts by weight per 100 parts by weight of the highly reactive modified phenolic resin.
Preferably, it is used in an amount of 50 to 600 parts by weight.

The modified phenolic resin molding material according to the present invention may further contain an additive, if necessary, such as an internal mold release agent such as silicone and wax. Agents, coupling agents, flame retardants, light stabilizers, antioxidants, pigments, extenders, and the like.

The modified phenolic resin molding material according to the present invention described above comprises (A) a highly reactive modified phenolic resin and (B) an epoxy resin, and if necessary, (C) a curing agent and / or a curing accelerator, (D) It is prepared by mixing an inorganic filler and various additives, and is applied to the production of a molded article.

In the present invention, the mixing order of (A) the highly reactive modified phenolic resin and (B) the epoxy resin and (C) the optional components such as the curing agent is not particularly limited. A phenol resin and an epoxy resin are kneaded, a curing agent (curing accelerator) is added, and the mixture is further mixed, and then, if necessary, an inorganic filler and other additives are added and mixed. (Compound).

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

The stirring mixture is mixed with other additives such as a curing agent and / or a curing accelerator and a wax. Add and mix the inorganic filler.

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

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

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

Further, the molded article is formed in a range 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.

As described above, the molded article obtained by molding the modified phenolic resin material according to the present invention is excellent not only in heat resistance and moisture absorption, but also in electrical insulation and mechanical strength. For example, it has the following physical properties.

[0113] Flexural strength at room temperature ^{8~22kgf / mm 2 150 ℃ 3~14kgf /} mm 2 flexural modulus at room temperature ^{400~2000kgf / mm 2 150 ℃ 40~1500kgf /} mm 2 Glass transition temperature (° C.) 120 to 260 ° C. Heat deformation Temperature 190 to 300 ° C or higher Insulation resistance Normal 1.8 × 10 ^{14 to} 5.0 × 10 ¹⁴ Ω Boiling 3.0 × 10 ^{13 to} 2.0 × 10 ¹⁴ Ω The modified phenolic resin molding material according to the present invention is modified Since the reactivity between the phenolic resin and the epoxy resin has been improved, the mechanical properties such as the dimensional stability of the molded article obtained therefrom and the thermal stability have been improved, and the highly reactive modified phenolic resin used has a low viscosity. Therefore, it has the characteristics that the moldability is particularly good and the reactivity with the epoxy resin is high. Further, in the modified phenolic resin molding material according to the present invention, since it does not substantially contain an acid, it is possible to reduce the corrosiveness to a metal member, and by adding an inorganic filler, the mechanical strength of the molded body, electric insulation, etc. It can be further improved.

Therefore, this modified phenolic resin molded article is an electric / electronic component such as a printed circuit board, an insulating material, a sealing material, etc., which dislikes moisture absorption and is required to have extremely strict standards for dimensional stability, heat resistance and moldability. It is particularly useful as a semiconductor encapsulant that is required to improve dimensional stability and hygroscopicity as a measure against stress damage due to heat resistance and high integration.

[0115]

According to the method for producing a highly reactive modified phenolic resin according to the present invention, the modified phenolic resin is produced by the above-mentioned polycondensation step and low molecular weight step, so that the resin melt viscosity is low and It is possible to provide a highly reactive modified phenol resin having extremely high reactivity with an epoxy resin.

Further, according to the method for producing a highly reactive modified phenolic resin according to the present invention, the highly reactive modified phenolic resin obtained in the above-mentioned depolymerization step is further purified to obtain unreacted components and acid catalysts. By removing such a component, it is possible to produce a highly reactive modified phenolic resin having substantially no acid in addition to the above-mentioned properties and thus having no corrosiveness.

The modified phenolic resin molding material according to the present invention contains the highly reactive modified phenolic resin obtained by the method of the present invention and an epoxy resin, has good moldability, and particularly has high heat resistance and low moisture absorption. Molding materials that can produce molded products with excellent mechanical properties such as dimensional stability
An electronic component material and a semiconductor encapsulant can be provided.

[0118]

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 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.

[0120]

[Table 1]

The number average molecular weight, reactivity with the epoxy resin (determined by the gelation time; the shorter the reactivity, the higher the reactivity), and the resin melt viscosity measured in the following Examples were determined by the following apparatus or measuring method. It was measured.

<Number average molecular weight> HLC-8020 GPC apparatus manufactured by Tosoh Corporation Column: TSKgel 3000HHR + TSKgel 200
0HHR standard substance: molecular weight converted by polystyrene <Viscosity measurement> ICI cone plate viscometer manufactured by ICI <Geling time> Measured at 170 ° C in accordance with JIS K6910.

<Glass transition temperature> Measurement method: dynamic viscoelasticity measurement equipment: Rheology Co., Ltd., DVE RHEOSPECTOLER DVE-
4V type Load method: Tensile method Measurement frequency: 10 Hz Temperature rise rate: 5 ° C./min Dynamic measurement displacement: ± 5 + 10 ^-4 cm Specimen: 4 mm wide, 1 mm thick, 30 mm span <OH equivalent> By acetyl chloride method Measurement

[0124]

Example 1 (Polycondensation step) 334 g of feedstock oil, 370 g of paraformaldehyde, p-toluenesulfonic acid monohydrate 1 shown in Table 1
37 g and 678.5 g of p-xylene were charged into a glass reactor and heated to 95 ° C. while stirring. 1 at 95 ° C
After holding for a period of time, 209 g of phenol was added dropwise at a dropping rate of 1.3 g / min, and after the addition of the phenol was completed, the mixture was further stirred for 15 minutes. Next, the reaction mixture was poured into 3,300 g of n-hexane to precipitate a reaction product, which was filtered to remove unreacted components and a reaction solvent. The precipitate was washed with 1,600 g of n-hexane, and then dried in vacuo to obtain an acid-containing crudely modified phenol resin.

This resin was dissolved in a 10-fold weight of toluene, and insolubles containing p-toluenesulfonic acid monohydrate as a main component were filtered. The obtained resin toluene solution was concentrated until the resin concentration became 50% by weight to obtain a varnish-like modified phenol resin. Further, a slight amount of triethylenetetramine was added for neutralization, and the modified phenol resin varnish was 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. (Step of lowering molecular weight and modifying naphthol) 100 g of powdery modified phenol resin obtained, 200 g of α-naphthol,
And 10 g of toluene and 10 g of 1-butanol as reaction solvents.
g into a 1 liter glass reaction vessel,
The temperature was raised to 110 ° C while stirring at a speed of 50 rpm,
5 g of p-toluenesulfonic acid dissolved in 5 g of -butanol
Was added, and reacted at 110 ° C. for 120 minutes to obtain a reaction product.

The above reaction product was added to and dissolved in 800 ml of methyl isobutyl ketone, and the resulting resin mixed solution was washed with distilled water to remove the acid, and then the solvent was removed with an evaporator.

Further, the crude highly reactive modified phenol resin obtained was subjected to steam distillation at 160 to 170 ° C., and nitrogen was blown at the same temperature to remove unreacted α-naphthol, thereby obtaining a highly reactive modified phenol resin. 220 g were obtained.

The number-average molecular weight and viscosity at 150 ° C. of the obtained highly reactive modified phenol resin were measured. The results are shown in Table 2 together with the reaction conditions such as the reaction temperature and the like for the reduction of the molecular weight and the naphthol denaturation reaction.

[0129]

Examples 2 to 4 Example 1 was repeated except that the reaction conditions in the lower molecular weight and naphthol denaturation steps were changed as shown in Table 2.
The same operation as described above was performed to obtain each highly reactive modified phenol resin in the yield shown in Table 2.

The number average molecular weight and the viscosity at 150 ° C. of the obtained highly reactive modified phenol resin were measured, and the results are shown in Table 2.

[0131]

Example 5 200 g of a varnish-like modified phenolic resin (resin content 50%) obtained in the polycondensation step of Example 1,
-200 g of naphthol and 10 g of 1-butanol as a reaction solvent were charged into a 1-liter glass reaction vessel,
The temperature was raised to 110 ° C. while stirring at a speed of 0 to 350 rpm, 5 g of p-toluenesulfonic acid dissolved in 5 g of 1-butanol was added dropwise, and the mixture was reacted at 110 ° C. for 120 minutes to obtain a reaction product.

The above reaction product was added to and dissolved in 800 ml of methyl isobutyl ketone, and the obtained resin mixed solution was washed with distilled water to remove the acid, and then the solvent was removed with an evaporator.

Further, the crude highly reactive modified phenol resin obtained was subjected to steam distillation at 160 to 170 ° C., and nitrogen was blown at the same temperature to remove unreacted α-naphthol, thereby obtaining a highly reactive modified phenol resin. 225 g were obtained.

The number-average molecular weight and the viscosity at 150 ° C. of the obtained highly reactive modified phenol resin were measured. The results are shown in Table 2 together with the reaction conditions such as the reaction temperature and the like for the reduction of the molecular weight and the naphthol denaturation reaction.

[0135]

Example 6 α-Naphthol used in the low molecular weight conversion step was converted to β
-The same operation as in Example 1 was carried out except that naphthol was used, to obtain a highly reactive modified phenol resin having a yield shown in Table 2.

The number average molecular weight and the viscosity at 150 ° C. of the obtained highly reactive modified phenol resin were measured, and the results are shown in Table 2.

[0137]

Example 7 100 g of the powdery modified phenol resin obtained in the polycondensation step of Example 1, 101 g of α-naphthol,
132 g of phenol and 5 g of p-toluenesulfonic acid in 1
A 1-liter glass reactor was charged, heated to 140 ° C. while stirring at a speed of 250 to 350 rpm, and kept at 140 ° C. for 60 minutes to obtain a reaction product.

The above reaction product was dissolved in 800 ml of toluene /
The solution was poured into methyl isobutyl ketone (mixing ratio: 7/3) to dissolve the resin, the resin mixed solvent solution was washed with distilled water to extract and remove the acid, and then the mixed solvent was removed by an evaporator.
Further, the obtained crude highly reactive modified phenol resin
After steam distillation at 170 ° C., unreacted α-naphthol was removed by blowing nitrogen at the same temperature to obtain 216 g of a highly reactive modified phenol resin.

The number average molecular weight and viscosity at 150 ° C. of the obtained naphthol-modified resin were measured, and the results are shown in Table 2.

[0140]

Comparative Example 1 100 g of the powdery modified phenolic resin obtained in the polycondensation step of Example 1, 200 g of phenol and p-
5 g of toluenesulfonic acid is charged into a 1 liter glassy reactor, and stirred while stirring at a speed of 250 to 350 rpm.
The temperature was raised to 5 ° C. and maintained at 95 ° C. for 90 minutes to obtain a reaction product.

The above reaction product was dissolved in 400 ml of toluene /
The solution was poured into methyl isobutyl ketone (mixing ratio: 7/3) to dissolve the resin. The resin mixed solvent solution was washed with distilled water to extract and remove the acid, and then the mixed solvent was removed with an evaporator to remove the acid.
75 g of a highly reactive modified phenolic resin was obtained.

The number average molecular weight and the viscosity at 150 ° C. of the obtained modified phenol resin were measured, and the results are shown in Table 2.

[0143]

Comparative Example 2 The same operation as in Comparative Example 1 was carried out except that the reaction conditions in the depolymerization step were changed as shown in Table 2, to obtain a highly reactive modified phenol resin having the yield shown in Table 2. .

The number average molecular weight and the viscosity at 150 ° C. of the obtained highly reactive modified phenol resin were measured, and the results are shown in Table 2.

[0145]

Example 8 11.71 parts by weight of the highly reactive modified phenolic resin obtained in Example 1 and a biphenyl type epoxy resin (trade name YX4000, manufactured by Yuka Shell Epoxy Co., Ltd.)
H) 12.35 parts by weight was mixed and stirred at room temperature using an automatic mortar, and 0.25 parts by weight of triphenylphosphine (TPP) was added and mixed as a curing catalyst to the stirred mixture to obtain a curing accelerator-containing resin mixture. Obtained.

The gelation time of this resin mixture containing a curing accelerator was measured and is shown in Table 3. Further, after adding and mixing 0.25 parts by weight of carnauba wax to the obtained resin mixture containing a curing accelerator, 0.20 parts by weight of carbon black and fused silica as an inorganic filler (manufactured by Tatsumori Co., Ltd.)
75 parts by weight of CRS1102-GT200T). The obtained mixture was further mixed for 3 to 10 minutes by a hot roll machine adjusted to 80 to 90 ° C., then 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.

[0148]

Examples 9 to 14 Instead of the highly reactive modified phenolic resin obtained in Example 1, the highly reactive modified phenolic resins obtained in Examples 2 to 7 were used, respectively. The curing accelerator-containing resin mixture, the compound, and the molded body were produced in the same manner as in Example 8 except that the compounding ratio of was set as shown in Table 3.

The gelation time of the obtained curing accelerator-containing resin mixture and the physical properties of the molded product (Shore hardness immediately after molding, glass transition point, bending characteristics, and moisture absorption) were measured. The results are shown in Table 3. .

[0150]

Example 15 In place of the highly reactive modified phenolic resin obtained in Example 1, the highly reactive modified phenolic resin obtained in Example 1 and the low viscosity modified phenolic resin obtained in Comparative Example 2 were used. The same procedure as in Example 8 was carried out except that the mixture was used in the ratio shown in Table 3 and the mixing ratio of the modified phenol resin and the epoxy resin was set to the value shown in Table 3, and the curing accelerator-containing resin mixture, compound and A molded body was manufactured.

The gelation time of the obtained resin mixture containing a curing accelerator and the physical properties of the molded product (Shore hardness immediately after molding, glass transition point, bending characteristics and moisture absorption) were measured. The results are shown in Table 3. .

[0152]

Comparative Examples 3 and 4 In place of the highly reactive modified phenolic resin obtained in Example 1, the modified phenolic resin obtained in Comparative Examples 1 and 2 was used, and the modified phenolic resin and the epoxy resin were mixed. A curing accelerator-containing resin mixture, a compound and a molded product were produced in the same manner as in Example 8, except that the ratio was changed to the value shown in Table 3.

The gelation time of the obtained curing accelerator-containing resin mixture and the physical properties of the molded product (Shore hardness immediately after molding, glass transition point, bending characteristics, and moisture absorption) were measured. The results are shown in Table 3. .

[0154]

Example 16 11.76 parts by weight of the highly reactive modified phenolic resin obtained in Example 1 and an orthocresol novolak type epoxy resin (trade name: EOC, manufactured by Nippon Kayaku Co., Ltd.)
N1020) was mixed and stirred at room temperature using an automatic mortar at room temperature, and 0.25 parts by weight of triphenylphosphine (TPP) was added and mixed as a curing catalyst to the stirred mixture to obtain a curing accelerator-containing resin mixture. Obtained.

The gelation time of the resin mixture containing the curing accelerator was measured, and the results are shown in Table 3. Further, after adding and mixing 0.25 parts by weight of the obtained curing accelerator-containing resin mixture and carnauba wax, 0.20 parts by weight of carbon black and fused silica as an inorganic filler (manufactured by Tatsumori Co., Ltd., C
(RS1102-GT200T) 75 parts by weight. The obtained mixture was further mixed for 3 to 10 minutes with a hot roll machine adjusted to 80 to 90 ° C., and then cooled to room temperature.
It was pulverized to obtain a compound (molding material). Table 4 shows the composition of this compound.

The obtained compound was heated at 175 ° C., 90
Transfer molding was performed under the conditions of seconds, and post-curing was further performed at 175 ° C. for 6 hours to obtain a molded body. The Shore hardness, glass transition point, bending properties, and moisture absorption of the obtained molded body immediately after molding were measured. The results are shown in Table 4.

[0157]

Examples 17 to 22 In place of the highly reactive modified phenolic resin obtained in Example 1, the highly reactive modified phenolic resins obtained in Examples 2 to 7 were used, respectively. The curing accelerator-containing resin mixture, the compound, and the molded body were produced in the same manner as in Example 16 except that the compounding ratio of was set as shown in Table 4.

The gelation time of the obtained resin mixture containing a curing accelerator and the physical properties of the molded product (Shore hardness immediately after molding, glass transition point, bending characteristics, and moisture absorption) were measured. The results are shown in Table 4. .

[0159]

Comparative Example 5 The procedure of Example 16 was repeated, except that the modified phenolic resin obtained in Comparative Example 1 was used instead of the highly reactive modified phenolic resin obtained in Example 1. Resin mixtures, compounds and moldings were produced.

The gelation time of the obtained resin mixture containing a curing accelerator and the physical properties of the molded product (Shore hardness immediately after molding, glass transition point, bending characteristics, and moisture absorption) were measured. The results are shown in Table 4. .

[0161]

[Table 2]

[0162]

[Table 3]

[0163]

[Table 4]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI H01L 23/31

Claims (9)

[Claims] 1. A polycondensation step of preparing a modified phenolic resin by polycondensing a petroleum heavy oil or pitches, a formaldehyde polymer, and a phenol in the presence of an acid catalyst. Reacting the modified phenol resin with a hydroxynaphthalene compound in the presence of an acid catalyst to reduce the molecular weight to a low molecular weight. 2. The method for producing a highly reactive modified phenolic resin according to claim 1, wherein the reaction temperature in the depolymerization step is 50 ° C. or more and 200 ° C. or less. 3. In the polycondensation step, the petroleum-based heavy oils or pitches and the formaldehyde polymer are combined with each other by converting the formaldehyde polymer into a formaldehyde-equivalent mole number of the petroleum-based heavy oils or pitches. The mixture containing 1 to 15 moles per mole was heated and stirred in the presence of an acid catalyst. The mixture was heated and stirred, and the phenols were added to the mixture. The modified phenolic resin is prepared by sequentially adding an amount of 0.3 to 5 with respect to 1 mol of heavy oils or pitches and subjecting these materials to polycondensation to prepare a modified phenol resin. 3. The method for producing a highly reactive modified phenol resin according to any one of 2. 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 most of the modified phenol resin, and the catalyst residue is extracted and purified. The method for producing a highly reactive modified phenolic resin according to any one of claims 1 to 3, wherein the obtained purified modified phenolic resin is used in the low-molecularization step. 5. (A) A highly reactive modified phenolic resin obtained by the method according to any one of claims 1 to 4,
(B) A modified phenolic resin molding material comprising an epoxy resin. 6. The modified phenolic resin molding material according to claim 5, further comprising (C) a curing agent and / or a curing accelerator, and (D) an inorganic filler. 7. The highly reactive modified phenolic resin (A)
And the epoxy resin (B) is from 10/90 to 90/10
The modified phenolic resin molding material according to claim 5 or 6, which is mixed at a ratio of (parts by weight). 8. A material for electric / electronic parts, obtained by molding the modified phenolic resin molding material according to claim 5. Description: 9. A semiconductor encapsulant comprising the modified phenolic resin molding material according to claim 5.