JPH10316732A - Production of highly reactive modified phenol resin, and molding material, material for electric and electronic part, and semiconductor sealing material containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a phenol resin which has a low melt viscosity and is highly reactive with an epoxy resin by a simple operation by subjecting a petroleum-derived heavy oil or pitch with a formaldehyde compd. to polycondensation in the presence of an acid catalyst and then mixing and reacting the resultant reaction mixture with a phenol. SOLUTION: The petroleum-derived heavy oil or pitch used as a raw material for the polycondensation is obtd. as a distillation residue or a hydrocracking residue or a catalytic cracking residue of crude oil, a thermal cracking residue of naphtha or LPG, or a vacuum distillation product or a solvent-extraction extract or a thermal treatment product of these residues. Though such a raw material may be used as it is, it may be subjected to a treatment to remove a 15-40C satd. hydrocarbon fraction contg. low-reactivity paraffins. Among thus treated raw materials, one having suitable arom. hydrocarbon ratio (±a value) and arom. ring hydrogen content (Ha value) is used. For example, a raw material heavy oil or pitch having a ± a value of 0. 5-0. 8 and an Ha value of 25-60 % is pref.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a low-viscosity, high-reaction molded article which, when combined with an epoxy resin, gives a molded article having excellent heat resistance, moisture resistance, corrosion resistance, and mechanical properties such as dimensional stability and strength. For producing highly reactive modified phenolic resin by simple operation, phenolic resin molding material containing highly reactive modified phenolic resin and epoxy resin obtained by this method, for electric and electronic parts The present invention relates to a material and a semiconductor sealing material.

[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. 6-228257 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. . The modified phenol resin substantially free of acid obtained in such a purification step is combined with an epoxy resin,
A molding material having excellent heat resistance and moisture resistance and having no corrosiveness to metal can be provided.

[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.

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

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

However, in these methods for producing a highly reactive modified phenol resin, the reaction product obtained in the polycondensation step is purified, and once the modified phenol resin is produced, it is used in the next step for depolymerization. Therefore, the resin production operation had to be complicated.

The present inventors have conducted various studies and studies to solve the problems of the prior art as described above. As a result, first, petroleum heavy oils or pitches and a formaldehyde compound were dissolved in the presence of an acid catalyst. Polycondensed in, and by reacting the resulting reaction mixture with phenols without particular purification, it has a high reactivity with the epoxy resin and a highly reactive modified phenol resin with low viscosity. The molding material obtained by combining this highly reactive modified phenolic resin and epoxy resin is excellent in moldability and has excellent heat resistance, moisture resistance, corrosion resistance, and dimensional stability, strength and other mechanical properties. The inventors have found that the molded article has characteristics, and have completed the present invention.

[0014]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and has a simple operation, a low melt viscosity and a high reactivity with an epoxy resin. It is an object of the present invention to provide a method for producing a modified phenol resin.

Further, the present invention comprises a highly reactive modified phenolic resin obtained by the method of the present invention and an epoxy resin, and has a mechanical property such as moldability, heat resistance, moisture resistance, corrosion resistance and dimensional stability. It is an object of the present invention to provide a molding material capable of producing a molded article having excellent mechanical strength, particularly a material for electric / electronic parts and a semiconductor encapsulant.

[0016]

SUMMARY OF THE INVENTION The method for producing a highly reactive modified phenolic resin according to the present invention is obtained after polycondensation of petroleum heavy oils or pitches and a formaldehyde compound in the presence of an acid catalyst. It is characterized in that the polycondensation reaction mixture is mixed and reacted with phenols.

In the method for producing a highly reactive modified phenolic resin according to the present invention, it is desirable that the above-mentioned polycondensation reaction mixture is added to phenols, mixed and reacted. Also,
In the production method of the present invention, it is desirable to use a Bronsted acid selected from the group consisting of organic acids, inorganic acids and solid acids as the acid catalyst. Further, among such acid catalysts, toluenesulfonic acid, oxalic acid, and sulfuric acid are preferable as the organic acid and the inorganic acid, and acidic cation exchange resin is preferable as the solid acid.

In the method for producing a highly reactive modified phenolic resin according to the present invention, the petroleum heavy oils or pitches may be used as they are, or a treatment for removing a paraffin fraction as a low-reactive component. May be used after applying.

In the production method of the present invention, the highly reactive modified phenolic resin obtained by the reaction of the polycondensation reaction mixture with phenols may be used as (i) an aliphatic hydrocarbon having 10 or less carbon atoms or an aliphatic hydrocarbon. A step of treating with a solvent containing at least one compound selected from the group consisting of petroleum fractions and alicyclic hydrocarbons having 10 or less carbon atoms to remove solvent-soluble components including unreacted components, (ii) catalyst Removing the residue and
(iii) It is desirable to purify in at least one step selected from the step of removing residual phenols by any of steam distillation, nitrogen gas blowing, and vacuum distillation.

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

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

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

[0023]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the present invention will be described more specifically. In the method for producing a highly reactive modified phenolic resin according to the present invention, first, a polycondensation reaction product is prepared by polycondensing a heavy petroleum-based oil or pitch and a formaldehyde compound in the presence of an acid catalyst. .

The petroleum heavy oils or pitches used as a raw material in the polycondensation reaction in the present invention may be a crude distillation residue, a hydrocracking residue, a catalytic cracking residue, naphtha or LP.
G can be obtained as a pyrolysis residue of G, a distillate of these residues under reduced pressure, an extract by solvent extraction or a heat-treated product.

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

The treatment for removing the paraffin fraction is as follows:
For example, the reaction can be performed at 80 to 120 ° C. using furfural, and can also be performed by column chromatography.

As the packing material to be packed in the column used for the column chromatography, there can be mentioned, for example, activated alumina gel, silica gel and the like. These fillers may be used alone or in combination of two or more.

The developing agents used in such chromatography include C 5-8, such as n-pentane, n-hexane, n-heptane and n-octane.
Aliphatic hydrocarbon compounds, ethers such as diethyl ether, halogenated hydrocarbons such as chloroform and carbon tetrachloride, and alcohols such as methyl alcohol and ethyl alcohol. It is desirable to use two or more of these developing agents as appropriate.

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

If desired, the petroleum heavy oils or pitches that have been subjected to such a paraffin fraction removal treatment can be used to adjust the aromatic hydrocarbon fraction fa value and the aromatic ring hydrogen amount Ha value from these. It is preferable to use one selected.

For example, petroleum heavy oils or pitches are 0.40 to 0.95, preferably 0.5 to 0.8,
More preferably, a fa value of 0.55 to 0.75 and 20
~ 80%, preferably 25-60%, more preferably 2
It is desirable to have a Ha value of 5 to 50%.

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

[0033]

(Equation 1)

F of raw petroleum heavy oils or pitches
If the value of a is smaller than 0.4, the aromatic content decreases, and the effect of modifying the phenolic resin of the resulting modified formaldehyde resin, particularly the effect of modifying 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 carbon and the formaldehyde compound tends to be low.
Ha value of petroleum heavy oils or pitches as raw material is 20%
When smaller, the amount of aromatic ring hydrogen that reacts with the formaldehyde compound decreases, and the reactivity decreases.Therefore, it is a polycondensate of petroleum heavy oils or pitches and the formaldehyde compound contained in the reaction mixture. The yield of the modified formaldehyde resin tends to decrease.

When a petroleum heavy oil or pitch having a Ha value of more than 80% is used as a raw material, a polycondensate (modified formaldehyde resin) mainly contained in the reaction mixture is polymerized and a desired resin is obtained. Can not be obtained.

The heavy petroleum oils or pitches used in the present invention are not particularly limited in the number of condensed aromatic hydrocarbons constituting the heavy oils or pitches, and may be 2 to 4 condensed polycyclic aromatic hydrocarbons. It is preferable to mainly configure. 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, a boiling point exceeding 450 ° C. As a result, the boiling point of the raw material varies greatly, making it difficult to collect those having a narrow boiling point range, and as a result, it becomes difficult to stabilize the quality of the product. In addition, petroleum heavy oils or pitches,
When a monocyclic aromatic hydrocarbon is mainly used, the reactivity with a formaldehyde compound is low, so that a high reforming effect may not be obtained.

The formaldehyde compound used in the polycondensation reaction with such petroleum heavy oils or pitches in the present invention includes, in addition to paraformaldehyde,
Examples thereof include linear polymers such as polyoxymethylene (especially oligomers), cyclic polymers such as trioxane, and aqueous formaldehyde (formalin).

Such a formaldehyde compound acts as a crosslinking agent, and paraformaldehyde is particularly preferred. In the method for producing a highly reactive modified phenolic resin according to the present invention, such a formaldehyde compound is used in an amount of 1 to 15 in terms of formaldehyde with respect to 1 mol of petroleum heavy oils or pitches calculated from the average molecular weight. Mole,
Preferably, it is used in an amount of preferably 2 to 12 mol, more preferably 3 to 11 mol.

When the amount of the formaldehyde compound is less than 1 mol per mol of the petroleum heavy oils or pitches, the yield of the target polycondensate (modified formaldehyde resin) mainly contained in the obtained reaction mixture is obtained. It is not preferable because the rate is low. On the other hand, if it is more than 15 mol, the performance and yield of the modified formaldehyde resin hardly change, so that it is not necessary to use more formaldehyde compound.

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

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

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

The acidic cation exchange resin as an acid catalyst is
Usually, it is desirable to use as a spherical body having a particle size of 15 to 50 mesh. Specific examples of such an acidic cation exchange resin include Diaion SKIB and PK21.
6, SK104 and PK208 (Mitsubishi Chemical: trade name), Amberlite IR-120B, IR-112
And Amberlyst S (manufactured by Organo: trade name), Dowex 50wx 8, HCR and HGR (manufactured by Dow Chemical: trade name), Duolite C-20 and C-25 (manufactured by Sumitomo Chemical: trade name), and the like. Strongly acidic cation exchange resin, and weaknesses such as Diaion WK10 (Mitsubishi Chemical: trade name), Amberlite IRc-50 (Organo: trade name), Duolite CS-101 (Sumitomo Chemical: trade name) An acidic cation exchange resin can be exemplified.

When such a solid acid is used as an acid catalyst, since the acid is not contained in a free state in the reaction mixture, the solid acid is converted from a reaction product obtained by a reaction with a phenol described below. Removal has the advantage that a modified phenol resin substantially free of acid can be obtained.

In the present invention, such an acid catalyst is used in a total of 100 parts by weight of a petroleum heavy oil or pitches and a formaldehyde compound calculated from the average molecular weight.
It is used in an amount of 0.1 to 30 parts by weight, preferably 1 to 20 parts 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 such a polycondensation reaction between a petroleum heavy oil or pitches and a formaldehyde compound in the presence of an acid catalyst, the polycondensation reaction temperature depends on the raw material composition and the properties of the resulting polycondensate. And the reaction time is controlled. It goes without saying that the reaction temperature and the reaction time also affect each other.

For example, the polycondensation reaction is usually performed at 50 to 200
° C, preferably 50 to 160 ° C, more preferably 60 to 160 ° C.
At a temperature of 120 ° C. for 30 minutes to 10 hours, preferably 1 hour
５5 hours.

The polycondensation reaction can be carried out without using a solvent. However, a suitable solvent may be used to lower the viscosity of the reaction mixture (reaction system) 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.

The reaction mixture obtained by the above-mentioned polycondensation reaction contains, in addition to a modified formaldehyde resin which is a polycondensate of petroleum heavy oils or pitches and a formaldehyde compound, an unreacted product, an acid catalyst and It contains a reaction solvent and the like used as desired. In the present invention, such a polycondensation reaction mixture is used as it is, mixed with phenols and reacted.

In the method of the present invention, the phenols are the heavy petroleum oil or the pitches 1 calculated from the average molecular weight.
Mix 1 to 15 moles per mole. In the method of the present invention, examples of the phenol mixed with the polycondensation reaction mixture include a hydroxybenzene compound and a hydroxynaphthalene compound. Examples of the hydroxybenzene compound include phenol, cresol, xylenol, resorcin, hydroquinone, catechol, phenylphenol, vinylphenol, nonylphenol, p-tert-butylphenol, bisphenol A, bisphenol F and the like. Examples of the hydroxynaphthalene compound include monohydroxynaphthalene compounds such as α-naphthol and β-naphthol, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, and 2,3-
Dihydroxynaphthalene, 3,6-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxynaphthalene compounds such as 2,7-dihydroxynaphthalene, And an alkyl group, an aromatic group, a mono- or dihydroxynaphthalene compound having a substituent such as a halogen atom, such as 2-methyl-1-naphthol, 4-phenyl-1-naphthol, 1-bromo-2-naphthol, 6- Brom-2-naphthol and the like can be exemplified. These phenols may be used alone or in combination of two or more.

In the present invention, such a mixing operation of the phenol and the polycondensation reaction mixture is not particularly limited in conditions and procedures, but, for example, the reaction mixture after completion of the polycondensation reaction is brought to a desired temperature in advance. It can be carried out by charging the mixture with the phenols maintained and stirring.

The reaction between the phenols thus mixed and the above-mentioned polycondensation reaction mixture is carried out at a temperature and at a temperature corresponding to the composition of the polycondensation reaction mixture, the amount of the phenols, and the properties of the obtained resin. Time is controlled. It goes without saying that the reaction temperature and the reaction time also affect each other.

Specifically, for example, the mixing and reaction of the polycondensation reaction mixture with phenols can be carried out according to the following procedure. First, the reaction mixture after the polycondensation reaction (normal temperature: 60 to 120 ° C.)
C., preferably 30-80.degree. C., and the phenols are charged and stirred to mix them. At this time, it is desirable to adjust the charging speed so that the temperature of the mixture does not exceed the reaction temperature, and take care to prevent a sharp rise in temperature. Such a rapid rise in temperature indicates that the reaction is rapidly progressing, and it is difficult to uniformly mix the raw materials.

Next, the obtained mixture is mixed with 50 to 200
C., preferably 70-180.degree. C., while heating and maintaining the temperature, and reacting for 0.5-10 hours, preferably 0.5-8 hours to obtain a highly reactive modified phenolic resin.

As for the reaction mechanism of the above reaction, when the reaction temperature is 120 ° C. or lower, the methylene ether and acetal bonds contained in the polycondensation reaction mixture are cleaved by the acid, and phenol is bonded at the relevant site. Furthermore, if the reaction temperature is 1
At 20 ° C. or higher, the methylene bond contained in the polycondensation reaction mixture, in addition to the methylene ether and acetal bond, is also cleaved by the acid, and the phenol is bonded to the site.

The reaction between the polycondensation reaction mixture and the phenol can be carried out without using a solvent. However, the viscosity of the reaction mixture (reaction system) is reduced by using an appropriate solvent, so that a uniform reaction can be achieved. May happen. As such a solvent, for example, the reaction solvent used in the above polycondensation reaction can be exemplified.

The method for producing a highly reactive modified phenolic resin according to the present invention described above is different from the method for producing a highly reactive modified phenolic resin disclosed in JP-A-7-252339 and the like in the polycondensation step. And the mixing operation of the polycondensation reaction mixture and the phenol can be performed continuously after the completion of the polycondensation reaction. This is significantly simplified.

The highly reactive modified phenolic resin produced by the method of the present invention has excellent moldability because of its low resin melt viscosity, high reactivity with epoxy resin, and dimensional stability by combining epoxy resin. It is possible to provide a modified phenolic resin molding material having excellent mechanical properties such as strength and strength, and excellent in moisture resistance and heat resistance.

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

As a method for purifying a reaction mixture, that is, a crude modified phenol resin containing an acid catalyst, unreacted substances, low molecular components and a reaction solvent, for example, (i) a reaction mixture containing a highly reactive modified phenol resin may be prepared by the following method. A purification treatment for treating and precipitating with a specific solvent to remove solvent-soluble components including unreacted components; (ii) a purification treatment for removing catalyst residues from the reaction mixture; A purification treatment for removing residual phenols by either blowing or distillation under reduced pressure can be mentioned.

In the above-mentioned 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 unreacted or unreacted components are contained in the reaction product. The components remaining in an insufficient state and the reaction solvent appropriately used in the reaction are removed.

In such a purification treatment (i), the reaction mixture obtained is obtained by subjecting the reaction mixture to an aliphatic hydrocarbon having 10 or less carbon atoms, an aliphatic petroleum fraction and an alicyclic having 10 or less carbon atoms at an arbitrary time. Poured into a solvent containing at least one compound selected from the group consisting of hydrocarbons to precipitate the resin main component, components soluble in the solvent, that is, unreacted and low-reacted components, and polycondensation reaction This is performed by removing the reaction solvent and the like at the time.

Examples of such hydrocarbon solvents include aliphatic or alicyclic hydrocarbons such as pentane, hexane, heptane and cyclohexane, and aliphatic petroleum distillates such as naphtha. Naphtha is preferred. The highly reactive modified phenolic resin obtained in the purification treatment (i) is in a powder form.

In the above purification treatment (ii), the acid catalyst remaining in the reaction mixture is removed, and a highly reactive modified phenol resin containing substantially no acid is obtained. In the case where an organic acid and an inorganic acid are used as the acid catalyst, such a purification treatment (ii) is performed by removing the catalyst residue by subjecting the reaction mixture as it is or dissolving it in a specific solvent, followed by washing with water. ing.

The solvent for dissolving the reaction mixture is not particularly restricted but includes, for example, toluene; methyl alcohol,
Alcohols such as ethyl alcohol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone;
Ether solvents such as tetrahydrofuran, diethyl ether, methyl tertiary butyl ether, etc., alone or in a mixed solvent can be mentioned.

In the purification treatment (ii), when a solid acid is used as the acid catalyst, the reaction mixture is filtered,
The catalyst residue can be easily removed. In the purification treatment (ii), the reaction mixture may be dissolved in the above-mentioned solvent in order to improve workability such as filtration.

The above purification treatments (i) and (ii)
It can be done in any order. However, in order to use the highly reactive modified phenolic resin in a solid state, especially in a powder state, for subsequent use, the extraction solvent is removed from the purified highly reactive modified phenolic resin or the purification treatment (i)
It is advantageous to finally perform the purification treatment (i) using n-hexane and naphtha.

In the purification treatment (iii), the reaction mixture is used as it is, or after the unreacted components and the acid catalyst are removed in the purification treatment (i) and / or the purification treatment (ii), steam distillation, nitrogen blowing is performed. Or by performing distillation under reduced pressure or the like to remove the remaining unreacted phenols. The removal of unreacted phenols may be performed by any one of these methods or by a combination of these methods.

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

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

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

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

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

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

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

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

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

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

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

The phenolic resin molding material according to the present invention comprises:
In addition to the highly reactive modified phenolic resin, epoxy resin, and, if necessary, a curing agent and / or a curing accelerator, the composition may further contain an inorganic filler.

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

The amount of such an inorganic filler is not particularly limited. For example, it is usually 20 to 800 parts by weight, preferably 20 to 800 parts by weight, based on 100 parts by weight of a resin component obtained by adding an epoxy resin to a highly reactive modified phenol resin. 50-600
Used in parts by weight.

[0086] The phenolic resin molding material according to the present invention may further contain additives, if necessary. Such additives include, for example, silicone,
Internal release agents such as waxes, coupling agents, flame retardants, light stabilizers, antioxidants, pigments, extenders and the like can be mentioned.

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

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

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

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

Further, after mixing for 3 to 10 minutes with a hot roll machine adjusted to 80 ° C. to 90 ° C., the mixture is returned to room temperature and pulverized to obtain a compound.

In this case, the addition of the inorganic filler and other additives is separately performed after mixing the highly reactive modified phenolic resin and the epoxy resin, but may be performed at any time.

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

More specifically, when a molded article is produced by transfer molding using the 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 to 3
00Kgf / cm ² , mold clamping pressure 50-250Kgf / cm
Molding conditions of 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.

The phenolic resin molding material according to the present invention uses a highly reactive modified phenolic resin having a low melt viscosity and a high reactivity with an epoxy resin. The mechanical properties such as dimensional stability, moisture resistance and heat resistance are improved. Further, in the phenolic resin molding material according to the present invention, the use of a phenolic resin substantially free of acid can reduce the corrosiveness to a metal member, and by adding an inorganic filler, the mechanical strength and electrical insulation of the molded body can be reduced. The properties and the like can be further improved.

Therefore, this phenolic resin molded article is useful as a material for electric / electronic parts such as printed circuit boards, insulating materials, sealing materials, etc., which require extremely strict standards for dimensional stability, heat resistance, moldability, and the like. Further, it is also useful as a semiconductor encapsulant which is required to improve dimensional stability and hygroscopicity as a measure against stress damage due to heat resistance and high integration.

[0098]

According to the method for producing a highly reactive modified phenolic resin according to the present invention, a heavy oil or pitches of petroleum and a formaldehyde compound are subjected to polycondensation in the presence of an acid catalyst, and the resulting polymer is obtained. A highly reactive modified phenolic resin is manufactured by mixing and reacting the condensation reaction mixture with phenols, so that a highly reactive modified phenolic resin with low resin melt viscosity and improved reactivity with epoxy resin can be easily prepared. Can be manufactured by simple operations.

Further, according to the method for producing a highly reactive modified phenolic resin according to the present invention, the modified formaldehyde resin obtained is purified and used to remove unreacted components, acid catalysts and the like. In addition to properties, it is possible to produce highly reactive modified phenolic resins that are substantially free of acids and thus have no corrosive properties.

The phenolic resin molding material according to the present invention comprises:
Manufactures 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 and excellent mechanical properties such as dimensional stability, moisture resistance and heat resistance. It is possible to provide a molding material that can be used, particularly a material for electric / electronic parts and a semiconductor sealing material.

[0101]

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.

[0103]

[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), the melt viscosity of the resin, the hydroxyl equivalent, etc., measured in the following examples, were determined by the following apparatus. Or it measured by the measuring method.

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

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

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

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

[0109]

Example 1 Raw material oil 111 g, paraformaldehyde 123 g and p-toluenesulfonic acid monohydrate 1 shown in Table 1
9 g was charged into a glass reactor and heated to 95 ° C. while stirring. After holding at 95 ° C. for 2 hours, the mixture was poured into another glassy reaction vessel charged with 415 g of phenol which had been held at 40 ° C. in advance, while stirring, while paying attention to heat generation. After pouring the whole amount, the temperature was raised to 95 ° C., and the mixture was kept under stirring for 2 hours to obtain a reaction product.

The above reaction product was added to 450 ml of a mixed solvent of toluene / methyl isobutyl ketone (mixing ratio: 2/1) to dissolve the resin, and the resulting resin mixed solution was washed with distilled water to remove the acid. The mixed solvent was removed with an evaporator. Further, unreacted phenol was removed by steam distillation at 160 ° C., and water was removed by blowing nitrogen at the same temperature to obtain 378.5 g of a crude highly reactive modified phenol resin.

Next, 5800 ml of heavy naphtha (boiling point: 80-1
(50 ° C.) to remove unreacted raw oil and precipitate the resin, followed by filtration and drying to obtain 323 g of a highly reactive modified phenol resin.

The highly reactive modified phenolic resin 1
The melt viscosity at 50 ° C., the number average molecular weight, and the hydroxyl equivalent were measured, and the results are shown in Table 2 together with the reaction conditions.

[0113]

Example 2 332 g of a highly reactive modified phenolic resin was obtained in the same manner as in Example 1 except that the reaction temperature after pouring the reaction product into phenol was 140 ° C.

The highly reactive modified phenolic resin 1
The melt viscosity at 50 ° C., the number average molecular weight, and the hydroxyl equivalent were measured, and the results are shown in Table 2 together with the reaction conditions.

[0115]

Example 3 111 g of raw material oil, 123 g of paraformaldehyde and 32 g of acidic ion exchange resin Diaion SK1B (manufactured by Mitsubishi Chemical Corporation) shown in Table 1 were charged into a glass reactor, and the temperature was raised to 95 ° C. while stirring. . 95 ° C 8
After holding for a time, 415 g of phenol previously held at 40 ° C.
Was poured into another glassy reaction vessel charged with stirring while paying attention to heat generation. 120 after the whole amount is poured
The temperature was raised to ° C. and maintained for 8 hours to obtain a reaction product.

The above reaction product was put into 450 ml of a mixed solvent of toluene / methyl isobutyl ketone (mixing ratio: 2/1) and dissolved, and a resin mixed solution obtained was filtered through a 60-mesh wire gauze and used for ion exchange. The resin was removed. The resin mixed solution from which the solid acid was removed was washed with distilled water to remove the acid, and then the mixed solvent and unreacted phenol were removed with an evaporator to obtain 384.5 g of a crude highly reactive modified phenol resin.

Next, the crude highly reactive modified phenol resin in a heated and molten state was poured into 5800 ml of n-hexane to remove unreacted raw material oil, precipitate the resin, and filtered and dried to obtain 329 g of highly reactive phenol resin. A modified phenolic resin was obtained.

The obtained highly reactive modified phenolic resin 1
The melt viscosity at 50 ° C., the number average molecular weight, and the hydroxyl equivalent were measured, and the results are shown in Table 2 together with the reaction conditions.

[0119]

Example 4 100 g of heavy oil shown in Table 1 was subjected to ASTM-D
According to 2549, paraffin content and low-reactive components were removed. The column was activated alumina gel (Wako Pure Chemical Industries, Ltd.) and silica gel (Fuji Devison Co., Ltd.), and the developing agents were n-pentane, diethyl ether,
Chloroform and ethyl alcohol were used.

56 g of the raw material oil obtained above, 123 g of paraformaldehyde and 19 g of p-toluenesulfonic acid monohydrate were charged into a glass reactor and stirred at 95 ° C.
Temperature. After holding at 95 ° C. for 2 hours, the mixture was poured into another glassy reaction vessel charged with 415 g of phenol which had been held at 40 ° C. in advance, while stirring, while paying attention to heat generation.
After pouring the whole amount, the temperature was raised to 140 ° C. and maintained for 2 hours to obtain a reaction product.

The above reaction product was poured into 450 ml of a mixed solvent of toluene / methyl isobutyl ketone (mixing ratio: 2/1) to dissolve the resin, and the resulting resin mixed solution was washed with distilled water to remove the acid. The mixed solvent was removed with an evaporator. Further, unreacted phenol was removed by steam distillation at 160 ° C., and water was removed by blowing nitrogen at the same temperature to obtain 331 g of a highly reactive modified phenol resin.

The highly reactive modified phenolic resin 1
The melt viscosity at 50 ° C., the number average molecular weight, and the hydroxyl equivalent were measured, and the results are shown in Table 2 together with the reaction conditions.

[0123]

Example 5 9.62 parts by weight of the highly reactive modified phenolic resin obtained in Example 1 and a biphenyl type epoxy resin (YX4000, manufactured by Yuka Shell Epoxy Co., Ltd.)
H) 14.68 parts by weight were 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 the results are 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.

[0126]

Example 6 Instead of the highly reactive low viscosity modified phenolic resin obtained in Example 1, the highly reactive low viscosity modified phenolic resin obtained in Example 2 was used, and the modified phenolic resin and epoxy resin were used. The curing accelerator-containing resin mixture, the compound, and the molded body were produced in the same manner as in Example 5 except that the compounding ratio of was set as shown in Table 3.

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. .

[0128]

Example 7 9.43 parts by weight of the highly reactive low-viscosity modified phenolic resin obtained in Example 3 and an ortho-cresol novolak type epoxy resin (trade name: EO, manufactured by Nippon Kayaku Co., Ltd.)
14.87 parts by weight of CN1020) 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 resin mixture containing a curing accelerator. Obtained.

The gelation time of this resin mixture containing a hardening 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 properties, and moisture absorption of the obtained molded body immediately after molding were measured. The results are shown in Table 4.

[0131]

Example 8 Instead of the highly reactive low viscosity modified phenolic resin obtained in Example 3, the highly reactive low viscosity modified phenolic resin obtained in Example 4 was used, and the modified phenolic resin and epoxy resin were used. Was prepared in the same manner as in Example 7 except that the compounding ratio of was set as shown in Table 3.

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. .

[0133]

[Table 2]

[0134]

[Table 3]

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shin Hasegawa 4 Kazu-gun, Kashima-gun, Toshima, Kashima Ishi Oil Co., Ltd.

Claims (9)

[Claims] 1. A polycondensation reaction between a petroleum heavy oil or pitches and a formaldehyde compound in the presence of an acid catalyst, and then the resulting polycondensation reaction mixture is mixed and reacted with phenols. A method for producing a highly reactive modified phenol resin. 2. The method according to claim 1, wherein the polycondensation reaction mixture is added to phenols, mixed and reacted.
A method for producing the highly reactive modified phenolic resin according to the above. 3. The production of a highly reactive modified phenolic resin according to claim 1, wherein the acid catalyst is a Bronsted acid selected from the group consisting of an organic acid, an inorganic acid, and a solid acid. Method. 4. The method for producing a highly reactive modified phenolic resin according to claim 3, wherein the acid catalyst is an acidic cation exchange resin. 5. The petroleum heavy oils or pitches,
The method for producing a highly reactive modified phenolic resin according to any one of claims 1 to 4, wherein the method is used after performing a paraffin fraction removal treatment. 6. A highly reactive modified phenolic resin obtained by reacting the polycondensation reaction mixture with phenols, wherein (i) an aliphatic hydrocarbon having 10 or less carbon atoms, an aliphatic petroleum fraction and 10 carbon atoms. Treating with a solvent containing at least one compound selected from the group consisting of the following alicyclic hydrocarbons, removing solvent-soluble components including unreacted components, (ii) removing catalyst residues and iii) at least one step selected from the steps of removing residual phenols by steam distillation, nitrogen gas blowing and vacuum distillation,
The method for producing a highly reactive modified phenolic resin according to any one of claims 1 to 5, wherein the method is refined. 7. A phenolic resin molding material comprising a highly reactive modified phenolic resin obtained by the method according to claim 1 and an epoxy resin. 8. A material for electric / electronic parts, obtained by molding the phenolic resin molding material according to claim 7. Description: 9. A semiconductor encapsulant comprising the modified phenolic resin molding material according to claim 7.