JPH10251364A - Production of highly reactive modified phenol resin, molding material, material for electric and electronic part and semiconductor sealing material containing the same highly reactive modified phenol resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce the subject resin having a low melt viscosity and high reactivity with an epoxy resin by carrying out the polycondensation of petroleum-based heavy oils, etc., with a resol resin in the presence of an acidic catalyst. SOLUTION: The polycondensation of (A) petroleum-based heavy oils or pitches, as necessary, subjected to a treatment for removing a paraffin fraction with (B) a resol resin is carried out in the presence of (C) an acidic catalyst which is preferably a Broensted acid selected from an organic acid, an inorganic acid and a solid acid to provide the objective resin. The rations of the components (A), (B) and (C) used are preferably regulated so as to provide 0.2-2mol component B, expressed in terms of the average molecular weight and based on 1mol component (A) calculated from the average molecular weight and 0.3-3mol component (C) based on 1mol component (A). The resultant resin is preferably purified in at least one step selected from, e.g. a step of removing a catalyst residue and then preferably used for various applications.

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. A method for producing a highly reactive modified phenol resin capable of producing a reactive modified phenol resin in one step, and a modified phenol resin molding material containing a highly reactive modified phenol resin and an epoxy resin obtained by this method,・ Related to materials for electronic components and semiconductor encapsulants.

[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.

JP-A-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. 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.

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

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

However, such a method for producing a modified phenol resin requires two steps of a polycondensation step and a low-molecular-weight step, which complicates the production step. The present inventors have conducted various studies and investigations to solve the problems of the prior art as described above, and as a result, polycondensation of petroleum heavy oils or pitches with a resole resin in the presence of an acid catalyst. By this, in one step, a highly reactive modified phenol resin having high reactivity with the epoxy resin and having a low viscosity can be obtained, and molding by combining this highly reactive modified phenol resin and the epoxy resin The material is
The inventors have found that the molded article has excellent moldability and excellent mechanical properties such as heat resistance, moisture resistance, corrosion resistance, dimensional stability and strength, and has completed the present invention.

[0013]

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

[0014] The present invention further 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.

[0015]

SUMMARY OF THE INVENTION The process for producing a highly reactive modified phenolic resin according to the present invention is characterized by polycondensing heavy petroleum oils or pitches with a resole resin in the presence of an acid catalyst.

In the method for producing a highly reactive modified phenolic resin according to the present invention, it is desirable to use a Bronsted acid selected from the group consisting of organic acids, inorganic acids and solid acids as the acid catalyst. Further, among such acid catalysts, hydrochloric acid, oxalic acid and sulfuric acid are preferable as organic acids and inorganic acids, and acidic cation exchange resins are preferable as solid acids.

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 after the paraffin fraction which is a low reactive component is removed. desirable.

Further, according to the production method of the present invention, the modified phenol resin obtained by the above polycondensation reaction is treated with (i) a C10-C
A solvent soluble component containing at least one compound selected from the group consisting of the following aliphatic hydrocarbons, alicyclic hydrocarbons having 10 or less carbon atoms, and aliphatic petroleum fractions, including unreacted components It is desirable to purify in at least one step selected from the step of removing the catalyst and (ii) the step of removing the catalyst residue and use it for various uses.

In the method for producing a highly reactive modified phenolic resin according to the present invention, the resole resin is converted from the average molecular weight to 0 with respect to 1 mol of the petroleum heavy oils or pitches calculated from the average molecular weight. 0.2 to 2 moles, and 0.3 to 3 moles of the catalyst.

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

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

[0023]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the present invention will be described more specifically. In the method for producing a highly reactive modified phenol resin according to the present invention, a highly reactive modified phenol resin is produced by polycondensing a heavy petroleum oil or pitch and a resole resin in the presence of an acid catalyst. .

The petroleum heavy oils or pitches used as a raw material in the polycondensation reaction of the present invention include crude oil distillation residue, hydrogenolysis residue, catalytic cracking residue, naphtha or LPG heat. It is obtained as a cracked residual oil, a vacuum distilled product of these residual oils, 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 aliphatic saturated hydrocarbon compounds having 5 to 8 carbon atoms, such as n-pentane, n-hexane, n-heptane and n-octane; Ethers such as ethers,
Examples thereof include halogenated hydrocarbons such as chloroform and carbon tetrachloride, and alcohols such as methyl alcohol and ethyl alcohol. It is desirable to use two or more of these developing agents as appropriate.

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

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

In the case of petroleum heavy oils or pitches having a fa value larger than 0.95, the reactivity between aromatic carbon and resole resin tends to be low. If the Ha value of the petroleum heavy oils or pitches as the raw material is less than 20%, the amount of aromatic ring hydrogen that reacts with the resole resin decreases, and the reactivity decreases. Tends to decrease.

When a petroleum heavy oil or pitch having a Ha value of more than 80% is used as a raw material, the strength of the modified phenol resin tends to decrease. The petroleum heavy oils or pitches used in the present invention are mainly composed of 2 to 4 condensed polycyclic aromatic hydrocarbons, although the number of condensed aromatic hydrocarbons constituting the heavy oils or pitches is not particularly limited. Is preferably performed. 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. When the petroleum heavy oils or pitches are mainly monocyclic aromatic hydrocarbons, the reactivity with the resole resin is low, and the effect of modifying the obtained phenol resin tends to be small. There is.

The resole resin used as a raw material together with petroleum heavy oils or pitches in the present invention is a resin produced by reacting a phenol and a formaldehyde compound in the presence of an alkali catalyst, and has an aromatic ring structure. And two or more reactive methylol groups bonded thereto.

Examples of the phenols used for producing the resole resin 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,
Dihydroxynaphthalene such as 3-dihydroxynaphthalene, 3,6-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene Compounds and mono- or dihydroxynaphthalene compounds having a substituent such as an alkyl group, an aromatic group, and a halogen atom, such as 2-methyl-1-naphthol, 4-phenyl-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol and the like can be exemplified. These phenols may be used alone or in combination of two or more.

Examples of the formaldehyde compound include, in addition to formaldehyde, linear polymers such as paraformaldehyde and polyoxymethylene (especially oligomers) and cyclic polymers such as trioxane.

As the alkali catalyst, sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, hexamethylenetetramine and the like can be used.

A method for producing a resol resin using such a phenol, a formaldehyde compound and an alkali catalyst is known, and is not particularly limited in the present invention. In the present invention, the type of resol resin is not particularly limited, and any conventionally known resin may be used. As such a resole resin, specifically, 2,6-dimethylolphenol, 4-methyl-2,6-dimethylolphenol,
2,4,6-trimethylolphenol can be exemplified. These may be used alone or in combination of two or more.

In the method for producing a highly reactive modified phenolic resin according to the present invention, such a resole resin is converted to an average molecular weight in terms of an average molecular weight with respect to 1 mol of petroleum heavy oils or pitches calculated from the average molecular weight. , 0.2 to 2 mol, preferably 0.2 to 1.5 mol, more preferably 0.2 to
It is desirable to use it in an amount of 1.0 mol.

When the amount of the resole resin is less than 0.2 mol per mol of petroleum heavy oils or pitches, the yield of the obtained resin is extremely low, which is not preferable.
On the other hand, if it is more than 2 mol, the resin obtained is polymerized due to the self-polycondensability of the resole, which is not preferable.

In the polycondensation reaction of the present invention, an acid catalyst is used to polycondense petroleum heavy oils or pitches and a resole resin. 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, hydrochloric acid, oxalic acid and sulfuric acid are preferred as the organic acid and the inorganic acid. The acidic cation exchange resin used as the solid acid is a resin in which a cation exchange group is covalently bonded to a base resin having a three-dimensional network structure.

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

The acidic cation exchange resin as an acid catalyst is
Usually, it is desirable to use as a spherical body having a particle size of 15 to 50 mesh. Specific examples of such an acidic cation exchange resin include Diaion SKIB and PK21.
6, SK104 and PK208 (Mitsubishi Chemical Corp .: trade name), Amberlite IR-120B and IR-1
12 (manufactured by Organo: trade name), Dowex 50w
x8, HCR and HGR (manufactured by Dow Chemical Company, trade name), strong acidic cation exchange resins such as Duolite C-20 and C-25 (manufactured by Sumitomo Chemical Co., Ltd.), and Diaion WK10 (Mitsubishi Chemical Corporation) , Amberlite IRc-50 (Organo: trade name), Dowex 50wx 8, HCR and HG
R (manufactured by Dow Chemical Company: trade name), Duolite CS-
101 (manufactured by Sumitomo Chemical Co., Ltd .: trade name).

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 removed from the polycondensation reaction product by a simple method such as filtration. Thus, there is an advantage that a low-viscosity, high-reactivity modified phenol resin containing substantially no acid can be obtained.

In the present invention, such an acid catalyst is used in an amount of 0.3 to 3.0 mol, preferably 0.5 to 3.0 mol per 1 mol of petroleum heavy oils or pitches calculated from the average molecular weight.
It is used in an amount of 2.0 mol. When an acidic cation exchange resin is used as the acid catalyst, the amount of the acid catalyst is an amount in terms of a cation exchange group.

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

In the method for producing a highly reactive modified phenolic resin according to the present invention, the above-described raw materials are subjected to a polycondensation reaction in the presence of an acid catalyst. In such a polycondensation reaction of petroleum heavy oils or pitches and a resole resin in the presence of an acid catalyst, the mixing temperature and mixing time of the raw materials and the polycondensation are adjusted according to the raw material composition and the properties of the obtained resin. The reaction temperature and reaction time are controlled. It goes without saying that the reaction temperature and the reaction time also affect each other.

In the polycondensation reaction of the present invention, for example, first, a petroleum heavy oil or pitch and a resole resin are mixed at a temperature of 50 to 200 ° C., preferably 70 to 150 ° C., and then an acid catalyst is added. Usually 50 to 200 ° C., preferably 80 to 200 ° C. while successively adding by a method such as dropping.
C., more preferably 80 to 180.degree. C., for 15 minutes to 30 hours, preferably 30 minutes to 24 hours.

In the present invention, such a polycondensation reaction of petroleum heavy oils or pitches and a resole resin can be carried out without using a solvent. The viscosity of the (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.

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

Further, the highly reactive modified phenolic resin produced in the present invention has excellent moldability due to low resin melt viscosity, and high reactivity with epoxy resin. A modified phenolic resin molding material having excellent mechanical properties such as strength, moisture resistance and heat resistance can be provided.

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 highly reactive modified phenol resin containing an acid catalyst, unreacted substances, low molecular components and a reaction solvent, for example, (i) treating the reaction mixture with a specific solvent A purification treatment of removing a solvent-soluble component including an unreacted component by precipitation and (ii) a purification treatment of removing a catalyst residue from the reaction mixture.

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

In such a purification treatment (i), the reaction mixture obtained by the polycondensation reaction is treated at any time with an aliphatic hydrocarbon having 10 or less carbon atoms, an alicyclic hydrocarbon having 10 or less carbon atoms, Put into a solvent containing at least one compound selected from the group consisting of aliphatic petroleum fractions, to precipitate the resin main component, components soluble in the solvent, that is, components that remain unreacted and low reaction, and It is carried out by removing a reaction solvent or 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 aliphatic petroleum fractions such as naphtha, and especially n-hexane. And naphtha are preferred. The highly reactive modified phenolic resin obtained in the purification treatment (i) is in a powder form.

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

The solvent for dissolving the reaction mixture is not particularly limited. For example, toluene; a mixed solvent of toluene and an alcohol such as ethyl alcohol; and toluene and a ketone such as acetone, methyl ethyl ketone and methyl isobutyl ketone And a mixed solvent of toluene and ethers such as tetrahydrofuran, diethyl ether and methyl tertiary butyl ether.

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. Also in this purification treatment (ii), the reaction mixture may be dissolved in the above 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, particularly in a powder state, for a later use, the solvent is removed from the highly reactive modified phenolic resin after purification or the purification treatment (i) is finally performed. It is advantageous to perform the purification treatment (i) using n-hexane at the end.

By performing such a purification treatment to remove acid catalysts, unreacted substances, reaction solvents, and the like which may remain in the resin, the resin is substantially free of 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 modified phenolic resin molding material according to the present invention contains an epoxy resin together with the highly reactive modified phenolic resin obtained by the method for producing a highly reactive modified phenolic resin according to the present invention. The epoxy resin has a small molding shrinkage, and is excellent in heat resistance, abrasion resistance, chemical resistance, and electrical insulation, and is used in combination with a curing agent and / or a curing accelerator, if necessary.

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

More specifically, 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 .; 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, but the total ratio of the highly reactive modified phenolic resin and the epoxy resin is 100 parts by weight, and (Parts by weight), more preferably 20/80.
８０80/20 (parts by weight).

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

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

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

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

The modified phenolic resin molding material according to the present invention comprises the highly reactive modified phenolic resin, epoxy resin,
In addition to the curing agent and / or curing accelerator used as necessary, 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 the 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.

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 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.

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

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

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

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

Further, the molded article is 150 to 30
By heating at a temperature of 0 ° C. for 0.5 to 24 hours,
It is desirable to perform post cure. By applying post cure to the molded body, the heat resistance of the molded body can be further improved.

In the modified phenolic resin molding material according to the present invention, a highly reactive modified phenolic resin having a low melt viscosity and a high reactivity with an epoxy resin is used. Mechanical properties such as dimensional stability of the body, moisture resistance and heat resistance are improved. Further, in the modified phenolic resin molding material according to the present invention, if a modified phenolic resin containing substantially no acid can be used, the corrosiveness to a metal member can be reduced, and by adding an inorganic filler, the mechanical strength of the molded body, Electrical insulation and the like can be further improved.

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

[0091]

According to the method for producing a highly reactive modified phenolic resin according to the present invention, a highly reactive modified phenolic resin is obtained by polycondensing a heavy petroleum oil or pitch and a resole resin in the presence of an acid catalyst. Since phenolic resin is manufactured, it is possible to reduce the low molecular weight process, which was indispensable in the conventional method, to produce a highly reactive modified phenolic resin with low resin melt viscosity and improved reactivity with epoxy resin in one process can do.

Further, according to the method for producing a highly reactive modified phenol resin according to the present invention, the highly reactive modified phenol resin obtained by the polycondensation reaction is further purified to remove unreacted components and acid catalysts. By removing, in addition to having a low resin melt viscosity and high reactivity with epoxy resin, to produce a highly reactive modified phenolic resin which does not substantially corrode because it does not contain acid. Is possible.

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

[0094]

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.

[0096]

[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 resin melt viscosity, 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 x 3, standard substance: polystyrene) From the obtained data, the molecular weight was determined using polystyrene as a standard substance. Converted. <Glass transition temperature> Measurement method: dynamic viscoelasticity measurement device: Rheology Co., Ltd., DVE RHEOSPECTOLER DVE-
4V type Load method: Tensile method Measurement frequency: 10 Hz Heating rate: 5 ° C./min Dynamic measurement displacement: ± 5 × 10 ⁻⁴ cm Test piece: width 4 mm × thickness 1 mm × span 30 mm <hydroxyl equivalent> acetyl chloride It was measured by the method.

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

<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.

<Moisture Absorption> 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.

[0102]

Example 1 200 g of raw oil and 57 g of 2,6-dimethylolphenol were charged into a 500 ml glass reaction vessel,
Maintain at 40 ° C. while stirring at a speed of 0-350 rpm. When the temperature was stabilized, 50 ml of concentrated hydrochloric acid was gradually added while paying attention to the temperature rise, and the whole amount was added, followed by reaction at 100 ° C. for 24 hours to obtain a reaction product.

The above reaction product was dissolved in 450 ml of a mixed solvent of toluene / methyl isobutyl ketone (mixing ratio: 2/1), and the obtained resin mixed solution was washed with distilled water to remove the acid. The mixed solvent was removed by an evaporator to obtain 230 g of a crude highly reactive modified phenol resin.

Next, the crude highly reactive modified phenol resin in the molten state by heating was poured into 5200 ml of n-hexane to remove unreacted raw oil and precipitate the resin, followed by filtration.
37 g of a highly reactive modified phenolic resin were obtained.

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

[0106]

Example 2 176 g of heavy oil shown in Table 1 was used in ASTM-D
According to 2549, a paraffin component and a component having low reactivity were removed using a developing solvent n-pentane, diethyl ether, chloroform and ethyl alcohol using a silica gel column to obtain 150 g of a feed oil.

150 g of raw material oil and 57 g of 2,6-dimethylolphenol were charged into a 500 ml glass reaction vessel.
Maintain at 40 ° C. while stirring at a speed of 0-350 rpm. When the temperature was stabilized, 50 ml of concentrated hydrochloric acid was gradually added while paying attention to the temperature rise, and the whole amount was added, followed by reaction at 100 ° C. for 24 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, by blowing nitrogen at 160 ° C., the mixed solvent and unreacted phenol were removed to obtain 119 g of a highly reactive modified phenol resin.

The number-average molecular weight, viscosity at 150 ° C. and hydroxyl equivalent of the obtained highly reactive modified phenolic resin were measured, and the results are shown in Table 2 together with the reaction conditions.

[0110]

Example 3 10.69 parts by weight of the highly reactive modified phenolic resin obtained in Example 1 and a biphenyl type epoxy resin (trade name XY-4000, manufactured by Yuka Shell Epoxy Co., Ltd.)
H) After mixing and stirring 13.37 parts by weight at room temperature using an automatic mortar, 0.49 parts by weight of triphenylphosphine (TPP) as a curing catalyst was mixed with the stirred mixture to obtain a resin mixture containing a curing accelerator. Was.

The gelation time of the resin mixture containing the 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 compound, 0.20 parts of carbon black was added as an inorganic filler.
Parts by weight and fused silica (CRS1102, manufactured by Tatsumori Co., Ltd.)
-GT200T) 75 parts by weight. The obtained mixture was heated to a temperature of 3 to 1 with a hot roll machine adjusted to 80 to 90 ° C.
After further mixing for 0 minutes, the mixture was cooled to room temperature and pulverized to obtain a compound (molding material). Table 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.

[0113]

Example 4 Instead of the highly reactive modified phenolic resin obtained in Example 1, each of the highly reactive modified phenolic resins obtained in Example 2 was used, and a highly reactive modified phenolic resin composition and an epoxy resin were used. A curing accelerator-containing resin mixture, a compound, and a molded article were produced in the same manner as in Example 1 except that the compounding ratio of the resin was changed to a value 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. .

[0115]

Example 5 Using the highly reactive modified phenolic resin obtained in Example 1, the epoxy resin was changed from YX-4000H to E
In the same manner as in Example 1 except that the composition was changed to OCN 1020 (manufactured by Nippon Kayaku Co., Ltd.) and the compounding ratio with the epoxy resin was set to the value shown in Table 3, the curing accelerator-containing resin mixture, compound, and molding were performed. Body 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. .

[0117]

[Table 2]

[0118]

[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 method for producing a highly reactive modified phenol resin, comprising subjecting a heavy petroleum oil or pitch to polycondensation with a resole resin in the presence of an acid catalyst. 2. The method for producing a highly reactive modified phenolic resin according to claim 1, wherein said acid catalyst is a Bronsted acid selected from the group consisting of organic acids, inorganic acids and solid acids. 3. The method for producing a highly reactive modified phenolic resin according to claim 2, wherein the acid catalyst is an acidic cation exchange resin. 4. The petroleum heavy oils or pitches,
The method for producing a highly reactive modified phenolic resin according to any one of claims 1 to 3, wherein the method is used after performing a paraffin fraction removal treatment. 5. The highly reactive modified phenolic resin obtained by the above polycondensation reaction is treated with (i) an aliphatic hydrocarbon having 10 or less carbon atoms, an alicyclic hydrocarbon having 10 or less carbon atoms, and an aliphatic petroleum distillate. Treating with a solvent containing at least one compound selected from the group consisting of: a step of removing solvent-soluble components including unreacted components and (ii) at least one step selected from a step of removing catalyst residues, The method for producing a highly reactive modified phenolic resin according to any one of claims 1 to 4, wherein the method is refined. 6. The mol of the resole resin is 0.2 to 2 mol, calculated from the average molecular weight, and the catalyst is 0.3 to 1, based on 1 mol of the petroleum heavy oils or pitches calculated from the average molecular weight. The method for producing a highly reactive phenolic resin composition according to any one of claims 1 to 5, wherein the compound is used in an amount of 3.0 mol. 7. A modified phenolic resin molding material comprising a highly reactive modified phenolic resin obtained by the method according to claim 1 and an epoxy resin. 8. A material for electric / electronic parts, obtained by molding the modified phenolic resin molding material according to claim 7. 9. A semiconductor encapsulant comprising the modified phenolic resin molding material according to claim 7.