JPH10251363A - Production of highly reactive phenol resin composition, molding material, material for electric and electronic part and semiconductor sealing material containing the same highly reactive phenol resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce the subject composition, having a low melt viscosity and high reactivity with an epoxy resin according to simple operations by mixing a specific modified formaldehyde resin with a phenolic novolak resin. SOLUTION: The polycondensation of (i) petroleum-based heavy oils or pitches, as necessary, subjected to a treatment for removing a paraffin fraction with (ii) a formaldehyde compound is carried out in the presence of (iii) an acidic catalyst which is preferably a Broensted acid selected from an organic acid, an inorganic acid and a solid acid to provide (A) a modified formaldehyde resin. The ratios of the components (i), (ii) and (iii) used are preferably regulated so as to provide 0.5-15mol component (ii), expressed in terms of formaldehyde and based on 1mol component (i) calculated from the average molecular weight and 0.5-3mol component (iii) based on 1mol component (i). The resultant resin A is mixed with a phenolic novolak resin at (5/95) to (5/50) weight ratio of the components A to B to afford the objective composition.

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 phenolic resin composition capable of producing a reactive phenolic resin composition, and easily adjusting the hydroxyl equivalent, the melt viscosity, and the like, and a highly reactive phenolic resin composition obtained by this method. The present invention relates to a phenol resin molding material containing an epoxy resin, a material for electric / electronic parts, and a semiconductor encapsulant.

[0002]

BACKGROUND OF THE INVENTION Phenolic resin molded products have excellent mechanical properties and have been widely used for a long time, either alone or in combination with other resins such as epoxy resins. In addition, there is a problem that the size and electric resistance are easily changed by absorbing moisture or alcohol, and the heat resistance, especially the oxidation resistance at high temperatures, is low.

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

For example, Japanese Patent Application Laid-Open No. 61-235413 discloses that a phenol resin having excellent heat resistance can be obtained by selecting a reaction component of a phenol-modified aromatic hydrocarbon resin. However, when a phenolic resin obtained by this method is used to produce a molded article, there is a disadvantage that the resin does not cure unless the resin is maintained at a high temperature for a long time.

Japanese Patent Application Laid-Open No. 2-274714 discloses that a conventional phenol resin can be obtained by using petroleum heavy oils or pitches, which are inexpensive raw materials, as a modifying material and selecting special reaction conditions. It is disclosed that a modified phenol resin having no heat resistance, oxidation resistance and mechanical strength and useful as a molding material can be provided.

Further, Japanese Patent Application Laid-Open No. 4-145116 discloses that, when such a modified phenolic resin is produced, a crude modified phenolic resin obtained by polycondensing a starting compound is neutralized, washed with water and / or washed. It is disclosed that by performing an extraction treatment to neutralize and remove the acid remaining in the crude modified phenolic resin, it is possible to provide a modified phenolic resin that does not corrode metal members in contact with the resin. .

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

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 tree requires two steps, a polycondensation step and a low-molecular-weight step, which complicates the production step. Further, in the conventional method for producing a modified phenol resin, it was difficult to arbitrarily adjust properties such as a hydroxyl equivalent. The present inventors have conducted various studies and studies to solve the problems of the prior art as described above, and as a result, first, polycondensation of petroleum heavy oils or pitches with a formaldehyde compound in the presence of an acid catalyst. By mixing the obtained modified formaldehyde resin with a phenol novolak resin, a highly reactive phenolic resin composition having high reactivity with an epoxy resin and having a low viscosity can be obtained by a simple operation. By changing the mixing ratio of the modified formaldehyde resin and the phenol novolak resin, the hydroxyl equivalent, the melt viscosity, etc. can be arbitrarily adjusted, and the molding material combining this highly reactive phenolic resin composition and the epoxy resin has improved moldability. It was found that the molded article had excellent heat resistance, moisture resistance, corrosion resistance, and mechanical properties such as dimensional stability and strength. It was completed.

[0013]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and has 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 phenolic resin composition, which can be produced by a simple operation, and in which the hydroxyl equivalent, the melt viscosity and the like can be arbitrarily adjusted.

Further, the present invention comprises a highly reactive phenolic resin composition obtained by the method of the present invention and an epoxy resin, and has properties 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 A method for producing a highly reactive phenolic resin composition according to the present invention comprises the steps of:
It is characterized in that a modified formaldehyde resin is produced by polycondensing a formaldehyde compound in the presence of an acid catalyst, and the resulting modified formaldehyde resin is mixed with a phenol novolak resin. In this specification, the term "modified formaldehyde resin" refers to a resin obtained by polycondensation of a petroleum heavy oil or pitches with a formaldehyde compound.

In the method for producing a highly reactive phenolic resin composition 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, oxalic acid, toluenesulfonic acid and sulfuric acid are preferred as organic acids and inorganic acids, and acidic cation exchange resins are preferred as solid acids.

In the method for producing a highly reactive phenolic resin composition according to the present invention, the petroleum heavy oils or pitches may be used as they are, or a paraffin fraction which is a low reactive component may be removed. You may use it after performing a process.

Further, in the production method of the present invention, the modified formaldehyde resin obtained by the polycondensation reaction may be used as (i) an aliphatic hydrocarbon having 10 or less carbon atoms, an alicyclic hydrocarbon having 10 or less carbon atoms and an aliphatic hydrocarbon. Treating with a solvent containing at least one compound selected from the group consisting of group petroleum fractions, removing a solvent-soluble component containing unreacted components, and (ii) removing at least a catalyst residue. It is desirable to purify in one step.

In the production method according to the present invention, the formaldehyde compound is 0.5 to 15 mol in terms of formaldehyde and the catalyst is 0 to 1 mol per 1 mol of the petroleum heavy oils or pitches calculated from the average molecular weight. It is desirable to use each in an amount of 0.5 to 3 mol.

Further, in the method for producing a highly reactive phenolic resin composition according to the present invention, the modified formaldehyde resin and the phenol novolak resin have a weight ratio of 5%.
/ 95 to 50/50.

The phenolic resin molding material according to the present invention comprises:
It is characterized by containing a highly reactive phenolic resin composition 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 phenolic resin composition and the 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 obtained by molding the above-mentioned phenol resin molding material. Further, the semiconductor encapsulant according to the present invention,
It is characterized by being made of the phenolic resin molding material.

[0024]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the present invention will be described more specifically. In the method for producing a highly reactive phenolic resin composition according to the present invention, first, petroleum heavy oils or pitches,
A highly reactive phenolic resin composition is manufactured by polycondensing a formaldehyde compound with an acid catalyst and mixing the resulting modified formaldehyde resin with a phenol novolak resin.

The petroleum heavy oils or pitches used as a raw material in the polycondensation reaction of the present invention include distillation residue of crude oil, hydrogenation 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, according to a conventional method, 80 to 120 using furfural.
C. and also 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 and silica gel. 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 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 may 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 based on the following formulas.

[0034]

(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 it is smaller, the amount of aromatic ring hydrogen which reacts with the formaldehyde compound decreases, and the reactivity decreases, so that 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, the resulting modified formaldehyde resin is polymerized and a desired resin cannot be obtained.

The heavy petroleum oils or pitches used in the present invention are not particularly limited in the number of condensed rings of the 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. If the content of the monocyclic aromatic hydrocarbons of the petroleum heavy oils or pitches is too large, it may not be possible to obtain a modified formaldehyde resin having a high modifying effect.

The formaldehyde compound used in the polycondensation reaction together 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 phenolic resin composition according to the present invention, such a formaldehyde compound has a formaldehyde equivalent of 0.1 mol per 1 mol of petroleum heavy oils or pitches calculated from the average molecular weight. 5-15
Moles, preferably 1 to 12 moles, more preferably 1 to 12 moles.
It is desirable to use it in an amount of 11 mol.

If the amount of the formaldehyde compound is less than 0.5 mol per 1 mol of the petroleum heavy oils or pitches, the yield of the modified formaldehyde resin obtained is not preferred. On the other hand, when it is more than 15 mol, the performance and yield of the resulting modified formaldehyde resin hardly change, so that it is not necessary to use more formaldehyde compound.

In the polycondensation reaction in the present invention, an acid catalyst is used for polycondensing a heavy oil such as petroleum oils or pitches 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, oxalic acid, toluenesulfonic acid and sulfuric acid are preferable 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 the 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 modified formaldehyde resin containing substantially no acid can be obtained.

In the present invention, such an acid catalyst is used in an amount of 0.5 to 3 mol, preferably 0.5 to 2.5 mol, per 1 mol of petroleum heavy oils or pitches calculated from the average molecular weight.
It is used in molar amounts. When an acidic cation exchange resin is used as the acid catalyst, the amount of the acid catalyst is
It is the amount in terms of cation exchange group.

When the amount of the acid catalyst used is small, the reaction time tends to be prolonged, 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 phenolic resin composition according to the present invention, first, the above-described raw materials are polycondensed in the presence of an acid catalyst to produce a modified formaldehyde resin.

In the polycondensation reaction of petroleum heavy oils or pitches with a formaldehyde compound in the presence of an acid catalyst, the polycondensation reaction temperature and reaction time are adjusted according to the raw material composition and the properties of the obtained resin. Controlled. It goes without saying that the reaction temperature and the reaction time also affect each other.

Such a polycondensation reaction is usually carried out at 50 to 20
0 ° C, preferably 80-200 ° C, more preferably 80 ° C.
The reaction is carried out at a temperature of １８０180 ° C. for 15 minutes to 30 hours, preferably for 30 minutes to 24 hours.

In the present invention, such a polycondensation reaction between petroleum heavy oils or pitches and phenols can be carried out without using a solvent, but the reaction mixture ( The viscosity of the reaction system) may be reduced so that a uniform reaction occurs.

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

The modified formaldehyde resin produced in this manner is mixed with a phenol novolak resin described below. However, since there is a possibility that unreacted components and acid catalysts may remain in the resin, the modified formaldehyde resin is appropriately purified. It is desirable to remove unreacted components, low molecular components, polymer components that have undergone excessive reaction, acid catalyst, reaction solvent, and the like by treatment.

As a method for purifying a reaction mixture, that is, a crude modified formaldehyde resin containing an acid catalyst, unreacted materials, low molecular components, a polymer component that has undergone excessive reaction, and a reaction solvent, for example, (i) the reaction mixture , Treated with specific solvent
A purification treatment for removing a solvent-soluble component including an unreacted component by precipitation and (ii) a purification treatment for removing a catalyst residue from the reaction mixture can be exemplified.

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 has an unreacted state or a reaction. 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.

Such hydrocarbon solvents include, for example, aliphatic or alicyclic hydrocarbons such as pentane, hexane, heptane and cyclohexane, and aliphatic petroleum fractions such as naphtha, especially n-hexane. And naphtha are preferred. The modified formaldehyde 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 modified formaldehyde resin containing substantially no acid is obtained. In such a purification treatment (ii), the reaction mixture is treated with an extraction solvent having a solubility of the acid catalyst used in the polycondensation step of 0.1 or less and capable of dissolving most of the modified phenol resin, and This is performed by removing the residue and the formaldehyde compound as a crosslinking agent.

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

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 modified formaldehyde resin in a solid state, particularly in a powder state, for later use, it is advantageous to remove the solvent from the purified modified formaldehyde resin or to finally perform the purification treatment (i). In particular, it is desirable that the purification treatment (i) using n-hexane and naphtha is performed last.

By performing such a purification treatment to prepare a modified formaldehyde resin from which an acid catalyst, unreacted substances, a reaction solvent, and the like which may remain in the resin are removed, the resin is substantially free of an acid, and thus has a high acid content. A non-corrosive modified formaldehyde resin 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 formaldehyde resin thus produced desirably has a number average molecular weight of 300 to 900. By using a modified formaldehyde resin having such properties, mixing with a phenol novolak resin described below becomes easy, and the highly reactive phenol resin composition obtained has low viscosity and high reactivity.

In the method for producing a highly reactive phenolic resin composition according to the present invention, the modified formaldehyde resin thus obtained is mixed with a phenol novolak resin to produce a resin composition.

The phenol novolak resin is a resin produced by polycondensing a phenol and a formaldehyde compound in the presence of an acid catalyst. Examples of such phenols 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 can be mentioned. 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.

Examples of the formaldehyde compound and the acid catalyst include the compounds used for producing the above-mentioned modified formaldehyde resin. In the present invention, any phenol novolak resin obtained by polymerizing such a raw material by a conventionally known method may be used. Moreover, you may select from commercially available phenol novolak resins.

However, the phenol novolak resin used in the present invention has a number average molecular weight of 200 to 600.
The melt viscosity at 150 ° C. is desirably 0.1 to 5 poise.

By using a phenol novolak resin having such characteristics, the viscosity of the highly reactive phenol resin composition obtained after mixing with the modified formaldehyde resin can be reduced.

The phenol novolak resin is commercially available and can be easily obtained. Examples thereof include Parkam TD-2131, TD-2106 and Plyofen VH-4150 manufactured by Dainippon Ink and Chemicals, Inc.

In the present invention, such a phenol novolak resin and a modified formaldehyde resin are in a weight ratio (phenol novolak resin / modified formaldehyde resin).
Is 95/5 to 50/50, preferably 95/5 to 60 /
40, more preferably 90/10 to 60/40.

By mixing in such an amount, a highly reactive phenolic resin composition having excellent moldability due to low resin melt viscosity and high reactivity with an epoxy resin can be provided. Further, by mixing the phenol novolak resin and the modified formaldehyde resin, the melt viscosity and the hydroxyl equivalent can be easily and arbitrarily adjusted.

The phenol novolak resin and the modified formaldehyde resin described above are mixed and kneaded at a temperature of usually 50 to 150 ° C., preferably 70 to 120 ° C., by introducing these resin materials into a kneading device such as a kneader and an extruder. By mixing, the composition of the present invention can be obtained.

In the present invention, the method of mixing the phenol novolak resin and the modified formaldehyde resin is not particularly limited as long as homogeneous mixing is possible, but both may be used in a suitable solvent, for example, in the above-mentioned purification step (ii). It is also possible to obtain a varnish-like composition by dissolving in a mixed solvent and mixing.

The phenolic resin molding material according to the present invention comprises:
It contains an epoxy resin together with the highly reactive phenolic resin composition 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, the glycidyl ether type (phenol type) includes bisphenol A type epoxy resin, biphenyl type epoxy resin, bisphenol F
Type epoxy resin, tetrabromobisphenol A type epoxy resin, tetraphenylolethane type epoxy resin,
Phenol novolak type epoxy resin, o-cresol novolak type epoxy resin, etc .; glycidyl ether type (alcohol type) includes polypropylene glycol type epoxy resin, hydrogenated bisphenol A type epoxy resin, etc .; Phthalic acid type epoxy resin, dimer acid type epoxy resin, etc .; as glycidylamine type, diaminodiphenylmethane type epoxy resin, isocyanuric acid type epoxy resin, hydantoic acid type epoxy resin, etc .; as mixed type, p-aminophenol type Epoxy resins, p-oxybenzoic acid type epoxy resins and the like can be mentioned. Among the above epoxy resins, a bisphenol A type epoxy resin, a biphenyl type epoxy resin, a glycidylamine type epoxy resin, and a phenol novolak type epoxy resin are preferable. A combination of two or more of the above epoxy resins can also be used.

In the present invention, the mixing ratio of the high-reactivity phenol resin composition and the epoxy resin is not particularly limited, but the mixing ratio of the high-reactivity phenol resin composition and the epoxy resin is 100/90 to 90/90 to 90/90. / 10 (parts by weight), more preferably 20/8
0 to 80/20 (parts by weight).

When the weight ratio of the phenolic resin composition 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 phenolic resin composition, the epoxy resin, and the curing agent and / or curing accelerator used as required, 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 100 to 100 parts by weight of a resin component obtained by adding an epoxy resin to a highly reactive phenol resin composition. Is 50-600
Used in parts by weight.

The phenolic resin molding material according to the present invention may further contain an additive, if necessary, such as 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 phenolic resin composition and an epoxy resin with, 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 phenolic resin composition and the epoxy resin with an optional component such as a curing agent is not particularly limited. For example, the highly reactive phenolic resin composition and the epoxy resin may be mixed with each other. After kneading, adding a curing agent (curing accelerator) and mixing well, if necessary, adding an inorganic filler and other additives, etc., and mixing to obtain a fine powdery molding powder (compound). it can.

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

[0092] A curing agent and / or other additives such as a curing 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 phenol resin composition and the epoxy resin, but may be performed at any time.

Such a 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 a 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.

[0096] Further, the molded article is 150 to 30 parts.
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 of the present invention uses a highly reactive phenolic resin composition having a low melt viscosity and a high reactivity with an epoxy resin. Mechanical properties such as dimensional stability of the body, 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 composition containing substantially no acid can reduce the corrosiveness to a metal member, and by adding an inorganic filler, the mechanical strength of the molded body, Electrical insulation 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.

[0099]

According to the process for producing a highly reactive phenolic resin composition according to the present invention, a modified product obtained by polycondensing a petroleum heavy oil or pitches with a formaldehyde compound in the presence of an acid catalyst. Formaldehyde resin and a phenolic novolak resin are used to produce a phenolic resin composition, so the resin melt viscosity is low, and a highly reactive phenolic resin composition having improved reactivity with an epoxy resin can be produced, and By changing the mixing ratio of the modified formaldehyde resin and the phenol novolak resin, the melt viscosity and the hydroxyl equivalent can be easily adjusted.

Further, according to the method for producing a highly reactive phenolic resin composition of the present invention, the modified formaldehyde resin obtained by the polycondensation reaction is subjected to a purification treatment to remove unreacted components and acid catalysts. By using this, it is possible to produce a highly reactive phenolic resin composition having substantially no acid and having no corrosive property in addition to the above-mentioned properties.

The phenolic resin molding material according to the present invention comprises:
A highly reactive phenolic resin composition obtained by the method of the present invention, and a molded article containing 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 manufactured, particularly a material for electric / electronic parts and a semiconductor encapsulant.

[0102]

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.

[0104]

[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 and 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 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 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 treatment under predetermined conditions was measured and determined.

[0110]

Example 1 227 g of feedstock oil, paraformaldehyde 9
0 g and 100 g of paratoluenesulfonic acid monohydrate, while removing water generated by the reaction,
The temperature was raised to 120 ° C., and the mixture was heated and stirred at 120 ° C. for 120 minutes to be reacted.

The reaction mixture was poured into 2000 ml of heavy naphtha (boiling point: 80 to 150 ° C.) to extract and remove unreacted oil and precipitate a modified formaldehyde resin. The precipitate was filtered and washed, and dried under reduced pressure at 25 ° C. to obtain 293 g of a crude modified formaldehyde resin containing acid.

The obtained crudely modified formaldehyde resin was
Dissolve in 0 times the weight of toluene and add p-toluenesulfonic acid 1
Hydrates and unreacted insolubles mainly composed of paraformaldehyde were filtered.

The obtained resin toluene solution was diluted with a resin concentration of 5
It was concentrated to 0% by weight to obtain a varnish-like modified phenol resin. Further, a slight amount of triethylenetetramine was added for neutralization, and the modified phenolic resin varnish was poured into 3.3 times by weight of the heavy naphtha to precipitate a resin and filtered. Then, it was vacuum-dried to obtain 143 g of a powdery modified formaldehyde resin.

40 g of the resulting modified formaldehyde resin
Was added to 160 g of phenol novolak resin (manufactured by Dainippon Ink and Co., Ltd., Percam TD-2131).
The mixture was melt-mixed using a kneader to obtain a highly reactive phenol resin composition.

[0115]

Example 2 The mixing ratio of modified formaldehyde resin and phenol novolak resin was changed to modified formaldehyde resin 8
The same operation as in Example 1 was performed except that the amount was changed to 120 g with respect to 0 g, to obtain a highly reactive phenol resin composition.

[0116]

Example 3 176 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.

The raw oil 150 obtained as described above
g, 90 g of paraformaldehyde and 100 g of acidic ion-exchange resin Diaion SK1B (manufactured by Mitsubishi Chemical Corporation), and while the water generated by the reaction was removed, the temperature was raised to 120 ° C. and the temperature was increased to 120 ° C. for 24 hours. The mixture was heated and stirred to react.

After removing the used ion-exchange resin by filtering the reaction mixture through a 60-mesh wire net, the reaction mixture was poured into 2000 ml of n-hexane to extract and remove unreacted oil and precipitate a denatured formaldehyde resin. . After washing the precipitate three times, the precipitate was dried under reduced pressure at 25 ° C. to obtain 160 g of an acid-containing crude modified formaldehyde resin.

40 g of the resulting modified formaldehyde resin
Was added to 160 g of phenol novolak resin (manufactured by Dainippon Ink and Co., Ltd., Percam TD-2131).
The mixture was melt-mixed using a kneader to obtain a highly reactive phenol resin composition.

[0120]

Example 4 9.48 parts by weight of the highly reactive modified phenolic resin composition obtained in Example 1 and a biphenyl type epoxy resin (trade name XY-400, manufactured by Yuka Shell Epoxy Co., Ltd.)
0H) After mixing and stirring 14.58 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, 0.25 parts by weight of carnauba wax was further mixed with the obtained compound under a ceiling, and 0.20 parts of carbon black was used 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.

[0123]

Example 5 The highly reactive modified phenolic resin composition obtained in Example 2 was used instead of the highly reactive modified phenolic resin composition obtained in Example 1, and the highly reactive modified phenolic resin was used. Table 3 shows the composition ratio of the composition and the epoxy resin.
In the same manner as in Example 4 except that the values shown in Table 1 were used, a resin mixture containing a curing accelerator, a compound, and a molded article were produced.

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

[0125]

Example 6 Instead of the highly reactive modified phenolic resin composition obtained in Example 1, the highly reactive modified phenolic resin composition obtained in Example 3 was used, and Y was used as an epoxy resin.
X-4000H was converted to EOCN 1020 (Nippon Kayaku Co., Ltd.)
Except that the mixing ratio of the highly reactive modified phenolic resin composition and the epoxy resin was set to the value shown in Table 3.
In the same manner as in Example 4, a curing accelerator-containing resin mixture, a compound, and a molded product were produced.

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

[0127]

[Table 2]

[0128]

[Table 3]

Continued on the front page (72) Inventor Shin Hasegawa 4 Kashima-gun, Kashima-gun, Kashima-gun, Kashima Ishi Oil Co., Ltd.

Claims (9)

[Claims] 1. A modified formaldehyde resin is produced by polycondensing a petroleum heavy oil or pitches with a formaldehyde compound in the presence of an acid catalyst, and the obtained modified formaldehyde resin and phenol novolak resin are A method for producing a highly reactive phenolic resin composition, which comprises mixing. 2. The method for producing a highly reactive phenolic resin composition according to claim 1, wherein said acid catalyst is a Bronsted acid selected from the group consisting of an organic acid, an inorganic acid and a solid acid. . 3. The method for producing a highly reactive phenolic resin composition according to claim 1, wherein the acid catalyst is an acidic cation exchange resin. 4. The petroleum heavy oils or pitches,
The method for producing a highly reactive phenolic resin composition according to any one of claims 1 to 3, wherein the method is used after performing a paraffin fraction removal treatment. 5. A modified formaldehyde resin obtained by the polycondensation reaction, comprising: (i) an aliphatic hydrocarbon having 10 or less carbon atoms, an alicyclic hydrocarbon having 10 or less carbon atoms, and an aliphatic petroleum fraction. Treating with a solvent containing at least one compound selected from the following, and purifying in at least one step selected from the step of removing solvent-soluble components including unreacted components and (ii) the step of removing catalyst residues. The method for producing a highly reactive phenolic resin composition according to any one of claims 1 to 4, characterized in that: 6. The modified formaldehyde resin and the phenol novolak resin in a weight ratio of 5/95 to 50/50.
The method for producing a highly reactive phenolic resin composition according to any one of claims 1 to 5, wherein the mixture is mixed at / 50. 7. A modified phenolic resin molding material comprising a highly reactive phenolic resin composition 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.