JPH0776617A - Novel epoxy resin-containing modified phenolic resin molding material - Google Patents

Abstract

PURPOSE:To provide the molding material comprising a specific modified phenolic resin, a specific epoxy resin and a specific curing agent, having no fear of corrosion of metals, etc., excellent in heat resistance, moldability, and dimensional stability, and suitable for electric and electronic parts, etc. CONSTITUTION:This molding material comprises (A) a modified phenolic resin produced by polycondensing a petroleum heavy oil or a pitch with a formaldehyde polymer and a phenol compound in the presence of an acid catalyst and subsequently removing the acid from the produced polymer, (B) an epoxy resin, e.g. a bisphenol type epoxy resin, containing low mol.wt. components having <=600 converted into PS in an amount of <=10%, (C) a curing agent such as hexamethylenetetramine, and furthermore preferably (D) an inorganic filler. The components A and B are preferably compounded in a weight ratio of 10/90 to 90/10.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel epoxy resin-containing modified phenolic resin molding material, an electronic / electrical component obtained thereby, and a semiconductor encapsulant using the molding material. Further, in detail, the novel epoxy resin-containing modified phenolic resin molding material of the present invention,
In particular, it is useful as an electronic / electrical component material and a semiconductor encapsulant, which require extremely strict standards for dimensional stability, heat resistance, moldability, and the like.

[0002]

2. Description of the Related Art Phenolic resin moldings have excellent mechanical properties and have been widely used for a long time, either alone or mixed with other resins such as epoxy resin. Alternatively, there is a problem that the size and the electric resistance are likely to change by absorbing alcohol and the heat resistance, particularly the oxidation resistance at high temperature is slightly low.

Therefore, various modifications of the phenolic resin itself have been studied. In particular, in order to impart resistance to changes due to light, chemicals, oxidation, etc., there is interest in modification with fats and oils, rosin, etc. In particular, heat resistance can be improved by selecting reaction components of phenol-modified aromatic hydrocarbon resins. Attempts to obtain phenolic resins with excellent properties are also known,
It has the drawback that it takes a long time to cure a molded product and requires a high temperature and a long time (JP-A-61-235413).

Then, the present inventors have used petroleum heavy oils or pitches, which are inexpensive raw materials, as modifiers,
We have found a modified phenolic resin excellent in heat resistance, oxidation resistance, and manifestation of mechanical strength, which cannot be obtained with conventional phenolic resins (JP-A-2-274714).

Further, a modified phenolic resin has been provided in which the residual acid is reduced by neutralizing the polycondensation product with amines and washing with water, and there is no risk of metal corrosion in the equipment (Japanese Patent Laid-Open No. Hei 4). No. -145116), even in that case, there is a possibility that a neutralized product of the residual acid may remain in the modified phenolic resin. Therefore, it has been found that an acid-free modified phenolic resin can be provided by subjecting the product after polycondensation to an extraction treatment with a specific extraction solvent (Japanese Patent Application No.
No. 40646), in producing a molded product by mixing with an epoxy resin, the reactivity with the epoxy resin, the heat resistance of the molded product, and the dimensional stability were not yet sufficient.

[0006]

Therefore, in producing a molded article by mixing with an epoxy resin, development of a modified phenol resin molding material excellent in reactivity with the epoxy resin, heat resistance and dimensional stability is desired. Was there.

[0007]

Means for Solving the Problems As a result of various studies on the above problems, the present inventor found that when a molded product was prepared by mixing with an epoxy resin, the molecular weight distribution of the modified phenolic resin was determined by the physical properties of the molded product. Affecting, that is, the smaller the molecular weight distribution of the modified phenolic resin on the low molecular weight component side, the more the reactivity with the epoxy resin and the physical properties (heat resistance, dimensional stability, etc.) of the molded product are expressed. The present invention was completed by discovering that it is excellent and using an acid-free modified phenolic resin having a low molecular weight component content of 10% or less as the modified phenolic resin as a main component of a molding material.

That is, the present invention is: (A) a modified phenolic resin obtained by polycondensing a heavy petroleum oil or pitches, a formaldehyde polymer and a phenol in the presence of an acid catalyst, (B) Epoxy resin, (C) epoxy resin-containing modified phenol resin molding material containing a curing agent, wherein the modified phenol resin constituting the molding material is (a) acid-free, and (b) polystyrene-equivalent molecular weight of 600 or less. An epoxy resin-containing modified phenolic resin molding material having a low molecular weight component content of 10% or less is provided. It is also characterized in that it further contains (D) an inorganic filler. It is also characterized in that the blending ratio of (A) modified phenol resin / (B) epoxy resin is 10/90 to 90/10 (parts by weight). Also,

There is provided an electric / electronic component obtained by molding the epoxy resin-containing modified phenolic resin molding material according to any one of (1) to (3). It is also characterized in that it provides a semiconductor encapsulant using the epoxy resin-containing modified phenolic resin molding material according to any one of (1) to (3).

The present invention will be described in detail below. In the present invention, the meanings of the elements which characterize the novel modified phenolic resin and the measuring methods thereof are as follows. Molecular weight distribution: The molecular weight distribution is measured by GPC (gel permeation chromatography). Measurement conditions; Column: Tosoh Corp., G3000H ₈ (column length 60
cm) + G2000H ₈ (column length 60 cm), column temperature 40 ° C. Detector: differential refractometer, detection temperature 40 ° C. Eluent: chloroform, flow rate 1.0 ml / min Sample solution: concentration 20 mg / ml-chloroform, injection amount 1
00 μl

Content of low molecular weight component: The content of low molecular weight component is calculated by the following formula (1) from the measurement result of the above GPC:

[Equation 1] Note) In Formula 1, the components that flow out after the retention time of 30 minutes are those having a reduced molecular weight of 600 or less in the polystyrene standard sample.

(I) Production of Modified Phenolic Resin Raw Material The modified phenolic resin used in the present invention is preferably produced by the following method. As a raw material for producing the modified phenolic resin, it is necessary to use petroleum heavy oils or pitches. For the petroleum heavy oils or pitches, it is desirable to use the aromatic hydrocarbon fraction fa value and aromatic ring hydrogen content Ha value shown in the following formula.

[0013]

[Equation 2] (The fa value can be determined by ¹³ C-NMR,
The a value can be determined by ¹ H-NMR. )

F of raw petroleum heavy oil or pitch
When the value of a becomes small, the aromatic content becomes small, so that the modification effect of the performance of the modified phenol resin obtained, particularly the modification effect of heat resistance and oxidation resistance tends to be small. In particular, when the fa value is less than 0.4, this modifying effect becomes extremely small, which is not desirable. Further, the fa value is 0.
Heavy petroleum oils or pitches of more than 95 are not desirable because the reactivity between the aromatic ring hydrogen and formaldehyde becomes low. Therefore, the fa value is 0.4 to 0.9.
5 is preferable, and more preferably 0.5 to 0.8.

Heavy petroleum oil as a raw material or H of pitches
If the value of a is small, the amount of aromatic ring hydrogen that reacts with formaldehyde will be small and the reactivity will be poor, and the effect of modifying the performance of the phenol resin will be poor, which is not desirable. It is considered that 20% or more has a practical Ha value. 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 be low, which is not desirable. Therefore, the Ha value is preferably 20 to 80%, more preferably 25 to 60%.

The number of condensed rings in the petroleum heavy oil or pitches as a raw material is not particularly limited, but is preferably a condensed polycyclic aromatic hydrocarbon mainly having 2 to 4 rings. 5
In the case of condensed polycyclic aromatic hydrocarbons having a ring or more, the boiling point exceeds 450 ° C. in most cases, so that it is difficult to collect those having a narrow boiling range, and there is a problem that the quality is not stable. Further, in the case of mainly monocyclic aromatic hydrocarbons, there is a problem that the effect of modifying the performance of the phenol resin is small because the reactivity with formaldehyde is low.

The heavy petroleum-based oils or pitches as raw materials are
It is obtained as a distillation residual oil of crude oil, a hydrogenolysis residual oil, a catalytic cracking residual oil, a thermal decomposition residual oil of naphtha or LPG and a vacuum distillate of these residual oils, an extract by solvent extraction or a heat-treated product. From these, the fa value and H
It is preferable to select and use a suitable a value.

The formaldehyde polymer, which is one of the raw materials for producing the modified phenol resin of the present invention, is a linear polymer such as paraformaldehyde, polyoxymethylene (particularly, oligomer) and a cyclic polymer such as trioxane. is there. The mixing ratio of the petroleum-based heavy oils or pitches to the formaldehyde polymer is the number of moles of formaldehyde-converted formaldehyde polymer to the average number of moles of 1 mol calculated from the average molecular weight of the petroleum-based heavy oils or pitches. , 1 to 15 are required.

If the mixing ratio is less than 1, the strength of the cured product of the modified phenolic resin obtained is low, which is not preferable. On the other hand, when it is more than 15, both the performance and yield of the obtained cured product are almost unchanged, so it is considered useless to use more formaldehyde polymer.

The mixing molar ratio of the formaldehyde polymer to the petroleum heavy oil or pitch which is the raw material of the modified phenol resin of the present invention is preferably 2 to 12.
As the acid catalyst used for producing the novel modified phenolic resin of the present invention, a Bronsted acid or a Lewis acid can be used, but a Bronsted acid is preferably used. As the Bronsted acid, toluenesulfonic acid,
Xylene sulfonic acid, hydrochloric acid, sulfuric acid, formic acid and the like can be used, but p-toluene sulfonic acid and hydrochloric acid are particularly excellent.

The amount of the acid catalyst used is preferably 0.1 to 30% by weight, more preferably 1 to 30% by weight based on the total amount of the petroleum heavy oil or pitches, the formaldehyde polymer and the phenols, which are raw materials for production. Is about 20% by weight. When the amount of the acid catalyst used is small, the reaction time tends to be long, and unless the reaction temperature is raised, the reaction tends to be insufficient. On the other hand, even if the amount of the acid catalyst used is large, the reaction rate may not be high, and the cost may be disadvantageous.

Phenols which are raw materials of the novel modified phenolic resin of the present invention are preferably phenol, cresol, xylenol, resorcin, bisphenol A,
It is one or more phenolic compounds selected from the group of bisphenol F. Phenols are added little by little by a method such as dropping and mixed. The rate of addition is from 0.05 to 5% by weight, based on the total weight of the reaction mixture.
Minutes, preferably 0.1 to 2% by weight / minute.

When the addition rate is less than 0.05% by weight / minute, the time required for the addition is too long and the cost is increased, which is not preferable. On the other hand, the addition rate is 5% by weight /
If the amount exceeds the limit, the added phenols react rapidly with the free formaldehyde, which makes it difficult to form a uniform mixture or cocondensate, which is not preferable. The cause of such non-uniformity is that phenols have a significantly higher reactivity to formaldehyde than petroleum heavy oils or pitches, and it is necessary to keep the initial concentration of phenols low. It is presumed that this is because formaldehyde selectively reacts with the phenols or the condensate of formaldehyde and phenol formed by the reaction, and becomes insoluble in the system.

Alternatively, the formaldehyde is first consumed in the reaction between the phenols or the phenols produced by the reaction and the condensate of formaldehyde, and the petroleum heavy oil or pitches or the petroleum heavy produced by the reaction. It is presumed that the condensate of formaldehyde with oils or pitches cannot further react with formaldehyde and is separated from the reaction system.

In the production of the modified phenolic resin of the present invention, the timing of starting addition of phenols is not particularly limited, but the reaction rate of formaldehyde estimated from the amount of residual free formaldehyde is 70% or less, preferably 50%.
Phenols are added when it is below%.

The addition start time may be a time when the reaction between the heavy petroleum oil or pitches and formaldehyde has not substantially progressed. If the reaction rate of formaldehyde exceeds 70%, the amount of formaldehyde that reacts with the phenols decreases, so that the performance of the resin produced is significantly reduced. The amount of phenols added is 0. 1 as the number of moles of phenols per 1 mole of the average number of moles calculated from the average molecular weight of heavy petroleum oils or pitches.
It is required to be 3 to 5.

When the amount added is less than 0.3, the reactivity of heavy petroleum oils or pitches with formaldehyde is inferior to that of phenols with formaldehyde, so that a sufficient crosslinking density is obtained. However, there is a problem that the strength of the cured product becomes lower than that of a general phenol resin.
In particular, it has a low impact resistance and is brittle. On the other hand, when the addition amount of the phenols exceeds 5, the modification effect by the modification of the phenol resin is small, which is not preferable. The addition amount of the phenols in the present invention is preferably 0.5 to
It is 3.

The reaction temperature is 50 to 160 ° C., preferably 6
It is 0 to 120 ° C. The reaction temperature is determined in consideration of the raw material composition, the reaction time, the properties of the resin produced, and the like. The reaction time is 0.5 to 10 hours, preferably 1 to 5 hours.
The reaction time is determined in consideration of the raw material composition, the reaction temperature, the addition rate of phenols, the properties of the resin produced, and the like.

In the production of the modified phenol resin of the present invention, when the reaction is carried out batchwise, it can be carried out in one step, and one step is preferable. When it is carried out in a continuous manner, it is used for conventional modified phenolic resin,
It is not necessary to use a device that is difficult to control, such as continuously mixing two or more types of reaction products in fixed amounts. Instead, place a complete mixing type reaction vessel in the middle and add phenols to be added in fixed amounts. Just send it in. Such a device is relatively inexpensive and has good operability.

In producing the modified phenol resin of the present invention, a solvent can be used during the reaction. The reaction can be performed without a solvent, but in that case, it is necessary to pay attention to the uniformity of the reaction. The use of a solvent reduces the viscosity of the reaction system and improves the homogeneity of the reaction.

The solvent is not particularly limited, but aromatic hydrocarbons such as benzene, toluene and xylene; halogenated aromatic hydrocarbons such as chlorobenzene; nitrated aromatic hydrocarbons such as nitrobenzene; nitroethane, nitro. Nitrated aliphatic hydrocarbons such as propane;
Halogenated aliphatic hydrocarbons such as perkrene, trichlene and carbon tetrachloride can be used.

(2) Purification Step of Modified Phenolic Resin According to the present invention, after the modified phenol resin is produced by the polycondensation step, the modified phenol resin is treated with the following (a) to
By carrying out the purification step of the step (c) in any order, the desired acid-free and low molecular weight component content is 1
It is possible to produce up to 0% modified phenolic resin.

(A) Treatment with a solvent composed of an aliphatic or alicyclic hydrocarbon having 10 or less carbon atoms or a mixture thereof to remove unreacted components soluble in the solvent and deposit a resin. A step (b) in which the acid catalyst has a solubility of 0.1 or less and is hardly soluble, but a catalyst residue such as an acid is extracted and removed by an extraction solvent which dissolves most of the modified phenolic resin;
(C) A step of extracting and removing unreacted components and low molecular weight components by treating with a mixed solvent composed of a combination of aromatic hydrocarbons and aliphatic hydrocarbons or alcohols.

That is, (a) a step of removing unreacted components and the like, and a resin precipitation step; the reactivity contained in the raw material petroleum heavy oil or pitches is low, and unreacted or insufficiently reacted. It is necessary to remove the components not used and the solvent used during the reaction. Specifically, at any time after the completion of the heating reaction, the reaction product is put into an aliphatic or alicyclic hydrocarbon having 10 or less carbon atoms or a mixture thereof to remove soluble components. Thus, a purified modified phenolic resin raw material is manufactured by removing unreacted components and the like soluble in the solvent and precipitating the resin.

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

(B) Extraction and removal step of residual catalyst residue such as acid; When the above-mentioned modified phenol resin is used as it is as a molding material or the like, catalyst residue such as acid remains in the modified phenol resin, resulting in metal corrosiveness. Since it is large and the heat resistance and moisture resistance are inferior, it is necessary to remove the catalyst residue such as acid from the modified phenolic resin to make it acid-free.

That is, in order to remove a catalyst residue such as an acid, the solubility of the acid catalyst is 0.1 or less, which is hardly soluble, but the extraction treatment is carried out using an extraction solvent capable of dissolving most of the modified phenol resin. It is necessary. As the extraction solvent,
Although the acid catalyst has a solubility of 0.1 or less and is hardly soluble, it is not particularly limited as long as it is a solvent capable of dissolving most of the modified phenolic resin, but aromatic hydrocarbons such as benzene, toluene and xylene are preferable, and more preferable. Is toluene.

Of course, the catalyst residue such as acid can be substantially removed only by the above extraction treatment, but if necessary, the extraction treatment may be followed by ordinary neutralization treatment or water washing treatment. Here, as the neutralization treatment, for example, hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide and the like, alkaline earth metals; ammonia, diethylenetriamine, triethylenetetramine, aniline, phenylene There may be mentioned various basic substances such as diamines.

The conditions such as the temperature during the above extraction treatment are not particularly limited, but they may be carried out according to a conventional method, and specifically, the modified phenol resin is added to the extraction solvent, or conversely, the modified phenol resin is added. It suffices to add an extraction solvent to the above, which is simple in operation. When there is a possibility that a small amount of acid catalyst or the like may remain in the extraction solution after the extraction treatment, it is preferable to perform the neutralization treatment.

(C) Extraction and removal treatment of unreacted components and low molecular weight components with a specific mixed solvent; In the present invention, further extraction treatment with the following specific mixed solvent is required. That is, as the specific mixed solvent used in the present invention, a mixed solvent of an aromatic hydrocarbon and an aliphatic hydrocarbon or alcohol in a specific range ratio is preferable.

As the aromatic hydrocarbon, benzene, toluene, xylene and the like are preferable, and toluene is more preferable. The aliphatic hydrocarbon used as a mixture with the aromatic hydrocarbon is preferably pentane, n-hexane, heptane or the like, more preferably n-hexane. On the other hand, as alcohols, methanol, ethanol and isopropyl alcohol are preferable, and methanol is more preferable. As the combination, a combination of toluene-n-hexane and toluene-methanol is preferable.

The mixing ratio of the aromatic hydrocarbons and the aliphatic hydrocarbons or alcohols is not necessarily constant depending on the combination of the respective solvents, but it is preferable to select variously in accordance with the extraction / removal ratio of the low molecular weight components, and in general. 100 to 300 parts by weight of aromatic hydrocarbon / 150 to 600 parts by weight of aliphatic hydrocarbon or alcohol. The main purpose of this treatment is to extract and remove low-molecular weight components, but it also plays a role of extracting and removing unreacted components.

Here, the conditions such as temperature at the time of the extraction treatment with the above-mentioned specific mixed solvent are not particularly limited, but they may be carried out according to a conventional method, and an operation at room temperature can be usually adopted. Preferably, in the step (c), the modified phenol resin is dissolved in an aromatic hydrocarbon solvent to obtain a resin concentration solution having a constant concentration, preferably 10 to 60% by weight, and the solution is added to the aromatic hydrocarbon. After pouring into a solution of a predetermined amount of the aliphatic hydrocarbons or alcohols in the above ratio and stirring, the mixture is filtered to remove a predetermined low molecular weight component and vacuum dried to have a low molecular weight component content of 10% or less. A new modified phenolic resin can be obtained.

The extraction treatment by a plurality of purification steps of the present invention can be carried out in any order, but preferably, immediately after the polymerization of the (A) modified phenol resin, unreacted components and low molecular weight components are mixed with a mixed solvent. Extraction and removal are carried out at the same time, and then catalyst residues such as acids are extracted and removed, and finally resin precipitation is carried out, or (B) modified phenolic resin is polymerized and then ordinary unreacted components are removed by solvent extraction and removal. ,
After that, the catalyst residue such as an acid is extracted and removed, and finally the low molecular weight component is extracted and removed by a mixed solvent, or (C) the modified phenol resin is polymerized, and then the normal unreacted component is removed by solvent extraction. After that, it is preferable to adopt a method in which a catalyst residue such as an acid is extracted and removed, a powdery resin is once obtained, and finally a low molecular weight component is extracted with a mixed solvent.

As a modification treatment method, it is possible to employ a method in which after the polymerization of the (D) modified phenolic resin, the unreacted components and the like, low molecular weight components and catalyst residues such as acids are simultaneously extracted and removed.

(3) Characteristics of the novel modified phenolic resin The novel modified phenolic resin of the present invention is (a) acid-free, and (b) 10 low molecular weight components having a polystyrene equivalent molecular weight of 600 or less measured by GPC. % Or less, preferably 8% or less. Thereby, when a molded product is prepared by mixing with an epoxy resin, the reactivity with the epoxy resin is improved as compared with a modified phenol resin having a large amount of low molecular weight components, and the physical properties of the manufactured molded product are also improved. There was a tendency that the physical properties were remarkably improved in terms of heat resistance and dimensional stability.

In the element defining the novel modified phenolic resin of the present invention, (a) acid-free means that the catalyst residue such as acid is removed by the above-mentioned specific solvent extraction treatment and the acid or the like does not remain at all. This means that acid and the like are substantially not contained to the extent that even if a very small amount remains, corrosiveness to metals is not significantly shown.

(B) If the low molecular weight component having a polystyrene equivalent molecular weight of 600 or less measured by GPC is 10% or more,
Improvement in heat resistance and dimensional stability of the molded product produced by mixing with the epoxy resin and the epoxy resin was insufficient. The ratio of extracting and removing the low molecular weight component is appropriately selected in consideration of both the required properties and the cost aspect of the molded body to be produced, because the resin yield also decreases by extracting and removing the low molecular weight component. It

(C) The reactivity with the epoxy resin can be judged by the gelling time (time to change from sol to gel; measured according to JIS-K 6910). High reactivity is preferable. (D) The heat resistance of the physical properties of the molded article can be judged by the glass transition point (the temperature at which many physical properties of the substance in the glass state change abruptly; according to the following measuring method). The higher this temperature is Excellent heat resistance. (E) Further, the dimensional stability can be judged by the coefficient of linear expansion (the rate of increase of the length of the solid material due to the temperature rise; according to the following measuring method), and the lower this value, the better the dimensional stability.

<Glass transition point measuring method> Measuring method: dynamic viscoelasticity measuring instrument: Rheology, DVE RHEOSPECTOLER DVE-
V4 type Loading method: Tensile method Measuring frequency: 10Hz Temperature rising rate: 5 ° C / min Dynamic measurement displacement: ± 5 × 10 ^-4 cm Specimen: Width 4 mm, thickness 1 mm, span 30 mm

<Measurement method of linear expansion coefficient> Measuring equipment: Rigaku Co., Ltd., TAS-200 system TMA 8140C
Mold heating rate: 5 ° C / min Specimen length: 10 mm Measuring temperature range: 50 ° C to 100 ° C

(4) Usefulness of the novel modified phenolic resin of the present invention: The novel modified phenolic resin of the present invention is substantially free of acid as described above and therefore is not corrosive to metals and is mainly Since the low molecular weight component having an average molecular weight of 600 or less is extracted and removed and the molecular weight distribution is narrow, the moldability, heat resistance, and dimensional stability of the molded product produced by mixing with the epoxy resin are high, and the content of the low molecular weight component is high. Compared with the modified phenolic resin, it is further improved and has excellent electrical insulation and moisture resistance, so it is particularly useful for materials for electric / electronic parts and semiconductor encapsulants, etc. that are extremely sensitive to hot air and humidity. . Therefore, the novel modified phenolic resin of the present invention is
It is particularly useful as a molding material, electronic / electrical material, and semiconductor encapsulant.

(5) Components mixed with the novel modified phenolic resin of the present invention: Epoxy resin: Generally, the epoxy resin mixed with the novel modified phenolic resin of the present invention has a small molding shrinkage and heat resistance. It has excellent properties, abrasion resistance, chemical resistance, and electrical insulation, and is used in combination with a curing agent. Examples of the epoxy resin include glycidyl ether type, glycidyl ester type, glycidyl amine 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 are used.
Type epoxy resin, tetrabromobisphenol A type epoxy resin, tetraphenylolethane type epoxy resin,
Phenol novolac type epoxy resin, o-cresol novolac type epoxy resin and the like;

As the glycidyl ether type (alcohol type), polypropylene glycol type epoxy resin, water-added bisphenol A type epoxy resin and the like; as the glycidyl ester type, hexahydrophthalic anhydride type epoxy resin, dimer acid type epoxy resin and the like;

Examples of the glycidylamine type include diaminodiphenylmethane type epoxy resin, isocyanuric acid type epoxy resin, hydantoic acid type epoxy resin, and the like; mixed types include p-aminophenol type epoxy resin, p-
Examples thereof include oxybenzoic acid type epoxy resin. Among the above epoxy resins, bisphenol A type epoxy resin, biphenyl type epoxy resin, glycidyl amine type epoxy resin, and phenol novolac type epoxy resin are preferable. A combination of two or more of the above epoxy resins can also be used.

The mixing ratio of the novel modified phenol resin of the present invention and the epoxy resin is not particularly limited, but in order to meet the purpose of the present invention, the total amount of the modified phenol resin and the epoxy resin is 100 parts by weight and 10 / 90-9
It is preferably 0/10 (parts by weight), and more preferably 20/80 to 80/20 (parts by weight). Here, the weight ratio of the novel modified phenolic resin of the present invention is 1
If it is less than 0 parts by weight, the heat resistance and moisture resistance of the resulting molded article are insufficiently improved, and if it exceeds 90 parts by weight, the molding temperature becomes high, which is not preferable.

Hardener: It is desirable to add a hardener to the resin base. As the curing agent, various ones can be mentioned and can be appropriately selected according to the purpose. For example, hexamethylenetetramine as a cyclic amine; diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperamine, isophoronediamine, bis (4-amino-) as aliphatic amines.
3-methylcyclohexyl) methane, menthanediamine and the like;

Polyamides include vegetable oil fatty acids (dimer or trimer acid), aliphatic polyamine condensates, etc .; aromatic polyamines include m-phenylenediamine,
4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, m-xylylenediamine and the like;
Examples of acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone anhydrous tetracarboxylic acid, chlorendic anhydride, dodecynyl succinic anhydride, and methyl tetrahydrophthalic anhydride. Acid, methyl endomethylene tetrahydrophthalic anhydride, etc. can be mentioned.

As the catalytic curing agent, boron trifluoride-
Lewis acids such as amine complexes and Lewis bases such as tris (dimethylaminomethyl) phenol, benzyldimethylamine, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, dicyandiamide, adipic acid dihydrazide, and other polymercaptans. , Polysulfide, etc. Moreover, these can also be used in combination of 2 or more types.

Inorganic filler: In the present invention, it is desirable to add an inorganic filler in order to enhance various physical properties such as strength and dimensional stability of the obtained molded product. As the inorganic filler that can be used in the present invention, any inorganic filler such as an inorganic filler or a reinforcing fiber can be used conventionally, but for example, a reinforcing fiber such as glass fiber, carbon fiber, phosphor fiber, or boron fiber. Hydrated metal oxides such as aluminum hydroxide and magnesium hydroxide; metal carbonates such as magnesium carbonate and calcium carbonate; metal borates such as magnesium borate; inorganic fillers such as silica and mica.

The mixing ratio of the inorganic filler is not particularly limited, but is generally preferably 20 to 600 parts by weight with respect to 100 parts by weight of the modified phenol resin. Other additives: In addition, various additives may be added to the novel modified phenolic resin of the present invention, such as silicone, waxes and other internal release agents, coupling agents, flame retardants, light stabilizers, if necessary. Antioxidants, pigments, extenders and the like can be added.

(6) Mixing and molding operation: There is no particular limitation to obtain a molding material containing the novel modified phenolic resin and the epoxy resin of the present invention, but in general, the novel modified phenolic resin is previously mixed with the epoxy resin. After kneading and mixing well with a curing accelerator, it is preferable to add an inorganic filler and other additives as necessary to form a fine powder molding compound (compound). The additive can be added at any time.

To mold the novel epoxy resin-containing modified phenolic resin molding material of the present invention, molding means known per se, such as compression molding, injection molding, extrusion molding, transfer molding and the like can be applied. For example, when a molded body is obtained by transfer molding, the molding temperature is 120 to 180.
C, injection pressure 20 to 300 kgf / cm ² , mold clamping pressure 50 to
The molding time is 250 kgf / cm ² , and the molding time is 1 to 10 minutes.

In the case of the present invention, after molding by a conventional method,
It is desirable to post-cure the obtained molded body by a heat treatment at 150 to 300 ° C. for about 0.5 to 24 hours. By this treatment, the heat resistance of the novel epoxy resin-containing modified phenolic resin molding obtained by the method of the present invention can be further improved.

In particular, when the novel modified phenolic resin of the present invention is mixed with an epoxy resin and used as a semiconductor encapsulating material, it is only suitable for low-pressure transfer molding which is the main method for molding a semiconductor encapsulating material. In addition, it is possible to provide a semiconductor encapsulant having excellent heat resistance, moisture resistance, dimensional stability, workability, and moldability as compared with conventional materials.

[0067]

The present invention is characterized in that the novel modified phenolic resin is a modified phenolic resin having a relatively low content of low molecular weight components and containing no acid. Further, since the novel modified phenolic resin of the present invention mainly extracts and removes low molecular weight components, it is required to have extremely strict standards for dimensional stability, heat resistance, moldability, etc. There is an advantage that an epoxy resin-containing modified phenol resin molding material suitable as a sealing material for semiconductors can be provided.

That is, in the case where the novel modified phenol resin of the present invention is mixed with an epoxy resin to prepare a molded article, the one having a relatively small low molecular weight component side in the modified phenol resin is the epoxy resin. And the physical properties of the molded article (especially heat resistance, dimensional stability, etc.) are excellent, and the effect is remarkable especially when the content of the low molecular weight component is 10% or less. In short, according to the present invention, the novel modified phenolic resin, when mixed with an epoxy resin, can improve its dimensional stability, moldability and heat resistance as compared with a resin having a high content of low molecular weight components, and has a moisture resistance. It has been found that it is possible to improve the heat resistance, metal corrosion resistance, etc., and to exhibit excellent characteristics as an electric / electronic component material or a sealing material for semiconductors, which is an alternative to conventional materials.
Furthermore, the novel epoxy resin-containing modified phenolic resin of the present invention can be provided with a molding material having excellent mechanical properties and electrical insulation by blending an inorganic filler.

[0069]

The present invention is illustrated by the following examples, which do not limit the scope of the invention. (Example 1) 334 g of feedstock oil shown in Table 1, 370 g of paraformaldehyde, p-toluenesulfonic acid monohydrate 1
37 g and p-xylene 678.5 g were charged into a glass reactor, and the temperature was raised to 95 ° C. with stirring. 95 ° C
After 1 hour of holding, 209 g of phenol was added dropwise at a dropping rate of 1.3 g / min.
The mixture was stirred for 5 minutes to react. Next, the reaction mixture is added to 3,3
The reaction product was precipitated by pouring it into 00 g of n-hexane and filtered to remove unreacted components and reaction solvent.
The precipitate was washed with 1,600 g of n-hexane and then vacuum dried to obtain an acid-containing modified phenol resin.

This resin was dissolved in 10 times the weight of toluene (the solubility of p-toluenesulfonic acid monohydrate in toluene is 0.01 or less), and insoluble with p-toluenesulfonic acid monohydrate as the main component. The minutes were filtered. The resulting resin toluene solution was concentrated to a resin concentration of 50% by weight,
Furthermore, a trace amount of triethylenetetramine was added to neutralize and an acid-free modified phenol resin toluene solution was obtained.

Toluene was added to and mixed with this solution to prepare five kinds of resin toluene solutions having different resin concentrations and solution amounts shown in Table 2. Then, the total amount of the solution was put into the precipitation solvent shown in Table 2 and stirred, and then filtered to remove the low molecular weight components by extraction. The precipitate on the filter paper was vacuum dried to obtain the novel modified phenolic resins (invention products 1 to 5) shown in Table 2.

GPC of the obtained new modified phenolic resins (Invention Products 1 to 5) was measured under the following conditions, and the results of calculating the content of low molecular weight components are shown in Table 4. Further, as a representative example, the GPC measurement result of the invention product 2 is shown in FIG.

Further, the obtained novel modified phenol resin (invention products 1 to 5) and biphenyl type epoxy resin (produced by Yuka Shell Epoxy Co., Ltd .; trade name YX-4000) are compounded (molding material) by the following method. After making 175
Transfer molding at 90 ℃ for 90 seconds
A molded body was obtained by post-curing at 5 ° C. for 6 hours. Its physical properties are also shown in Table 4.

The gelation time was measured according to JIS K69 using the sample before adding the filler in the compound preparation as a sample.
According to 10, the measurement was performed at 170 ° C. The results are also shown in Table 4.

[0075]

[Table 1]

[0076]

[Table 2]

<GPC measurement conditions> Column: Tosoh Corp., G3000H ₈ (column length 60
cm) + G2000H ₈ (column length 60 cm), column temperature 40 ° C. Detector: differential refractometer, detection temperature 40 ° C. Eluent: chloroform, flow rate 1.0 ml / min Sample solution: concentration 20 mg / ml-chloroform, injection amount 1
00 μl

<Calculation Method for Low Molecular Weight Component in Resin> The content of low molecular weight component in the resin is calculated by the following formula.

[0079]

[Equation 3]

<Compound preparation method> 100 parts by weight of the modified phenolic resin and 80 parts by weight of the epoxy resin are melt-mixed at 120 ° C., cooled and pulverized. 2-Ethyl-4-methyl-imidazole (manufactured by Wako Pure Chemical Industries, Ltd., 1
Grade) 3.67 parts by weight and 1.48 parts by weight of carnauba wax are added and mixed, and further fused silica (trade name: CRS1102-RD8, manufactured by Tatsumori Co., Ltd.) 555.
5 parts by weight were added and mixed to obtain a compound.

Comparative Example 1 The same operation as in Example 1 was carried out to obtain a toluene solution having a concentration of the acid-free modified phenolic resin before treatment with the mixed solvent of 50% by weight. This resin toluene solution was poured into 3.3 times by weight of n-hexane to precipitate a resin, which was then filtered. Then, vacuum drying was performed to obtain 580 g of an acid-free modified phenol resin (comparative product).

GP of the Acid-Free Modified Phenolic Resin Obtained
The result of having measured C on the same conditions as Example 1 is shown in FIG. From this GPC measurement result, the content of low molecular weight component in the resin was calculated by the same formula as in Example 1, and it was 14.1% as shown in Table 4. Further, using the obtained acid-free modified phenolic resin (comparative product), a compound was prepared and a molded body was molded in the same manner as in Example 1, and the gelation time and the physical properties after molding were measured. The results are shown in Table 4.

(Example 2) After carrying out the reaction operation in the same manner as in Example 1, 850 g of toluene was added to and mixed with the reaction mixture, and the mixture was cooled to 60 ° C. The total amount of the mixture was poured into 3,300 g of n-hexane, stirred and filtered to extract and remove unreacted components and low molecular weight components in the resin. The extract on the filter paper was washed with 1,600 g of n-hexane and then vacuum dried to obtain an acid-containing novel modified phenol resin.

This resin was dissolved in 10 times the weight of toluene, and the insoluble matter containing p-toluenesulfonic acid monohydrate as the main component was filtered. The obtained resin toluene solution was concentrated to a resin concentration of 50% by weight, and a trace amount of triethylenetetramine was added to neutralize the resin. This resin toluene solution was poured into 3.3 times by weight of n-hexane to precipitate a resin, which was then filtered. Then, it was vacuum dried to obtain 490 g of a novel modified phenol resin (Invention Product 6). Further, in the same manner as in Example 1, the low molecular weight component content, the gelation time,
The physical properties of the molded body were measured. The results are shown in Table 4.

Example 3 The acid-free modified phenolic resin obtained in Comparative Example 1 was dissolved in toluene to prepare two kinds of resin toluene solutions having different resin concentrations and solution amounts shown in Table 3. Then, the whole amount of the same solution was put into the precipitation solvent shown in Table 3 and stirred, and then filtered to remove the low molecular weight components by extraction. The deposit on the filter paper was vacuum dried to obtain a novel modified phenol resin (Invention Products 7 and 8) having the weight shown in Table 3. Further, in the same manner as in Example 1, the low molecular weight component content, the gelation time, and the physical properties of the molded body were measured. The results are shown in Table 4.

[0086]

[Table 3]

[0087]

[Table 4]

* 1; Glass transition point measuring method Measuring method: dynamic viscoelasticity measuring instrument: Rheology, DVE RHEOSPECTOLER DVE-
V4 type Loading method: Tensile method Measuring frequency: 10Hz Temperature rising rate: 5 ° C / min Dynamic measurement displacement: ± 5 × 10 ^-4 cm Specimen: Width 4 mm, thickness 1 mm, span 30 mm

* 2: Linear expansion coefficient measuring method Measuring equipment: Rigaku Co., Ltd., TAS-200 system TMA 8140C
Mold heating rate: 5 ° C / min Specimen length: 10 mm Measuring temperature range: 50 ° C to 100 ° C

(Example 4) After carrying out the reaction operation in the same manner as in Example 1, 1,250 g of toluene was added to and mixed with the reaction mixture, and the mixture was cooled to 60 ° C. The whole amount of the mixture was poured into 3,300 g of methanol, and the mixture was stirred and filtered to extract and remove unreacted components, low molecular weight components in the resin, and most of p-toluenesulfonic acid monohydrate. The precipitate on the filter paper was washed with 1,600 g of methanol and then vacuum dried to obtain a novel modified phenol resin containing an extremely small amount of acid.

This resin was dissolved in 10 times the weight of toluene, and the insoluble matter was filtered. The obtained resin toluene solution was concentrated to a resin concentration of 50% by weight, and a trace amount of triethylenetetramine was added to neutralize the resin. This resin toluene solution was poured into 3.3 times by weight of n-hexane to precipitate a resin, which was then filtered. Then, vacuum drying was performed to obtain 519 g of a novel modified phenol resin (Invention Product 9) from which low molecular weight components were extracted and removed. Furthermore, in the same manner as in Example 1,
The content of the low molecular weight component, the gelation time, and the physical properties of the molded product were measured. The results are shown in Table 4.

Example 5 The invention product 3 obtained in Example 1 was used as the modified phenolic resin, and the epoxy resin was manufactured by Yuka Shell Epoxy Co., Ltd. under the trade name Epicoat 828.
(Bisphenol A type epoxy resin), as a filler, manufactured by Tatsumori Co., Ltd., fused silica CRS1102-RD8 was used to prepare a compound by the same operation as in Example 1 except that the composition was as shown in Table 5, Transfer molding was performed under the molding conditions shown in Table 6, and then post cure was performed under the conditions shown in Table 6 to obtain a molded product. The gelation time of the compound and the physical properties of the obtained molded product were measured in the same manner as in Example 1, and the results are shown in Table 6.

Comparative Example 2 The gelation time of the compound and the physical properties of the molded product were measured in the same manner as in Example 5 except that the modified phenolic resin was changed from the invention product 3 to the comparative product obtained in Comparative Example 1. The results are also shown in Table 6.

Example 6 The invention product 9 obtained in Example 4 was used as the modified phenol resin, and the epoxy resin was manufactured by Yuka Shell Epoxy Co., Ltd. under the trade name Epicoat 152.
(Phenol novolac type epoxy resin), as a filler, manufactured by Tatsumori Co., Ltd., fused silica CRS1102-RD8
Example 1 except that the composition described in Table 5 was used.
A compound was produced by the same operation as described above, transfer molding was carried out under the molding conditions shown in Table 6, and post-curing was carried out under the conditions shown in Table 6 to obtain a molded product. The gelation time of the compound and the physical properties of the obtained molded product were measured in the same manner as in Example 1, and the results are shown in Table 6.

Comparative Example 3 The gelation time of the compound and the physical properties of the molded product were measured in the same manner as in Example 6 except that the modified phenolic resin was changed from the invention product 9 to the comparative product obtained in Comparative Example 1. The results are also shown in Table 6.

Example 7 The invention product 6 obtained in Example 2 was used as the modified phenol resin, and the epoxy resin was manufactured by Nippon Ciba-Geigy Co., Ltd. under the trade name Araldite MY9.
512 (glycidyl amine type tetrafunctional epoxy resin),
A compound was prepared in the same manner as in Example 1 except that the composition described in Table 5 was used and a compound was prepared by using Unitika Short Fiber ES-30T manufactured by Unitika Yum Glass Co., Ltd. as a filler. Transfer molding was performed under the molding conditions, and then post-curing was performed under the conditions shown in Table 6 to obtain a molded body. The gelation time of the compound and the physical properties of the obtained molded product were measured in the same manner as in Example 1, and the results are shown in Table 6.

Comparative Example 4 The gelation time of the compound and the physical properties of the molded product were measured in the same manner as in Example 7 except that the modified phenolic resin was changed from the invention product 6 to the comparative product obtained in Comparative Example 1. The results are also shown in Table 6.

Example 8 The invention product 7 obtained in Example 3 was used as the modified phenol resin, and the epoxy resin was manufactured by Nippon Ciba-Geigy Co., Ltd. under the trade name Araldite MY9.
512 (glycidyl amine type tetrafunctional epoxy resin),
A compound was prepared in the same manner as in Example 1 except that the composition described in Table 5 was used and a compound was prepared by using Unitika Short Fiber ES-30T manufactured by Unitika Yum Glass Co., Ltd. as a filler. Transfer molding was performed under the molding conditions, and then post-curing was performed under the conditions shown in Table 6 to obtain a molded body. The gelation time of the compound and the physical properties of the obtained molded product were measured in the same manner as in Example 1, and the results are shown in Table 6.

Comparative Example 5 The gelation time of the compound and the physical properties of the molded product were measured in the same manner as in Example 8 except that the modified phenolic resin was changed from the invention product 7 to the comparative product obtained in Comparative Example 1. The results are also shown in Table 6.

[0100]

[Table 5]

[0101]

[Table 6]

* 1) E828: manufactured by Yuka Shell Epoxy Co., Ltd., trade name Epicoat 828 EI52: manufactured by Yuka Shell Epoxy Co., Ltd., trade name Epicoat 152 MY9512: Nippon Ciba-Geigy Co., Ltd., Araldite MY9512 * 2) Fused silica: manufactured by Tatsumori Co., Ltd., CRS1102-
RD8 GF: Unitika Umglass Co., Ltd., Short fiber ES-30T * 3) Wako Pure Chemical Industries, Ltd., 2-Ethyl-4-methylimidazole (Reagent 1st grade) * 4) Measurement conditions are the same as in Table 4. * 5) Measurement conditions are the same as in Table 4.

[0103]

As described above, the novel epoxy resin-containing modified phenolic resin molding material according to the present invention has the following excellent performances. Since it does not contain acid, there is no risk of corrosion to metals. Since the low molecular weight component content is low, heat resistance, moldability, and dimensional stability are further improved. When an inorganic filler is blended, a molding material having excellent mechanical strength is provided. Has good electrical insulation.

[Brief description of drawings]

FIG. 1 is a graph showing the molecular weight distribution of Invention 2 by GPC.

FIG. 2 GPC of acid-free phenol resin as a comparison product
3 is a graph showing a molecular weight distribution according to.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Haruhiko Takeda 4 Towada, Kamisu-cho, Kashima-gun, Kashima-gun, Ibaraki Kashima Sekiyu Oil Co., Ltd. Kashima Refinery

Claims (5)

[Claims] 1. A modified phenolic resin (A) obtained by polycondensing a heavy petroleum oil or pitches, a formaldehyde polymer and a phenol in the presence of an acid catalyst.
(B) Epoxy resin, (C) Epoxy resin-containing modified phenol resin molding material containing a curing agent, wherein the modified phenol resin constituting the molding material is (a) acid-free, and (b) polystyrene equivalent The content of low molecular weight components having a molecular weight of 600 or less is 10% or less,
Modified phenol resin molding material containing epoxy resin. 2. The epoxy resin-containing modified phenolic resin molding material according to claim 1, further comprising (D) an inorganic filler. 3. The epoxy resin-containing product according to claim 1, wherein the compounding ratio of (A) modified phenol resin / (B) epoxy resin is 10/90 to 90/10 (parts by weight). Modified phenol resin molding material. 4. An electric / electronic part obtained by molding the epoxy resin-containing modified phenolic resin molding material according to claim 1. Description: 5. An encapsulant for semiconductors, which uses the epoxy resin-containing modified phenolic resin molding material according to any one of claims 1 to 3.