JP2003192771A - Phenolic resin, its preparation method, curing agent for epoxy resin, epoxy resin composition and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a phenolic resin composed of a novel polyhydric phenolic compound which gives an epoxy resin cured product having excellent low hygroscopicity and low stress, and its preparation method. <P>SOLUTION: The phenolic resin is composed of a polyhydric phenolic compound to be represented by formula (1) [wherein R<SP>1</SP>is a group to be selected from an alkyl group, an alkoxy group, a halogen, or a phenyl group or an aralkyl group which is nonsubstituted or substituted; the entire Z or part of Z is a group to be represented by formula (2) (wherein R<SP>2</SP>is a group to be selected from an alkyl group, an alkoxy group, a halogen, or a phenyl group or an aralkyl group which is nonsubstituted or substituted; b is an integer of 0-5); n is an average of numbers of 0-8; and a is an integer of 0-4], and the balance is a direct bond or an alkylene group. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel phenol resin containing a polyhydric phenol compound, a method for producing the same, a curing agent for an epoxy resin containing the phenol resin containing the polyhydric phenol compound, and a curing agent for the epoxy resin. The present invention relates to an epoxy resin composition, and a semiconductor device manufactured using the epoxy resin composition, which has excellent solder crack resistance. INDUSTRIAL APPLICABILITY The novel polyhydric phenol compound of the present invention can give an epoxy resin cured product excellent in low hygroscopicity and low stress, and is particularly useful for semiconductor encapsulation.

[0002]

2. Description of the Related Art Epoxy resins are used in a wide variety of applications because of their excellent cured properties and ease of handling. In addition, various kinds of curing agents can be used for the epoxy resin, and the physical properties of the cured material largely change depending on the selection of the curing agent, so that the epoxy resin is used properly according to the purpose of each application. recent years,
As the usage conditions of polymer materials have become more severe, various characteristics imposed on polymer materials have become more severe. Even in applications where a curing agent for an epoxy resin is used, various commonly used curing agents have been unable to sufficiently satisfy the required characteristics.

For example, an epoxy resin composition containing a novolac type phenol resin as a curing agent is used for semiconductor encapsulation, but the required performance is becoming severe in this field as well. That is, due to the high integration of semiconductor devices, the size of semiconductor elements is increasing, and the packages are becoming smaller and thinner, and the mounting method is also shifting to surface mounting. in this case,
During mounting, the entire semiconductor device is exposed to a high temperature near the melting temperature of the solder, which causes vapor pressure due to the rapid vaporization of moisture absorbed by the package, resulting in large stress on the entire package and cracking. ing. Therefore, low hygroscopicity and low stress (that is, low elastic modulus) are required for a sealing material having good solder crack resistance. This requirement has become more severe in recent years due to an increase in melting point associated with lead-free solder.

At present, phenol novolac resins (phenol-formaldehyde resins), which are mainly used as a curing agent, have become insufficient in low hygroscopicity and low stress. Recently, in order to solve these problems,
Using a composition consisting of a phenol resin in which a hydrocarbon group having a ring structure is introduced between phenol nuclei and a tetramethylbiphenol type epoxy resin, such as dicyclopentadiene phenol resin and phenol aralkyl resin,
Although it has been proposed to improve low hygroscopicity and low stress (Japanese Patent Laid-Open No. 61-47725), neither low hygroscopicity nor low stress is sufficient for recent severe requirements.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is to provide a cured product which can be used in various applications and has low hygroscopicity and low stress, especially when used as a curing agent for epoxy resins. Providing a phenol resin comprising a novel polyhydric phenol compound, providing a method for producing the polyhydric phenol compound, providing a curing agent for an epoxy resin containing the polyhydric phenol compound as a main component, and curing the same. And an epoxy resin composition for semiconductor encapsulation containing the epoxy resin composition and an inorganic filler and a cured product of the epoxy resin composition for semiconductor encapsulation. Another object of the present invention is to provide a resin-encapsulated semiconductor device.

[0006]

The inventors of the present invention have conducted various studies to solve the above-mentioned problems, and as a result, as a curing agent for epoxy resin, a specific hydrophobic and flexible structure between phenol nuclei has been obtained. It has been found that the object can be achieved by using a phenolic resin having a hydrocarbon group as a main component of a curing agent for an epoxy resin, and has reached the present invention. The present invention includes the following inventions.

(1) A phenol resin comprising a polyhydric phenol compound represented by the following general formula (1).

[Chemical 7]

[In the formula, R ^{1 s} may be the same or different from each other and are selected from an alkyl group having 1 to 10 carbon atoms, an unsubstituted or alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom. Selected from a phenyl group substituted with a group, an unsubstituted or alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom, an aralkyl group substituted with a group, an alkoxy group having 1 to 10 carbon atoms and a halogen atom. It is a group that is All or part of Z is a group represented by the following general formula (2), and the rest is a direct bond or an alkylene group having 1 to 10 carbon atoms.

[0009]

[Chemical 8]

(In the formula, R ^{2 s} may be the same or different and are selected from an alkyl group having 1 to 10 carbon atoms, an unsubstituted or alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom. Selected from a phenyl group substituted with a group, an unsubstituted or alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom, an aralkyl group substituted with a group, an alkoxy group having 1 to 10 carbon atoms and a halogen atom. R ³ may be the same or different from each other and are selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an unsubstituted or alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom. Selected from a phenyl group and an unsubstituted or alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom which are substituted with a group It is a group selected from aralkyl groups substituted with a group represented by b. B is an integer of 0 to 5.) n is a number of 0 to 8 on average. a is an integer of 0-4. ]

(2) In the general formula (1), a is 0 and Z
Is a group in which the substituent R ³ in the group represented by the general formula (2) is hydrogen and b is 0 (1)
A phenolic resin comprising the polyhydric phenol compound according to the item.

(3) For an epoxy resin, which comprises 10 to 100% by mass of a phenolic resin comprising the polyhydric phenol compound according to the above (1) or (2) in a total epoxy resin curing agent. Hardener.

(4) An epoxy resin composition containing an epoxy resin and the curing agent for an epoxy resin described in the above item (3) as an essential component.

(5) Reaction of at least one phenol compound selected from bisphenol A, bisphenol F, biphenol, tetramethylbiphenol, terpene diphenol, dicyclopentadiene phenol resin and cresol novolac resin with epihalohydrin, The epoxy resin composition according to item (4), which is an epoxy resin obtained by.

(6) The epoxy resin composition according to the above (4) or (5), and 80 to 95% by mass of the total composition of fused silica powder and / or spherical fused silica powder and / or An epoxy resin composition for semiconductor encapsulation containing an inorganic filler made of crystalline silica powder.

(7) A resin-encapsulated semiconductor device which is encapsulated with a cured product of the epoxy resin composition for semiconductor encapsulation according to the item (6).

(8) The following general formula (3)

[Chemical 9]

(In the formula, R ^{1 s} may be the same as or different from each other and are selected from an alkyl group having 1 to 10 carbon atoms, an unsubstituted or alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom. Selected from a phenyl group substituted with a group, an unsubstituted or alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom, an aralkyl group substituted with a group, an alkoxy group having 1 to 10 carbon atoms and a halogen atom. And a is 0 to
It is an integer of 4. ) A phenolic compound represented by

The following general formula (4)

[Chemical 10]

(In the formula, R ^{2 s} may be the same as or different from each other and are selected from an alkyl group having 1 to 10 carbon atoms, an unsubstituted or alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom. Selected from a phenyl group substituted with a group, an unsubstituted or alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom, an aralkyl group substituted with a group, an alkoxy group having 1 to 10 carbon atoms and a halogen atom. R ³ may be the same or different from each other and are selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an unsubstituted or alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom. Selected from a phenyl group and an unsubstituted or alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom which are substituted with a group R ⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and b is an integer of 0 to 5). And, in the presence of an acidic catalyst, an addition condensation reaction,

The following general formula (1)

[Chemical 11]

[Wherein R ^{1 s} may be the same or different from each other and are selected from an alkyl group having 1 to 10 carbon atoms, an unsubstituted or alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom. Selected from a phenyl group substituted with a group, an unsubstituted or alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom, an aralkyl group substituted with a group, an alkoxy group having 1 to 10 carbon atoms and a halogen atom. It is a group that is All or part of Z is a group represented by the following general formula (2), and the rest is a direct bond or an alkylene group having 1 to 10 carbon atoms.

[0023]

[Chemical 12]

(In the formula, R ^{2 s} may be the same as or different from each other and are selected from an alkyl group having 1 to 10 carbon atoms, an unsubstituted or alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom. Selected from a phenyl group substituted with a group, an unsubstituted or alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom, an aralkyl group substituted with a group, an alkoxy group having 1 to 10 carbon atoms and a halogen atom. R ³ may be the same or different from each other and are selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an unsubstituted or alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom. Selected from a phenyl group and an unsubstituted or alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom which are substituted with a group It is a group selected from aralkyl groups substituted with a group represented by b. B is an integer of 0 to 5.) n is a number of 0 to 8 on average. a is an integer of 0-4. ] The manufacturing method of the phenol resin which consists of the polyhydric phenol compound represented by these.

(9) The phenol compound represented by the general formula (3) is phenol, cresol, xylenol, propylphenol, butylphenol, butylcresol, phenylphenol, cumylphenol, methoxyphenol, ethoxyphenol, phenoxyphenol, Dihydroxydiphenyl ether, benzylphenol, bisphenol A, bisphenol F, bisphenol AD, biphenol, terpene diphenol, bisphenol S, thiodiphenol, dihydroxydiphenyl ether, dihydroxybenzophenone,
4,4'-benzylidene bisphenol, 4,4 '-(4
-Methylbenzylidene) bisphenol, tetramethylbiphenol, and bromophenol, and the compound represented by the general formula (4) is 3-phenyl-2-propen-1-ol, 2-methyl-3. -Phenyl-2-propen-1-ol, 1-
A phenol resin comprising a polyphenol compound as described in the item (8), which is a compound selected from methoxy-3-phenyl-2-propene and 1-methoxy-2-methyl-3-phenyl-2-propene. Manufacturing method.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION As long as the phenol resin comprising the polyhydric phenol compound of the present invention has a structure represented by the above general formula (1), its production method is not limited, and usually, It can be produced by various methods which are carried out for oligomerizing a phenol compound into a phenol resin.

The polyvalent phenol represented by the general formula (1)
Represented by the general formula (3) used for the production of
Is a substituent in the general formula (3)
(R¹) Is an alkyl group having 1 to 10 carbon atoms, unsubstituted or
Alkyl group, hydroxyl group, alkoxy group, aralkyl group and
Phenyl substituted with groups selected from halogen atoms
Group, unsubstituted or alkyl group, hydroxyl group, alkoxy group,
Substituted with a group selected from aralkyl groups and halogen atoms
Aralkyl groups, alkoxy groups having 1 to 10 carbon atoms and
And a phenol compound that is a group selected from halogen atoms
And the substituent (R ¹) If the value a in a is 2
In some cases, the substituent (R¹) Are the same as each other
It may be different.

Examples of such a phenol compound include phenol, cresol, xylenol, propylphenol, butylphenol, butylcresol,
Phenylphenol, cumylphenol, methoxyphenol, ethoxyphenol, propoxyphenol,
Examples include butoxyphenol, benzylphenol, bromophenol, phenoxyphenol, dihydroxydiphenyl ether and the like. Among these phenol compounds, phenol and cresol are preferable from the viewpoint of physical properties of the obtained polyvalent compound and easy availability as a raw material.

The compound represented by the general formula (4) used for producing the polyhydric phenol compound represented by the general formula (1) has a substituent (R ² ) which is an alkyl group having 1 to 10 carbon atoms. , Unsubstituted or alkyl group, hydroxyl group, alkoxy group,
A phenyl group substituted with a group selected from an aralkyl group and a halogen atom, an unsubstituted or alkyl group, a hydroxyl group,
Aralkyl group substituted with a group selected from an alkoxy group, an aralkyl group and a halogen atom, having 1 to 10 carbon atoms.
Which is a group selected from the alkoxy group and the halogen atom, wherein the numerical value b in the substituent (R ² ) b is 2
In the above cases, the substituents (R ² ) may be the same or different from each other.

Similarly, the substituent R ³ may be the same or different from each other, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an unsubstituted or alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom. A group selected from a phenyl group substituted with a group selected from the following, an unsubstituted or alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group, and an aralkyl group substituted with a group selected from a halogen atom. Similarly, the substituent R ⁴ is a hydrogen atom or has 1 carbon atom.
It is a group selected from alkyl groups of 10 to 10.

As the compound represented by the general formula (4),
Although various compounds defined above can be used, 3-phenyl-2-propen-1-ol and 2-methyl-3 are used because of the physical properties of the obtained polyhydric phenol compound and the availability as a raw material. -Phenyl-2-propen-1-ol and alkyl ethers thereof are preferred, especially 1
-Methoxy-3-phenyl-2-propene, 1-ethoxy-3-phenyl-2-propene, their methyl ethers and ethyl ethers, 1-methoxy-2-methyl-3-phenyl-2-propene, 1- Ethoxy-2
-Methyl-3-phenyl-2-propene is preferred.

There are various methods for oligomerizing the phenol compound represented by the general formula (3).
In order to bond the phenol compounds of the general formula (3) to each other by the group represented by the general formula (2), the phenol compound of the general formula (3) and the compound represented by the general formula (4) are combined. The method of the present invention comprising the addition condensation reaction in the presence of an acidic catalyst is particularly preferable in that a polyhydric phenol compound with good purity can be obtained by an easy operation.

When the phenol compound of the general formula (3) and the compound represented by the general formula (4) are subjected to an addition condensation reaction,
General formula (4) for the phenol compound of general formula (3)
Regarding the usage rate of the compound represented by the formula (4),
As the proportion of the compound becomes larger, the obtained polyhydric phenol compound has a higher molecular weight and contributes to the improvement of the heat resistance of the cured product. On the other hand, since the resin has a high viscosity, the flowability of the composition deteriorates. Therefore, the use ratio thereof needs to be adjusted according to the purpose of use, but usually 0.1 to 10 of the compound represented by the general formula (4) per 1 mol of the phenol compound of the general formula (3). Mol, preferably 0.15-0.8
It is a mole. As the reaction conditions for the addition condensation reaction, general novolak reaction conditions can be used. That is, in the presence of an acidic catalyst, at a temperature of 20 to 200 ° C.
The condition of reacting for 20 hours can be adopted.

Examples of the acidic catalyst to be used include mineral acids such as hydrochloric acid and sulfuric acid; organic acids such as oxalic acid and toluenesulfonic acid; heteropolyacids such as silicotungstic acid and phosphotungstic acid; activated clay; Acidic catalysts for producing novolak resins such as organic acid salts can be used. The amount of the acidic catalyst used is 0.1 to 5 parts by mass, preferably 0.3 to 3 parts by mass, relative to 100 parts by mass of the phenol compound of the general formula (3). In the condensation reaction, an inert solvent such as aromatic hydrocarbons, alcohols and ethers is used. A ketone solvent can also be used by selecting the reaction conditions.

After completion of the reaction, if necessary, an acidic catalyst, a salt thereof when neutralized, an unreacted phenol compound, a reaction solvent, and the like are removed to obtain a phenol resin comprising the polyhydric phenol compound of the present invention. can get. When the obtained phenol resin is used for semiconductor encapsulant, in order to prevent corrosion of the manufactured semiconductor device, the acidic catalyst or its salt may be removed by a method such as washing with water, filtration or adsorption. preferable.

The general formula (1) produced as described above
The quality properties of the phenolic resin composed of the polyhydric phenol compound of the present invention are:
Although it varies depending on the purification method and the like, when the phenol resin comprising the polyhydric phenol compound of the present invention is used as a curing agent for epoxy resin, the polyhydric phenol compound produced has a hydroxyl group equivalent of 130 to 230 g / eq. , Preferably 150 to 200 g / eq. And the average value of n in the general formula (1) is 0 to 8, preferably 0.2 to 3,
A softening point of 50 to 140 ° C., preferably 60 to 100 ° C.,
It is preferable to adjust various conditions in the reaction so that the melt viscosity at 150 ° C. is 0.8 Pa · s or less, preferably 0.5 Pa · s or less.

The curing agent for an epoxy resin of the present invention is a curing agent containing a polyhydric phenol compound obtained as described above as a main component, and is an epoxy resin curing agent excellent in low hygroscopicity and low stress. You can give things. That is, the curing agent for epoxy resin of the present invention may be the one using the polyhydric phenol compound alone, or may be the one using the other curing agent for epoxy resin in combination. Examples of other curing agents for epoxy resins that can be used in combination include phenol resins such as novolac type phenol resin, phenol aralkyl resin, dicyclopentadiene phenol resin, and terpene phenol resin; tetrahydrophthalic anhydride, pyromellitic anhydride, etc. Acid anhydrides; amines such as diaminodiphenylmethane and the like.

When the epoxy resin curing agent of the present invention is used for semiconductor encapsulation, other curing agents used in combination include novolac type phenol resin, phenol aralkyl resin, dicyclopentadiene phenol resin and terpene phenol. Phenolic resins such as resins are preferred. The amount of other curing agents used together is 9 with respect to the total amount of curing agents.
It is 0 mass% or less, preferably 50 mass% or less, and more preferably 30 mass% or less. If the combined amount of other curing agents is too large, the effect of the phenol resin of the present invention as a curing agent will not be sufficiently exhibited.

The polyhydric phenol compound, which is the main component of the curing agent for epoxy resin of the present invention, and the above-mentioned other curing agent for epoxy resin which can be used in combination may be mixed in advance before being made into a composition. The required amount of each can be provided individually when the composition is blended.

The quality properties of the curing agent for an epoxy resin of the present invention produced as described above vary depending on the type of each component, the usage ratio, etc., but the hydroxyl equivalent is 130 to 230 g.
/ Eq. , Preferably 150 to 200 g / eq. , The softening point is 50 to 140 ° C., preferably 60 to 100 ° C., 15
The melt viscosity at 0 ° C. is 0.8 Pa · s or less, preferably 0.
It is preferable to adjust various conditions so that the pressure is 5 Pa · s or less. If the hydroxyl equivalent is too small, it is inferior in low hygroscopicity,
If it is too large, the curability deteriorates. If the softening point is too low, it will be difficult to handle it as a solid, and if it is too high, it will be difficult to mix it with an epoxy resin or the like. If the melt viscosity is too high, the fluidity during molding will be impaired.

Next, the epoxy resin composition of the present invention is an epoxy resin composition obtained by mixing the epoxy resin and the curing agent for epoxy resin of the present invention as essential components. The epoxy resin used in this epoxy resin composition is not particularly limited, and a general epoxy resin can be used. Examples of the epoxy resin used include bisphenol A, bisphenol F, bisphenol AD, biphenol, tetramethylbiphenol, terpene diphenol, hydroquinone, methylhydroquinone, dibutylhydroquinone, resorcin, methylresorcin,
Various phenols such as bisphenol S, thiodiphenol, dihydroxydiphenyl ether, dihydroxynaphthalene, phenol novolac resin, cresol novolac resin, bisphenol A novolac resin, dicyclopentadiene phenol resin, terpene phenol resin, phenol aralkyl resin and naphthol novolac resin,

The polyhydric phenol resin obtained by the condensation reaction of various phenols with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde and glyoxal, petroleum heavy oil or pitches, formaldehyde polymer and phenols are prepared. Various phenolic compounds such as modified phenolic resin polycondensed in the presence of an acid catalyst, and various amine compounds such as epoxy resin and diaminodiphenylmethane, aminophenol, xylenediamine, and epihalohydrin, and epihalohydrin And epoxy resins produced from various carboxylic acids such as methylhexahydroxyphthalic acid and dimer acid, and epihalohydrin.

When the epoxy resin composition of the present invention is used for semiconductor encapsulation, the epoxy resin is selected from bisphenol A, bisphenol F, biphenol, tetramethylbiphenol, terpene diphenol and cresol novolac resin. It is preferable to use an epoxy resin produced from at least one phenol compound and epihalohydrin.

The amount of the curing agent for epoxy resin of the present invention used in the epoxy resin composition of the present invention is such that 1 mol of epoxy groups in all epoxy resin components reacts with epoxy groups in all curing agents. The amount of the group to be added is preferably 0.5 to 2.0 mol, more preferably 0.7 to 1.2 mol.

Various additives can be added to the epoxy resin composition of the present invention in the same manner as other general epoxy resin compositions. Examples of these various additives include, for example,
A curing accelerator, an inorganic filler, a coupling agent, a flame retardant, a plasticizer, a reactive diluent, a pigment and the like can be mentioned, and they can be appropriately blended if necessary.

Examples of the curing accelerator include phosphine compounds such as tributylphosphine, triphenylphosphine, tris (dimethoxyphenyl) phosphine, tris (hydroxypropyl) phosphine, tris (cyanoethyl) phosphine, tetraphenylphosphonium tetraphenylborate, and the like. Phosphonium salts such as methyltributylphosphonium tetraphenylborate and methyltricyanoethylphosphonium tetraphenylborate, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2- Methylimidazole, 2,4-dicyano-6- [2-methylimidazolyl- (1)]-ethyl S-triazine, 2,4-dicyano-6- [2-undecyl Imidazolyl - (1)] - imidazoles, such as ethyl S- triazine, 1-cyanoethyl-2-undecyl imidazolium trimellitate Te -
2-methylimidazolium isocyanurate, 2-
Imidazolium salts such as ethyl-4-methylimidazolium tetraphenylborate and -1,4-dimethylimidazolium tetraphenylborate,

Amine such as 2,4,6-tris (dimethylaminomethyl) phenol, benzyldimethylamine, tetramethylbutylguanidine, N-methylpiperazine, 2-dimethylamino-1-pyrroline, triethylammonium tetraphenylborate, etc. Ammonium salt of 1,5-diazabicyclo (5.4.0) -7-undecene, 1,5-diazabicyclo (4.3.0) -5
-Nonene, diazabicyclo compounds such as 1,4-diazabicyclo (2.2.2) -octane, tetraphenylborate, phenol salt, phenol novolac salt and 2-ethylhexanoate of these diazabicyclo compounds may be mentioned. Among the compounds serving as the curing accelerator, phosphine compounds, imidazole compounds, diazabicyclo compounds, and salts thereof are preferable.

Examples of the filler include fused silica, crystalline silica, glass powder, alumina and calcium carbonate. When the epoxy resin composition of the present invention is used for semiconductor encapsulation, a crushed and / or spherical fused and / or crystalline silica powder filler is used as the inorganic filler in an amount of 80% of the total composition. It is preferable to mix it in an amount of ˜95 mass%.

As the flame retardant, halogen-based flame retardants such as brominated epoxy resins and brominated phenol resins, antimony compounds such as antimony trioxide, phosphorus-based flame retardants such as red phosphorus, phosphoric acid esters and phosphines. , Nitrogen-based flame retardants such as melamine derivatives and aluminum hydroxide,
Examples include inorganic flame retardants such as magnesium hydroxide.

In the resin-encapsulated semiconductor device of the present invention, a semiconductor element such as an integrated circuit, a large-scale integrated circuit, a transistor, a thyristor, a diode and / or a semiconductor integrated circuit is the epoxy resin composition for semiconductor encapsulation of the present invention. It is a semiconductor device sealed with a cured product, and is not particularly limited to the type of semiconductor element and / or semiconductor integrated circuit, the sealing method, the package shape, and the like. The sealing method includes a low pressure transfer molding method, an injection molding method, a press molding method and the like.

The curing conditions at the time of molding and / or after molding differ depending on the type of each component of the epoxy resin composition and the compounding amount, but it is usually from 30 seconds to 10 at a temperature of 150 to 220 ° C.
It's time. The package shape of the resin-encapsulated semiconductor device is a lead frame type such as DIP, ZIP, SOP, SOJ, and QFP, a single-sided encapsulation type such as BGA, and T.
AB, CSP, etc.

The phenolic resin comprising the novel polyhydric phenol compound of the present invention can be used for various purposes. When the phenolic resin is used as the main component of the curing agent for epoxy resin, it has low hygroscopicity and high heat resistance. It provides a cured product having excellent properties and low stress. Further, the epoxy resin composition of the present invention using the curing agent is excellent in low hygroscopicity and heat resistance, and further gives a cured product excellent in low stress, so that it is useful for electrical and electronic fields, particularly for semiconductor encapsulation applications. Is. Further, the semiconductor device of the present invention is excellent in solder crack resistance.

[0053]

[Examples] The following are production examples of a phenol resin comprising the polyhydric phenol compound of the present invention, examples of a curing agent for an epoxy resin of the present invention, and further examples and comparative examples of an epoxy resin composition of the present invention. I will give you.

[Manufacturing Example of Polyhydric Phenol Compound] <Manufacturing Example 1> A three-necked flask having an internal capacity of 2 L equipped with a thermometer, a stirrer, and a cooling tube was charged with 564 g of phenol and 1.4 g of paratoluenesulfonic acid. The temperature was raised to ° C.
While stirring, 201 g of 3-phenyl-2-propen-1-ol was added dropwise over 1 hour. The temperature in the flask rose to 140 ° C. due to the heat of reaction. In the meantime, the produced water was distilled off. After dropping, keep the temperature at 140 ° C and
The reaction was held for a time period. Then, after cooling to 80 ° C., 500 g of toluene was added, and the system was washed with water until it became neutral. Then, toluene and unreacted phenol were distilled off under reduced pressure of 160 ° C. and 5 torr to obtain a target polyhydric phenol compound. This polyhydric phenol compound has a phenolic hydroxyl group equivalent of 176 g / eq. , Softening point 71 ° C,
It was a reddish brown solid having a melt viscosity of 0.06 Pa · s at 150 ° C. Its chemical structure is, by NMR and GPC analysis, in the general formula (1), a = 0, n has an average value of 0.6, and all Z's have all R ³ hydrogen atoms, It was a group represented by the above general formula (2) in which b = 0.

FIG. 1 shows an NMR chart of the polyhydric phenol compound obtained in Production Example 1 above. ¹ H-NMR 270 MHz solvent; CDCl _{3 A} GPC chart is shown in FIG. Column; Tosoh TSK Gel H4000 + H300
0 × 2 + H2000 detector; UV 254 nm flow rate; THF 0.5 ml / min Injection; 10 μL Sample; 1% wt

<Production Example 2> A polyhydric phenol compound was obtained in the same manner as in Production Example 1 except that the amount of phenol used was 282 g. This polyhydric phenol compound has a phenolic hydroxyl group equivalent of 181 g /
eq. , Softening point 88 ℃, melt viscosity at 150 ℃ 0.28
It was a Pa · s reddish brown solid. Its chemical structure is a = 0 in the general formula (1), n has an average value of 1.2, all Z's are all R ³ hydrogen atoms, and b = 0.
Was a group represented by the general formula (2).

<Production Example 3> Phenol 376 was placed in a three-necked flask having an internal volume of 2 L equipped with a thermometer, a stirrer, and a cooling tube.
g, p-toluenesulfonic acid 1.9 g, and 80 ° C
The temperature was raised to. While stirring, 83.3 g of 36% aqueous formaldehyde solution was added dropwise over 1 hour. Subsequently, 148 g of 1-methoxy-3-phenyl-2-propene was added dropwise over 1 hour. The temperature in the flask is 140 ° C due to heat of reaction
Rose to. Meanwhile, water and methanol were distilled off. After the completion of the dropping, the reaction was carried out by maintaining the temperature at 140 ° C. for 3 hours. Then, after cooling to 80 ° C., 500 g of toluene was added, and the system was washed with water until it became neutral. Then, toluene and unreacted phenol were distilled off under reduced pressure of 160 ° C. and 5 torr to obtain a target polyhydric phenol compound. This polyhydric phenol compound has a phenolic hydroxyl group equivalent of 141 g / eq. It was a reddish brown solid having a softening point of 83 ° C. and a melt viscosity of 0.18 Pa · s at 150 ° C. Its chemical structure is represented by the general formula (1) in which Z is about 50 mol%.
Is a group represented by the general formula (2) in which all R ³ are hydrogen atoms and b = 0, the remaining Z is a methylene group, a = 0, and n is 1. It was 3.

<Production Example 4> Phenol 376 was placed in a three-necked flask having an internal volume of 2 L equipped with a thermometer, a stirrer, and a cooling tube.
g, p-toluenesulfonic acid 1.9 g, and 120
The temperature was raised to ° C. While stirring, 100 g of α, α′-dimethoxyparaxylene was added dropwise over 1 hour. Then 3
88 g of -phenyl-2-propen-1-ol was added dropwise over 1 hour. The temperature in the flask is 140 ° C due to heat of reaction
Rose to. Meanwhile, water and methanol were distilled off. After the completion of the dropping, the reaction was carried out by maintaining the temperature at 140 ° C. for 3 hours. Then, after cooling to 80 ° C., 500 g of toluene was added, and the system was washed with water until it became neutral. Then, toluene and unreacted phenol were distilled off under reduced pressure of 160 ° C. and 5 torr to obtain a target polyhydric phenol compound. This polyhydric phenol compound has a phenolic hydroxyl group equivalent of 180 g / eq. It was a reddish brown solid having a softening point of 85 ° C. and a melt viscosity of 0.20 Pa · s at 150 ° C. Its chemical structure is represented by the general formula (1) in which Z is about 70 mol%.
Is a group represented by the general formula (2) in which all R ³ are hydrogen atoms and b = 0, the remaining Z is a paraxylylene group, a = 0, and n is 1. It was 3.

[Curing Agent for Epoxy Resin] Examples 1 to 5 Phenol novolac resins and phenol aralkyl resins are listed as other epoxy resin curing agents that can be used in combination with the phenol resins of Production Examples 1 to 4 as polyhydric phenol compounds. Each of the epoxy resin curing agents was manufactured by melt-mixing with the composition shown in 1. Table 1 shows the melt viscosity, hydroxyl group equivalent and softening point of these epoxy resin curing agents.

[Epoxy Resin Compositions] Examples 6 to 11 and Comparative Examples 1 to 2 Epoxy resins, epoxy resins derived from biphenol and tetramethyl biphenol, and Examples 1 to 5 with the formulations shown in Table 2. Hardener for epoxy resin, manufactured by
Using inorganic filler, triphenylphosphine as a curing accelerator, epoxysilane as a coupling agent, and carnauba wax as a release agent,
Each epoxy resin composition was manufactured. Then, each composition was melt-kneaded for 5 minutes at a temperature of 70 to 120 ° C. using a mixing roll. Each of the obtained molten mixtures was taken out in the form of a thin plate, cooled, and then pulverized to obtain each molding material. Each of these molding materials was molded by a low-pressure transfer molding machine at a mold temperature of 175 ° C. for a molding time of 180 seconds to obtain each test piece, which was post-cured at 180 ° C. for 8 hours.

Table 2 shows the results of testing the moisture absorption rate, glass transition temperature, high temperature elastic modulus, and flame retardancy of each test piece after post-curing. Further, the results of testing the solder crack resistance of the simulated semiconductor device sealed with each molding material are shown in Table 2.
It was shown to. As is clear from these test results, each of the molding materials of Examples 6 to 11 has lower hygroscopicity and lower stress (that is, lower high temperature elastic modulus) than the molding materials of Comparative Examples 1 and 2. Excellent balance and resistance to solder cracking.

[0062]

[Table 1]

[0063]

[Table 2]

[0064]

INDUSTRIAL APPLICABILITY The polyhydric phenol compound of the present invention, when used as a main component of a curing agent for epoxy resin, can give a cured product excellent in low hygroscopicity and low stress. The epoxy resin composition of the present invention using can be advantageously used for semiconductor encapsulation.

[Brief description of drawings]

FIG. 1 is a nuclear magnetic resonance spectrum diagram of a polyhydric phenol compound obtained in Production Example 1.

FIG. 2 is a gel permeation chromatography chart of the polyhydric phenol compound obtained in Production Example 1.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Akihiro Ito             Japane, Shiohama-cho, Yokkaichi-shi, Mie             Poxy Resin Co., Ltd. F-term (reference) 4J032 CA00 CA04 CB03 CB13 CC01                       CE05 CE22 CG01                 4J036 AD08 AF05 AF06 AF08 AF19                       AF22 AF26 AF27 AF29 AK01                       BA02 BA03 BA06 DB17 DC03                       DC09 DC10 DC41 DC45 DC46                       DD07 FA02 FA03 FA05 FA06                       FA12 FB06 FB07 FB08 GA01                       GA04 JA07                 4M109 EA02 EB03 EB13

Claims (9)

[Claims] 1. A phenol resin comprising a polyhydric phenol compound represented by the following general formula (1). [Chemical 1] [In the formula, R ^{1 s} may be the same as or different from each other, and are substituted with a group selected from an alkyl group having 1 to 10 carbon atoms, an unsubstituted group, an alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom. A phenyl group, an unsubstituted or alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom, which are substituted with a group selected from an aralkyl group, an alkoxy group having 1 to 10 carbon atoms and a halogen atom. is there. All or part of Z is a group represented by the following general formula (2), and the rest is a direct bond or an alkylene group having 1 to 10 carbon atoms. [Chemical 2] (In the formula, R ^{2 s} may be the same as or different from each other, and are substituted with a group selected from an alkyl group having 1 to 10 carbon atoms, an unsubstituted group, an alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom. A phenyl group, an unsubstituted or alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom, which are substituted with a group selected from an aralkyl group, an alkoxy group having 1 to 10 carbon atoms and a halogen atom. R ^{3 s} may be the same or different from each other and are a group selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an unsubstituted or alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom. A substituted phenyl group and an unsubstituted or alkyl group,
It is a group selected from an aralkyl group substituted with a group selected from a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom. b is an integer of 0-5. ) N is a number from 0 to 8 on average. a is an integer of 0-4. ] 2. In the general formula (1), a is 0, Z is a group in which the substituent R ³ in the group represented by the general formula (2) is hydrogen, and b is 0. A phenolic resin comprising the polyhydric phenol compound according to claim 1. 3. A curing agent for an epoxy resin, comprising 10 to 100% by mass of a phenolic resin comprising the polyhydric phenol compound according to claim 1 or 2 in the total curing agent for an epoxy resin. 4. An epoxy resin composition containing an epoxy resin and the curing agent for an epoxy resin according to claim 3 as essential components. 5. The epoxy resin is prepared by reacting at least one phenol compound selected from bisphenol A, bisphenol F, biphenol, tetramethylbiphenol, terpene diphenol, dicyclopentadiene phenol resin and cresol novolac resin with epihalohydrin. The epoxy resin composition according to claim 4, which is the obtained epoxy resin. 6. An inorganic material comprising the epoxy resin composition according to claim 4 or 5, and a fused silica powder and / or a crystalline silica powder, which is 80 to 95% by mass of the total composition and is crushed and / or spherical. An epoxy resin composition for semiconductor encapsulation containing a filler. 7. A resin-encapsulated semiconductor device, which is encapsulated with a cured product of the epoxy resin composition for semiconductor encapsulation according to claim 6. 8. The following general formula (3): (In the formula, R ^{1 s} may be the same as or different from each other, and are substituted with a group selected from an alkyl group having 1 to 10 carbon atoms, an unsubstituted group, an alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom. A phenyl group, an unsubstituted or alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom, which are substituted with a group selected from an aralkyl group, an alkoxy group having 1 to 10 carbon atoms and a halogen atom. A is an integer of 0 to 4) and a phenol compound represented by the following general formula (4): (In the formula, R ^{2 s} may be the same as or different from each other, and are substituted with a group selected from an alkyl group having 1 to 10 carbon atoms, an unsubstituted group, an alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom. A phenyl group, an unsubstituted or alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom, which are substituted with a group selected from an aralkyl group, an alkoxy group having 1 to 10 carbon atoms and a halogen atom. R ^{3 s} may be the same or different from each other and are a group selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an unsubstituted or alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom. A substituted phenyl group and an unsubstituted or alkyl group,
It is a group selected from an aralkyl group substituted with a group selected from a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom. R ⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. b is an integer of 0-5. And a compound represented by the formula (1)) in the presence of an acidic catalyst for addition condensation reaction. [In the formula, R ^{1 s} may be the same as or different from each other, and are substituted with a group selected from an alkyl group having 1 to 10 carbon atoms, an unsubstituted group, an alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom. A phenyl group, an unsubstituted or alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom, which are substituted with a group selected from an aralkyl group, an alkoxy group having 1 to 10 carbon atoms and a halogen atom. is there. All or part of Z is a group represented by the following general formula (2), and the rest is a direct bond or an alkylene group having 1 to 10 carbon atoms. [Chemical 6] (In the formula, R ^{2 s} may be the same as or different from each other, and are substituted with a group selected from an alkyl group having 1 to 10 carbon atoms, an unsubstituted group, an alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom. A phenyl group, an unsubstituted or alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom, which are substituted with a group selected from an aralkyl group, an alkoxy group having 1 to 10 carbon atoms and a halogen atom. R ^{3 s} may be the same or different from each other and are a group selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an unsubstituted or alkyl group, a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom. A substituted phenyl group and an unsubstituted or alkyl group,
It is a group selected from an aralkyl group substituted with a group selected from a hydroxyl group, an alkoxy group, an aralkyl group and a halogen atom. b is an integer of 0-5. ) N is a number from 0 to 8 on average. a is an integer of 0-4. ] The manufacturing method of the phenol resin which consists of the polyhydric phenol compound represented by these. 9. The phenol compound represented by the general formula (3) is phenol, cresol, xylenol, propylphenol, butylphenol, butylcresol, phenylphenol, cumylphenol, methoxyphenol, ethoxyphenol, phenoxyphenol, dihydroxy. Diphenyl ether, benzylphenol, bisphenol A, bisphenol F, bisphenol AD, biphenol, terpene diphenol, bisphenol S, thiodiphenol, dihydroxydiphenyl ether, dihydroxybenzophenone, 4,
A phenol compound selected from 4'-benzylidene bisphenol, 4,4 '-(4-methylbenzylidene) bisphenol, tetramethylbiphenol and bromophenol, wherein the compound represented by the general formula (4) is
3-phenyl-2-propen-1-ol, 2-methyl-3-phenyl-2-propen-1-ol, 1-methoxy-3-phenyl-2-propene and 1-methoxy-
The method for producing a phenol resin comprising a polyhydric phenol compound according to claim 8, which is a compound selected from 2-methyl-3-phenyl-2-propene.