JP2003147052A - Flame-retardant epoxy resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant epoxy resin composition having high level flame retardance and excellent in moldability and heat resistance to soldering. SOLUTION: This flame-retardant epoxy resin composition comprises an epoxy resin, a curing agent, a metal hydroxide and an expansive graphite. The curing agent is a phenolic resin (C) containing a unit derived from phenols (A) and a unit derived from aromatics (B) excluding these phenols (A) in the molecular chain.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to flame resistance, heat resistance,
The present invention relates to a flame-retardant epoxy resin composition having excellent moldability and safety, and a varnish solution, a prepreg, a laminated board and a semiconductor device produced by using the flame-retardant epoxy resin composition.

[0002]

2. Description of the Related Art Conventionally, in order to prevent fire, when an epoxy resin composition is required to have a flame retardant property, a halogen-based flame retardant is usually used as a flame retardant and an antimony trioxide is used as a flame retardant aid. Came.

However, when the above-mentioned flame retardant or flame retardant aid is used in the epoxy resin composition, in addition to the problem of safety,
Since it promotes metal corrosion, there is a problem in its application in this respect. For example, when such an epoxy resin composition is used as an insulating material for an electronic component, the wiring corrosion resistance particularly at high temperature is lowered, and the reliability of the electronic component may be impaired. Therefore, it has been desired to develop an epoxy resin composition that does not use a halogen-based flame retardant or antimony trioxide.

As a method of imparting flame retardancy without using a halogen-based flame retardant or the like, a method of blending a metal hydroxide in an epoxy resin composition is known. However, the flame retardant effect due to the metal hydroxide is mainly due to the combustion suppressing action by lowering the temperature of the resin cured body (endothermic),
It is positioned as an auxiliary means for imparting flame retardancy. Therefore, in order to obtain sufficient flame retardancy by the above endothermic action, it is necessary to add a large amount. For this reason, in electronic parts and the like, its formability and the like are significantly reduced, and its application is difficult. Also, when using a metal hydroxide, although the flame retardancy is improved,
Sufficient flame retardance (For example, UL94V-
With the addition amount of metal hydroxide necessary to satisfy 0),
In some cases, high solder heat resistance could not be satisfied. In other words, the lead-free soldering process, which has been widely used recently as a means for mounting electric / electronic components (including semiconductor devices) on a laminated board, has a wider range of use than the conventional lead soldering process. Since the laminated plate was exposed to high temperature, defects sometimes occurred. Further, it is well known that the dielectric properties of the laminated plate tend to decrease (the relative dielectric constant increases) as the amount of the metal hydroxide is increased, and it is almost the same as that of the conventional FR-4 grade laminated plate. In order to satisfy the above-mentioned dielectric properties, it has been desired to reduce the amount of metal hydroxide used as much as possible.

Particularly, regarding a flame-retardant epoxy resin composition for producing a laminated plate obtained by impregnating and curing an epoxy resin composition in glass fiber or the like, when a large amount of metal hydroxide is added, various flame retardant epoxy resin compositions are produced. Challenges arise. in this regard,
This will be described below.

The first problem is that the workability of the laminated plate is impaired. In this regard, for example, in "Latest Flame Retardant / Flame Retardant Technology (Technical Information Institute, issued July 30, 1999)", pages 270 to 271, a large amount of aluminum hydroxide is added (epoxy resin composition). UL94V-0 can be achieved by adjusting the total amount to 75% by mass, but the compounding amount is unrealistic from a practical point of view. "Punching / drilling workability in the printed wiring board working process, and component mounting There is a problem in the solder processing step at that time. ”

The second problem is that the dielectric constant increases and the moisture resistance and solder heat resistance decrease. In laminated plate applications, it is essential that these physical properties be maintained well, but since metal hydroxide easily absorbs moisture and has a high dielectric constant, it causes a decrease in the above physical properties when added in a large amount. is there.

In particular, among the above-mentioned second problems, the problems of deterioration in moisture resistance and solder heat resistance also occur in semiconductor device applications. Therefore, by using a combination of an existing epoxy resin and a curing agent with a metal hydroxide alone, a high level of flame retardancy is realized while maintaining various properties required for laminated boards and semiconductor device applications at high levels. Things could be difficult.

On the other hand, various studies have been made to impart flame retardancy by changing the molecular structures of epoxy resins and curing agents. JP-A No. 11-140277 discloses a novolak structure phenolic resin containing a biphenyl derivative and / or a naphthalene derivative in the molecule, a novolak structure epoxy resin containing a biphenyl derivative and / or a naphthalene derivative in the molecule, and an inorganic filler. Also disclosed is a semiconductor encapsulating epoxy resin composition containing no flame retardant and containing a curing accelerator as an essential component.

The above-mentioned epoxy resin composition for semiconductor encapsulation is
Since a phenolic resin or epoxy resin containing polyaromatics such as a biphenyl derivative or a naphthalene derivative reacts in the structure to form a crosslinked structure, when ignited,
The surface of the resin composition expands like a rubber to form a foam layer. This foamed layer cuts off the supply of heat and oxygen to the unburned portion, and exhibits high flame retardancy.

However, the above resin composition is designed so as to be suitable for semiconductor encapsulation applications, and when it is applied to other applications such as laminated board applications, sufficient flame retardancy is not always obtained. . This is because there is a base material such as glass woven fabric or glass non-woven fabric that prevents the deformation (expansion) of the resin component in the structure of the laminated plate, so that it is difficult to form a stable foam layer at the time of ignition. It is a thing.

[0012]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and provides a flame-retardant epoxy resin composition which realizes an unprecedentedly high level of flame retardancy and safety. With the goal.

In particular, in the flame-retardant epoxy resin composition used for manufacturing laminated boards and semiconductor devices, various physical properties required for laminated boards and semiconductor devices, that is, solder heat resistance,
The purpose is to impart high flame retardancy while maintaining good moldability (flowability) and the like.

[0014]

According to the present invention for solving the above problems, an epoxy resin, a curing agent, a metal hydroxide and expandable graphite are contained, and at least one of the epoxy resin and the curing agent is A flame-retardant epoxy containing a compound having a constitutional unit derived from a phenol (A) and a constitutional unit derived from an aromatic (B) excluding the phenol (A) in the molecule. A resin composition is provided.

Further, according to the present invention, in the above flame-retardant epoxy resin composition, the curing agent is a structural unit derived from a phenol (A) and the phenol (A).
A flame-retardant epoxy resin composition comprising a phenolic resin (C) containing a structural unit derived from an aromatics (B) except for in a molecular chain. According to the invention, in the flame-retardant epoxy resin composition,
The epoxy resin is a phenolic resin (C) containing a structural unit derived from a phenol (A) and a structural unit derived from an aromatic (B) excluding the phenol (A) in a molecular chain. There is provided a flame-retardant epoxy resin composition comprising the epoxy resin (D) in which the phenolic hydroxyl group of (1) is glycidyl etherified. Here, both the epoxy resin and the curing agent can employ the compound having the specific structure. In this case, with the epoxy resin and the curing agent, phenols (A), aromatics (B),
The phenolic resins (C) may be the same or different.

The above flame-retardant epoxy resin composition can be suitably used for laminated plate applications, encapsulating material applications, liquid encapsulating material applications, and the like. The purpose of laminated plate is to impregnate and cure the base material,
Refers to the application used to form the laminate. The encapsulating material application refers to an application used in a package such as an LSI to seal a semiconductor element. In particular, the use of a liquid encapsulant refers to an application of encapsulating with a liquid resin.

In the use of laminated plates, the workability of the substrate is required, so that it is required to reduce the compounding amount of the metal hydroxide, and the flame retardant epoxy resin composition is preferably 1 to The content is 50% by mass.

For use as a sealing material, from the viewpoint of reducing the coefficient of thermal expansion and the like, it is preferable to add silica to the composition, for example, containing 30 to 99% by mass of silica.

For liquid encapsulant applications, the composition should be at 20 ° C to 8 ° C.
Viscosity at any temperature of 0 ° C is 10,000 cps
The following is preferable. By doing so, the flame-retardant epoxy resin composition according to the present invention sufficiently penetrates into the gaps of the semiconductor element, and good sealing characteristics are obtained. In addition,
Any temperature of 20 ° C. to 80 ° C. corresponds to the temperature at which the composition is used, and is appropriately selected depending on the application and the properties of the composition. The liquid resin encapsulant can be produced by sufficiently mixing the respective components, further kneading with, for example, a disper, a kneader, a triple roll, etc., and then defoaming under reduced pressure. The liquid resin encapsulant thus produced is discharged onto a semiconductor chip mounted in a syringe and mounted using a dispenser and cured by heating to produce a semiconductor device encapsulated with a cured product of the liquid resin encapsulant. You can In this case, the tip of the syringe may be heated to improve the fluidity of the liquid resin sealing material before use.

According to the present invention, an epoxy resin varnish solution obtained by dispersing the flame-retardant epoxy resin composition in an organic solvent, a prepreg obtained by impregnating a substrate with the flame-retardant epoxy resin composition and curing the same. Further, a laminated plate is provided in which a plurality of the prepregs are stacked and heated and pressed. Also provided is a semiconductor device obtained by encapsulating a semiconductor element using the flame-retardant epoxy resin composition.

The present invention realizes a high flame-retardant effect by using the above-mentioned phenolic resin or epoxy resin having a specific structure and further using a metal hydroxide and expansive graphite in combination. In particular, when the phenolic resin having the above specific structure and the epoxy resin having the above specific structure are used in combination, a more remarkable flame retardant effect can be obtained. Further, by using the metal hydroxide and the expandable graphite in combination, a marked flame retarding effect that can be expected when each component is used alone is exhibited. In addition, the laminate and the semiconductor device using the flame-retardant epoxy resin composition of the present invention, since the total amount of the metal hydroxide and expandable graphite contained can be minimized, solder heat resistance, moldability,
It is extremely excellent in practicality such as electrical characteristics.

The flame-retardant epoxy resin composition of the present invention comprises a phenolic resin containing a structural unit derived from a phenol (A) and a structural unit derived from an aromatic (B) in a molecular chain ( C) and / or the epoxy resin (D) obtained by glycidyl etherifying the phenolic hydroxyl group of the phenolic resin (C), and further contains a metal hydroxide and expandable graphite. Therefore, as shown below, a high degree of flame retardant effect due to these synergistic effects can be obtained.

A cured product of an epoxy resin composition in which a phenolic resin (C) and / or an epoxy resin (D) containing an aromatic compound (B) in a molecular skeleton forms a crosslinked structure is a cured product upon ignition. The decomposition gas internally generated inherently has a property that the resin layer on the surface expands like a rubber to form a stable foam layer. However, when there is a base material such as glass woven cloth or non-woven glass cloth that prevents deformation (expansion) of the resin component in the structure, a stable foam layer is not sufficiently formed at the time of ignition, and good flame retardancy is obtained. Becomes difficult.

On the other hand, the addition of the metal hydroxide promotes the formation of the foamed layer and improves the flame retardancy, but the addition amount of the metal hydroxide is related to the demand for various practical physical properties. However, it was difficult to balance the practical physical properties including flame retardancy with this method.

In the expansive graphite, the foaming agent of graphite evaporates and the interlayer expands, and exhibits a flame retardant effect by blocking heat. The expandable graphite is a graphite having a layered structure and a foaming agent supported between the layers.
It is disclosed in Japanese Patent No. 7405. As a foaming agent,
Sulfuric acid, nitric acid, etc. are used, and these foaming agents are supported between graphite layers having weak interaction to form expandable graphite. When the expansive graphite is heated to 200 ° C. or higher, the foaming agent between the layers evaporates, and the gas pressure expands the layers of the graphite to expand.
It has the property of increasing the volume. By incorporating this expansive graphite, the cured product of this resin composition causes a foaming phenomenon when it comes into contact with a flame, and flame retardation can be achieved by blocking heat. In the present invention, this expansive graphite,
It is not simply used as a flame retardant improver, but is used as a material for promoting the formation of a foam layer of a resin cured product having a specific structure. In a structure including a substrate that prevents deformation (expansion), the foamed layer of the epoxy cured product having the above-described specific structure is not sufficiently formed, and the original flame retardant effect of the epoxy resin cannot be obtained. There is. On the other hand, when expandable graphite is used in combination, the resin cured body constrained by the base material or the like is deformed by the volume expansion of the expandable graphite, and the foamed layer of the epoxy resin cured body is easily formed. . The foam layer once formed has high heat resistance and hot strength, and also contains water vapor generated by the thermal decomposition of metal hydroxide, which is a non-flammable gas even when the foam is broken. Will be emitted toward the combustion section.

As described above, in the present invention, the expandable graphite is used to form a foam layer having a higher flame-retardant effect derived from the epoxy cured product having a specific structure than the effect of imparting the flame retardancy of the expandable graphite itself. The acceleration contributes greatly to the effect obtained, and thereby realizes a high flame retardancy that has never been achieved.

As described above, according to the present invention, the combined use of the epoxy resin or the curing agent having the specific structure, the metal hydroxide and the expansive graphite promotes the formation of the expansive body having high hot strength and suppresses the combustion. The structure is suitable for
It is presumed that it has achieved a high degree of flame retardancy. For example, even in a structure that has a base material that prevents deformation (expansion) of resin components such as glass woven cloth and glass nonwoven cloth,
At the time of ignition, the flame contact part spontaneously expands (self-expanding) to become an expander that effectively blocks heat and oxygen, and exhibits a high degree of self-extinguishing performance.

According to the flame-retardant epoxy resin composition of the present invention, the epoxy resin having the above-mentioned specific structure, the curing agent, the metal hydroxide and the expansive graphite are used in combination, and the synergistic action thereof brings about high flame retardancy and practical use. Sex can be achieved. This allows
Since a remarkable flame retarding effect which is not available in the prior art can be obtained and the contents of metal hydroxide and expandable graphite can be minimized, a laminated board or a semiconductor device using the flame retardant epoxy resin composition of the present invention can be obtained. Satisfies the practical requirements such as high solder heat resistance and moldability.

In the present invention, an inorganic filler such as silica can also be used in combination. Inorganic fillers such as silica do not show an endothermic effect when burned like metal hydroxides, but they can be uniformly dispersed in the resin body, so that they function as a support and strengthen the expander. It is thought to play a role. Thus, it is considered that the inorganic filler such as silica plays a role of increasing the strength of the expandable body and improving the self-extinguishing performance of the expandable body.

The content ratio of each constituent in the present invention is appropriately designed according to its use. For example, the total amount of the epoxy resin and the curing agent is 1 with respect to the total amount of the flame-retardant epoxy resin composition. ~ 98% by mass, 1 to 1% metal hydroxide
50 mass% and expandable graphite are contained by 1 to 20 mass%.

[0031]

BEST MODE FOR CARRYING OUT THE INVENTION The phenol (A) in the present invention is not particularly limited as long as it is an aromatic compound having a phenolic hydroxyl group, and examples thereof include phenol, allylphenol, and α-naphthol. Naphthols such as β-naphthol, bisphenolfluorene type phenols, alkylphenols such as cresol, xylenol, ethylphenol, butylphenol, nonylphenol, octylphenol, polyphenols such as bisphenol A, bisphenol F, bisphenol S, resorcin, catechol, phenyl Examples include phenol and aminophenol. In addition, these phenols are not limited to one kind in use, and two or more kinds can be used in combination.

The aromatics (B) in the present invention are one or more aromatic compounds excluding the phenols (A). The aromatics (B) are not particularly limited and include, for example, condensates of benzene and its derivatives, biphenyl and its derivatives, benzene and its derivatives, diphenyl ether and its derivatives, fluorene and its derivatives, bisphenolfluorene and its derivatives. Examples thereof include derivatives, bisphenol S and its derivatives, bisphenol F and its derivatives, and bisphenol A and its derivatives. Of these, condensates of benzene and its derivatives, biphenyl and its derivatives,
Benzene and its derivatives are preferably used. This is because the flame-retardant effect is extremely high and the hydrophobicity is excellent, so that when these are introduced, the moisture resistance of the resin composition is significantly improved. Aromatic compounds (B) containing a biphenyl derivative
Is preferable because it has a high effect of improving flame retardancy. The reason for this is
Although it is not always clear, it is considered that the fact that the cured product of the resin containing the biphenyl derivative is easily foamed and that the biphenyl derivative itself has a high flash point influences. That is, when the biphenyl derivative is contained, the distance between the cross-linking points of the resin cured product becomes longer than that of the benzene derivative and the like, so that foaming is more likely to occur at the time of ignition and it can be assumed that flame retardancy is promoted. Further, in the resin composition of the present invention, a gaseous thermal decomposition product generated at the time of ignition foams the resin surface, but the thermal decomposition product itself is difficult to ignite, which also affects flame retardancy. I think I am doing it.
Since biphenyl itself is also generated from the resin composition containing the biphenyl derivative, the high flash point (110 ° C. for biphenyl, −10 ° C. for benzene) is also likely to have contributed to flame retardancy.

The aromatics (B) preferably have a bonding group having a chain structure containing an unsaturated bond having 1 to 6 carbon atoms or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.

An allyl group is an example of the linking group having a chain structure containing an unsaturated bond. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group and propyl group.

The phenolic resin (C) in the present invention is not particularly limited as long as it is a phenolic resin containing phenols (A) and aromatics (B) excluding phenols. Fused polycyclic aromatic type phenolic resin (pitch type phenolic resin), phenol aralkyl type resin (for example, phenol biphenylene aralkyl type resin, phenol phenylene aralkyl type resin, phenol diphenyl ether aralkyl type resin, etc.), naphthalene-containing phenol novolac type resin,
Examples thereof include anthracene-containing phenol novolac type resin, fluorene-containing phenol novolac type resin, bisphenol fluorene-containing phenol novolac type resin, bisphenol S-containing phenol novolac type resin, bisphenol F-containing phenol novolac type resin, and bisphenol A-containing phenol novolac type resin.
In addition, these phenolic resins are not limited to one kind in use, and two or more kinds can be used in combination.

Specific examples of the phenolic resin (C) are shown below. However, the present invention is not limited to these examples.

[0037]

[Chemical 1]

[0038]

[Chemical 2]

[0039]

[Chemical 3]

[0040]

[Chemical 4]

Further, the following condensed polycyclic aromatic type phenolic resin (pitch type phenolic resin) can also be used.

[0042]

[Chemical 5]

Among these, the condensed polycyclic aromatic phenolic resin (pitch phenolic resin) in which the aromatic compound (B) is a condensed product of benzene and its derivative, biphenyl and its derivative, or benzene and its derivative ) Or a phenol biphenyl aralkyl type resin or a phenol phenylene aralkyl type resin. This is preferable in that an epoxy resin composition having an appropriately low crosslink density can be obtained, and a rubber-like foam layer having excellent thermal decomposition resistance at the time of ignition is more preferably formed.
Furthermore, the condensate of benzene and its derivative, the biphenyl and its derivative, and the benzene and its derivative are excellent in hydrophobicity. Therefore, when these are introduced, the moisture resistance of the resin composition is also improved.

Phenolic resin (C) in the present invention
Preferably contains, for example, a repeating unit represented by any of the following formulas (I) to (IV).

[0045]

[Chemical 6] (In the formula, X ₁ and X ₂ each independently have 1 carbon atom.
A bond group having a chain structure containing an unsaturated bond of 1 to 6 or a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, R ₁
Represents a phenylene group, a biphenylene group, or a derivative thereof, and R ₂ represents hydrogen or a bonding group having a chain structure containing an unsaturated bond having 1 to 6 carbon atoms. By using a resin having such a repeating unit, a rubber-like foamed layer having excellent thermal decomposition resistance at the time of ignition is more preferably formed, and the moisture resistance of the resin composition is also improved.

In the flame-retardant epoxy resin composition of the present invention, a phenol resin other than the above-mentioned phenol resin (C) may be used in combination. In this case, the equivalent ratio of the phenolic resin (C) to the total amount of phenolic resin (1.0) is preferably 0.1 or more, more preferably 0.3 or more. If the content is too low, the flame retardancy may be insufficient.

In the flame-retardant epoxy resin composition of the present invention, in addition to the above-mentioned phenolic resin (C), other phenolic resins and amine compounds can be used in combination as a curing agent.

The phenolic resin which can be used in combination is not particularly limited, but examples thereof include phenol biphenylene triazine type resin, phenol phenylene triazine type resin, phenol triazine type resin and biphenyl resin.
4,4'-dihydroxyl tail and 3,3 ', 5
5'-tetramethylbiphenyl-4,4'-dihydroxyl ether, tetraphenylolethane, trisphenylolethane, phenol novolac resin, cresol novolac resin, bisphenol A type resin, bisphenol F type resin, bisphenol S type resin, polyphenol type Examples thereof include resins, resorcinol type resins, aliphatic phenol resins, aromatic ester type phenol resins, cycloaliphatic ester type phenol resins and ether ester type phenol resins.

The amine compound that can be used in combination is not particularly limited, and examples thereof include dicyandiamide, diaminodiphenylmethane, diethylenetriamine and diaminodiphenylsulfone.
These phenolic resins and amine compounds may be used alone or in combination of several kinds. Among these, phenol biphenylene triazine type resin, phenol phenylene triazine type resin, and phenol triazine type resin are particularly preferable from the viewpoint of flame retardancy enhancement.

The epoxy resin (D) in the present invention comprises a structural unit derived from a phenol (A) and a structural unit derived from an aromatic (B) excluding the phenol (A) in the molecular chain. Is an epoxy resin in which the phenolic hydroxyl group of the phenolic resin (C) contained in 1) is glycidyl etherified. As such an epoxy resin, for example, a condensed polycyclic aromatic type epoxy resin (epoxy compound of pitch-based phenol resin), a phenol aralkyl type epoxy resin (for example, phenol biphenylene aralkyl type epoxy resin, phenol phenylene aralkyl type epoxy resin, phenol Diphenyl ether aralkyl type epoxy resin, etc.), naphthalene-containing novolac type epoxy resin, anthracene-containing novolac type epoxy resin, fluorene-containing novolac type epoxy resin, bisphenol fluorene-containing novolac type epoxy resin, bisphenol S-containing novolac type epoxy resin, bisphenol F-containing novolac type epoxy resin Examples thereof include epoxy resin and bisphenol A-containing novolac type epoxy resin. Further, these epoxy resins are not limited to one kind in use, and two or more kinds can be used in combination.

Specific examples of the epoxy resin (D) of the present invention are shown below. However, the present invention is not limited to these examples. In the formula, "G" represents a glycidyl group.

[0052]

[Chemical 7]

[0053]

[Chemical 8]

[0054]

[Chemical 9]

[0055]

[Chemical 10]

Among these, the condensed polycyclic aromatic type epoxy resin (of the pitch-based phenolic resin) in which the aromatic compound (B) is a condensate of benzene and its derivative, biphenyl and its derivative, or benzene and its derivative Epoxide)
Alternatively, it is preferably a phenol biphenylene aralkyl type epoxy resin or a phenol phenylene aralkyl type epoxy resin. This is preferable in that an epoxy resin composition having an appropriately low crosslink density can be obtained, and a rubber-like foam layer having excellent thermal decomposition resistance at the time of ignition is more preferably formed. Furthermore, since the condensation product of benzene and its derivative, the biphenyl and its derivative, and the benzene and its derivative are excellent in hydrophobicity, the introduction of them also improves the moisture resistance of the resin composition.

In the flame-retardant epoxy resin composition of the present invention, other epoxy resin can be used in combination with the above epoxy resin (D). in this case,
The equivalent ratio of the epoxy resin (D) to the total epoxy resin amount (1.0) is preferably 0.1 or more, and more preferably 0.3 or more. If the content is too low, the flame retardancy may be insufficient.

The epoxy resin which can be used in combination with the epoxy resin (D) is not particularly limited, but for example,
Phenol biphenylene triazine type epoxy resin, phenol phenylene triazine type epoxy resin, phenol triazine type epoxy resin, biphenyl-4,4 '
At least one or a mixture of diglycidyl ether and 3,3 ′, 5,5′-tetramethylbiphenyl-4,4′-diglycidyl ether, tetraphenylolethane type epoxy resin, trisphenylolethane type Epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, resorcinol type epoxy resin, polyphenol type epoxy resin, aliphatic epoxy resin, aromatic ester type Examples thereof include epoxy resins, cycloaliphatic ester type epoxy resins, ether ester type epoxy resins, and the like. Further, glycidyl compounds of amine compounds such as diaminodiphenylmethane, diethylenetriamine and diaminodiphenylsulfone can also be used. These epoxy resins may be used alone or in combination of several kinds. Among these, a phenol biphenyl triazine type epoxy resin, a phenol phenylene triazine type epoxy resin, and a phenol triazine type epoxy resin are particularly preferable from the viewpoint of flame retardancy enhancement.

Phenolic resin (C) and epoxy resin (D) contained in the flame-retardant epoxy resin composition of the present invention
The weight average molecular weight of is not particularly limited, but is, for example, 200
Set to 10,000. The weight average molecular weight can be measured by GPC (gel permeation chromatography).

Further, regarding the curing agent and the epoxy resin constituting the flame-retardant epoxy resin composition of the present invention, the total number (Ep) of epoxy groups in the epoxy resin relative to the total number (OH) of hydroxyl groups in the curing agent The ratio (OH / Ep) is
If 0.5 ≦ (OH / Ep) ≦ 2.0, it is more suitable for improving the flame retardancy of a cured product obtained by curing these. When the (OH / Ep) is less than 0.5, a combustible component such as allyl alcohol derived from the epoxy group remaining in the crosslinked structure formed by the curing agent and the epoxy resin in the cured product Since the amount of generation increases, there is a possibility that the improvement of flame retardancy will be hindered. In addition, the above (OH
/ Ep) exceeds 2.0, the cross-linking density of the cured product obtained by reacting the epoxy resin with a curing agent may be too low and curing may be insufficient, resulting in heat resistance of the cured product. The properties and strength may be insufficient.

The metal hydroxide contained in the flame-retardant epoxy resin composition of the present invention includes aluminum, magnesium, zinc, boron, calcium, nickel, cobalt,
It is preferably a metal hydroxide composed of at least one element selected from tin, molybdenum, copper, iron and titanium. Specific examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, zinc borate, calcium hydroxide, nickel hydroxide, cobalt hydroxide, tin hydroxide, zinc molybdate, copper hydroxide, and hydroxide. Examples of the metal hydroxide include iron as a main component. These metal hydroxides may be used alone or as a mixture or solution of several kinds,
Alternatively, the surface of one metal hydroxide may be coated with another metal hydroxide before use. Among these,
Aluminum hydroxide, magnesium hydroxide, and zinc borate are preferable from the viewpoint of improving flame retardancy. Furthermore, aluminum hydroxide is particularly preferable because it has excellent resistance to acids and alkalis and also has excellent processability of a cured product.

The content of the metal hydroxide with respect to the total weight of the flame-retardant epoxy resin composition of the present invention is preferably 1% by mass and 50% by mass or less. Here, the total amount of the flame-retardant epoxy resin composition means an amount including various additives such as an epoxy resin and a curing agent, as well as a curing accelerator and a filler, in the case of being used for a laminated board or the like. It means the amount excluding the base material such as glass fiber. With the above content, a high degree of flame retardancy can be realized while maintaining good solder heat resistance, moldability and electrical characteristics (dielectric characteristics). For this reason, when it is used for a laminated plate in particular, it is possible to obtain a high quality laminated plate having a high degree of flame retardancy. When the content is 45 mass% or less, solder heat resistance, moldability, and electric characteristics are remarkably improved. Therefore, for example, when used for a laminated board, a high-quality laminated board having excellent solder heat resistance can be obtained. Further, when the content is 40% by mass or less, solder heat resistance, moldability, and electrical characteristics (dielectric characteristics) are further improved, which is preferable. on the other hand,
The lower limit of the content is preferably 5% by mass or more. In this way, sufficient flame retardancy can be realized.

Further, if necessary, a metal oxide may be used in combination with the metal hydroxide contained in the flame-retardant epoxy resin composition of the present invention. Specific examples of the metal oxide that can be used in combination include iron oxide, copper oxide, calcium oxide and the like, but are not particularly limited. These metal oxides may be used alone or as a mixture or solution of several kinds thereof, mixed with a metal hydroxide, coated on the surface of a metal hydroxide or solid-solubilized with a metal hydroxide. Absent. It is also possible to use those obtained by surface-treating the metal hydroxide constituting the epoxy resin composition of the present invention with an organic substance such as various polymers including phenol resin. Further, the surface of the metal hydroxide coated with the metal oxide, or the metal hydroxide solid-solubilized with the metal oxide, was surface-treated with an organic substance such as various polymers including a phenolic resin. A thing can also be used.

The content of expandable graphite contained in the flame-retardant epoxy resin composition of the present invention is 1% by mass to 10% by mass.
The following is more preferable. Here, the total amount of the flame-retardant epoxy resin composition means an amount including various additives such as an epoxy resin and a curing agent, as well as a curing accelerator and a filler, in the case of being used for a laminated board or the like. It means the amount excluding the base material such as glass fiber. With the above content, a high degree of flame retardancy can be realized while maintaining good solder heat resistance and moldability. That is, when the content is less than 1% by mass, flame retardancy may be insufficient. Moreover, when the said content rate exceeds 10 mass%, the solder heat resistance and moldability of an epoxy resin composition may fall.
Therefore, if the expandable graphite is used in the above content range, particularly when the flame-retardant epoxy resin composition of the present invention is used for a laminate, a high-quality laminate with high flame retardancy is obtained. It becomes possible to obtain a plate.

The flame-retardant epoxy resin composition of the present invention contains, if necessary, a curing accelerator, a coloring agent, a low stress component,
You may contain various additives and fillers, such as a flexible agent, a mold release agent, a surface treatment agent, and an ion capture agent.

Among the above various additives, as the curing accelerator, those generally used for curing the epoxy resin and the curing agent can be used. For example, diazabicycloalkene such as 1,8-diazabicyclo (5,4,0) undecene-7 and its derivatives, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, etc. Secondary amines, 2-methylimidazole, 2
-Ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2
-Imidazoles such as heptadecyl imidazole, organic phosphines such as tributylphosphine, methyldiphenylphosphine and triphenylphosphine, tetra-substituted phosphonium / tetra-substituted borate such as tetraphenylphosphonium / tetraborate, 2-ethyl-4-methylimidazole / Examples thereof include tetraphenylboron, tetraphenylboron salts such as N-methylmorpholine / tetraphenylborate, and the like. These curing accelerators are
One kind may be used alone, or two or more kinds may be mixed and used.

The flame-retardant epoxy resin composition of the present invention comprises
If necessary, coloring agents such as carbon black, low stress components such as silicone oil and silicone rubber, flexible agents such as silicone powder, natural wax, synthetic wax, higher fatty acid, higher fatty acid metal salt, ester wax, and polyolefin. Various additives such as system waxes, mold release agents such as paraffin, organic silane compounds, organic titanate compounds, surface treatment agents such as coupling agents such as organic aluminate compounds, ion trapping agents such as hydrotalcite, etc. It doesn't matter.

The flame-retardant epoxy resin composition of the present invention may be used in combination with a known filler. For example, carbon fiber, fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, boron nitride, beryllia, talc, titanium oxide, zirconia, or the like, or spherical beads or titanium of these. Examples thereof include single crystal fibers such as potassium acid, silicon carbide, silicon nitride and alumina. These fillers may be used alone or in combination of two or more. In particular, powders of fused silica and crystalline silica are preferable.

The flame-retardant epoxy resin composition of the present invention is more effective when used for a composite material obtained by impregnating and curing a substrate such as glass fiber, paper, aramid fiber or the like. In particular, when a glass fiber base material or a paper base material is impregnated with the flame-retardant epoxy resin composition of the present invention and cured to produce a prepreg or a laminated board, various properties such as solder heat resistance, moldability, and electrical characteristics are excellent. High flame retardancy can be achieved while maintaining

The flame-retardant epoxy resin composition of the present invention comprises
In addition to these, nitrogen-based flame retardants such as melamine and isocyanuric acid compounds, and phosphorus-based flame retardants such as red phosphorus, phosphoric acid compounds, and organic phosphorus compounds can be appropriately added as flame retardant aids. However, in the flame-retardant epoxy resin composition of the present invention, the amount of the flame retardant added may be small, and deterioration of other physical properties such as moisture resistance can be suppressed.

The flame-retardant epoxy resin composition of the present invention is diluted with a suitable organic solvent such as methyl ethyl ketone, propylene glycol monomethyl ether or dimethylformamide to form a varnish, and the varnish is porous such as glass woven cloth or glass non-woven cloth. A prepreg can be manufactured by a usual method of coating and impregnating a glass substrate and heating. Also, after stacking a plurality of this prepreg, and after laminating copper foil on one or both sides of the laminated structure,
This can be heated and pressed under normal conditions to produce a glass epoxy copper clad laminate. At this time, if a copper foil is not used, a laminated board is obtained. The multi-layer board is formed by forming a circuit on a copper clad laminate (inner layer board), etching the copper foil, and then superimposing a prepreg and a copper foil on at least one side of the inner layer board. It can be produced by a usual method of heating for 60 minutes. Further, the printed wiring board can be manufactured by a usual method in which a through hole is formed in a copper clad laminate or a multilayer board, a through circuit is plated, and then a predetermined circuit is formed. The laminated board of the present invention produced in this manner has excellent flame retardancy and safety.

When the flame-retardant epoxy resin composition of the present invention is used as an encapsulating material for semiconductor devices, it is preliminarily kneaded with a ribbon blender or a Henschel mixer.
The mixture of the flame-retardant epoxy resin composition of the present invention obtained by using a heating roll, a kneader or the like is used after deaerating water as necessary. This mixture is heated under a predetermined molding condition by a transfer molding machine or the like and melted, and is applied as a sealing material for a semiconductor device.

The semiconductor device using the flame-retardant epoxy resin composition of the present invention as an encapsulant is particularly excellent in flame retardancy and safety. As the above-mentioned semiconductor device, a semiconductor device in which a semiconductor element is mounted on a die pad of a lead frame and these are connected by wire bonding and sealed with a resin, a lead-on-chip type resin-sealed semiconductor Examples of the device include, but are not limited to, resin-encapsulated semiconductor devices such as ball grid array (BGA), and electronic components such as semiconductor elements are encapsulated with the epoxy resin composition of the present invention. Includes all that you do. For example, electrolytic capacitors such as tantalum capacitors and niobium capacitors are also included.

In addition, the flame-retardant epoxy resin composition of the present invention has flame retardancy and safety even when it is used for other purposes, that is, as a molding material, a casting material, an adhesive, a paint, etc. Excel.

[0075]

The present invention will be described in more detail with reference to the following examples.

First, the raw materials used in Examples and Comparative Examples will be described.

(Glass Woven Cloth) As the glass woven cloth, 0.18 mm thick E glass cloth manufactured by Nitto Boseki was used.

(Curing acceleration catalyst) 2 ethyl 4 methyl imidazole: 2E manufactured by Shikoku Chemicals
4MZ triphenylphosphine: manufactured by Kanto Kagaku, T.I. P. P

(Phenolic resin and epoxy resin)
A phenolic resin and an epoxy resin represented by the following formula were used.

Pitch type phenol resin (condensed polycyclic aromatic type phenol resin, phenol type resin 1: made by Kashima Oil Co., Ltd.,
FPI-5136, hydroxyl equivalent 132g / eq)

Phenol biphenylene aralkyl type resin (phenolic resin 2)

[0082]

[Chemical 11]

(MEH-7851S, manufactured by Meiwa Kasei Co., softening point 120 ° C., hydroxyl group equivalent 205 g / eq) Phenol phenylene aralkyl type resin (phenolic resin 3)

[0084]

[Chemical 12]

(Meiwa Kasei, MEH-7800M, softening point 83 ° C., hydroxyl group equivalent 175 g / eq) Allyl group-containing phenol biphenylene aralkyl type resin (phenolic resin 4)

[0086]

[Chemical 13]

(MEH-L-7851-5, manufactured by Meiwa Kasei Co., Ltd.
L, hydroxyl equivalent 154 g / eq) Phenol novolac resin (phenolic resin 5)

[0088]

[Chemical 14]

(Maywa Kasei Co., H-1, softening point 106 ° C.,
Hydroxyl equivalent 107 g / eq) Allyl group-containing phenol novolac resin (phenolic resin 6)

[0090]

[Chemical 15]

(MEH-8000H, manufactured by Meiwa Kasei Co., Ltd., hydroxyl group equivalent: 141 g / eq) Allyl group-containing phenol phenylene aralkyl type resin (phenolic resin 7)

[0092]

[Chemical 16]

(MEH-L-7800-5, manufactured by Meiwa Kasei Co., Ltd.
L, hydroxyl equivalent 147 g / eq) Dicyandiamide

[0094]

[Chemical 17]

(Amine-based curing agent 1: manufactured by Air Products Japan, AMICURE CG-NA, active hydrogen equivalent 21 g / eq) Phenol biphenylene aralkyl type epoxy resin (epoxy resin 2)

[0096]

[Chemical 18]

(In the formula, G represents a glycidyl group. NC-3000P manufactured by Nippon Kayaku Co., softening point 57 ° C., epoxy equivalent 270 g / eq) Phenol phenylene aralkyl type epoxy resin (epoxy resin 3) Formula (4)

[0098]

[Chemical 19]

(In the formula, G represents a glycidyl group. E-XLC-3L manufactured by Mitsui Chemicals, softening point 55 ° C., epoxy equivalent 236 g / eq) Cresol novolac epoxy resin (epoxy resin 4)

[0100]

[Chemical 20]

(In the formula, G represents a glycidyl group. Sumitomo Chemical Co., Ltd. ESCN-195LL, epoxy equivalent 199 g /
eq) Bisphenol A type epoxy resin (epoxy resin 5)

[0102]

[Chemical 21]

(In the formula, G represents a glycidyl group. Made by Japan Epoxy Resin, Epicoat 828, epoxy equivalent 189 g / eq) Methylresorcinol type epoxy resin (epoxy resin 6)

[0104]

[Chemical formula 22]

(Nippon Kayaku, RE-600NM, epoxy equivalent 127g / eq) diallyl bisphenol A type epoxy resin (epoxy resin 7)

[0106]

[Chemical formula 23]

(Manufactured by Nippon Kayaku, RE-810NM, epoxy equivalent 195 g / eq)

(Metal hydroxide and expansive graphite) Aluminum hydroxide: Sumitomo Chemical CL-310 Surface treated aluminum hydroxide: Sumitomo Chemical CL-32
10SP Expandable Graphite: GREP-EG (particle size <15
0 μm) (Inorganic filler) Fused spherical silica: FB-35 manufactured by Denki Kagaku Kogyo (average particle size 10 μm, −48 μm is 95 wt% or more) Next, flame retardancy, solder heat resistance, and moldability in Examples and Comparative Examples. And the evaluation method of the electrical characteristics is shown. (Flame-retardant) The molded plate is fixed with a sample support (clamp) so that the length direction of the molded plate (length 13 cm × width 13 mm × thickness 1.6 mm) is perpendicular to the ground. next,
After indirect flame for 10 seconds with a burner on the end surface of the molded plate on the side opposite to the clamp, move away from the burner and measure the time (flame remaining time, second) that the flame remains on the molded plate (first afterflame time) = T1). When this flame is extinguished, the indirect flame is again used for 10 seconds by the burner, the burner is moved away, and the afterflame time (second afterflame time = t2) is measured in the same manner as the first time. This test was conducted using 5 molded plates for each cured resin, and the flame retardancy was evaluated. However, if the flame retardancy criteria are arranged in order from the highest to the lowest, UL94
The order is V-0, V-1, V-2, and NOT.

UL94V-0.SIGMA.F.ltoreq.50 seconds (.SIGMA.F represents the total afterflame time of the test conducted using five molded plates. That is, t1 and t2 were measured for one molded plate, The total time of these is defined as the total afterflame time F per formed plate.
Measure F on five molded plates and add up to Σ
It was set to F. The “afterflame time” in the table indicates the value of ΣF. ) Fmax ≦ 10 seconds (Fmax is t1 obtained in the test)
Or, it shows the longest afterflame time in t2. ) ・ No ignition of marking cotton due to fuming substances or drops, and it does not burn up to the clamp.

UL94V-1 .SIGMA.F.ltoreq.250 seconds, Fmax.ltoreq.30 seconds, no ignition of marking cotton due to fuming substances or drops, and no burning until clamp.

UL94V-2 .SIGMA.F.ltoreq.250 seconds, Fmax.ltoreq.30 seconds, marking cotton ignited by fuming substances or drops, and did not burn up to the clamp.

NOT -ΣF> 250 seconds or Fmax> 30 seconds.

After etching the double-sided copper-clad laminate, the appearance of the laminate was visually evaluated.

(Moldability) Good moldability: ○ Poor moldability (generation of streaks): Δ (Lead-free solder heat resistance) A laminate obtained by etching a copper foil of a double-sided copper-clad laminate The other molded bodies were cut into a predetermined shape (4 cm square × 1.6 mm thick) to give a test piece. This test piece was subjected to PCT (pressure cooke) for 2 hours under predetermined conditions (121 ° C / relative humidity 100% / 2atm).
r test) treatment, the product was floated in a solder bath at 288 ° C. for 20 seconds, and the change in appearance was visually evaluated to evaluate the heat resistance of the solder.

The evaluation criteria of solder heat resistance are as follows. No blistering or peeling → ○ Blistering or peeling occurred → △

(Dielectric Property) Based on JIS-C-6481, the dielectric constant of the laminated plate (100 × 140 × thickness 1.6 mm <7 layers of glass cloth>) at a frequency of 1 MHz was measured. In addition, the compounding quantity of the curing agent and the epoxy resin in Tables 1 to 3 shows the numerical value of the compounding ratio of epoxy / curing agent.

Example 1 The total resin content of pitch-based phenolic resin (phenolic resin 1), phenol-phenylene aralkyl type resin (phenolic resin 3) and phenol-phenylene aralkyl type epoxy resin (epoxy resin 3) was 69.7 mass. % In the ratio shown in Table 1 (OH / Ep =
1.0), aluminum hydroxide 25% by mass, expandable graphite 5% by mass, and 2E4MZ 0.3 as a curing acceleration catalyst.
% By mass (2E4MZ is 0.
(Blended at a ratio of 4% by mass) to give an epoxy resin composition. Methyl ethyl ketone was added as a solvent to this epoxy resin composition to make the content of the epoxy resin composition about 65.
A mass% epoxy resin varnish solution was prepared.

A glass woven fabric was continuously coated with and impregnated with the obtained epoxy resin varnish, and dried in an oven at 120 ° C. to produce a prepreg. Eight sheets of this prepreg (7 sheets were used for measurement of dielectric properties) A laminated body was laminated with copper foil (thickness 18 μm) and pressed (about 3 MPa)
Then, after raising the temperature to 180 ° C. at a temperature rising rate of 5 ° C./min, the temperature is kept at this temperature for 60 minutes, and then 80 ° C. over 30 minutes.
After cooling to 1.6 mm, a double-sided copper-clad glass epoxy resin laminate having a thickness of 1.6 mm was obtained.

With respect to the obtained laminated plate, flame retardancy, moldability,
Solder heat resistance and dielectric properties were evaluated. The results are shown in Table 1.

Examples 2-10, Comparative Examples 1-8, 11-1
4 to 16, Reference Examples 12 and 13 A laminated plate was molded in the same manner as in Example 1 except that the flame-retardant epoxy resin composition having the composition shown in Table 1 was used, and the flame-retardant evaluation and moldability were performed. And solder heat resistance were evaluated. The results are shown in Tables 1 and 2.

Comparative Example 9 A solution A prepared by dissolving dicyandiamide in dimethylformamide (DMF) and a solution B prepared by dissolving bisphenol A type epoxy resin and aluminum hydroxide in methyl ethyl ketone (MEK) were prepared. Next, to a solution C obtained by mixing these solutions A and B, 2
E4MZ is added, and the epoxy resin composition is 63% by mass.
An epoxy resin varnish solution of was prepared. The epoxy resin composition in this varnish means a resin component mixed in an equivalent ratio such that the total of dicyandiamide (amine curing agent 1) and bisphenol A type epoxy resin (epoxy resin 4) is 69.7 mass%. , Aluminum hydroxide 25% by mass,
Expandable graphite 5% by mass and 2E4MZ 0.3% by mass
(2E4MZ was added at a ratio of 0.4% by mass to 100% by mass of resin content). The breakdown of the solvent in the varnish is 50% by mass of MEK and 10% by mass of DMF with respect to 100% by mass of the epoxy resin composition.

A glass woven fabric was continuously coated and impregnated with the obtained epoxy resin varnish solution and dried in an oven at 130 ° C. to produce a prepreg. This prepreg is 8
Laminated body (7 pieces are used for measuring dielectric properties)
Both sides of the sheet are sandwiched with copper foil (18 μm) and pressed (about 3 MPa)
Then, after raising the temperature to 180 ° C. at a temperature rising rate of 5 ° C./min, the temperature is kept at this temperature for 60 minutes, and then 80 ° C. over 30 minutes.
After cooling to 1.6 mm, a double-sided copper-clad glass epoxy resin laminate having a thickness of 1.6 mm was obtained. Using this laminate, flame retardancy, moldability, solder heat resistance and dielectric properties were evaluated in the same manner as in Example 1. The results are shown in Table 2. Comparative Example 10 A molded article was prepared in the same manner as in Comparative Example 9 except that the epoxy resin having the composition shown in Table 2 was used, and flame retardancy, moldability, solder heat resistance and dielectric properties were obtained in the same manner as in Example 1. The characteristics were evaluated respectively. The results are shown in Table 2.

Example 11 Allyl group-containing phenol biphenylene aralkyl type resin (phenolic resin 4) and methylresorcinol type epoxy resin (epoxy resin 6) had a total resin content of 39.
6% by mass was added in the ratio shown in Table 3 (OH
/Ep=1.0), surface-treated aluminum hydroxide 25% by mass, expandable graphite 5% by mass, fused spherical silica 30% by mass
Also, 0.4% by mass of triphenylphosphine (T.P.P.) (compounding T.P.P at a ratio of 1.0% by mass to 100% by mass of resin content) was combined as a curing acceleration catalyst. The materials were premixed at room temperature to obtain an epoxy resin composition. This epoxy resin composition was heated at 100 ° C. for 15 minutes.
What was cast after vacuum degassing was cured at 175 ° C. for 6 hours to obtain a molded body. The flame retardancy of the obtained molded body was evaluated. The results are shown in Table 3.

Comparative Examples 17 and 18 A molded article was prepared in the same manner as in Example 11 except that the epoxy resin composition having the composition shown in Table 3 was used, and the flame retardancy was evaluated. The results are shown in Table 3.

[0125]

[Table 1]

[0126]

[Table 2]

[0127]

[Table 3]

From the results shown in the table, it is found that the flame-retardant epoxy resin composition according to the present invention is superior in flame retardancy to the flame-retardant epoxy resin composition of each comparative example according to the prior art. It was It was also found that various properties such as moldability and solder heat resistance can be effectively improved by appropriately setting the amounts of metal hydroxide and expandable graphite added.

The structural units derived from the phenols (A) and the aromatics (B) excluding the phenols (A)
The structure containing a structural unit derived from is introduced into the epoxy resin side or into the curing agent side, but it is more effective to introduce into the epoxy side. The reason for this is not clear, but the generation process of the three-dimensional crosslink density differs depending on which side the structure containing (A) and (B) is, and the average value of the distances between crosslink points of the obtained cured product is different. It is assumed that this is due to the difference in distribution. It is clear from the results of Examples 7 and 8 that the flame retardancy improving unit has a higher flame retarding effect than the epoxy resin side than the curing agent side.

Next, the effect of adding expandable graphite is shown in Table 4.
And it demonstrates based on the experimental result shown in Table 5. In Tables 4 and 5, "the flame-retardant structural unit in the cured product" means
A structural unit composed of a combination of a structural unit derived from a phenol (A) and a structural unit derived from an aromatic (B) excluding the phenol (A). Each example and comparative example are excerpted from Tables 1-2. In Table 4, the composition of Comparative Example 8 is obtained by adding expansive graphite to the composition of Comparative Example 15. Comparative Example 1
The composition of Comparative Example 16 was obtained by substituting the resin material with the one having the specific structure according to the present invention for the composition of No. 5. Also,
The composition of Example 3 is obtained by substituting the resin material of the specific structure according to the present invention for the composition of Comparative Example 8 and incorporating expansive graphite.

From the results shown in Table 4, the flame retardancy-improving effect obtained by substituting the resin material having the specific structure according to the present invention with the expansive graphite is difficult to obtain by using the resin having the specific structure. It is understood that it is greater than the sum of the flame-retarding effect and the flame-retarding improving effect obtained by blending expansive graphite.

[0132]

[Table 4]

Table 5 shows the system in which no metal hydroxide was added.
It shows the result of confirming the synergistic effect of the epoxy resin having a specific structure used in the present invention and graphite. The compound of Reference Example 3 is a mixture of expandable graphite with respect to the compound of Reference Example 1. Further, the compound of Reference Example 2 is obtained by substituting the resin material having the specific structure according to the present invention for the compound of Reference Example 1. Further, the compound of Reference Example 4 is the compound of Reference Example 1 in which the resin material is replaced with the one having the specific structure according to the present invention and the expansive graphite is compounded.

On the other hand, the composition of Reference Example 6 is one in which expansive graphite is mixed with the composition of Reference Example 5.

From the results shown in Table 5, the flame retardancy-improving effect obtained by substituting the resin material of the specific structure according to the present invention with the expansive graphite is difficult to obtain by using the resin of the specific structure. It is understood that it is greater than the sum of the flame-retarding effect and the flame-retarding improving effect obtained by blending expansive graphite. In addition, it was confirmed from the comparison between Reference Examples 1 and 3 and the comparison between Reference Examples 5 and 6 that a sufficient flame retardancy improving effect could not be obtained only by adding expandable graphite.

[0136]

[Table 5]

[0137]

As described above, in the flame-retardant epoxy resin composition of the present invention, the constitutional unit derived from the phenol (A) and the constitutional unit derived from the aromatic (B) are used as molecules. A phenolic resin (C) contained in a chain and / or an epoxy resin (D) obtained by glycidyl etherifying a phenolic hydroxyl group of the phenolic resin (C),
Further, it contains metal hydroxide and expandable graphite. For this reason, it is possible to realize a high level of flame retardancy and safety that have never been achieved. Especially when used in the manufacture of laminates,
It is possible to impart a high degree of flame retardancy while maintaining various physical properties required for a laminated plate, that is, the formability of the laminated plate, solder heat resistance and the like.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 5/18 C09D 5/18 161/06 161/06 163/00 163/00 163/02 163/02 H01L 23/29 H01L 23/30 R 23/31 F term (reference) 4F072 AA04 AA07 AB09 AB28 AB29 AD23 AE01 AE07 AF02 AF14 AG03 AG16 AG19 AH02 AH21 AL13 4J002 CC03Y CD00W CD00X DE027 DE076 DE086 DE096 DE106 DE1460137 DE076 DE01 DK006 AFD01136 FA02 FB07 JA05 JA07 JA08 JA11 KA01 4J038 DA062 DB051 DB061 DB071 DB091 DB151 HA036 HA116 HA166 HA216 HA446 HA476 KA03 KA06 MA07 MA10 MA15 NA14 NA15 4M109 AA01 EA02 EB02 EB03 EB12 EC20

Claims (18)

[Claims] 1. A constitutional unit containing an epoxy resin, a curing agent, a metal hydroxide and expandable graphite, wherein at least one of the epoxy resin and the curing agent is derived from a phenol (A) and the phenol. A flame-retardant epoxy resin composition comprising a compound having a constitutional unit derived from an aromatic compound (B) other than (A) in a molecule. 2. The flame-retardant epoxy resin composition according to claim 1, containing 1 to 20% by mass of expandable graphite with respect to the total amount of the flame-retardant epoxy resin composition. Epoxy resin composition. 3. The flame-retardant epoxy resin composition according to claim 1 or 2, wherein the curing agent is a structural unit derived from a phenol (A) and the phenol (A).
A flame-retardant epoxy resin composition comprising a phenolic resin (C) containing a structural unit derived from an aromatics (B) except for in a molecular chain. 4. The flame-retardant epoxy resin composition according to any one of claims 1 to 3, wherein the epoxy resin is a structural unit derived from a phenol (A) and an aroma excluding the phenol (A). Flame-retardant epoxy, characterized in that it contains an epoxy resin (D) in which the phenolic hydroxyl group of a phenolic resin (C) containing a structural unit derived from group (B) in the molecular chain is glycidyl etherified. Resin composition. 5. The flame-retardant epoxy resin composition according to claim 1, wherein the aromatic compound (B) is a condensate of benzene and its derivative, biphenyl and its derivative,
Benzene and its derivatives, diphenyl ether and its derivatives, fluorene and its derivatives, condensed polycyclic aromatic phenolic resins, bisphenolfluorene and its derivatives,
A flame-retardant epoxy resin composition, which is any compound selected from the group consisting of bisphenol S and its derivatives, bisphenol F and its derivatives, and bisphenol A and its derivatives. 6. The flame-retardant epoxy resin composition according to claim 1, wherein the aromatic compound (B) is
A flame-retardant epoxy resin composition, which is any compound selected from the group consisting of a condensate of benzene and its derivative, biphenyl and its derivative, and benzene and its derivative. 7. The flame-retardant epoxy resin composition according to claim 1, wherein the phenolic resin (C) is a phenol biphenylene aralkyl type resin,
A flame-retardant epoxy resin composition comprising any compound selected from the group consisting of a phenol phenylene aralkyl type resin. 8. The flame-retardant epoxy resin composition according to claim 1, wherein the metal hydroxide is aluminum, magnesium, zinc, boron, calcium, nickel, cobalt, tin, molybdenum, copper. A flame-retardant epoxy resin composition, which is a metal hydroxide containing at least one element selected from the group consisting of iron, titanium and titanium. 9. The flame-retardant epoxy resin composition according to claim 1, wherein the base material is impregnated and cured,
A flame-retardant epoxy resin composition, which is used for forming a laminate. 10. The flame-retardant epoxy resin composition according to any one of claims 1 to 8, characterized by containing 30 to 99 mass% of silica based on the total amount of the flame-retardant epoxy resin composition. Flame-retardant epoxy resin composition. 11. The flame-retardant epoxy resin composition according to claim 10, which is used for a sealing material. 12. The flame-retardant epoxy resin composition according to any one of claims 1 to 8, wherein the viscosity at any temperature of 20 ° C. to 80 ° C. is 10,000 cps or less. Resin composition. 13. The flame-retardant epoxy resin composition according to claim 12, which is used for a liquid encapsulating material. 14. An epoxy resin varnish solution obtained by dispersing the flame-retardant epoxy resin composition according to claim 9 in an organic solvent. 15. A prepreg obtained by impregnating and curing a base material with the epoxy resin varnish solution according to claim 14. 16. The prepreg according to claim 15, wherein a copper foil is bonded to at least one surface. 17. A laminated plate obtained by stacking a plurality of prepregs according to claim 16 and heating and pressing the prepregs. 18. A semiconductor device, comprising a semiconductor element encapsulated with the flame-retardant epoxy resin composition according to any one of claims 10 to 13.