JP2001288339A - Method for flame retarding epoxy resin composition and flame retardant epoxy resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a technique for highly flame retarding an epoxy, resin composition for the resin of sealing electronic parts and to obtain a flame retarded epoxy resin composition. SOLUTION: This method for flame retarding the epoxy resin composition comprises adding a compound having a dihydrobenzoxazine ring in an amount within the range of 0.5-30 wt.% based on a resin component except an inorganic filler in the epoxy resin composition composed of an epoxy resin, a curing agent and the inorganic filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for making an epoxy resin composition flame-retardant, a highly flame-retardant epoxy resin composition, and a semiconductor device using the flame-retardant resin composition.

[0002]

2. Description of the Related Art Conventionally, electronic components such as diodes, transistors, and integrated circuits are mainly sealed with an epoxy resin composition. Since this epoxy resin composition is basically flammable, it is obliged by the UL standard to impart flame retardancy in order to ensure safety in the event of a fire.

[0003] Therefore, the epoxy resin composition includes:
Usually, tetrabromobisphenol A (TBB) is used as a flame retardant.
A halogen-based flame retardant represented by A) is used together with a harmful antimony trioxide as a flame retardant auxiliary. Halogen-based flame retardants thermally decompose during combustion to generate hydrogen halide and act as radical scavengers, and react with hydrogen halide and antimony trioxide to form antimony halide compounds such as antimony tribromide. It is believed that the spread of fire is prevented by the synergistic effect of blocking the generated oxygen.

However, some of the halogen-based flame retardants change into harmful organic halogen gases typified by dioxins during combustion, and in addition, antimony trioxide, which is a flame retardant aid, is chronic. Because it is a toxic substance suspected of being toxic, etc., the environment of these flame retardants and flame retardant
Hygiene issues have been pointed out. Further, in the conventional semiconductor encapsulation resin, the halogen or antimony derived from the above-described flame retardant or flame retardant promotes the corrosion of the wiring of the semiconductor device, especially at a high temperature, so that the reliability of the semiconductor device is reduced. It is also a cause.

Therefore, as an alternative technology to halogen-based flame retardants, phosphorus-based flame retardants such as red phosphorus and phosphate esters have now begun to be partially used. It is believed that the phosphorus-based flame retardant forms polyphosphoric acid when burned, and this coats the surface of the resin carbonized film, thereby shutting off the supply of heat, oxygen or flammable gas, and preventing fire spread. Phosphorus-based flame retardants are useful for making epoxy resin compositions flame-retardant, but also suffer from problems such as high hygroscopicity and the reaction with trace amounts of moisture to produce phosphine and corrosive phosphoric acid. Therefore, it is difficult to obtain sufficient physical properties for use in encapsulating electronic components, which are particularly demanding for moisture resistance.

[0006] The use of metal hydroxides such as aluminum hydroxide and magnesium hydroxide and boron compounds as flame retardants has also been studied. The mechanism by which the metal hydroxide exhibits the flame-retardant properties is due to the combustion suppression effect of lowering the resin temperature of the flame contact surface due to heat absorption accompanied by a dehydration reaction at the time of heating. ~
(200 parts by weight). This is because flame-retardant technology using metal hydroxides and boron compounds is an auxiliary means for imparting flame-retardant properties, and has the same high level of flame retardancy as halogen-based and phosphorus-based flame retardants. This is because, in order to obtain the properties, it must be blended in a large amount (about 80 to 200 parts by weight) with respect to the resin composition, but this causes the physical properties and moldability of the epoxy resin composition to deteriorate. There was a problem.

Further, instead of using a flame retardant compounded, an inorganic filler is added to the epoxy resin composition at a high level, for example, by adding 87 to 95% by weight,
An epoxy resin composition for semiconductor encapsulation with improved flame retardancy, and a semiconductor device (JP-A-8-301984);
83% by volume of inorganic filler based on epoxy resin composition
(A 91% by weight of spherical silica powder) or more, an epoxy resin composition having improved combustion resistance by being highly filled, and a semiconductor sealing device (Japanese Patent Application Laid-Open No. 9-208808)
Has been proposed. These provide high flame retardancy and high safety to the environment and hygiene at the same time without newly adding harmful flame retardants and flame retardant auxiliaries. However, while providing high flame retardancy without adding a new flame retardant and being able to respond to environmental and hygiene problems, the semiconductor device is sealed because the filling rate of the inorganic filler is extremely high. In such a case, there are problems such as insufficient moldability or difficulty in controlling and managing molding conditions. Furthermore, since it significantly lowers the fluidity of the resin composition, it is basically difficult to apply to a liquid type epoxy resin composition,
It is not suitable as a flame-retardant technique for liquid sealants, whose demand is increasing in recent years.

On the other hand, a thermosetting resin having a dihydrobenzoxazine ring has been known as a material which gives a cured product having excellent hygroscopicity, heat resistance and mechanical strength. For example, JP-A-2000-007901 describes a thermosetting resin composition containing a resin containing a compound having a dihydrobenzoxazine ring and an epoxidized polybutadiene. In this case, the wet heat resistance is improved by including a phosphorus-based flame retardant as a flame retardant, or by including a halogen-based resin or a halogen-based additive. Alternatively, by adding a large amount of aluminum hydroxide, a flame retardant effect is obtained without using a non-halogen flame retardant. However, when a halogen-based flame retardant, a phosphorus-based flame retardant, or aluminum hydroxide is used, there is a problem as described above.

Japanese Patent Application Laid-Open No. 9-059333 discloses a curable resin composition capable of increasing the curing rate of a compound having a dihydrobenzoxazine ring and obtaining high toughness. JP-A-10-204255 discloses a thermosetting resin composition having low hygroscopicity, flame retardancy and good mechanical properties as a thermosetting resin having a dihydrobenzoxazine ring and an epoxy resin having an isocyanuric ring. Are described as essential thermosetting resin compositions.

JP-A-10-251380 describes a thermosetting resin composition comprising a thermosetting resin having a dihydrobenzoxazine ring, a halogenated phenol compound and an epoxy resin as essential components. Furthermore, JP-A-11-060988 and JP-A-11-140278
Japanese Patent Application Laid-Open Publication No. H11-260, discloses that a thermosetting resin having a dihydrobenzoxazine ring has a content of 2 to 87% by weight and an epoxy resin has a content of 3 to 67% by weight.
And a resin composition for semiconductor encapsulation comprising 10 to 31% by weight of a phenol resin and an additive. In the above examples, the hygroscopicity, heat resistance, for the compound having a dihydrobenzoxazine ring with excellent mechanical strength, particularly in order to improve the flame retardancy, epoxy resin, a phenol resin is added and used, at least A flame retardant effect is obtained by using a halogen-based compound and a halogen-based resin together, and those without the addition of these do not have sufficient flame retardancy.

JP-A-11-158352 discloses a phenol resin composition comprising a reaction product of an epoxy resin and a phenolic resin or a compound having a triazine ring and an aldehyde, and an epoxy having a compound having a dihydrobenzoxazine ring is essential. A resin composition is described.
It is considered that the flame retardant effect due to the introduction of the compound having a triazine ring is exhibited by a flame-extinguishing mechanism of a nonflammable gas mainly composed of a nitrogen compound, which is generated by decomposition of triazines. However, in this case, the moisture resistance of the resin composition decreases. This is because, since the triazine ring is hydrophilic, the amount of moisture absorption increases due to an increase in the amount (nitrogen content) of the triazine ring in the cured resin. Furthermore, when the nitrogen concentration is higher than that of the resin composition, harmful nitrogen compounds generated during combustion, such as hydrogen cyanide and NOX, are generated, and the safety during combustion is not sufficient.

[0012]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and has additives such as a halogen-based flame retardant, an antimony-based flame retardant auxiliary, and a phosphorus-based flame retardant. Without any use, and without extremely high filling of inorganic fillers, and also achieve a high degree of flame retardancy to liquid type epoxy resin compositions, and further, have a dihydrobenzoxazine ring When a compound is added, a flame-retardant method of a flame-retardant epoxy resin composition capable of obtaining a superior flame-retardant effect as compared with the prior art, a flame-retardant epoxy resin composition, and a semiconductor using the same It is intended to provide a device.

[0013]

SUMMARY OF THE INVENTION In order to achieve the above object, the present invention provides an epoxy resin, a curing agent, an inorganic filler, a compound having a dihydrobenzoxazine ring as essential components, and having a dihydrobenzoxazine ring. The compound is used in an amount of 0.5 to 3 with respect to the resin component excluding the inorganic filler.
It is characterized by being added in the range of 0% by weight, and the epoxy resin cured product of this resin composition achieves high flame retardancy without adding any halogen-based or phosphorus-based flame retardant.

In the present invention, the term "resin component excluding inorganic filler" refers to silica powder added for the purpose of lowering the coefficient of thermal expansion of a cured resin, glass fiber used in a laminated board, or the like. Excludes a resin mixture consisting of resin and other additives. Additives contained in the resin component excluding the inorganic filler include, for example, metal hydroxide used as a heat absorbing agent, an organic flame retardant other than a halogen-based material, a flame retardant auxiliary, and a coupling agent. , Curing accelerator, silicone
Trace additives such as waxes, waxes and release agents.

According to the method for making an epoxy resin composition flame-retardant according to the present invention, it is possible to exhibit excellent flame retardancy that has not been achieved in the past. This is because the flame retarding mechanism of the epoxy resin composition was found, and a flame retarding method for leading the flame retarding mechanism was found. As a means for this, in an epoxy resin composition comprising an epoxy resin, a curing agent, and an inorganic filler, the amount of the compound having a dihydrobenzoxazine ring is set to 0.5 to 0.5% with respect to the resin component excluding the inorganic filler. 3
That is, it is added in the range of 0% by weight.

The flame retarding mechanism of the epoxy resin composition of the present invention will be described.

When a cured epoxy resin containing an epoxy resin, a curing agent, and an inorganic filler as main components is exposed to a high temperature, the cured resin softens at a glass transition temperature or higher,
Further, at 400 to 500 ° C. at which thermal decomposition starts, the cured resin with thermal decomposition of the molecular structure changes to a molten state,
Further, a part thereof becomes a flammable pyrolysis gas and volatilizes on the resin surface and burns. When this series of reactions is caused in a chain, a fire spreads.

In general, regarding the relationship between the melt viscosity at the time of ignition and flame contact of the resin and the flammability, it has been found that the resin tends to burn when the melt viscosity is extremely low and extremely high.

As a remarkable example in the case where the melt viscosity is extremely low, there is a drip phenomenon in which a part of the resin drippings in the course of burning. When such a phenomenon is involved, it is first necessary to devise measures to prevent drip, but specific measures are to use a combination of an anti-drip agent, high filling of inorganic filler, and thermal decomposition resistance of resin. And the like.

On the other hand, one of the characteristics of combustion when the melt viscosity of the resin at the time of ignition and flame contact is extremely high is that the properties of the carbide remaining after combustion become dense and uniform. In the combustion mode in which such combustion residues are formed, the heat from the flame is efficiently transmitted to the inside of the resin, thereby promoting the thermal decomposition of the resin, and the flammable pyrolysis gas is continuously supplied to spread the fire. Will spread. Even when polyimide or some liquid crystal polymer is burned, a case in which a dense carbide as described above is formed is found.However, since these resins exhibit extremely high thermal decomposition resistance, they are chain-like. The difference is that the thermal decomposition reaction hardly occurs.

The present inventor has formed a heat insulating structure for reducing heat conduction from the resin ignition surface and / or a gas shielding structure for shutting off flammable pyrolysis gas as a flame retarding method for this combustion mechanism. It was found that it was effective to do so. In other words, if the resin melt viscosity at the time of flame contact or ignition can be adjusted appropriately, the gas generated by the thermal decomposition of the resin becomes bubbles inside the softened resin and forms a heat insulating structure such as a foamed structure or a void structure in which the gas aggregates. Easy to form. Further, promoting the formation of such a heat insulating structure also means that a portion of the flammable gas generated by the thermal decomposition of the resin is trapped inside the softened resin, so that the flammable gas is transferred to the combustion surface. It acts to inhibit continuous supply. These heat-insulating structures have the effect of suppressing the conduction of heat from the flame contact surface and the effect of reducing the amount of combustible gas generated, and a high level of flame retardancy is imparted by their synergistic action. Furthermore, if the thermal decomposition property of the epoxy resin or the curing agent is improved, it is expected that even higher flame retardancy is obtained.

In the present invention, it has been found that by adding a compound having a dihydrobenzoxazine ring to the epoxy resin composition in a specific composition, a high degree of flame retardancy is imparted to the epoxy resin cured product. That is, by changing the compound having a dihydrobenzoxazine ring, the resin melt viscosity at the time of flame contact or ignition of the cured epoxy resin can be adjusted appropriately. When the addition amount of the compound having a dihydrobenzoxazine ring is 0.5 to 30% by weight with respect to the resin component excluding the inorganic filler, formation of a heat insulating structure that reduces heat conduction from the resin ignition surface, and Alternatively, it has been found that it is effective to form a gas shielding structure for shielding combustible pyrolysis gas. This allows
The flame retardancy of the cured epoxy resin can achieve the V-0 level defined by the UL94 flame retardant standard.

When a compound having a dihydrobenzoxazine ring is added in a proportion exceeding 30% by weight, the melt viscosity of the cured epoxy resin at the time of flame contact or ignition becomes too high, so that a foamed structure or a void exhibiting a heat insulating effect is obtained. The formation of a structure is hindered, and a dense and uniform carbide is formed. As a result, the flame retardancy of the cured epoxy resin material is significantly reduced. In addition, since the reactivity of the compound having a dihydrobenzoxazine ring is lower than the reactivity between the epoxy resin and the phenol resin, the curing speed of the entire resin composition is significantly reduced, and the workability and molding efficiency are reduced. It worsens the sex.

On the other hand, when the compound having a dihydrobenzoxazine ring is used at a concentration lower than 0.5% by weight, the melt viscosity of the epoxy resin cured product at the time of flame contact or ignition becomes insufficient, and the foamed structure And the formation of a void structure is not promoted, which is insufficient for improving the flame retardancy of the cured epoxy resin.

The reason why the resin melt viscosity at the time of flame contact or ignition of the cured epoxy resin can be adjusted appropriately by changing the amount of the compound having a dihydrobenzoxazine ring is as follows.

The compound having a dihydrobenzoxazine ring is a compound having a pheno-type formed by its own ring-opening polymerization reaction.
Since it forms a hydroxyl group, it is possible to react with the epoxy group of the epoxy resin,
A phenolic resin and a compound having a dihydrobenzoxazine ring give a cured resin bonded by a chemical bond. When a large amount of a compound having a dihydrobenzoxazine ring is added, the compound having a dihydrobenzoxazine ring has a smaller molecular weight than an epoxy resin or a phenol resin. growing. The crosslink density of the cured epoxy resin varies with the molecular structure of the curing agent used, the molecular structure of the epoxy resin, and the amount of the inorganic filler added. By adding a compound having a dihydrobenzoxazine ring showing a higher crosslink density to the epoxy resin composition, an effect of increasing the crosslink density of the finally obtained cured epoxy resin resin can be obtained.

When a compound having a dihydrobenzoxazine ring is used for controlling the crosslink density of a cured epoxy resin, the following advantageous characteristics can be mentioned. That is,
Since the curing reaction of the compound having a dihydrobenzoxazine ring does not involve generation of a volatile substance, when added to the epoxy resin composition, in the molding step, a uniform resin cured product in which bubbles and voids are hardly formed is obtained. . When a compound having a liquid dihydrobenzoxazine ring is used, the fluidity of the liquid type epoxy resin composition can be improved, and the amount of the inorganic filler added can be reduced. Further, the most important feature is a feature that can achieve high flame retardancy without using any halogen-based or phosphorus-based flame retardant.

The flame retardant used in the conventional epoxy resin composition flame-retarding technology has the disadvantage that the addition thereof reduces the hygroscopicity and heat resistance of the resin composition and the reliability of the product. Although there were cases, the flame-retardant epoxy resin composition obtained by the flame-retarding method of the present invention,
A small amount of a compound having a dihydrobenzoxazine ring, which itself has low hygroscopicity, is added and finally incorporated into a part of the resin structure, so that the original epoxy resin cured product such as water absorption properties, heat resistance, mechanical properties, etc. A high degree of flame retardancy of the cured epoxy resin can be achieved without impairing the basic characteristics.

As a technique relating to an epoxy resin composition using a compound having a dihydrobenzooxy ring, as described above, for example, JP-A Nos. 11-60898 and 1-1985.
1-1158352, JP-A-11-140278 and JP-A-9-59333 provide a technique for providing an epoxy resin composition for a semiconductor encapsulating resin using an epoxy resin, a phenol resin and a compound having a dihydrobenzoxazine ring in combination. Also known as

These conventional techniques aim at maintaining and improving various properties of the thermosetting resin having a benzoxazine ring, for example, water absorption properties, mechanical properties, curability, flame retardancy, storage stability and the like. This is a technique in which an epoxy resin or a phenol resin is added and used in combination, which is different from the mechanism of the present invention. This is because the present invention positions a compound having a benzoxazine ring as an additive for obtaining high flame retardancy while maintaining and improving the basic properties of the original epoxy resin cured product. different. In the present invention, a compound having a dihydrobenzoxazine ring, for example, a compound such as (1) to (6) is used as an additive to an epoxy resin or a phenol resin to form a resin composition. In the above prior art, the formalin is added to the phenolic resin, and a dihydrobenzoxazine-modified resin is synthesized by a heating step and then blended to obtain a resin composition. it is obvious.

In the present invention, the flame-retardant mechanism as described above was found, and in an epoxy resin composition comprising an epoxy resin, a curing agent and an inorganic filler, the amount of the compound having a dihydrobenzoxazine ring was determined by the amount of the inorganic filler. By adding 0.5 to 30% by weight to the resin components to be removed, a high level of V-0 flammability can be achieved without using a flame retardant in combination.

The compound having a dihydrobenzoxazine ring used in the present invention is not particularly limited as long as it is a compound having a dihydrobenzoxazine ring. For example, a compound represented by the following formulas (1) to (6) is used as a main component. Is desirable.

[0033]

Embedded image (R and R ′ in the formula are hydrogen, methyl group, allyl group, alkyl group having 2 to 10 carbon atoms, benzene and derivatives thereof,
Biphenyl and its derivatives, cyclohesican and its derivatives, diphenyl ether and its derivatives, condensed aromatic and its derivatives are shown. R ″ in the formula represents hydrogen and / or a methyl group. )

In particular, since the compound (1) is in a liquid state, a decrease in the fluidity of the resin composition is small when a liquid type epoxy resin composition is used. Further, for example, (1)-
Since the compounds (6) have different hygroscopicity and cross-link density, the amount of these compounds is changed, and when two or more types are added, the combination thereof is changed to change the resin. The nature of the composition can be varied as needed.

The compound having a dihydrobenzoxazine ring of the present invention is a ring-opened polymer composed of at least one compound having a dihydrobenzoxazine ring, and at least one or more dihydrobenzoxazine rings are included in the molecular structure of the ring-opened polymer. It is characterized by containing a benzoxazine ring.

The curing agent of the present invention is characterized by being a phenolic resin, and has a constitutional unit derived from phenols (A) and an aromatic compound (A) excluding phenols (A). A phenolic resin (C) containing in its molecule a structural unit derived from B). The aromatic (B) is a compound selected from the group consisting of benzene and its derivatives, naphthalene and its derivatives, and biphenyl and its derivatives.

The curing agent of the present invention is characterized in that it is a phenol resin having a repeating unit represented by the following formulas (7) and (8).

[0038]

Embedded image (X1 represents a bond having a chain structure containing an unsaturated bond having 1 to 6 carbon atoms or a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, and B represents an aromatic group.)

Although the phenolic resin of the present invention is not particularly limited, phenylene, polyaromatics,
It is desirable to use a special novolak phenolic resin containing at least one of the phenylenes to which condensed aromatics are added in the molecule. This is because the functional group contains aromatics, so that the crosslink density is lower than that of a conventional epoxy resin cured product, and this epoxy resin cured product softens when exposed to a high temperature due to flame contact or the like. It becomes a rubber-like material and promotes formation of a heat insulating structure such as a foamed structure and a void structure. In addition, since aromatics and condensed aromatics are contained in the resin structure, thermal decomposition resistance is improved and thermal decomposition becomes difficult, which gives an effect of reinforcing flame retardancy.

The epoxy resin of the present invention comprises bisphenol A and its derivatives, allyl-modified bisphenol A and its derivatives, bisphenol F and its derivatives, bisphenol AD and its derivatives, and bisphenol S and its derivatives. Its derivatives, benzene and its derivatives, naphthalene and its derivatives,
Anthracene and its derivatives, biphenyl and its derivatives,
It is any epoxy resin selected from the group consisting of fluorene and its derivatives, and diphenyl ether and its derivatives biphenyl.

The epoxy resin has a structure in which a phenolic hydroxyl group of a phenolic resin having the repeating units represented by the formulas (7) and (8) is glycidyl etherified, and the aromatic (B) Is a compound selected from the group consisting of benzene and its derivatives, naphthalene and its derivatives, and biphenyl and its derivatives.

Although the epoxy resin of the present invention is not particularly limited, it is an epoxy resin containing at least one of phenylene, phenylene, polyaromatics and condensed aromatics added in the molecular structure in the molecule. It is desirable.
This is because the functional group contains aromatics,
Crosslinking density is lower than conventional epoxy resin cured product,
The cured epoxy resin softens when exposed to high temperatures due to flame contact or the like to become a rubber-like material, and promotes the formation of a heat insulating structure such as a foamed structure or a void structure. In addition, since aromatics and condensed aromatics are contained in the resin structure, thermal decomposition resistance is improved and thermal decomposition becomes difficult, which gives an effect of reinforcing flame retardancy.

The amount of the inorganic filler of the present invention is 40 to 900 parts by weight based on the total weight of the resin mixture containing the compound having a dihydrobenzoxazine ring of 100.

By using the flame-retardant epoxy resin composition of the present invention, a semiconductor device having excellent flame retardancy can be provided. In the semiconductor device using the flame-retardant epoxy resin composition of the present invention, the range of the addition amount of the compound having a dihydrobenzoxazine ring varies depending on the resin used, but a sealing resin (mold resin) for electronic components. When used as a liquid epoxy resin or a liquid phenolic resin structure, in the case of a resin containing a benzene or biphenyl group, the resin component other than the inorganic filler is 2 to 2.
A blending ratio of 20% is particularly preferable because the flame retardancy is increased.

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. Examples thereof include phenol and naphthol such as α-naphthol and β-naphthol. , Bisphenol fluorene type phenol,
Alternatively, alkylphenols such as cresol, xylenol, ethylphenol, butylphenol, nonylphenol, octylphenol, bisphenol A,
Polyphenols such as bisphenol F, bisphenol S, resorcinol, catechol, phenylphenol,
Aminophenol and the like. The use of these phenols is not limited to one kind, 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, biphenyl and its derivatives, phenylene and its derivatives, diphenyl ether and its derivatives, naphthalene and its derivatives, anthracene and its derivatives, fluorene and its derivatives, and bisphenolfluorene. And its derivatives, bisphenol S and its derivatives, bisphenol F and its derivatives, bisphenol A and its derivatives, and the like.

Of these, biphenyl and its derivatives,
Phenylene and its derivatives are particularly preferred. The reason for this is that by having these aromatics in the resin structure, in addition to obtaining higher flame retardancy, the moisture resistance of the resin composition is also greatly improved.

The aromatics (B) preferably have a chain-like bonding group containing an unsaturated bond having 1 to 6 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. Examples of the binding group having a chain structure containing an unsaturated bond include an allyl group. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, and a propyl group.

Hereinafter, specific examples of the phenolic resin (C) are shown in formulas (9) to (20). However, the present invention is not limited to these examples.

[0050]

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[0051]

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[0052]

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[0053]

Embedded image (A in the formula represents CH2 = CHCH2-. N is from 0 to 10. However, when n is 11 or more, the resin viscosity becomes too large and the fluidity is lowered, which is not preferable.)

The phenolic resin containing an aromatic compound in the flame-retardant resin composition of the present invention is preferably a phenol-biphenyl resin in which the structure of the aromatic (B) is biphenyl or a derivative thereof, or And phenylene and its derivatives, phenol-phenylene resins.

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 that can be used in combination is not particularly limited. For example, phenol biphenyl triazine type resin, phenol phenylene triazine type resin, phenol triazine type resin, biphenyl-4,4′-dihydroxyl ether and 3,3 ', 5,5'-tetramethylbiphenyl-4,
4'-dihydroxyl ether, tetraphenylolethane, trisphenylolethane, phenol novolak resin, cresol novolak resin, bisphenol A
Type resin, bisphenol F type resin, bisphenol S type resin, polyphenol type resin, aliphatic phenol resin,
An aromatic ester type phenol resin, a cyclic aliphatic ester type phenol resin, an ether ester type phenol resin and the like can be mentioned.

The amine compound that can be used in combination is not particularly limited, and examples thereof include diaminodiphenylmethane, diethylenetriamine, and diaminodiphenylsulfone. These phenolic resins and amine compounds may be used alone or as a mixture of several types. Among these, phenol biphenyl triazine type resin, phenol phenylene triazine type resin, and phenol triazine type resin are particularly preferable in terms of enhancing flame retardancy.

The phenolic resin (C) may be a liquefied material that exhibits fluidity at room temperature or by heating. Specifically, the phenolic resin (C) may be an alkyl-modified phenolic resin and its derivative, or an allyl-modified phenolic resin. And its derivatives. Particularly, the aromatic (B) is phenylene and an allyl-modified phenol-phenylene aralkyl-type resin that is a derivative thereof, or the aromatic (B) is an allyl-modified phenol-biphenyl aralkyl-type resin that is biphenyl and a derivative thereof. Is desirable for flame retardancy.

The following formulas (21) and (22) show specific examples of the alkyl-modified phenolic resin showing fluidity at room temperature.

[0059]

Embedded image (The number of n in the formula is preferably from 0 to 3. The mixture is usually obtained as a mixture having different numbers of n, and the higher the composition ratio of 0, the better the fluidity. Is too large to reduce the fluidity. A in the structural formula represents an allyl group or a C1 to C4 alkyl group.)

The novolak type epoxy resin used in the present invention comprises a structural unit derived from phenols (A) and a structural unit derived from aromatics (B) other than phenols (A). Is a novolak-type epoxy resin in which the phenolic hydroxyl group of the phenolic resin (C) containing in its molecule glycidyl ether.

Examples of such novolak type epoxy resins include phenol biphenyl aralkyl type epoxy resin, phenol phenylene aralkyl type epoxy resin, phenol diphenyl ether aralkyl type epoxy resin, naphthalene containing novolak type epoxy resin, anthracene containing novolak type epoxy resin, biphenylene Novolak-containing epoxy resin containing fluorene, novolak epoxy resin containing fluorene, novolak epoxy resin containing bisphenolfluorene, novolak epoxy resin containing bisphenol S, novolak epoxy resin containing bisphenol F, and novolak epoxy resin containing bisphenol A. In addition, these epoxy resins are not limited to one type when used, and two or more types can be used in combination.

Formulas (23) to (34) show specific examples of the novolak type epoxy resin.

[0063]

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[0064]

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[0065]

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[0066]

Embedded image (A in the formula represents CH2 = CHCH2-. N is from 0 to 10. However, if n is 11 or more, the resin viscosity becomes too large and the fluidity is lowered, which is not preferable.)

The epoxy resin in the flame-retardant resin composition of the present invention is preferably a phenol-biphenyl resin in which the structure of the aromatic (B) is biphenyl or a derivative thereof, or a phenylene resin in which phenylene and a derivative thereof are phenylene. -It is desirable for the flame retardancy to be a ruphenylene type resin.

In the flame-retardant resin composition of the present invention, the epoxy resin is a phenolic compound of an alkyl-modified phenolic resin having fluidity at room temperature, represented by the formulas (23) to (34). A novolak-type liquid epoxy resin in which a hydroxyl group is glycidyl-etherified, and a derivative thereof can be used. In particular, the structure of the aromatic (B) is preferably a phenyl-biphenyl-type resin which is biphenyl and its derivative, or a phenol-phenylene-type resin which is phenylene and its derivative. Formulas (35) to (36) show specific examples of novolak-type epoxy resins that exhibit fluidity at room temperature.

[0069]

Embedded image (The number of n in the formula is preferably from 0 to 3. The mixture is usually obtained as a mixture having different numbers of n, and the higher the composition ratio of 0, the better the fluidity. Is undesirably too large to reduce the fluidity. In the structural formula, G represents a glycidyl group, A represents an allyl group, or a C1-C4 alkyl group.)

In the flame-retardant epoxy resin composition of the present invention, in addition to the above epoxy resin, bisphenol A and its derivatives, diallyl bisphenol A and its derivatives, bisphenol F and its derivatives, naphthalene and its derivatives, anthracene And an epoxy resin characterized by being a compound selected from the group consisting of phenylene and its derivatives, biphenyl and its derivatives, and fluorene and its derivatives.

Among these epoxy resins, diallyl bisphenol A type epoxy resin is an epoxy resin which is negative in the Ames test and has very low mutagenicity. When the composition is used as an epoxy resin, a major feature is that in addition to high flame retardancy, an epoxy resin composition exhibiting no mutagenic property and excellent in safety can be provided.

The weight average molecular weight of the phenolic resin and the epoxy resin contained in the flame-retardant epoxy resin composition of the present invention is not particularly limited, but is, for example, 300 to 10,000. The weight average molecular weight can be measured by GPC (gel permeation chromatography).

Further, for the curing agent and the epoxy resin constituting the flame-retardant epoxy resin composition of the present invention, the ratio (Ep) of the total number of epoxy groups of the epoxy resin to the total number of hydroxyl groups (OH) of the curing agent (Ep) OH / Ep) 0.7 to
When it is 2.5, it is more suitable for improving the flame retardancy of a cured product obtained by curing these. (OH / E
When p) is less than 0.7, the amount of combustible components such as allyl alcohol generated from the epoxy group remaining in the crosslinked structure formed by the curing agent and the epoxy resin in the cured product increases. Therefore, there is a possibility that the improvement of the flame retardancy is hindered. When the (OH / Ep) is more than 2.5, the crosslinking density of the cured product obtained by reacting the epoxy resin with the curing agent may be too low, resulting in insufficient curing. The heat resistance and strength of the cured product may be insufficient.

As the inorganic filler of the present invention, known fillers generally used for semiconductor encapsulating resins can be used. For example, fused silica, crystalline silica, alumina,
Powders of zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, beryllia, talc, titanium oxide, zirconia and the like, and / or fibers such as glass fiber and carbon fiber. One of these inorganic fillers may be used alone, or two or more thereof may be used in combination. Particularly, for an epoxy resin composition for a semiconductor device, a powder of fused silica or crystalline silica is preferable.

The content of the inorganic filler used in the flame-retardant epoxy resin composition of the present invention is 40 to 900 parts by weight based on 100 of the total weight of the resin component containing the benzoxazine compound. The addition amount of the inorganic filler is not particularly limited within this range because the optimum addition amount varies depending on the intended use. For example, in the epoxy resin composition used in the liquid sealing material, high fluidity is required in a low temperature range including around room temperature, so the addition amount of the silica inorganic filler is slightly lower, from 40 parts by weight to 200 parts by weight. It also becomes important to use it. Alternatively, in an epoxy resin composition for a semiconductor which is resin-encapsulated by a normal transfer molding method, further,
Since a high inorganic filler composition is required, the use of 200 to 900 parts by weight is important. When the content of the inorganic filler is less than 40 parts by weight based on the weight of the resin component containing the benzoxazine compound, the coefficient of thermal expansion is large and is not suitable for a semiconductor sealing resin.

In the flame-retardant epoxy resin composition of the present invention, in order to further improve the flame retardancy, an epoxy resin having a nitrogen-containing heterocycle in the molecule or a phenol resin is used. Can be.

Epoxy resins having a nitrogen-containing heterocyclic ring in the molecule include triazine derivatives, pyridine derivatives, pyrimidine derivatives, pyridazine derivatives, pyrrole derivatives, 2H-pyrrol derivatives, pyridine derivatives, oxadizole derivatives. , Isoxadizole derivatives, thiazo-
Derivatives, isothiazole derivatives, furazane derivatives, imidazole derivatives, pyrazol derivatives, indole derivatives, isoindole derivatives, carbazole derivatives, quinoline derivatives, isoquinoline derivatives, 4H-quinoline derivatives, phenanthridine Derivatives, acridine derivatives, 1,
8-naphthyridine derivative, benzimidazole derivative, 1
H-indazole water body, quinoxaline derivative, quinazoline derivative, cinnoline derivative, phthalazine derivative, purine derivative, pteridine derivative, perimidine derivative,
An epoxy resin containing at least one of a 1,10-phenancholine derivative, a phenoxazine derivative, a phenothiazine derivative, and a phenazine derivative in a molecule can be used. Among them, an epoxy resin containing a triazine derivative is more preferable. Equations (37) to (3)
9) shows a general formula.

[0078]

Embedded image (Wherein R 1 is methylene, —CH 2 NH—, phenylene,
Phenylene to which an alkyl group has been added, a glycidyloxyphenyl derivative, a polyaromatic, a condensed aromatic, and
Two or more substituents selected from these are linked, and R2 is hydrogen, an amine derivative, an aromatic, a hydrocarbon having 1 to 10 carbon atoms, and an analog thereof; R3 represents a hydrogen amine derivative, an aromatic compound, a glycidyloxyphenylene derivative, or an analog thereof, and G represents a glycidyl group. Further, the number of n in the formula is 1 to 10, and when it is larger than that, the resin viscosity becomes too high and the fluidity decreases.)

Among the epoxy resins having a nitrogen-containing heterocycle in the molecule used in the flame-retardant epoxy resin composition of the present invention, the epoxy resin containing a triazine derivative in the molecule has a particularly preferable chemical structure. The following equation (4)
0) to (42).

[0080]

Embedded image (Wherein G is a glycidyl group, and the numbers of n and m are 0 to 1)
0 and R2 are hydrogen, an amine derivative, an aromatic compound, and having 1 to 1 carbon atoms.
Shows 10 hydrocarbons. If n and m are further increased, the resin viscosity becomes too high and the fluidity is reduced. )

The phenolic resin having a nitrogen-containing heterocyclic ring in the molecule used in the liquid resin composition of the present invention includes triazine derivatives, pyrazine derivatives, pyrimidine derivatives,
Pyridazine derivative, pyrrole derivative, 2H-pyrrol derivative, pyridine derivative, oxadizole derivative, isoxadizole derivative, thiazole derivative, isothiazo-derivative
Derivatives, furazane derivatives, imidazole derivatives, pyrazol derivatives, indole derivatives, isoindole derivatives, carbazole derivatives, quinoline derivatives, isoquinoline derivatives, 4H-quinoline derivatives, phenanthridine derivatives, acridine derivatives, 1,8-naphthyridine derivative, benzimidazole derivative, 1H-indazole water body, quinoxaline derivative, quinazoline derivative, cinnoline derivative, phthalazine derivative, purine derivative, pteridine derivative, perimidine derivative, 1,10-phenancholine derivative A phenol resin containing at least one of a phenoxazine derivative, a phenothiazine derivative, and a phenazine derivative in a molecule can be used. Among them, a phenol resin containing a triazine derivative is more preferable, and particularly preferable structures are represented by the following formulas (43) to (45).
Shown in

[0082]

Embedded image (Wherein R 1 is methylene, —CH 2 NH—, phenylene,
Phenylene to which an alkyl group has been added, a glycidyloxyphenyl derivative, a polyaromatic, a condensed aromatic, and
Two or more substituents selected from these are linked, and R and 2 are hydrogen, amine derivatives, aromatics,
Hydrocarbons having 1 to 10 carbon atoms and analogs thereof, and R3 is a hydrogenamine derivative, an aromatic compound, a glycidoxyphenylene derivative, and an analog thereof. The number of n is from 1 to 10, and if it is larger than that, it is not preferable because the resin viscosity becomes too high and the fluidity decreases.

Among the phenolic resins used in the flame-retardant epoxy resin composition of the present invention and having a heterocyclic ring containing a nitrogen atom in the molecule, a phenolic resin containing a triazine derivative in the molecule.
Formulas (46) to (48) below show specific examples of the chemical structure particularly desirable as a toluene-based resin.

[0084]

Embedded image (R2 in the above formula is hydrogen, an amine derivative, an aromatic, a hydrocarbon having 1 to 10 carbon atoms, or an analog thereof. The number of n and m is 0 to 10, and is larger than that. If this is the case, the resin viscosity becomes too high and the fluidity decreases, which is not preferred.)

In addition to the epoxy resin and / or phenolic resin having a nitrogen-containing heterocyclic ring in the molecule, other components containing a nitrogen atom may be used alone or in combination. May be used in combination.

The epoxy resin composition of the present invention may further comprise, if necessary, triphenylphosphine, 2-methylimidazo-, which promotes a curing reaction between an epoxy group and a phenolic hydroxyl group. 1,8-diazabi-sicco (5,4,0) undecene, aromatic dimethylurea, alicyclic dimethylurea, curing accelerator for bicyclic amidine compounds, colorant such as carbon black, γ-gly Various additives such as silane coupling agents such as sidoxypropyltrimethoxysilane, low-stress components such as silicone oil and silicone rubber, release agents such as natural wax, synthetic wax, higher fatty acids and their metal salts, and paraffin are suitably used. It can be mixed.

In the flame-retardant epoxy resin composition of the present invention, a metal hydroxide can be used to further improve the flame retardancy. If necessary, a phosphorus-based flame retardant can be used in combination. In this case, a higher-grade flame retardancy can be obtained.

The hydroxides used in the present invention include aluminum, magnesium, zinc, boron, calcium, nickel, cobalt, tin, molybdenum, copper, iron, and the like.
The metal hydroxide is preferably composed of at least one element selected from titanium. Specific examples of metal hydroxides include aluminum hydroxide, magnesium hydroxide, zinc borate, calcium hydroxide, nickel hydroxide, cobalt hydroxide, tin hydroxide, zinc molybdate, copper hydroxide, and hydroxide. Metal hydroxide mainly composed of iron or the like can be used. In addition, a solid solution composed of two or more kinds of metal oxides, specifically, a hydrate mainly composed of a solid solution of magnesium oxide and nickel oxide can be used. Alternatively, one of the metal hydroxides may be coated with another metal hydroxide for use.

Alternatively, the surface of the metal hydroxide may be modified with an organic surface treatment agent such as a silane coupling agent, a titanate coupling agent, stearic acid, or an epoxy resin. Depending on the type and combination of resin systems, processability, heat resistance, and adhesion are improved.
More preferable characteristics are obtained. Among these, aluminum hydroxide, magnesium hydroxide, and zinc borate are preferred from the viewpoint of improving flame retardancy. In addition, aluminum hydroxide
It is particularly preferable because it has excellent resistance to acids and alkalis and also has excellent processability of the cured product.

As a catalyst for promoting the ring-opening polymerization reaction of a compound having a dihydrobenzoxazine ring, benzoic acid, malonic acid, succinic acid, maleic acid, maleic anhydride, glutaric acid, adipic acid, phthalic acid, phthalic anhydride And organic carboxylic acids such as dodecanoic acid and dodecane diacid, and other organic acids and organic acid salts such as organic dicarboxylic acid and carboxylate, and toluenesulfonic acid, and are not limited to the above compounds. When a compound having a dihydrobenzoxazine ring is added to a mixture of an epoxy resin and a phenol resin, the curing reaction rate between the epoxy resin and the phenol resin decreases due to an increase in the amount of the compound. If the aforementioned organic acids are used in combination, the curing speed of the resin composition can be increased. In the prior art, a technique for improving the curing rate of a resin composition mainly containing a compound having a dihydrobenzoxazine ring by using a phenol resin in combination has been disclosed. Instead of using a phenolic resin for improvement, it is necessary to improve the flame retardancy and adhesive strength of the epoxy resin and phenolic resin, which are expected to have certain physical properties, in advance. For this reason, it is different in that a small amount of a compound having a dihydrobenzoxazine ring is added, and the insufficiency of the curing reaction rate is supposed to be improved by using various organic acids in combination as necessary.

The chemical structures of the phenolic resin and the epoxy resin used in the resin composition of the present invention may be the same or different, and the combination is not limited. In particular, when the unique phenolic resin and the unique epoxy resin of the present invention have a remarkable flame retardant effect, but only one of the epoxy resin and the curing agent has a unique structure described in the present invention. High flame retardancy can be obtained.

The flame-retardant epoxy resin composition of the present invention includes a liquid type. However, it is not necessary that both the epoxy resin and / or the phenolic resin be of the liquid type. A combination that is liquid and exhibits fluidity when mixed and dissolved. Alternatively, a non-reactive diluent or a reactive diluent may be added to impart fluidity, and the combination thereof is not limited, but the addition of a diluent or the like tends to reduce the flame retardancy. It is more preferable to use an epoxy resin or a curing agent having high fluidity. Here, fluidity refers to room temperature (2
5 ° C.) before the curing reaction at 100 ° C. poise. By using such a fluid epoxy resin and / or phenol resin, an effect of good compatibility can be obtained when a liquid type compound having a dihydrobenzoxazine ring is used.

The epoxy resin composition of the present invention includes, for example,
It can be manufactured by pre-kneading the constituent materials with a ribbon blender or a Henschel mixer and then mixing them using a heating roll or a kneader. Then, after degassing the organic solvent and moisture as required, the epoxy resin composition is heated under a predetermined molding condition by a transfer molding machine or a heat press molding machine to cause a crosslinking reaction to be cured. Thereby, a molded article of a cured epoxy resin having high flame retardancy can be obtained.

The semiconductor device of the present invention is one in which an electronic component such as a semiconductor is sealed using the flame-retardant epoxy resin composition of the present invention. In this case, as the semiconductor device of the present invention, for example, a semiconductor device in which a semiconductor element mounted on a die pad of a lead frame is sealed with resin, a lead-on-chip type resin-sealed semiconductor device, a ball grid array Examples include, but are not limited to, resin-encapsulated semiconductor devices, and semiconductor devices of the present invention include all electronic components such as semiconductors sealed with the epoxy resin composition of the present invention. Include.

In addition, the flame-retardant epoxy resin composition of the present invention has good flame-retardant properties and safety even when used for other purposes, that is, when used as molding materials, casting materials, adhesives, paints and the like. Excellent.

Further, it can be used for a laminated board such as a printed board. When used in a laminate, a higher degree of flame retardancy can be achieved by using a metal hydroxide in combination as a heat absorbing agent, but the amount of the metal hydroxide to be added is lower than when a conventional resin is used. Since it can be reduced, drill workability and the like are improved.

[0097]

EXAMPLES Next, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples. First, raw materials used in Examples and Comparative Examples will be described.

[Compound having a dihydrobenzoxazine ring] 3,4-dihydro-3-phenyl-2H-1,3
-Benzoxazine (molecular weight: 211.26, viscosity 1
(7.8P / 25 ° C)

[Silane coupling agent] N-phenyl-
γ-aminopropyltrimethoxysilane

[Inorganic filler] Fused spherical silica (average particle size: 4.5 μm, specific surface area (measured by BET method): 2.9 m 2 /
g) [Curing acceleration catalyst] triphenylphosphine (molecular weight 262.29, melting point 78-82 ° C, JIS reagent special grade)

[Metal hydroxide] Aluminum hydroxide (average particle size 8 μm)

[Phenolic resin 1] phenol novolak resin (hydroxyl equivalent 106 g / eq) [phenolic resin 2] phenolphenylene resin (hydroxyl equivalent 175 g / eq) [phenolic resin 3] phenol biphenyl resin (hydroxyl equivalent 208 g / eq) [Phenol resin 4] Liquid phenol phenylene resin (viscosity: 760 poise / 25 ° C., hydroxyl equivalent: 155 g)
/ Eq) [Phenolic resin 5] Liquid phenol biphenyl resin (viscosity: 2000 poise / 25 ° C, hydroxyl equivalent: 165)
g / eq)

[Epoxy resin 1] bisphenol A diglycidyl ether (viscosity of 120 to 150 poise / 25
° C, epoxy equivalent 184-194 g / eq) [Epoxy resin 2] diallyl bisphenol A diglycidyl ether (viscosity 35.50 poise / 25 ° C, epoxy equivalent 223 g / eq) [Epoxy resin 3] phenol phenylene epoxy resin ( (Epoxy equivalent: 238 g / eq) [Epoxy resin 4] phenol biphenyl epoxy resin (Epoxy equivalent: 270 g / eq) [Epoxy resin 5] Phenol novolak type epoxy resin (Epoxy equivalent: 194 g / eq)

[Nitrogen-containing resin] Phenol triazine resin (nitrogen atom content: 19% by weight, hydroxyl equivalent: 220 g /
eq)

[Evaluation of Flame Retardancy] The flame retardancy of the epoxy resin cured products shown in Examples and Comparative Examples was measured according to UL-94. That is, the formed plate is fixed by the sample support (clamp) so that the length direction of the formed plate is perpendicular to the ground. Next, after an indirect flame was applied to the end face of the molded plate on the side opposite to the clamp with a burner for 10 seconds, the burner was moved away and the time during which the flame remained on the molded plate (after-flame time, seconds) was measured (first time). Afterflame time = F1). When this flame goes out, after indirect flame with the burner again for 10 seconds, move the burner away,
Residual flame time as in the first time (second residual flame time = F
Measure 2). This test was performed using five molded plates for one cured resin to evaluate the flame retardancy. However, when the criteria for determining the flame retardancy are arranged in the order from the highest to the lowest, UL94V-0, V-1, V-2, NOT
The order is V-2.

(1) UL94V-0 ΣF ≦ 50 seconds (Σ
F shows the total afterflame time of the test performed using five molded plates. That is, F1 and F2 are measured for one formed plate, and the sum of these is defined as the total afterflame time F of one formed plate. This was measured for five molded plates, and the sum was defined as ΔF. Fmax ≦ 1
0 seconds (Fmax indicates the longest after-flame time among F1 or F2 obtained in the test.) No drip (a phenomenon in which a cured product drops due to flame contact) and does not burn to the clamp.

(2) UL94V-1 ΔF = 250 seconds,
Fmax ≦ 30 seconds, no drip, does not burn up to the clamp.

(3) UL94V-2 ΔF ≦ 250 seconds,
Fmax ≦ 30 seconds, drip, not burning up to the clamp.

(4) UL94 NOT V-2 ΔF>
250 seconds, Fmax> 30 seconds, burns out to clamp.

[Examples] Examples and comparative examples will be described below in detail.

Example 1 An epoxy resin and a phenolic resin were mixed at a ratio (OH / Ep) of 1.0 to the total number of epoxy groups (OH) of the epoxy resin and the total number of hydroxyl groups of the curing agent (OH). 10% by weight of a compound having a dihydrobenzoxazine ring was added thereto, and 100 parts by weight of a fused spherical silica powder was added to 100 parts by weight of the total resin containing the compound having a dihydrobenzoxazine ring.
Further, based on 100 parts by weight of the resin composition containing the resin and the silica inorganic filler, 0.5 parts by weight of triphenylphosphine, 0.3 parts by weight of carnauba wax and 0. 2 parts by weight and 1.0 part by weight of a silane coupling agent were added, and the mixture was preliminarily mixed at room temperature, kneaded on a roll at 100 ° C. for about 5 minutes, and then cooled and pulverized to obtain a tree composition. A tablet (tablet) obtained by compressing the resin composition described in Example 1 into a tablet is preheated to 85 ° C. to obtain a single plunger type transfer.
-Using a molding machine, injection time 15 seconds, injection pressure 100k
g / cm2 (execution pressure), molding temperature 175 ° C, molding time 1
After molding for 20 seconds in accordance with the UL94 flame retardant standard, it was cured (175 ° C., 6 hours) to obtain a molded plate for a flame retardant test. The molded plate obtained in Example 1 was processed to prepare a flame contact test piece, and a flame contact test according to UL94 flame retardant standard was performed to evaluate the flame retardancy. The evaluation results are shown in Table 1 described later.

[Examples 2 to 5] Hereinafter, in Examples 2 to 5 according to the respective formulations described in Examples 2 to 5 in Table 1, epoxy resin curing was performed in the same procedure as in Example 1. A molded plate of the product was prepared, and the flame retardancy was evaluated by a vertical flame contact test of UL94 flame retardant standard. Table 1 shows the evaluation results.

[Examples 6 to 9] The number of epoxy groups (E
p) and the ratio of the total number of hydroxyl groups (OH) of the curing agent (OH) (OH /
Ep) was weighed in such a manner as to give a value of 1.0. First, triphenylphosphine as a curing accelerating catalyst was added to the phenolic resin, and the mixture was heated to 100 ° C. to prepare triphenylphosphine and the phenolic resin. After the compatibilization, the mixture was cooled to room temperature, the previously weighed epoxy resin was added, and a compound having a dihydrobenzoxazine ring was added to the mixture of the epoxy resin and the phenol resin by 10% by weight to form a dihydrobenzoxazine ring. Total weight of resin containing compound having 100
100 parts by weight of fused spherical silica powder, 0.3 parts by weight of carnauba wax, 0.2 parts by weight of carbon black and 100 parts by weight of silane cup with respect to 100 parts by weight of the resin composition containing a silica inorganic filler. 1.0 part by weight of a ring agent was added, and the mixture was stirred and mixed for about 5 minutes using a mixer, and subjected to vacuum degassing for 15 minutes while heating at 90 ° C. to obtain a resin composition. The resin compositions described in Examples 6 to 9 were heated to about 90 ° C., sandwiched between two 10 mm-thick glass sheets via a Teflon (registered trademark) sheet, and cured at 175 ° C. After curing for 24 hours, a molded plate for a flame retardant test was obtained. This molded plate was processed into a test piece shape conforming to the UL flame retardant standard to obtain a flame contact test piece. Example 4
Using the flame contact test piece obtained in the above, a vertical flame contact test of UL94 flame retardant standard was performed to evaluate the flame retardancy. The evaluation results are shown in Table 1 described later.

[0114]

[Table 1]

[Examples 10 to 15] Printed board 1
After a predetermined amount of methyl ethyl ketone and a silane coupling agent were put into a varnish control flask, a predetermined amount of aluminum hydroxide was added, and the mixture was stirred at room temperature for 1 hour to perform a surface treatment. The treatment liquid was heated to 50 ° C., and the epoxy resin 4, the phenol resin 5, and the compound containing a dihydrobenzoxazine ring were introduced. After confirming that all of these components were dissolved, a curing accelerator was added and the mixture was stirred for 30 minutes to prepare a varnish by adjusting a varnish solution (a nonvolatile component at 70% by weight).

After a varnish was impregnated into a glass cloth having a thickness of 0.2 mm, it was dried for a predetermined time by a solvent dryer set at 160 ° C. to obtain a prepreg.

Four molded prepregs were stacked, and 18 μm copper foils were arranged on both surfaces thereof to perform press molding. The pressing conditions were as follows: a heating rate of 5 ° C./min, and holding at 180 ° C. for 60 minutes.
Cooled to 30 ° C. for 30 minutes. The molding pressure is 2.45
The measurement was carried out at a pressure of 40 mmHg at a pressure of MPa.

Evaluation of Flame Retardancy The above double-sided copper-clad laminate was
The exterior copper foil that had been etched on both sides was subjected to a UV94V flame retardancy test (0.8 mm plate thickness).

Preparation of varnish on printed board 2 Amount of silicone oligomer-1 having about 20 repeating units of siloxane with a polymer of tramethoxysilane becomes 1% by weight based on metal hydrate. In this way, a solution in which a predetermined amount of methyl ethyl ketone, silicone oligomer-1, and aluminum hydroxide were charged was stirred at room temperature for 1 hour to perform a surface treatment. Heating the above processing solution to 50 ° C.,
The epoxy resin, curing agent, and benzoxazine were charged. After confirming that the input components were dissolved, a curing accelerator was added and the mixture was stirred for 30 minutes to prepare a varnish solution (nonvolatile content: 70% by weight).

Surface Treatment of Glass Cloth A polymer obtained by mixing tetramethoxysilane and dimethoxymethylsilane in a molar ratio of 2: 1.
Epoxy-modified silicone oligomer 2 was obtained by blending 1 mol of allyl glycidyl ether with 3 mol of about 5 silicone oligomers. A glass cloth from which oil has been removed by heat treatment is immersed in a treatment solution in which the silicone oligomer 2 and methanol are blended in a predetermined ratio, and the glass cloth is heated and dried at 120 ° C., so that the adhesion amount of the silicone glue is 0. It was adjusted to be 1% by weight. The coating, molding, and evaluation of flame retardancy were performed in the same manner as described above.

The epoxy resin and the curing agent used in Examples 16 to 21 shown in Table 2 were the total of the number of epoxy groups (Ep) of the epoxy resin and the number of hydroxyl groups of the curing agent (OH).
And (OH / Ep) was 1.0. The numerical values described in the table represent the weight ratio between the epoxy resin and the phenol resin. The amount of the dihydrobenzoxazine ring-containing material 2 described in Examples 16 to 21 is based on the total weight of the nonvolatile components of the resin composition containing the epoxy resin, the phenol resin, the aluminum hydroxide, and other minor additives. Indicates the weight ratio (% by weight). The addition amount of the silane coupling agent and the silicone oligomer 1 described in Examples 16 to 21 represents a weight ratio to the total weight of aluminum hydroxide. Silico described in Examples 16 to 21
The amount of the oligomer 2 added represents a weight ratio to the total weight of the glass cloth. The amounts of the curing accelerators described in Examples 16 to 21 represent the weight ratio to 100 parts by weight of the epoxy resin.

[0122]

[Table 2]

[Comparative Examples] [Comparative Examples 1 to 7] Also in Comparative Examples 1 to 7, the solid epoxy resin cured product was prepared according to the preparation procedure described in Example 1 and the liquid type epoxy resin cured product was obtained. An epoxy resin cured product was produced according to the production procedure described in Example 6, and the flame retardancy was evaluated by a vertical flame contact test of UL94 flame retardant standard. Table 3 shows details of the evaluation results of each test piece.

[0124]

[Table 3]

In Examples 1 to 4, the epoxy resin having a phenol-biphenyl structure and the phenol resin
It is a cured resin to which a compound having a dihydrobenzoxazine ring is added in an amount of up to 30% by weight. When a compound having a dihydrobenzoxazine ring is added in this range, UL9 is added without adding any other flame retardant.
4 High flame retardancy of V-0 level of flame retardant standard is achieved.

In Example 5, the use of other resins was examined.
It is a cured resin using a phenol-phenylene type epoxy resin and a curing agent. Also in this case, it is understood that a high degree of flame retardancy can be obtained as in the case of using the phenol-biphenyl structure.

On the other hand, Comparative Examples 1 to 7 show resin compositions obtained by adding a compound having a dihydrobenzoxazine ring to various epoxy resins and phenol resins in a proportion other than 1 to 30% by weight. It is a cured product. Comparative Example 1 in which no compound having a dihydrobenzoxazine ring was added at all
Comparative Example 4, Comparative Example 5 used at less than 0.5%, and Comparative Examples 6 and 8 used at more than 30% by weight
Did not provide high flame retardancy, but rather became more flammable.

Examples 6 to 9 are resin cured products using a phenolic resin, which is a liquid type epoxy resin.
When the addition ratio of the compound having a dihydrobenzoxazine ring is in the range of 0.5 to 30% by weight, high flame retardancy can be obtained. In addition, by combining a general-purpose type bisphenol A type liquid epoxy resin with a curing agent having a phenol-phenylene or phenol-biphenyl structure having excellent thermal decomposition resistance, a high degree of flame retardancy of the cured resin is obtained. Is obtained.

Example 9 is a cured resin obtained by adding phenol triazine as a nitrogen-containing resin to Example 8. It can be seen that the flame retardancy was improved by the combined use of the nitrogen-containing resin. Such flame-retardant reinforcing cures are also found in other resin systems.

Examples 10 to 15 are cured products obtained when the resin composition of the present invention is used for a laminate used for a printed wiring board or the like. The compound having a dihydrobenzoxazine ring is also added to the laminate in an amount of 0.5 to 30 with respect to the total weight of the non-volatile components excluding glass cloth.
It can be seen that a high degree of flame retardancy can be obtained by adding within the range of weight%. In addition, by using aluminum hydroxide in combination as a heat absorbing agent, the thickness of the laminated board becomes 0.8
High flame retardancy is achieved even for test specimens of mm. Aluminum hydroxide used as a heat-absorbing agent has a higher flame retardant effect as its addition amount increases, but when the addition amount increases, there arises a problem that the formability and drill workability of the laminated board decrease, Since the cured resin using a compound having a benzoxazine ring is highly flame-retardant,
This has the effect of reducing the amount of aluminum hydroxide added.

Incidentally, the properties of the cured resin products described in Examples 1 to 15 such as the thermal decomposition resistance, the moisture absorption properties, the solder heat resistance, and the electrical properties were confirmed to be at a sufficient level.

[0132]

As described above, the flame-retardant epoxy resin composition of the present invention comprises an epoxy resin composition comprising an epoxy resin, a curing agent, and an inorganic filler, wherein the compound having a dihydrobenzoxazine ring is replaced with an inorganic filler. By adding in the range of 0.5 to 30% by weight with respect to the resin components to be removed, no conventional flame retardant such as a halogen-based flame retardant or a phosphorus-based flame retardant is used, and the inorganic filler is highly filled. The high flame retardancy of the cured epoxy resin can be obtained without performing the method, and a molded article or a semiconductor device using the flame-retardant epoxy resin composition can be provided.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 23/29 H01L 23/30 R 23/31 F-term (Reference) 4J002 CC03X CC04X CD00W CD04W CD05W CD06W CD07W CD20W DA016 DE096 DE136 DE146 DE236 DJ006 DJ016 DJ046 DK006 DL006 EU237 FA046 FD016 FD137 GQ00 GQ05 4J036 AD01 AD08 AF01 AF05 AF06 DC02 DC06 DC10 FA01 FA12 FB07 JA07 4M109 AA01 BA01 CA21 EA04 EB03 EB04 EB06 EB08 EB09 EB13

Claims (21)

[Claims] 1. An epoxy resin composition comprising an epoxy resin, a curing agent and an inorganic filler, wherein a compound having a dihydrobenzoxazine ring is contained in an amount of 0.5 to 30% by weight based on a resin component excluding the inorganic filler. A method for making an epoxy resin composition flame-retardant, characterized by adding in (1). 2. An epoxy resin composition comprising an epoxy resin, a curing agent, and an inorganic filler, wherein a compound having a dihydrobenzoxazine ring has a structure represented by the following formula (1) to formula (6) as a main component: The method for flame retarding an epoxy resin composition according to claim 1, wherein the epoxy resin composition is added in an amount of 0.5 to 30% by weight based on a resin component excluding the inorganic filler. Embedded image (R and R ′ in the formula are hydrogen, methyl group, allyl group, alkyl group having 2 to 10 carbon atoms, benzene and derivatives thereof,
Biphenyl and its derivatives, cyclohesican and its derivatives, diphenyl ether and its derivatives, condensed aromatic and its derivatives are shown. R ″ in the formula represents hydrogen and / or a methyl group. ) 3. An epoxy resin composition comprising an epoxy resin, a curing agent, and an inorganic filler, wherein the compound having a dihydrobenzoxazine ring has a dihydrobenzoxazine ring having a structure represented by the above formulas (1) to (6). 3. The method for flame-retarding an epoxy resin composition according to claim 1, wherein the mixture is a mixture of two or more compounds having the following formula: 4. An epoxy resin composition comprising an epoxy resin, a curing agent and an inorganic filler, wherein the compound having a dihydrobenzoxazine ring is represented by the formula (1) to the formula (6).
A ring-opening polymer comprising at least one compound having a dihydrobenzoxazine ring having a structure represented by the formula, characterized in that the ring-opening polymer contains at least one or more dihydrobenzoxazine rings in its molecular structure. Claim 1
3. The method for making an epoxy resin composition flame-retardant according to item 1. 5. An epoxy resin composition comprising an epoxy resin, a curing agent, and an inorganic filler, wherein the curing agent is a phenolic resin. A method for making an epoxy resin composition flame-retardant. 6. An epoxy resin composition comprising an epoxy resin, a curing agent and an inorganic filler, wherein a compound having a dihydrobenzoxazine ring is contained in an amount of 0.5 to 30% by weight based on a resin component excluding the inorganic filler. A flame-retardant epoxy resin composition characterized by being added in the following. 7. An epoxy resin composition comprising an epoxy resin, a curing agent and an inorganic filler, wherein the compound having a dihydrobenzoxazine ring has a structure represented by the following formulas (1) to (6) as a main component. The flame-retardant epoxy resin composition according to claim 6, wherein the composition is added in an amount of 0.5 to 30% by weight based on a resin component excluding the inorganic filler. 8. An epoxy resin composition comprising an epoxy resin, a curing agent and an inorganic filler, wherein the compound having a dihydrobenzoxazine ring is represented by the formula (1) to the formula (6).
The flame-retardant epoxy resin composition according to claim 6, which is a mixture of two or more compounds having a dihydrobenzoxazine ring having a structure represented by the following formula: 9. An epoxy resin composition comprising an epoxy resin, a curing agent and an inorganic filler, wherein the compound having a dihydrobenzoxazine ring is represented by the formula (1) to the formula (6).
A ring-opened polymer comprising one or more compounds having a dihydrobenzoxazine ring represented by the formula, characterized in that the ring-opened polymer contains at least one or more dihydrobenzoxazine rings in the molecular structure thereof, The flame-retardant epoxy resin composition according to claim 6. 10. An epoxy resin composition comprising an epoxy resin, a curing agent and an inorganic filler, wherein the curing agent is pheno
The flame-retardant epoxy resin composition according to any one of claims 6 to 9, wherein the composition is a polyester resin. 11. The curing agent according to claim 1, wherein the curing agent is composed of a structural unit derived from phenols (A) and a structural unit derived from aromatics (B) excluding the phenols (A). The flame-retardant epoxy resin composition according to any one of claims 6 to 10, which is a phenolic resin (C) contained therein. 12. The method according to claim 6, wherein the curing agent is a phenolic resin having a repeating unit represented by the following formulas (7) and (8). The flame-retardant epoxy resin composition according to the above. Embedded image (X1 represents a bond having a chain structure containing an unsaturated bond having 1 to 6 carbon atoms or a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, and B represents an aromatic group.) 13. The curing agent is a phenolic resin having the repeating units represented by the formulas (7) and (8), and the aromatics (B) constituting the phenolic resin. Is a compound selected from the group consisting of benzene and its derivatives, naphthalene and its derivatives, and biphenyl and its derivatives.
The flame-retardant epoxy resin composition according to claim 12. 14. An epoxy resin comprising bisphenol A and a derivative thereof, allyl-modified bisphenol A and a derivative thereof, bisphenol F and a derivative thereof, bisphenol AD and a derivative thereof, and bisphenol S and a derivative thereof. An epoxy resin selected from the group consisting of derivatives, benzene and its derivatives, naphthalene and its derivatives, anthracene and its derivatives, biphenyl and its derivatives, fluorene and its derivatives, and diphenyl ether and its derivatives biphenyl. The flame-retardant epoxy resin composition according to any one of claims 6 to 10, which is characterized in that: 15. The pheno resin wherein the epoxy resin has a repeating unit represented by the formulas (7) and (8).
A phenolic hydroxyl group of a phenolic resin, wherein the aromatic (B) is selected from the group consisting of benzene and its derivatives, naphthalene and its derivatives, and biphenyl and its derivatives. The flame-retardant epoxy resin composition according to claim 14, wherein: 16. The curing agent is a phenolic resin having the repeating units represented by the formulas (7) and (8), and the epoxy resin is represented by the formulas (7) and (8). It has a structure in which a phenolic hydroxyl group of a phenolic resin having a repeating unit is glycidyl-etherified, and the aromatics (B) constituting these epoxy resin and phenolic resin structures are benzene and its derivatives. The flame-retardant epoxy resin composition according to any one of claims 6 to 10, wherein the compound is selected from the group consisting of: naphthalene and a derivative thereof, and biphenyl and a derivative thereof. . 17. An epoxy resin composition comprising an epoxy resin, a curing agent, and an inorganic filler, wherein a ratio (OH) of a total number of epoxy groups (Ep) of the epoxy resin to a total number of hydroxyl groups (OH) of the curing agent. / Ep) is 0.7
The flame-retardant epoxy resin composition according to any one of claims 6 to 16, wherein 18. An epoxy resin composition comprising an epoxy resin, a curing agent, and an inorganic filler, wherein one of the epoxy resin and the curing agent exhibits high fluidity. The flame-retardant epoxy resin composition according to claim 1. 19. The amount of the inorganic filler is 40 to 900 parts by weight based on the total weight of the resin mixture containing the compound having a dihydrobenzoxazine ring of 100. The flame-retardant epoxy resin composition according to any one of claims 6 to 18. 20. A flame-retardant resin composition using the flame-retardant epoxy resin composition according to claim 6. 21. A semiconductor device using the flame-retardant epoxy resin composition according to claim 6.