JP2000281760A - Epoxy resin molding material for sealing and electronic component device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin molding material for sealing a semiconductor, which shows a flame retardance without containing any halogen or antimony, exerts a good moldability and has a highly reliable reflow resistance, water vapor resistance and high-temperature properties, and an electronic component device. SOLUTION: An epoxy resin molding material for sealing essentially comprises (A) an epoxy resin having two or more epoxy groups per molecule, (B) a hardener, (C) an accelerator and (D) an inorganic filler, wherein the hardener (B) contains a polycondensate (E) of a phenol resin (a), a triazine derivative (b) and an aldehyde group-containing compound (c). An electronic component device is equipped with an element which is sealed with this epoxy resin molding material for sealing.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sealing epoxy resin molding material, particularly a non-halogen, non-antimony sealing epoxy resin molding material required from the viewpoint of environmental friendliness. The present invention relates to a molding material suitable for sealing a VLSI that requires strict reliability such as standing characteristics, and an electronic component device including an element sealed with the molding material.

[0002]

2. Description of the Related Art Conventionally, epoxy resin molding materials have been widely used in the field of sealing electronic components such as transistors and ICs. The reason for this is that the epoxy resin is balanced in various properties such as electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesiveness to insert products. Flame retardation of these epoxy resin molding materials is mainly carried out by a combination of a brominated resin such as diglycidyl ether of tetrabromobisphenol A and antimony oxide.
Further, as a technique for achieving flame retardancy without using a brominated resin or antimony oxide, those using red phosphorus disclosed in JP-A-9-227765, JP-A-9-23
Japanese Patent Application Laid-open No. Hei 9-252, using a phosphoric acid ester compound disclosed in Japanese Patent Application Laid-Open No. H05-225714, using a phosphazene compound disclosed in Japanese Patent Application Laid-Open No. 8-225714.
Japanese Patent Application Laid-Open No. 41483/1990 using a metal hydroxide, Japanese Patent Application Laid-Open No. 9-100377 discloses a metal hydroxide and a metal oxide used in combination, Techniques such as those disclosed in JP-A-82343, in which the proportion of filler is increased, are mainly known.

[0003]

In recent years, the problem of dioxin originated from the viewpoint of environmental protection, and there has been a movement to regulate halogenated resins such as decabrom. Similarly, antimony compounds are being regulated from the viewpoint of toxicity, and epoxy resin molding materials for encapsulation are being required to be dehalogenated (debrominated) and deantimonized. It is also known that bromide ions have an adverse effect on the high-temperature storage characteristics of plastic-sealed ICs. From this viewpoint, it is desired to reduce the amount of brominated resin. Various flame retardants such as phosphorus compounds, nitrogen compounds, and metal compounds have been studied to meet the requirements for dehalogenation and deantimonization. However, the composition using red phosphorus as disclosed in Japanese Patent Application Laid-Open No. 9-227765 described above has a problem in that the reliability due to the decrease in the moisture resistance reliability and the hammering property of the red phosphorus,
A composition using a phosphate compound as disclosed in JP-A-9-235449 or JP-A-8-225
The composition using a phosphazene compound disclosed in Japanese Patent Application Laid-Open No. 714-714 discloses a problem of a decrease in moldability and a decrease in moisture resistance reliability due to plasticization, and the use of a metal hydroxide disclosed in Japanese Patent Application Laid-Open No. 9-241483. Composition or JP-A-9-100
No. 337, a composition using a combination of a metal hydroxide and a metal oxide, and a composition disclosed in JP-A-7-823.
No. 43, the composition having a high proportion of filler has a problem of a decrease in fluidity, and in each case, the moldability and reliability are equivalent to those of the composition using a brominated resin and antimony oxide. Has not yet gained sex. The present invention has been made in view of the above circumstances, and is a dehalogenating, deantimonizing, epoxy resin for sealing which has good moldability and excellent reliability such as reflow resistance, moisture resistance and high temperature storage characteristics. An object is to provide a material and an electronic component device using the same.

[0004]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, it has been found that the above object can be achieved by blending a specific curing agent into an epoxy resin molding material. And completed the present invention.

That is, the present invention relates to (1) (A) an epoxy resin having two or more epoxy groups in one molecule;
A curing agent, a curing accelerator (C), and an inorganic filler (D) are essential components, and the curing agent (B) is a compound (c) having a phenol resin (a), a triazine derivative (b), and an aldehyde group. And (2) a phenolic resin (a) used for the polycondensate (E) is a phenol novolak resin. The epoxy resin molding material for sealing according to the above (1), wherein (3) the triazine derivative (b) used for the polycondensate (E) is benzoguanamine and / or melamine. ) Or the epoxy resin molding material for sealing according to (2), and (4) the polycondensate (E) has a number average molecular weight of 300 to 1.
The epoxy resin molding material for sealing according to any one of the above (1) to (3), wherein the weight average molecular weight is 500 and the weight average molecular weight is 650 to 10,000, and (5) the molecular weight of the polycondensate (E). Distribution (weight average molecular weight / number average molecular weight)
Is an epoxy resin molding material for sealing according to the above (4), wherein the component (A) contains an epoxy resin represented by the following general formula (I). The epoxy resin molding material for sealing according to any one of the above (1) to (5),

Embedded image (Here, R ^{1 to} R ⁴ are selected from hydrogen and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, all of which may be the same or different. N represents 0 to 3. ) (7)
The epoxy resin molding material for sealing according to any one of the above (1) to (6), wherein the component (B) further comprises a curing agent represented by the following general formula (II):

Embedded image (Here, R is selected from hydrogen and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents 0 to 8.) (8) Phosphorus represented by the following formula (III) The epoxy resin molding material for sealing according to any one of the above (1) to (7), further comprising a compound (F).

Embedded image (Eight Rs in the formula represent an alkyl group having 1 to 4 carbon atoms,
All may be the same or different. Ar represents an aromatic ring. (9) An electronic component device including an element sealed with the sealing epoxy resin molding material according to any one of (1) to (8).

[0006]

DETAILED DESCRIPTION OF THE INVENTION (A) used in the present invention
The epoxy resin component is generally used in molding epoxy resin molding materials and is not particularly limited. Examples thereof include phenol novolak type epoxy resins, phenols such as orthocresol novolak type epoxy resins, cresols, and xylenols. And phenols such as resorcinol, catechol, bisphenol A, bisphenol F and / or naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene and compounds having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde And epoxidized novolak resin obtained by condensation or co-condensation with an acidic catalyst, bisphenol A, bisphenol F, bisphenol S, alkyl-substituted or unsubstituted Diglycidyl ethers such as biphenol, phthalic acid, glycidyl ester type epoxy resins obtained by the reaction of polychlorinated acids such as dimer acid and epichlorohydrin, and glycidylamine type epoxy resins obtained by the reaction of polyamines such as diaminodiphenylmethane and isocyanuric acid with epichlorohydrin Epoxidized co-condensation resin of dicyclopentadiene and phenols, epoxy resin having naphthalene ring, epoxidized naphthol aralkyl resin, trimethylolpropane type epoxy resin, terpene-modified epoxy resin, olefin bond of peracetic acid, etc. Examples thereof include a linear aliphatic epoxy resin and an alicyclic epoxy resin obtained by oxidation with a peracid, and a biphenyl type epoxy resin represented by the following general formula (I) is preferable from the viewpoint of reflow resistance.

Embedded image (Here, R ^{1 to} R ⁴ are selected from hydrogen and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, all of which may be the same or different. N represents 0 to 3. Examples of this are 4,4'-bis (2,3-epoxypropoxy) biphenyl and 4,4'-bis (2,3-epoxypropoxy) -3,3 ', 5,5'-tetramethylbiphenyl Epoxy resin containing epichlorohydrin and 4,4'-biphenol or 4,4 '-(3,3',
An epoxy resin obtained by reacting with (5,5′-tetramethyl) biphenol is exemplified. Among them, 4,4'-
Bis (2,3-epoxypropoxy) -3,3 ', 5
An epoxy resin containing 5′-tetramethylbiphenyl as a main component is preferred. When this biphenyl-type epoxy resin is used, its blending amount is preferably at least 60% by weight based on the total amount of the epoxy resin. If the content is less than 60% by weight, the epoxy resin has low moisture absorption and high adhesiveness, and the effect on the reflow resistance tends to be small. These epoxy resins may be used alone or in combination of two or more.

The curing agent of the component (B) used in the present invention contains at least a polycondensate (E) of a phenol resin (a), a triazine derivative (b) and a compound (c) having an aldehyde group. In addition, a curing agent generally used in an epoxy resin molding material for sealing may be used in combination. Examples of the curing agent used in combination with the polycondensate (E) include phenols such as phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, and aminophenol, or α-naphthol, β-naphthol, and dihydroxynaphthalene. Obtained by condensing or co-condensing naphthols such as aldehydes with compounds having an aldehyde group such as formaldehyde, and phenol aralkyl resins synthesized from phenols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl And naphthol-aralkyl resins. Among them, phenol-aralkyl resins represented by the following general formula (II) are preferable from the viewpoint of reflow resistance. When the curing agent of the general formula (II) is used, the amount is preferably 60% by weight or more based on the total amount of the curing agent in order to exhibit its performance.

Embedded image (Here, R is selected from hydrogen and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents 0 to 8.) Among them, represented by the following formula (IV), Is 0 on average
To 8 are preferred.

Embedded image These curing agents may be used alone or in combination of two or more.

The equivalent ratio of the epoxy resin (A) to the curing agent (B) containing the polycondensate (E), that is, the ratio of the number of epoxy groups in the epoxy resin to the number of hydroxyl groups in the curing agent is as follows: Although not particularly limited, it is preferably set in the range of 0.7 to 1.3 in order to reduce the amount of each unreacted component. In order to obtain a molding material excellent in moldability and reflow resistance, it is particularly preferable to set the ratio to 0.7 to 1.3. It is preferable to set in the range of 8 to 1.2.

[0009] The curing accelerator of the component (C) used in the present invention is not particularly limited. For example, a curing accelerator which is generally used in an epoxy resin molding material for sealing and comprises 1,8-
Diaza-bicyclo (5,4,0) undecene-7,1,
5-diaza-bicyclo (4,3,0) nonene, 5,6-
Dibutylamino-1,8-diaza-bicyclo (5,4,
0) Cycloamidine compounds such as undecene-7 and the like, and maleic anhydride, 1,4-benzoquinone,
2,5-toluquinone, 1,4-naphthoquinone, 2,3-
Dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone,
Quinone compounds such as phenyl-1,4-benzoquinone, diazophenylmethane, compounds having an intramolecular polarization obtained by adding a compound having a π bond such as phenol resin, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (Dimethylaminomethyl)
Tertiary amines such as phenol and derivatives thereof;
Methylimidazole, 2-phenylimidazole, 2-
Imidazoles such as phenyl-4-methylimidazole and derivatives thereof, organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine and phenylphosphine, and phosphines thereof Phosphorus compound having intramolecular polarization obtained by adding a compound having a π bond such as maleic anhydride, the above-mentioned quinone compound, diazophenylmethane, phenolic resin, etc., tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, And tetraphenylboron salts such as -ethyl-4-methylimidazole tetraphenylborate and N-methylmorpholine tetraphenylborate, and derivatives thereof. These curing accelerators may be used alone or in combination of two or more.

The amount of the curing accelerator of the component (C) is not particularly limited as long as the curing acceleration effect is achieved, but 0.005 to 2% by weight based on the whole molding material.
Is more preferable, and more preferably 0.01 to 0.5% by weight.

The inorganic filler of the component (D) used in the present invention is blended into a molding material for the purpose of absorbing moisture, reducing linear expansion coefficient, improving thermal conductivity and improving strength.
For example, fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, Examples thereof include powders of titania and the like, spherical beads and glass fibers thereof. Further, examples of the inorganic filler having a flame-retardant effect include aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate and the like. These inorganic fillers may be used alone or in combination of two or more. Among the above-mentioned inorganic fillers, fused silica is preferred from the viewpoint of reducing the coefficient of linear expansion, and alumina is preferred from the viewpoint of high thermal conductivity, and the filler shape is spherical from the viewpoint of fluidity during molding and mold abrasion. Is preferred. The amount of the inorganic filler is preferably 70% by weight or more based on the entire molding material, from the viewpoint of flame retardancy, moldability, hygroscopicity, reduction of linear expansion coefficient and improvement of strength, and 80 to 95% by weight. % Is more preferable, and 88 to
More preferred is 92% by weight. If it is less than 70% by weight, the reflow resistance tends to decrease, and if it exceeds 95% by weight, the fluidity tends to be insufficient.

The polycondensate (E) contained in the curing agent of the component (B) used in the present invention is a polycondensation of a phenol resin (a), a triazine derivative (b) and a compound (c) having an aldehyde group. Things. The phenolic resin (a) used here is not particularly limited as it is generally used in a molding epoxy resin molding material.
For example, phenol, cresol, xylenol, ethylphenol, butylphenol, nonylphenol,
Alkylphenols such as octylphenol, polyhydric phenols such as resorcinol, catechol, bisphenol A, bisphenol F, bisphenol S, naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene, or phenols such as phenylphenol and aminophenol Resins obtained by condensing or co-condensing the derivative with a compound having an aldehyde group such as formaldehyde in the presence of a catalyst such as an acidic catalyst.
Among them, phenol-novolak resin, which is a polycondensate of phenol and formaldehyde, is preferred from the viewpoint of moldability.

The phenol resin (a) is available as a commercial product such as H-1 (trade name, manufactured by Meiwa Kasei Co., Ltd.) and HF-1 (trade name, manufactured by Meiwa Kasei Co., Ltd.). It can be synthesized by a general method such as polycondensation with a compound having an aldehyde group by an addition condensation polymerization reaction or the like. After the reflux reaction, the polycondensation can be carried out by heating and dehydrating. When synthesizing the phenolic resin (a), the use ratio of the phenol derivative to the compound having an aldehyde group is preferably 0.01 to 2 mol per 1 mol of the phenol derivative. More preferably, the amount is in the range of 0.5 to 1 liter. If the amount is less than 0.01 mol, the reaction becomes insufficient, the molecular weight does not increase, and the moldability, heat resistance, water resistance, flame retardancy, strength, and the like tend to decrease. If it exceeds 2 mol, the molecular weight increases. Too much, and the kneadability tends to decrease. The reaction temperature is preferably set to 50 to 250 ° C, more preferably 80 to 220 ° C, and further preferably 100 to 250 ° C.
180 ° C. If the temperature is lower than 50 ° C., the reactivity becomes insufficient, the molecular weight tends to be small, and the moldability tends to decrease.
If it exceeds 50 ° C., there is a tendency that it is disadvantageous in terms of production equipment when synthesizing the phenolic resin (a). The reaction time is
It is preferable to set it for about 1 to 30 hours. In addition, a reaction catalyst such as an amine catalyst such as trimethylamine and triethylamine, an acid catalyst such as p-toluenesulfonic acid and oxalic acid, and an alkali catalyst such as sodium hydroxide and ammonia may be added to the phenol derivative per mole as needed. for,
You may use about 0.00001-0.01 mol. The pH of the reaction system is preferably about 1 to 10. Further, after reacting the phenol derivative with the compound having an aldehyde group, unreacted components, water and the like can be removed under heating and reduced pressure, if necessary. As for the conditions, the temperature is 80 to 220 ° C, more preferably 100 to 180 ° C,
Pressure is 100 mmHg or less, more preferably 60 mmHg
g or less, and the time is preferably 0.5 to 10 hours.

The triazine derivative (b) used in the polycondensate (E) is not particularly limited as long as it has a triazine nucleus in the molecule. Examples thereof include guanamine derivatives such as melamine, benzoguanamine and acetoguanamine, and cyanuric acid. Examples thereof include acids and cyanuric acid derivatives such as methyl cyanurate. These may be used alone or in combination of two or more. Among them, guanamine derivatives such as melamine and benzoguanamine are preferred from the viewpoint of moldability and reliability. Examples of the compound (c) having an aldehyde group used in the polycondensate (E) include formaldehyde, formalin, paraformaldehyde and the like.

The method for producing the polycondensate (E) is not particularly limited, and the polycondensate (E) can be produced by reacting each raw material of the phenol resin (a), the triazine derivative (b) and the compound (c) having an aldehyde group. For example, it can be synthesized by a general method such as polycondensation of a phenol resin (a), a triazine derivative (b) and a compound (c) having an aldehyde group by an addition condensation polymerization reaction or the like.
After the reflux reaction, the polycondensation can be carried out by heating and dehydrating. The reaction temperature when synthesizing the polycondensate (E) is 50
To 250 ° C., more preferably 60 ° C.
To 220 ° C, more preferably 80 to 180 ° C.
If the temperature is lower than 50 ° C, the reaction becomes insufficient, the molecular weight does not increase, and the moldability, heat resistance, water resistance, flame retardancy, strength and the like tend to decrease. If the temperature exceeds 250 ° C, the component (E) is synthesized. In this case, there is a tendency that production equipment is disadvantageous. The reaction time is preferably from 1 to 30 hours, more preferably from 1 to 15 hours, even more preferably from 2 to 10 hours.
If the reaction time is less than 1 hour, the reaction tends to be insufficient, the molecular weight does not increase, and the moldability, heat resistance, water resistance, flame retardancy, strength, and the like tend to be reduced. It is economically disadvantageous because it cannot be obtained. After the completion of the reaction, if necessary, unreacted components, water and the like can be removed under reduced pressure under heating or the like.
220 ° C, more preferably 100 to 180 ° C, pressure 1
00 mmHg or less, more preferably 60 mmHg or less,
The time is preferably set to 0.5 to 10 hours. Also,
In the reaction, an amine-based catalyst such as trimethylamine or triethylamine, or an acid catalyst such as oxalic acid, if necessary, is used as a reaction catalyst in an amount of 0.00001 to 1 mol per phenol resin.
You may add about 0.01 mol. The pH of the reaction system is 1 to
It is preferred to be about 10.

The mixing ratio of the phenolic resin (a), the triazine derivative (b) and the compound (c) having an aldehyde group used in the production of the polycondensate (E) is such that the nitrogen content of the polycondensate (E) is It is preferably set to 1 to 20% by weight, more preferably 1 to 15% by weight, further preferably 2 to 10% by weight. Specifically, the triazine derivative (b) is preferably 3 to 50 g, preferably 4 to 30 g, based on 100 g of the phenol resin (a).
Is more preferable. Further, the amount of the compound (c) having an aldehyde group is preferably 5 to 100 g, more preferably 6 to 50 g, based on 100 g of the phenol resin (a). With such a range,
The nitrogen content, molecular weight distribution and the like of the finally obtained polycondensate (E) can be adjusted to a desired range.

The polycondensate (E) of the present invention has a number average molecular weight (Mn) (measured by gel permeation chromatography and converted to standard polystyrene) of 300 to 150.
0, more preferably 35.
It is 0-1200, more preferably 380-1000. If the number average molecular weight is less than 300, moldability and reflow resistance tend to decrease, and if it exceeds 1500, fluidity tends to decrease. The weight-average molecular weight (Mw) of the polycondensate (E) (measured by gel permeation chromatography and converted to standard polystyrene) is 650 to 10
000, more preferably 700 to 8000, even more preferably 800 to 9000.
It is. If the weight average molecular weight is less than 650, reflow resistance tends to decrease, and if it exceeds 10,000, fluidity tends to decrease. The molecular weight distribution (weight average molecular weight Mw / number average molecular weight Mn) of the polycondensate (E) is 1.6.
It is preferably in the range of from 15 to 15, more preferably from 1.8 to 12. When the molecular weight distribution is less than 1.6, the reflow resistance tends to decrease, and when it exceeds 15, the fluidity tends to decrease. Further, the polycondensate (E) of the present invention has a point corresponding to a molecular weight of 2050 in terms of standard polystyrene (gel permeation) in terms of moldability, heat resistance, water resistance, flame retardancy, strength, reflow resistance and the like. Ratio a / b between intensity a at a point on the graph measured by chromatography and intensity b at a point corresponding to a molecular weight of 655
Is preferably 0.2 to 1.2, and 0.3 to
More preferably, it is 1.0. When the intensity ratio a / b is 0.
If it is less than 2, the moldability and reflow resistance tend to decrease, and if it exceeds 1.2, the fluidity tends to decrease.

The polycondensate (E) is a phenol derivative
The nucleus content is preferably 15 to 40% by weight,
More preferably, it is 20 to 40% by weight. When the binuclear content of the phenol derivative is less than 15% by weight, the softening point tends to increase, and the fluidity and kneading properties tend to decrease.
If it exceeds 0% by weight, moldability and flame retardancy tend to decrease. The softening point of the polycondensate (E) is preferably from 40 to 150 ° C, more preferably from 60 to 100 ° C. If it is lower than 40 ° C., the moldability tends to decrease,
If it exceeds 150 ° C., the fluidity and kneading properties tend to decrease. As described above, the nitrogen content of the polycondensate (E) is preferably 1 to 20% by weight from the viewpoint of flame retardancy and reliability.

Examples of the polycondensate (E) of the present invention include resins represented by the following structural formulas (V) to (XII).

Embedded image

Embedded image

Embedded image M, n, and l in the above formulas (V) to (XII) each independently represent a number of 1 to 10. These formulas indicate any of m, n, and l constituent units at random, alternately, regularly, and in blocks. Among them, on average, 2 to 15 nuclei, that is, m
Those having an average value of + n + 1 of 2 to 15 are preferred.

The polycondensate (E) in the present invention is
It is preferable that 2% by weight or more is added to the total amount of the curing agent (B), more preferably 5% by weight or more. When the blending amount of the polycondensate (E) is less than 2% by weight, the flame retardancy tends to decrease.

It is preferable that the epoxy resin molding compound for sealing of the present invention further contains a phosphorus compound (F) represented by the following structural formula (III) from the viewpoint of flame retardancy.

Embedded image (Eight Rs in the formula represent an alkyl group having 1 to 4 carbon atoms,
All may be the same or different. Ar represents an aromatic ring. )

Examples of the phosphorus compound (F) of the above formula (III) include phosphorus compounds represented by the following structural formulas (XIII) to (XVII).

Embedded image

Embedded image

The amount of the phosphorus compound (F) to be added is 0.2 to 2.0 parts by weight of phosphorus atoms with respect to all other components except the filler.
Preferably it is in the range of 3.0% by weight. If it is less than 0.2% by weight, the flame-retardant effect is weak. If it exceeds 3.0% by weight, the moldability and moisture resistance may be deteriorated, or the phosphorus compounds may exude during molding to impair the appearance. is there.

The epoxy resin molding material of the present invention may contain, if necessary, epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, vinyl silane, etc., in order to enhance the adhesion between the resin component and the filler. Known coupling agents such as various silane compounds, titanium compounds, aluminum chelates, and aluminum / zirconium compounds can be added. When these are exemplified, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy)
Silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane Γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropylmethyldimethoxysilane, γ- [bis (β-hydroxyethyl)] aminopropyltriethoxy Silane, N-β- (aminoethyl)-
γ-aminopropyltrimethoxysilane, γ- (β-aminoethyl) aminopropyldimethoxymethylsilane,
N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, N-β-
Silane coupling agents such as (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, isopropyl Triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate,
Tetraoctylbis (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-)
Butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropyl Titanate coupling agents such as isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, tetraisopropyl bis (dioctyl phosphite) titanate, and the like. These may be used in combination.

The amount of the coupling agent is preferably 0.05 to 5% by weight, more preferably 0.1 to 2.5% by weight, based on the inorganic filler of the component (D). . If it is less than 0.05% by weight, the adhesion to the frame tends to decrease, and if it exceeds 5% by weight, the moldability of the package tends to decrease.

Further, a conventionally known flame retardant can be added to the sealing epoxy resin molding material of the present invention. For example, nitrogen-containing compounds such as red phosphorus, melamine, melamine derivatives, compounds having a triazine ring, cyanuric acid derivatives and isocyanuric acid derivatives, and phosphorus / phosphorus compounds such as cyclophosphazene
Nitrogen-containing compounds, zinc oxide, iron oxide, molybdenum oxide,
And metal compounds such as ferrocene.

Further, an anion exchanger can be added to the sealing epoxy resin molding material of the present invention from the viewpoint of improving the moisture resistance and high-temperature storage characteristics of the IC. The anion exchanger is not particularly limited, and conventionally known ones can be used. Examples thereof include hydrotalcites, and hydrated oxides of elements selected from magnesium, aluminum, titanium, zirconium, and bismuth. These can be used alone or in combination of two or more. Among them, hydrotalcite represented by the following formula (XVI) is preferable.

Embedded image Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O (XVI) (0 <X ≦ 0.5, m is a positive number)

Other additives include higher fatty acids, higher fatty acid metal salts, ester waxes, polyolefin waxes, release agents such as polyethylene and polyethylene oxide, colorants such as carbon black, silicone oil and silicone rubber powder, and the like. A stress relieving agent or the like can be added as needed.

The sealing epoxy resin molding material of the present invention comprises:
As long as the various raw materials can be uniformly dispersed and mixed, it can be prepared by any method, but as a general method,
A method in which raw materials having a predetermined compounding amount are sufficiently mixed by a mixer or the like, melt-kneaded by a mixing roll, an extruder, or the like, and then cooled and pulverized can be used. It is easy to use if it is tableted with dimensions and weight that match the molding conditions.

For supporting members such as lead frames, wired tape carriers, wiring boards, glass and silicon wafers,
Semiconductor chips, transistors, diodes, active elements such as thyristors, capacitors, resistors, passive elements such as coils are mounted, and necessary parts are sealed with the sealing epoxy resin molding material of the present invention. An electronic component device can be manufactured. As such an electronic component device, for example, a semiconductor chip connected to a tape carrier by a bump is sealed with a sealing epoxy resin molding material of the present invention.
CP can be mentioned. Also, active elements such as semiconductor chips, transistors, diodes, thyristors, and / or passive elements such as capacitors, resistors, and coils are connected to wiring formed on a wiring board or glass by wire bonding, flip chip bonding, soldering, or the like. , A COB module, a hybrid IC, a multi-chip module, and the like, which are sealed with the epoxy resin molding material for sealing of the present invention. As a method for sealing an element using the epoxy resin molding material for sealing of the present invention, a low pressure transfer molding method is most common, but an injection molding method, a compression molding method, or the like may be used.

[0031]

Next, the present invention will be described with reference to examples, but the scope of the present invention is not limited to these examples.

A polycondensate (E) of a phenol resin (a), a triazine derivative (b) and a compound (c) having an aldehyde group was synthesized as follows. Synthesis Example 1 Synthesis of Polycondensate 1 In a flask equipped with a stirrer, a reflux condenser and a thermometer, 94 g (1 mol) of phenol and 37% by weight formalin water 3 were added.
2.4 g (0.4 mol) was added, and the pH was adjusted to 2 using 10% by weight of oxalic acid.
The reaction was heated at 120 ° C. for 6 hours. Thereafter, unreacted phenol, unreacted formaldehyde and water were removed at 120 ° C. under a reduced pressure of 60 mmHg to obtain 21.7 g of a phenol resin. Further, 8.0 g (0.064 mol) of melamine and 24.3 g (0.3 mol) of 37% by weight formalin water were added and reacted at 100 ° C. for 8 hours. Thereafter, unreacted phenol, unreacted aldehyde and water were removed at 140 ° C. under a reduced pressure of 60 mmHg to obtain a polycondensate 1 represented by the following general formula (V). The amount of the purified polycondensate 1 was 35.6 g.

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Synthesis Example 2: Synthesis of polycondensate 2 In a flask equipped with a stirrer, reflux condenser and thermometer, 94 g (1 mol) of phenol and 37% by weight formalin water 3
2.4 g (0.4 mol) was added, the pH was adjusted to 9 with triethylamine, the temperature was raised to 140 ° C. for 8 hours while refluxing and dehydrating, and then the reaction was carried out at 140 ° C. for 6 hours. Thereafter, unreacted phenol, unreacted formaldehyde and water were removed at 140 ° C. under a reduced pressure of 60 mmHg to obtain 21.7 g of a phenol resin. Further, 1.89 g (0.015 mol) of melamine and 3.2 g (0.04 mol) of 37% by weight formalin water were added, and oxalic acid was used.
After adjusting to 2, the reaction was carried out at 100 ° C. for 8 hours. Then 1
Unreacted aldehyde and water were removed at 40 ° C. under a reduced pressure of 60 mmHg to obtain polycondensate 2 represented by the above general formula (V). The amount of the purified polycondensate 2 was 18.5 g.

Synthesis Example 3: Synthesis of polycondensate 3 A flask equipped with a stirrer, a reflux condenser and a thermometer was charged with 94 g (1 mol) of phenol and 48% by weight of 37% by weight formalin water.
g (0.6 mol), and using 10% by weight of oxalic acid, pH
After adjusting the temperature to 2, the mixture was heated to 140 ° C. in 8 hours while refluxing and dehydrating, and then reacted at 140 ° C. for 6 hours to obtain a phenol resin. Then, 4.345 g of melamine (0.
034 mol), 8.0 g of 37% by weight formalin water (0.
1 mol), and the mixture was heated to 140 ° C. for 4 hours while refluxing and dehydrating, and then reacted at 140 ° C. for 8 hours. Thereafter, unreacted aldehyde and water were removed at 140 ° C. under a reduced pressure of 60 mmHg to obtain polycondensate 3 represented by the above general formula (V). The amount of the purified polycondensate was 72 g.

Synthesis Example 4: Synthesis of polycondensate 4 In a flask equipped with a stirrer, a reflux condenser and a thermometer, 94 g (1 mol) of phenol and 37% by weight formalin water 6
4.8 g (0.8 mol) was added, the pH was adjusted to 2 using 10% by weight of oxalic acid, and the temperature was raised to 140 ° C. in 8 hours while refluxing and dehydrating, followed by a reaction at 140 ° C. for 6 hours. Thereafter, unreacted phenol, unreacted formaldehyde and water were removed at 140 ° C. under a reduced pressure of 60 mmHg to obtain 53.8 g of a phenol resin. Further, 2.9 g (0.023 mol) of melamine and 4.3 of benzoguanmine were used.
g (0.023 mol), 37% by weight formalin water
0 g (0.2 mol) was added and reacted at 100 ° C. for 8 hours. Thereafter, unreacted aldehyde and water were removed at 140 ° C. under a reduced pressure of 60 mmHg to obtain a polycondensate 4 represented by the following general formula (XI). The amount of the purified polycondensate 4 is 8
It was 8.6 g.

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Synthesis Example 5: Synthesis of Polycondensate 5 A flask equipped with a stirrer, a reflux condenser and a thermometer was charged with 94 g (1 mol) of phenol and 6% by weight of 37% by weight formalin water.
4.8 g (0.8 mol) was added, the pH was adjusted to 2 using 10% by weight of oxalic acid, and the temperature was raised to 140 ° C. in 8 hours while refluxing and dehydrating, followed by a reaction at 140 ° C. for 6 hours. Thereafter, unreacted phenol, unreacted formaldehyde and water were removed at 140 ° C. under a reduced pressure of 60 mmHg to obtain 53.8 g of a phenol resin. Further, 20.6 g (0.11 mol) of benzoguanamine and 33.6 g (0.42 mol) of 37% by weight formalin water were added and reacted at 100 ° C. for 8 hours. Then, at 140 ° C., 60 mmHg
The unreacted aldehyde and water were removed under reduced pressure to obtain a polycondensate 5 represented by the following general formula (VII). The amount of the purified polycondensate 5 was 83.2 g.

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Synthesis Example 6: Synthesis of polycondensate 6 A commercially available phenolic resin H having a number average molecular weight of 460 and a softening point of 84 ° C. was placed in a flask equipped with a stirrer, a reflux condenser and a thermometer.
-1 (trade name, manufactured by Meiwa Kasei Co., Ltd.), 21.7 g, melamine 8.0 g (0.064 mol), 37% by weight formalin water 24.3 g (0.3 mol) were added, and 10% by weight oxalic acid was used. After adjusting the pH to 2, the reaction was carried out at 100 ° C. for 8 hours. Thereafter, unreacted phenol, unreacted aldehyde and water were removed at 140 ° C. under reduced pressure of 60 mmHg to obtain polycondensate 6 represented by the above general formula (V). The amount of the purified polycondensate 6 was 35.1 g.

As a comparative material, a polycondensate of phenol, a triazine derivative and a compound having an aldehyde group was synthesized as follows. Comparative Synthesis Example: Synthesis of Comparative Polycondensate (Polycondensate 7) A flask equipped with a stirrer, a reflux condenser and a thermometer was charged with 94 g (1 mol) of phenol and 37% by weight formalin water 2
5.1 g (0.3 mol), 4.34 g of melamine (0.0
34 mol), and triethylamine was used to adjust the pH to 8
Then, the mixture was heated to 140 ° C. for 4 hours while refluxing and dehydrating, and then reacted at 140 ° C. for 5 hours. afterwards,
Unreacted aldehyde, unreacted phenol and water were removed at 140 ° C. under reduced pressure of 60 mmHg to obtain polycondensate 7 as a comparative polycondensate. The amount of the purified polycondensate 7 is 4
0.8 g.

Number average molecular weight, weight average molecular weight, molecular weight distribution (weight average molecular weight Mw / number average molecular weight Mn) of polycondensate 7 obtained in Synthesis Examples 1 to 6 and Comparative Synthesis Example, molecular weight 2 in terms of standard polystyrene , 050, the intensity ratio a / b of the intensity a at the point (retention time = 26 min) corresponding to the molecular weight 655 (retention time = 30 min), the phenol binuclear content, the softening point and the nitrogen Table 1 shows the content. Here, the number-average molecular weight and the weight-average molecular weight were calculated by gel permeation chromatography using a calibration curve using standard polystyrene. The molecular weight distribution (weight average molecular weight Mw / number average molecular weight Mn), phenol binuclear content and unreacted phenol content were calculated by gel permeation chromatography using an area method. The nitrogen content was calculated from the elemental analysis. The gel permeation chromatography was performed under the following conditions. Column: Gelpack GL R-420 + R-430 + R-440 (trade name, manufactured by Hitachi Chemical Co., Ltd.) Column temperature: 40 ° C. Detector: RI Eluent: tetrahydrofuran Flow rate: 1.6 ml / min The calibration curve has a molecular weight of 186,000 (part number) F-20), 43,900 (article number F-4), 10,300 (article number F-1), 2,800 (article number A-2500) and average 456 (article number A-300, molecular weight 578, 402, 370, 266, 16)
Using five standard polystyrenes (including five fractions of No. 2) (trade name: TSK standard, manufactured by Tosoh Corporation), the retention time (minutes) was plotted on the horizontal axis, and the logarithm of the molecular weight was plotted on the vertical axis.

[0040]

[Table 1]

Examples 1 to 7, Comparative Examples 1 to 3 Epoxy equivalents: 196, melting point: 106
C. biphenyl type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd .; Epicoat YX-4000H), or a brominated bisphenol A type epoxy resin having an epoxy equivalent of 375, a softening point of 80 ° C. and a bromine content of 48% by weight. A phenol-aralkyl resin (manufactured by Mitsui Toatsu Chemicals, Inc .; Millex XL-225) at a point of 70 ° C., polycondensates 1 to 6 shown in Table 1 obtained in Synthesis Examples 1 to 6 as polycondensates (E), As a comparative polycondensate, polycondensate 7 shown in Table 1 synthesized in Comparative Synthesis Example using phenol in place of phenol resin (a), and as a curing accelerator, an adduct of triphenylphosphine and p-benzoquinone ( Curing accelerator 1), spherical fused silica having an average particle size of 17.5 μm and a specific surface area of 3.8 m ² / g as an inorganic filler, γ-glycid as a coupling agent Xypropyltrimethoxysilane (epoxysilane), as a flame retardant, the following structural formula (XIV)
The phosphorus compound 1, and carnauba wax, carbon black, and antimony trioxide as the other additives were blended at the weight ratios shown in Table 2, and kneaded at a kneading temperature of 80 to 90 ° C. and a kneading time of 10 minutes by roll kneading. Molding materials of Examples 1 to 7 and Comparative Examples 1 to 3 were produced.

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[0042]

[Table 2]

The molding materials of the examples and comparative examples thus produced were evaluated by the following tests. (1) Spiral flow (indicator of fluidity) Molding was performed using a spiral flow measurement mold according to EMMI-1-66, and the flow distance (cm) was determined. (2) Hardness during heating 180mm diameter disc x 3mm thickness disk is transferred by 180.
Molding was performed under the conditions of ± 3 ° C., 6.9 ± 0.17 MPa, and 90 seconds, and measurement was performed using a Shore D hardness meter immediately after molding. (3) Hot hardness after moisture absorption After storage for 72 hours under the condition of 25 ° C./50% RH, the hot hardness was measured in the same manner as in (2) above. (4) Reflow resistance 20 × 14 with 8 × 10mm silicone chip mounted
A × 2 mm 80-pin flat package is manufactured by transfer molding, humidified under the conditions of 85 ° C./85% RH, reflowed at a predetermined time of 240 ° C./10 seconds, and observed for cracks. Evaluation was made based on the number of defective packages / the number of measurement packages. The flat package was manufactured by molding a molding material under the conditions of 180 ± 3 ° C., 6.9 ± 0.17 MPa, and 90 seconds with a transfer press, and then performing post-curing at 180 ± 5 ° C. for 5 hours. (5) Moisture resistance 6 × 6 × 0.4 with aluminum wiring of line width 10μm and thickness 1μm
External dimensions 19 × with silicone test chip
A 14 × 2.7 mm 80-pin flat package was prepared by transfer molding, pre-treated, humidified, and inspected for disconnection failure due to aluminum wiring corrosion every predetermined time, and evaluated by the number of defective packages / the number of measurement packages. The flat package is 180 ± 3 ° C, 6.9
Mold the molding material under the conditions of ± 0.17MPa and 90 seconds, and then
It was prepared by performing post-curing at ± 5 ° C. for 5 hours. Pre-processing is 85
The flat package was humidified at a temperature of 85 ° C. and a relative humidity of 85% for 72 hours, and a vapor phase reflow treatment was performed at 215 ° C. for 90 seconds. Thereafter, the humidification test was performed under the conditions of 2.02 × 10 ⁵ Pa and 121 ° C. (6) High-temperature storage characteristics A 42 silver alloy with a partial silver plating using a test element in which an aluminum wiring with a line / space of 10 μm was formed on a silicon substrate having an outer size of 5 × 9 mm and an oxide film of 5 μm was formed. The device was connected to a lead frame with a silver paste, and the bonding pad of the element and the inner lead were connected with an Au wire at 200 ° C. using a thermonic wire bonder. Then, by transfer molding, a 16-pin DIP (D
ual InlinePackage) and transfer the obtained test IC to 200
It was stored in a high-temperature bath at ℃, taken out at predetermined time intervals and subjected to a continuity test to check the number of defective packages, and evaluated by the ratio to the number of measured packages. The test IC was manufactured by molding a molding material under the conditions of 180 ± 3 ° C., 6.9 ± 0.17 MPa, and 90 seconds using a transfer press, and then performing curing at 180 ° C. ± 5 ° C. for 5 hours. (7) Flame retardancy Using a mold for molding a 1/16 inch thick test piece, transfer molding is used to mold the molding material at 180 ± 3 ° C, 6.9 ± 0.17MPa for 90 seconds, and then After curing at 180 ± 5 ° C for 5 hours, the flame retardancy was evaluated according to the UL-94 test method. Table 3 shows the evaluation results.

[0044]

[Table 3]

None of the comparative examples containing the polycondensate of the component (E) in the present invention satisfy the characteristics of the present invention. That is, Comparative Examples 1 and 2 using a polycondensate prepared using phenol instead of phenol resin (a)
Has low heat hardness, particularly low heat hardness after moisture absorption, and thus has poor moldability and poor reflow resistance and moisture resistance. Also,
Comparative Example 3 using a Br-epoxy resin and an antimony compound as flame retardants instead of the polycondensate (E) is inferior in high-temperature storage characteristics. On the other hand, (A)-
In Examples 1 to 7 containing all of the component (E) and being non-halogen and non-antimony, all of the fluidity, hardness when heated, moisture resistance, and high-temperature storage characteristics were good, and all the flame retardancy was V-0. It is. In particular, Examples 5 and 7 are also excellent in reflow resistance.

[0046]

The epoxy resin molding material for sealing obtained by the present invention can achieve flame retardancy with non-halogen and non-antimony as shown in the examples.
If electronic components such as LSI are sealed, the moldability is good,
Products having excellent reliability such as reflow resistance, moisture resistance and high-temperature storage characteristics can be obtained, and their industrial value is great.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) H01L 23/31 (72) Inventor Shinsuke Hagiwara 48 Wadai, Tsukuba-shi, Ibaraki Pref. Tsukuba Development Laboratory, Hitachi Chemical Co., Ltd. (72) Inventor Yasushi Kojima 5-1 Oaza-san, Hazaki-cho, Kashima-gun, Ibaraki Prefecture Inside the Kashima Plant of Hitachi Chemical Co., Ltd. (72) Inventor Hiroshi Adachi 5-1 Oaza-san, Hasaki-cho, Kashima-gun, Ibaraki Prefecture Hitachi Chemical Kashima Co., Ltd. Inside plant (72) Inventor Kenji Horie 5-1 Oyama-san, Hazaki-cho, Kashima-gun, Ibaraki Prefecture Inside Kashima Plant of Hitachi Chemical Co., Ltd. (72) Inventor Junichi Chihama 172-1 Kagobo, Yuki-shi, Yuki City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. F-term in Shimodate factory (reference) 4J002 CC043 CC27X CC28X CD01W CD02W CD03W CD05W CD06W CD10W CD11W CD13W CD17W CD20W CE004 DE077 DE097 DE13 7 DE147 DE187 DE237 DF017 DJ007 DJ017 DK007 DL007 EE056 EL146 EN026 EN106 EQ036 EU106 EU116 EU136 EW016 EW048 EY016 FA047 FA087 FD017 FD090 FD130 FD138 FD14X FD140 FD144 FD153 FD156 DBFD01AG04A07AD01 DB28 DC02 DC34 DC41 DD07 DD09 FA01 FA12 FB06 FB08 JA07 4M109 AA01 CA21 EA02 EB03 EB04 EB12 EC01 EC05 ED10

Claims (9)

[Claims] (1) an epoxy resin having two or more epoxy groups in one molecule, (B) a curing agent, (C) a curing accelerator,
(D) An inorganic filler is an essential component, and the curing agent of the component (B) is a phenol resin (a) and a triazine derivative (b).
And a polycondensate (E) of a compound (c) having an aldehyde group. 2. The epoxy resin molding material for sealing according to claim 1, wherein the phenol resin (a) used for the polycondensate (E) is a phenol novolak resin. 3. The molding epoxy resin molding material according to claim 1, wherein the triazine derivative (b) used in the polycondensate (E) is benzoguanamine and / or melamine. 4. A polycondensate (E) having a number average molecular weight of 300 to 300.
1500 and a weight average molecular weight of 650 to 10,000
The epoxy resin molding material for sealing according to any one of claims 1 to 3, wherein: 5. The epoxy resin molding material for sealing according to claim 4, wherein the molecular weight distribution (weight average molecular weight / number average molecular weight) of the polycondensate (E) is 1.6 to 15. 6. The epoxy resin molding material for sealing according to claim 1, wherein the component (A) contains an epoxy resin represented by the following general formula (I). Embedded image (Here, R ^{1 to} R ⁴ are selected from hydrogen and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, all of which may be the same or different. N represents 0 to 3. ) 7. The epoxy resin molding material for sealing according to claim 1, wherein the component (B) further contains a curing agent represented by the following general formula (II). Embedded image (Here, R is selected from hydrogen and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents 0 to 8.) 8. An epoxy resin molding material for sealing according to claim 1, further comprising a phosphorus compound (F) represented by the following formula (III). Embedded image (Eight Rs in the formula represent an alkyl group having 1 to 4 carbon atoms,
All may be the same or different. Ar represents an aromatic ring. ) 9. An electronic component device comprising an element sealed with the sealing epoxy resin molding material according to any one of claims 1 to 8.