JPH0813863B2 - Ether-imide composition and use - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a composition containing an ether unsaturated imide compound having excellent heat resistance and flexibility, and having low water absorption and moisture permeability,
The present invention relates to a semiconductor device encapsulant comprising the composition, and a laminated plate material comprising the composition.

[Conventional technology]

Conventionally, a sealing resin composition for a resin-encapsulated semiconductor device has been
Epoxy materials using a novolak type phenol resin as a curing agent have become mainstream. However, with the increase in the degree of integration of semiconductor devices and the expanded use of resin-encapsulated semiconductor devices,
Further, it is strongly desired to develop a resin composition for encapsulation, which has excellent heat resistance, flexibility, moisture resistance, and adhesiveness, and can have a low dielectric constant and a low stress. .

[Problems to be Solved by the Invention]

However, the phenol novolak resin-cured epoxy composition has a limit in improving the heat resistance, particularly the glass transition point, and has a relatively large water absorption rate and moisture permeability, and therefore, it cannot be contained in a package of water from the cured product bulk. There was an essential problem in preventing intrusion. As a countermeasure against this, attempts have been made to modify by adding a siloxane-based or fluoro-based surface treatment agent, but in this case, problems such as mold stains and appearance of molded products should be improved during molding. There is.

An object of the present invention is to provide a composition having excellent heat resistance and flexibility, a low water absorption rate and a low moisture permeability, and a low dielectric constant, a sealant for a semiconductor device including the composition, and the composition. It is to provide a material for a laminated plate.

[Means for solving the problem]

The above object is achieved by adopting the following items. The gist is as follows: (1) General formula [I] [In the formula, R _{1 to} R ₄ are any of H, a lower alkyl group, a fluoroalkyl group, and a halogen atom. R ₅ and R ₆ are
CH ₃ , CF ₃ , H, Is one of. D is a divalent organic group having an ethylenically unsaturated double bond. ] And an ether unsaturated bisimide compound represented by the general formula [II] X-O-Z-N = Y [II] [wherein Z is (R ₇ is -CH _2- , -S -, - SO ₂ - is either in the. ) Is either. Also, X is (R ', R ", R is _{F, CF 3, C 2 F} 5, C 3 F 7 are either in, or different from each other the same as each other.), And (M is 1 to 40.). Also, Y is (D is a divalent organic group having an ethylenically unsaturated double bond.), And Is one of. ] The fluorine-containing amino derivative represented by these, The ether imide type composition characterized by the above-mentioned.

(2) The general formula [II] is the following formula [III] [Wherein R ′, R ″ and R are the same as defined above], which is a fluorine-containing phenylmaleimide.

(3) The general formula [II] is the following formula [III] [M is the same as above. ] The composition according to (1), which is a fluorine-containing phenylmaleimide represented by the following formula.

(4) The general formula [II] is the following formula [V] [In the formula, R ′, R ″, R and D are the same as above. Further, R ₈ and R ₉ are any of H, CH ₃ and CF ₃ , and are the same or different. The composition according to (1), which is a fluorine-containing unsaturated imide compound represented by the formula [1].

(5) The general formula [II] is the following formula [VI] [In the formula, D, R ₈ , R ₉ , and m are the same as defined above. ] The composition according to (1), which is a fluorine-containing unsaturated imide compound represented by

Is.

[Action]

The cured molded article obtained from the composition of the present invention has heat resistance,
The reason why the water absorption rate and the moisture permeability are excellent, which are excellent in flexibility, is considered as follows. That is, in the present invention, the ether-unsaturated bisimide compound represented by the general formula [I] is effective in exerting heat resistance and flexibility-imparting effect, and is represented by the general formula [II]. It is speculated that the fluorine amino derivative exerts the effects of imparting heat resistance and moisture resistance (reduction of water absorption rate, reduction of moisture permeability), and the synergistic effect of the two results in obtaining the above-described effects of the present invention. It

Further, in the composition of the present invention, the compound represented by the general formula [I]
By relatively increasing the combination ratio of the compound represented by the general formula [II] with respect to the compound represented by, the moisture resistance of the cured product is further improved and the effect of lowering the dielectric constant is obtained. . Due to such a synergistic effect, the composition is characterized in that it is easy to achieve a balance among heat resistance, flexibility, moisture resistance, and low dielectric constant, which have hitherto been extremely difficult.

Therefore, various application materials using the composition of the present invention,
It greatly contributes to high performance and high reliability of applied products.

For example, by using it as a material for a multilayer wiring board for a computer, the characteristics of the present invention can be fully exhibited. In particular, the low dielectric constant is greatly contributed to the improvement of the computer calculation speed. Further, by applying it to an interlayer insulating film such as a memory LSI, a covering material, a sealing material, etc., it is possible to greatly improve the moisture resistance reliability and the cold / heat cycle resistance. Further, when applied as a magnetic disk material, it is extremely effective in improving the characteristics of the sliding portion (head floating portion). In addition, the effects of the present invention can be exhibited in a wide variety of applications such as vehicle insulating varnishes, liquid crystal alignment films, sealing materials, structural adhesives, paints and the like.

In the present invention, the above general formula [I] [In the formula, R _{1 to} R ₄ are any of H, a lower alkyl group, a fluoroalkyl group, and a halogen atom. R ₅ and R ₆ are
CH ₃ , CF ₃ , H, Is one of. D is a divalent organic group having an ethylenically unsaturated double bond. Examples of the ether unsaturated bisimide compound represented by the following are as follows. That is, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-
Methyl-4- (4-maleimidophenoxy) phenyl]
Propane, 2,2-bis [3-chloro-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3
-Bromo-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-ethyl-4- (maleimidophenoxy) phenyl] propane, 2,2-bis [3
-Propyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-isopropyl-4-
(4-maleimidophenoxy) phenyl] propane, 2,
2-bis [3-butyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-sec-butyl-4- (4-maleimidophenoxy) phenyl] propane, 2, 2-bis [3-methoxy-4- (4-maleimidophenoxy) phenyl] propane, 1,1-bis [4-
(4-maleimidophenoxy) phenyl] ethane, 1,1
-Bis [3-methyl-4- (4-maleimidophenoxy) phenyl] ethane, 1,1-bis [3-chloro-4-
(4-maleimidophenoxy) phenyl] ethane, 1,1
-Bis [3-bromo-4- (4-maleimidophenoxy) phenyl] ethane, bis [4- (4-maleimidophenoxy) phenyl] methane, bis [3-methyl-4-
(4-maleimidophenyloxy) phenyl] methane, bis [3-chloro-4- (4-maleimidophenoxy) phenyl] methane, bis [3-bromo-4- (4-maleimidophenoxy) phenyl] Methane, 1,1,1,3,3,3-hexafluoro-2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 1,1,1,3,3,3-hexachloro -2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 3,3-bis [4- (4-maleimidophenoxy) phenyl] pentane, 1,1-bis [4-
(4-maleimidophenoxy) phenyl] propane, 1,
1,1,3,3,3-hexafluoro-2,2-bis [3,5-dibromo-4 (4-maleimidophenoxy) phenyl] propane, 1,1,1,3,3,3- Hexafluoro-2,2-bis [3-methyl-4 (4-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (3-maleimidophenoxy)
Phenyl] propane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] hexafluoropropane, 2,
2-bis [4- (3-citraconimidophenoxy) phenyl] propane, 2,2-bis [4- (3-endomethylenephthalimidophenoxy) phenyl] propane, 2,
2-bis [4- (3-itaconimidophenoxy) phenyl] propane, 2,2-bis [4- (4-citraconimidophenoxy) phenyl] propane, 2,2-bis [4
-(4-Citraconimidophenoxy) phenyl] hexafluoropropane and the like.

In the present invention, examples of the fluorine-containing amino derivative represented by the general formula (II) include those shown below.

The fluorine-containing unsaturated imide compound of the present invention has, for example, the general formula [VII] And / or the general formula [VIII] In the formula, R ₁₀ and R ₁₁ are hydrogen, a lower alkyl group, a halogen atom, and a perfluoroalkyl group. R ₈ and R ₉ are hydrogen, a lower alkyl group and a perfluoroalkyl group. ] An unsaturated imide compound having a hydroxyl group represented by the following formula [In the formula, m is 1 to 40. ] It can be obtained by a reaction with a perfluoroalkyl ether compound represented by Further, as another production method, an aminophenol compound and the above-mentioned perfluoroalkyl ether compound are first reacted to form a fluorine-containing amino compound, and then a dicarboxylic acid anhydride having an ethylenic double bond. There is also a method of obtaining a fluorine-containing unsaturated imide compound by reacting

[In formula, n is 1-40. ] The perfluoroalkyl ether compound represented by, for example, and so on. All of these are liquid at room temperature.

The above is shown in the following specific manufacturing synthesis process.

In addition, the general formula [VII] and / or the general formula [VII]
An unsaturated imide compound having a hydroxyl group represented by the formula [I] [Wherein R ', R ", and R are the same as those described above] in the presence of a basic catalyst by heating to obtain a compound. , Pp. 253, 1978, Journal of the Chemical Society of Japan.

formula [Wherein R is F or CF ₃ , and R ′, R ″ and R are
Any one of F, CF ₃ , C ₂ F ₅ , and C ₃ F ₇ , which may be the same or different. Examples of the fluorine-based compound represented by] include hexafluoropyrene and / or hexafluoropyrene oligomer, and specifically, Etc., and is marketed by ICI Mond Division and others. Among these compounds, in exerting the effect of the present invention, Alternatively, D-2, T-1 is preferred.

A conventionally known unsaturated N-substituted imide compound can be used in combination with the composition of the present invention. In particular, the formula [IX] [In the formula, D ₁ and D ₂ are dicarboxylic acid residues having an ethylenically unsaturated double bond. Z ₀ represents an alkylene group, an arylene group, or a substituted divalent organic group thereof. ] N, N'-substituted bis unsaturated imide compounds represented by the following are useful, such as, for example,
N, N'-ethylene bismaleimide, N, N'-hexamethylene bismaleimide, N, N'-dodecamethylene bismaleimide, N, N'-m-phenylene bismaleimide, N, N'-
p-phenylene bismaleimide, N, N'-p-phenylene biscitracone imide, N, N'-p-phenylene bisitaconimide, N, N'-p-phenylene bispyroconic imide, N, N '-P-phenylene-endomethylene tetrahydrophthalimide, N, N'-4,4'-diphenylmethane bismaleimide, N, N'-4,4'-dicyclohexylmethane bismaleimide, N, N'-m-xylene Bismaleimide, N, N'-diphenylcyclohexane bismaleimide, 4,4'-bismaleimide cinnamanilide, 6,6 '
-Bismaleimide-2,2'-bipyridine, or and so on. Also, and so on.

Further, for the purpose of imparting flame retardancy, the addition of the next-mentioned unsaturated imide compound containing a neighboring compound is effective.

Further, conventionally known fluorine-containing compounds can be used in combination with the composition of the present invention. As such,
For example Further, conventionally known fluorine-containing compounds can be used in combination with the composition of the present invention. As such,
For example and so on.

In addition, the following general formula [X] [In the formula, X ₁ and X ₂ are —O—, -S -, - SO ₂ - is either in the. Z ₁ is a direct bond, -CH _2- , (R ₅ and R ₆ are any of a lower alkyl group, a fluoroalkyl group and alkylene.), —O—, -S -, - SO ₂ - is either in the. ] It is also effective to add a phthalonitrile compound represented by Specifically, the general formula [] is Is a phthalonitrile compound represented by, for example,
below The combined use of the above does not impede the effects of the present invention.

In the present invention, a polyfunctional epoxy compound may be used in combination. For example, diglycidyl ether of bisphenol A, butadiene diepoxide, 3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexanecarboxylate, vinylcyclohexane dioxide, 4,
4'-di (1,2-epoxyethyl) dibiphenyl ether, 4,4 '-(1,2-epoxyethyl) biphenyl, 2,2
-Bis (3,4-epoxycyclohexyl) propane, resorcin diglycidyl ether, phloroglucin diglycidyl ether, methyl phloroglucin diglycidyl ether, bis- (2,3-epoxycyclopentyl) ether, 2- (3, 4-epoxy) cyclohexane-5,5-spiro (3,4-epoxy) cyclohexane-m-
Difunctional epoxy compounds such as dioxane, bis- (3,4-epoxy-6-methylcyclohexyl) adipate, N, N'-m-phenylene bis (4,5-epoxy-1,2-cyclohexane) dicarboximide, Para-aminophenol triglycidyl ether, polyallyl glycidyl ether, 1,3,5-tri (1,2-epoxyethyl) benzene, 2,2 ', 4,4'-tetraglycidoxybenzophenone, tetraglycidyl ether Citetraphenylethane, phenol formaldehyde novolac polyglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, or
The following formula (R ₁₂ and R ₁₃ are H, a lower alkyl group, a fluoroalkyl group, Is one of the ) Trifunctional or higher functional epoxy compounds.

Further, the epoxy compound shown below has liquid crystal alignment in a molten state. It is very effective in imparting heat resistance to cured products, improving mechanical strength, adhesion, and improving electrical properties.

Such compounds include, for example, and so on.

Further, an epoxy compound having at least one terminal vinyl group or terminal allyl group and at least one terminal epoxy group (ethylene oxide group) in one molecule is also useful. For example, the general formula (Wherein R ₁₄ is H or CH ₃ ) is a monomer having a structure of glycidyl acrylate, glycidyl methacrylate, β-methylglycidyl acrylate, and β-methylglycidyl methacrylate. . Also, the general formula (In the formula, R ₁₅ and R ₁₆ are H or CH ₃ ), and (methyl) glycidyl (meth) acryl ether is a typical example. Also, the general formula (In the formula, R ₁₇ and R ₁₈ represent H or CH ₃ , and R ₁₂ is Or a direct bond) having 6 to 12 carbon atoms, such as an ethylenically unsaturated epoxy monomer, and an olefinically unsaturated monoepoxide. Also, the general formula (In the formula, R ₁₉ is H, or a lower alkyl group having 1 to 4 carbon atoms, or CH ₂ Cl, x is an integer of 1 to 9, and y is an integer of 0 to 10.) Compounds such as allyl glycidyl ether, (2-allyloxy) ethylene glycidyl ether, and 4-butenyl glycidyl ether. Also, Alternatively, the general formula (In the formula, one of R _{20 to} R ₂₅ represents a hydrogen atom, a methyl or allyl group, and the other R represents a hydrogen atom).

In addition, vinylcyclohexene monooxide, furfuryl alcohol glycidyl ether or and so on. At least one of these is used.

In the present invention, the blending ratio of the ether imide compound represented by the general formula [I] and the amino derivative having at least one fluorine-containing group in one molecule is 10
The latter is generally in the range of 10 to 1000 parts by weight with respect to 0 parts by weight. When the latter ratio is low, the heat resistance is high, but the dielectric constant is high, and as the ratio is high, the opposite tendency is exhibited.

The method for curing the resin composition of the present invention is not particularly limited, but it can be easily cured by heating at 100 to 250 ° C for 1 to 30 minutes. The cured product thus obtained has, for example, a glass transition point of 180 ° C. or higher, and
It is also possible to obtain a cured product having a bending strength at 80 ° C of 150 kg / cm ² or more and a strength retention rate after standing at 200 ° C for 30 days of 80% or more. In addition, the elastic modulus of bending strength is 1.30 × 10 ³ kg / mm ² or less, and metal insert (70φ × 4 mm thick C-shaped washer)
The crack resistance when molded is 40 ° C / 2 hours ~
Room temperature / 2 hours ~ 140 ℃ 20 even under heat cycle of 2 hours No crack is generated after the above period.

In addition, the resin composition of the present invention can be modified by adding at least one monomer containing a polymerizable CH ₂ ═C group, which can be vinyl, allyl or acrylic type, depending on the purpose and application. . Here, the monomer is, for example, styrene, vinyltoluene, α-methylstyrene,
Divinylbenzene, diallyl phthalate, diallyl phthalate prepolymer, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene, diallylbenzenephosphonate, diallylarylphosphyl acid ester, acrylic acid, methacrylic acid ester, triallyl cyanurate, triallyl Allyl cyanurate prepolymer,
Tribromophenol allyl ether, or conventionally known N, N'- substituted bismaleimide compounds and the like,
These can be used alone or in combination of two.

It is desirable to add a polymerization initiator to the resin composition of the present invention for the purpose of completing the curing by heating for a short time. Such polymerization initiators include benzoyl peroxide, p-chloro-benzoyl peroxide, 2.4
-Dichlorobenzoyl peroxide, oprylyl peroxide, lauroyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, bis (1-hydroxycyclohexyl peroxide), hydroxyheptyl peroxide, t
-Butyl hydroperoxide, p-menthane hydroperoxide, t-butyl perbenzoate, t-butyl peracetate, t-butyl peroctoate, t-
Organic peroxides such as butyl peroxyisobutyrate and di-t-butyl diperphthalate are useful, and one or more of them can be used.

Also, tertiary amines such as triethylamine, tetramethylbutanediamine, tetramethylpentanediamine, tetramethylhexanediamine, triethylenediamine, and dimethylaniline; oxyalkylamines such as dimethylaminoethanol and dimethylaminopentanol; and tris (dimethylaminomethyl). Amines such as phenol and N-methylmorpholine, also cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, dodecyltrimethylammonium iodide, trimethyldodecylammonium chloride, benzyldimethyltetradecylammonium chloride,
Benzyl dimethyl palmityl ammonium chloride,
Quaternary ammonium salts such as allyl dodecyl trimethyl ammonium bromide, benzyl dimethyl stearyl ammonium bromide, stearyl trimethyl ammonium chloride, benzyl dimethyl tetradecyl ammonium acetate, and further 2-methyl imidazole,
2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-methyl-4-
Ethyl imidazole, 1-butyl imidazole, 1-propyl-2-methyl imidazole, 1-benzyl-2-
Methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-azine-2-methylimidazole, 1-azine-2-undecylimidazole Imidazoles, such as
Triphenylphosphine tetraphenylborate, triethylamine tetraphenylborate, N-methylmorpholine tetraphenylborate, pyridine tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, 2-ethyl-1,4- Calibor salts such as dimethylimidazole tetraphenylborate are useful. At least one of these catalysts is preferably used in the range of 0.01 to 10% by weight based on the above-mentioned compounded composition. Further, these catalysts may be used in combination with the above-mentioned peroxide catalyst.

In the present invention, the above-mentioned polymerization catalyst may be used in combination with known accelerators such as mercaptans, sulfites, β-diketones, metal chelates, and metal tartaric acid. Further, in order to improve the storage stability of the resin composition at room temperature, for example, quinones such as p-benzoquinone, naphthoquinone, and phenanthraquinone, hydroquinone, pt-butylcatechol, 2,5-di- Known polymerization inhibitors such as phenols such as t-butylhydroquinone, nitro compounds and metal salts can be used depending on the application.

Furthermore, the resin composition of the present invention can be blended with various materials depending on its use.

That is, for example, for use as a molding material, zircon, silca, alumina, aluminum hydroxide, titania, zinc white, calcium carbonate, magnesite, clay,
Kaolin, talc, silica sand, glass, fused silica glass, asbestos, mica, various whiskers, carbon black, graphite, inorganic fillers such as molybdenum disulfide, mold release agents such as higher fatty acids and waxes, epoxysilane, vinylsilane, borane, etc. At least one coupling agent such as an alkoxy titanate compound can be blended. If necessary, a halogen-containing compound, a flame retardant imparting agent such as antimony oxide or a phosphorus compound, and the like can be used.

It can also be used as a solution, such as a varnish. The solvent used at that time is N-methyl-2.
-Pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N-methylformamide, dimethyl sulfoxide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, hexamethylphosformamide, pyridine, dimethyl There are sulfone, tetramethyl sulfone, dimethyl tetramethylene sulfone, etc., and the phenolic solvent group includes phenol, cresol,
There is xylenol.

The above can be used singly or as a mixture of two or more kinds.

By the way, the composition of the present invention is used for an interlayer insulating film in a multilayer wiring structure of a semiconductor device, an element coating film such as a δ-ray shielding film, a laminated material of a multilayer wiring board for a computer, an LSI sealing material, an adhesive, There are a wide range of fields of application such as liquid crystal alignment films, sealing materials for display devices, paints for various purposes, and sliding materials (surface coating materials) for magnetic recording disks.

For example, when applied to a semiconductor device, it is desirable that the solution containing the compound represented by the general formula [I] and the general formula [II] of the present invention is applied to the surface of a semiconductor element or the like, and the solvent is, for example, , Aromatic hydrocarbons such as benzene, toluene, xylene, methanol, ethanol, 2-
In addition to alcohols such as propanol, ketones such as methyl ethyl ketone and acetone, cellosolve acetates such as ethyl cellosolve, chlorinated hydrocarbons,
Alternatively, polar solvents such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone and the like can be mentioned.

Solutions of these compounds are applied to the surface of semiconductor devices, lead wires, and the like. Examples of the coating method include dipping the element and the lead wire in a solution, dropping the solution on the element and the lead wire, spraying, and spinner coating.

By such a method, the semiconductor element or the lead wire coated with the compound solution is then heat-baked at least at 100 ° C. or higher, particularly preferably at 120 to 250 ° C. By this treatment, the compound has a higher molecular weight and is crosslinked to form a protective coating layer. The thickness of the coating layer is not particularly limited. A material having an excellent effect is appropriately used according to the purpose and application.

For example, the interlayer insulation film of multi-layer wiring type LSI is 500Å to several μ
A film thickness of m and a film thickness of the δ-ray shielding film of 10 to 200 μm are effective in achieving the purpose. (FIG. 1, FIG. 2 and FIG. 3) [Examples] <Examples 1 to 20> Twenty kinds of blended compositions shown in Tables 1 and 2 were prepared.

Each compounded composition was kneaded at 50 to 70 ° C. for 10 minutes and then cooled to obtain the desired heat resistant resin composition.

Each composition was transfer-molded under the conditions of 170 ° C., 70 kg / cm ² , and 5 minutes to prepare test pieces for measuring various characteristics. First
Table 2 and Table 2 show the glass transition point, bending strength at 180 ℃, flexural modulus, 200 ℃, and heat deterioration characteristics after standing for 30 days.
The storage stability of the material was demonstrated.

All of the cured products have a glass transition point of 180 ° C or higher, a bending strength of 180 ° C, 450 kg / cm ² or higher, 200 ° C, a strength retention rate of 80% or more after being left for 30 days, and a bending elastic modulus of 1.30 × 10 ³ kg. It has excellent heat resistance and flexibility of / mm ² or more.

As a fluorine-containing amino derivative which is an essential component of the present invention,
The following studies were performed using the following (A) to (F).

<Examples 21 to 28> Five kinds of the above-mentioned fluorine-containing amino derivatives (A) to (E) were selected. In addition to these, bisphenol A type epoxy DER332 (manufactured by Dow Chemical Co., Ltd.), orthodiallyl bisphenol F, 2,2-bis [4- (4-maleimidophenoxy) phenyl] hexafluoropropane (abbreviated as:
DAPP-FMI), triallyl isocyanurate (TAIC),
Eight kinds of compounds were prepared by separately mixing the predetermined amounts (parts by weight) shown in Table 3 with each other.

To these compounds, dicyandiamide, benzoguanamine, and dicumyl peroxide (DCPO) were added as curing accelerators, and epoxysilane KBM403 (manufactured by Shin-Etsu Chemical Co., Ltd.) was added as a coupling agent in predetermined amounts.

Next, these compounded compositions were dissolved in an equal amount mixed solution of N-methyl-2-pyrrolidone (NMP) and methyl ethyl ketone (MEK) to obtain a varnish containing 45 to 48% by weight of solid content.

Using this varnish solution, a glass cloth (WE-1 manufactured by Nitto Boseki Co., Ltd.
16P, BY-54) was impregnated with a resin and dried at 160 ° C for 15 minutes to prepare a coated cloth having a resin content of 45 to 48% by weight.

Next, use 8 sheets of this coated cloth, 35μm above and below
Overlaid with thick TAI-treated copper foil (Furukawa Electric-CFC), 170-1
Laminated and bonded for 80 minutes under the conditions of 85 ℃, 40kgf / cm ² and thickness of about 1.
A 6 mm double-sided copper clad laminate was created.

The copper-clad laminate was further post-cured at 200 ° C. for 4 hours. Table 3 shows various characteristics of the obtained eight kinds of copper-clad laminates.

 The measuring method of each characteristic is as follows.

(A) Copper foil peeling strength After cutting a test piece into a size of 25 mm x 100 mm from a copper-clad laminate, a copper foil having a width of 10 mm was left in the central portion and other copper foils were removed by etching. Next, move the copper foil in the center vertically
It was peeled off at a speed of 5 mm / min, and its strength was measured.

(B) Solder heat resistance A test piece was a 25 mm square piece cut from a copper clad laminate. Float this test piece in a solder bath heated to 300 ℃,
The time at which abnormalities such as blistering occur was measured.

(C) Inflammability Measured according to the UL-94 vertical method. A test piece was obtained by cutting the above copper-clad laminate to a width of 12 mm and a length of 125 mm and etching a copper foil. Ten test pieces are measured,
It was represented by the average extinction time.

The average extinction time is within 5 seconds, the maximum extinction time within 10 seconds is UL-94, V-0, the average extinction time is within 25 seconds, and the maximum extinction time is 3 seconds.
UL-94, V-1 is within 0 seconds.

<Examples 29 to 39, Comparative Example> As a polyfunctional epoxy compound, orthocresol novolak type epoxy resin EOCN-102S (manufactured by Nippon Kayaku Co., epoxy equivalent 211, softening point 66.4 ° C), relative to 100 parts by weight, Predetermined amount of fluorine-containing amino derivative (A) and (B), novolak type phenol resin HP-607N (manufactured by Hitachi Chemical Co., Ltd., softening point 78-82 ° C), p-hydroxy aggregate M resin (manufactured by Maruzen Oil Co., Ltd.) , Number average molecular weight 4800) and N, N′-bismaleimide diphenylmethane (DOM bismaleimide) were taken, and the predetermined amounts shown in Table 4 were blended.

In these compounds, 2.0 parts by weight of triphenylphosphine as a curing accelerator, 2.0 parts by weight of an epoxysilane KBM303 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a coupling agent, 0.8 parts by weight of an acylate-type titanate compound, and a release agent 1.0 parts by weight of calcium stearate and Hoechstwax E
1.0 part by weight (Hoechst Japan Co., Ltd.), 5 parts by weight of addition type imide-coated red phosphorus as a flame retardant, 50% by weight of spherical alumina having an average particle size of 1 μm as a filler (based on the total composition), and 10 to 44 μm. 30 weight percent fused silica glass powder with an average particle size (based on the total composition) and 2.0 parts by weight of carbon black (manufactured by KYABOT) as a colorant were added separately to obtain 12 kinds of composition compositions. It was created.

Next, these blends were kneaded by heating for 8 minutes with a two-roll roll of 8 inch diameter heated to 75 to 85 ° C., then cooled and coarsely pulverized to obtain a molding material composition for semiconductor encapsulation. .

Using these compositions, 1M bit D-RAM LSI, fifty pieces, using a transfer molding machine, 180 ° C, 70 kgf / c
Sealing molding was performed under the condition of m ² for 2 minutes to obtain a resin-sealed semiconductor device.

The obtained resin-encapsulated semiconductor device was put into a supersaturated steam kettle (pre-tucker / cuter kettle) at 121 ° C and 2 atm for a predetermined time and then taken out to check whether the semiconductor device operates electrically normally. For those that checked and showed a defective operation (defective disconnection), it was confirmed by destructive inspection that the wiring on the element had a disconnection failure due to corrosion. Table 4 shows the occurrence of defects.

FIG. 1 is a sectional view of a semiconductor device according to an embodiment of the present invention, and FIGS. 2 and 3 are partial sectional views of elements of the semiconductor device of the present invention. In the figure, 1 is a lead wire, 2 is a semiconductor element, 3 is a protective coating resin, 4 is wiring, 5 is a polyimide resin, 6 is a molding resin, and 7 is a thermal oxide film.

〔The invention's effect〕

The ether imide composition of the present invention is highly effective in imparting heat resistance, flexibility, moisture resistance and low dielectric constant.

[Brief description of drawings]

FIG. 1 is a sectional view of a semiconductor device according to an embodiment of the present invention, and FIGS. 2 and 3 are partial sectional views of elements of the semiconductor device of the present invention. 1 ... Lead wire, 2 ... Semiconductor element, 3 ... Protective coating resin, 3-I ... First layer protective coating resin, 3-II ... Second layer protective coating resin, 4-I ... First Layer wiring, 4-II. Second layer wiring, 5 ... Polyimide resin, 6 ... Mold resin, 7 ... Thermal oxide film.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location H01L 23/29 23/31 H05K 1/03 D 7511-4E

Claims (8)

[Claims] 1. A general formula [I] [In the formula, R _{1 to} R ₄ are any of H, a lower alkyl group, a fluoroalkyl group, and a halogen atom. R ₅ and R ₆ are
CH ₃ , CF ₃ , H, Is one of. D ₁ and D ₂ are divalent organic groups having an ethylenically unsaturated double bond. ] And an ether unsaturated bisimide compound represented by the general formula [II] X-O-Z-N = Y [II] [wherein Z is (R ₇ is -CH _2- , -S -, - SO ₂ - is either in the. ) Is either. Also, X is (R ', R ", R is _{F, CF 3, C 2 F} 5, C 3 F 7 are either in, or different from each other the same as each other.), And (M is 1 to 40.). Also, Y is (D is a divalent organic group having an ethylenically unsaturated double bond.), And Is one of. ] The fluorine-containing amino derivative represented by these, The ether imide type composition characterized by the above-mentioned. 2. The general formula [II] is represented by the following formula [III] The ether imide composition according to claim 1, which is a fluorine-containing phenylmaleimide represented by the formula: wherein R ′, R ″ and R are the same as above. 3. The general formula [II] is represented by the following formula [IV] [M is the same as above. ] The ether imide composition according to claim 1, which is a fluorine-containing phenylmaleimide represented by the following formula. 4. The general formula [II] is represented by the following formula [V] [In the formula, R ′, R ″, R and D are the same as above. Further, R ₈ and R ₉ are any of H, CH ₃ and CF ₃ , and are the same or different. The ether imide composition according to claim 1, which is a fluorine-containing unsaturated imide compound represented by the formula: 5. The general formula [II] is represented by the following formula [VI]: [In the formula, D, R ₈ , R ₉ and m are the same as above. ] The ether imide composition according to claim 1, which is a fluorine-containing unsaturated imide compound represented by the following formula. 6. A molding material for semiconductor encapsulation, comprising the etherimide composition according to claim 1. 7. A semiconductor device characterized by being covered and / or encapsulated with the etherimide composition according to claim 1. 8. A laminated plate material comprising the etherimide composition according to claim 1 as a constituent component.