JPH02127408A - Etherimide compositions and uses - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] (Industrial application field) The present invention has excellent heat resistance, flexibility, and water absorption.

A composition containing an ether unsaturated imide compound with low moisture permeability, an encapsulant for a semiconductor device comprising this composition, and
The present invention relates to a laminate material comprising the composition.

[Conventional technology]

Conventionally, epoxy-based materials using a novolac type phenol resin as a curing agent have been the mainstream for resin compositions for encapsulating resin-encapsulated semiconductor devices. However, with the increase in the degree of integration of semiconductor devices and the expansion of applications for resin-encapsulated semiconductor devices, resin compositions for encapsulation are required to have excellent heat resistance, flexibility, moisture resistance, and adhesive properties. Furthermore, there is a strong desire to develop a resin composition that can have a lower dielectric constant and lower stress.

[Problem to be solved by the invention]

However, phenol novolac resin-cured epoxy compositions have a limited ability to improve heat resistance, especially the glass transition point, and have relatively high water absorption and moisture permeability, and water from the bulk of the cured product does not enter the package. There was an essential problem in preventing the intrusion of As a countermeasure to this problem, attempts have been made to modify the property by adding siloxane-based or fluoro-based surface treatment agents, but in this case, there are problems such as mold stains during molding and problems that need to be improved in the appearance of the molded product. There is.

The purpose of the present invention is to have excellent heat resistance, flexibility, water absorption rate,
An object of the present invention is to provide a composition having a low moisture permeability and a low dielectric constant, a sealant for a semiconductor device made of this composition, and a material for a laminate made of this composition.

[Means to solve the problem]

The above objective will be achieved by adopting the following items. The gist is as follows: (1) - Shipman [I] [In the formula, R1'' Ra is either a H9 lower alkyl group, a fluoroalkyl group, or a halogen atom.
5 and Re are CHs y CF s , H, a divalent organic group with an unsaturated double bond. ] and an ether unsaturated bisimide compound represented by the general formula (II) X-0-Z-N=Y [I[]C-
0-S-5O2-.

Either.

Also, X is \ R' CzF I5+ Cs　F　7, each other They may be the same or different.

as well as 1 to 40.

Either.

Also, Either.

] fluorine-containing amino represented by With derivatives, A composition comprising:

General formula [■] [In the formula, R', R', and R'' are the same as above.]
Composition 6(3)-Funejin (n) according to (1) is characterized in that it is a fluorine-containing phenylmaleimide represented by
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) - Sailor [■] is represented by the following formula (V) [wherein R', R', R''' and D are the same as above. Also, Rδ and Re are H and CHa.

CFs, and may be the same or different from each other. The composition according to (1), which is a fluorine-containing unsaturated imide compound represented by the following formula.

(5) - Sailor (II) is given the following formula (VI) CVI) [In the formula, D, Re, Re, and m are the same as above.

The composition according to (1), which is a fluorine-containing unsaturated imide compound represented by the following formula.

It is.

[Effect]

The cured molded product obtained from the composition of the present invention has excellent heat resistance and flexibility. The water absorption rate and moisture permeability decrease because
This is thought to be due to the following reasons. That is, in the present invention, the ether unsaturated bisimide compound represented by -Funenin (1) is effective in exerting the effect of imparting heat resistance and ductility; The fluorine-containing amino derivative shown in FIG. It is inferred.

Furthermore, in the composition of the present invention, by relatively increasing the combination ratio of the compound represented by -Funenin CI) to the compound represented by -Funenin CI), the moisture resistance of the cured product can be improved. Further improvements in properties are achieved, and the effect of lowering the dielectric constant can be obtained. Because of such a synergistic effect, the composition is characterized in that it is easy to balance heat resistance, flexibility, moisture resistance, and low dielectric constant, which have been considered extremely difficult in the past.

For this reason, various materials using the composition of the present invention greatly contribute to improving the performance and reliability of the products to which they are applied.

For example, the features of the present invention can be fully exhibited by using it as a material for multilayer wiring boards for computers. In particular, providing a low dielectric constant greatly contributes to improving computer calculation speed. Furthermore, by applying the present invention to glabellar insulating films, covering materials, sealing materials, etc. of memory LSIs, etc., it is possible to greatly improve moisture resistance reliability and cold/heat cycle resistance. In addition, by applying it as a magnetic disk material,
This is extremely effective in improving the characteristics of the sliding part (the part to which the head flies). In addition, the effects of the present invention can be exhibited in a wide range of other applications such as insulating varnish for vehicles, liquid crystal alignment films, sealing materials, structural adhesives, paints, and others.

In the present invention, the above-mentioned shipman (1) [wherein R1-R4 are H2 lower alkyl groups, fluoroalkyl groups, or halogen atoms].

Either.

Also.

D is a divalent organic group having an ethylenically unsaturated double bond. ] Examples of the ether unsaturated bisimide compound represented by the formula include the following. 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]furopane, 2.2-bis[ 3-Butyl-4-(4-
maleimidophenoxy)phenyl]propane, 2゜2-
Bis(3-see-butyl-4-(4-maleimidophenoxy)phenyl)propane, 2.2=bisC3-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)phenylcomethane, bis[3-methyl-4-(4-maleimidophenoxy)phenylcomethane, bis[3-chloro-4-(4
-maleimidophenoxy)phenylcomethane, bis[3
-Bromo-4-(4-maleimidophenoxy)phenylcomethane, 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. i, 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)funyl)
Propane, 2,2-bis(4-(4-citraconimidophenoxy)phenyl)propane, 2,2-bis(4-
Examples include (4-citraconimidophenoxy)phenyl]hexafluoropropane.

Further, in the present invention, the fluorine-containing amino derivative represented by the above-mentioned -Funenin (n) is, for example.

below There are some things shown below.

haze haze Mu.

C-〇=! The fluorine-containing unsaturated imide compound of the present invention has, for example, the following formula: % Formula % General formula [■] In the formula, RIO and R11 are hydrogen, a lower alkyl group, a halogen atom, or a perfluoroalkyl group. Further, R8 and R9 are hydrogen, a lower alkyl group, or a perfluoroalkyl group. ] and an unsaturated imide compound having a hydroxyl group represented by the following formula [wherein 5m is 1 to 4o].

] It can be obtained by reaction with a perfluoroalkyl ether compound represented by the following. In addition, 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 is produced. There is also a method in which a fluorine-containing unsaturated imide compound is obtained by reacting.

[In the formula, n is 1 to 40. Examples of perfluoroalkyl ether compounds represented by the formula include the following. All of these are liquid at room temperature.

The above-mentioned process is shown in a concrete manufacturing and synthesis process as follows.

CFs CFs F -f-c F CF2-0-+-CF -COF Also, an unsaturated imide compound having a hydroxyl group represented by the above-mentioned shipman and/or the general formula [■], and the formula R'R' [In the formula, R', R', and R'' are the same as above.]
It is obtained by subjecting a fluorine compound represented by the following formula to a heating reaction in the presence of a basic catalyst. A detailed explanation of this reaction can be found at
The method described in Journal of the Chemical Society of Japan, 1978, p. 253 may be referred to.

Formula % Formula % [In the formula, R is F or CFa, and R', R' and R' are F, CF3. CzFa, C3F7 (7), and may be either the same or different. ]
Examples of the fluorine-based compound represented by include hexafluoropyrene and/or hexafluoropyrene oligomer, specifically, CFa FzCFa / (CFa)2C=C \ CF2CF2CF3 F 3 CFII CF2CF3, etc., and ICT Mond. It is commercially available from companies such as Division. Among these compounds, CFa\/F3 or D-2 and T-1 are preferred in order to exhibit the effects of the present invention.

The composition of the present invention can be used in combination with conventionally known unsaturated N-substituted imide compounds. In particular, the formula (IX) [wherein DI
, D2 is a dicarboxylic acid residue having an ethylenically unsaturated double bond. In addition, Zo is an alkylene group, an arylene group,
or indicates those substituted divalent organic groups. ].

N'-substituted bis-unsaturated imide compounds are useful, such as N,N'-ethylene bismaleimide, N,N'-hexamethylene bismaleimide, N,N'-dodecamethylene. Bismaleimide, N
, N'-m-phenylene bismaleimide, N, N'
-p-phenylenebismaleimide, N,N' -p-phenylenebiscitraconimide, N,N' -p-phenylenebisitaconimide, N,N' -p-phenylenebispirociconimide, N,N' -p -phenylene-endomethylenetetrahydrophthalimide, 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 /=\ \=/ \2/ \Tech/ \Tech/ ／=\N Tech/ \Tech/ ゝMogo' \Tech/ ／=\ \=/ \ ＝／ ＼＝／ ゝもGo′ ゝ−−′ ／＝＼ 〜工／ −ノ etc.

Also, and so on.

Also, For the purpose of imparting flame retardancy, The following phosphorus-containing unsaturated imi Addition of compound based on hydrogen is effective.

H'''-='H Δh・shiyohe In addition, conventionally known fluorine-containing compounds can be used in combination with the composition of the present invention. Examples of such compounds include (m: 1-40 ) ○H 18shishir(shi148)2 aC Fa etc.

Also, The following general formula [During the ceremony, and X2 teeth, 10- C- It's either inside.

Also, is a direct bond, a fluoroalkyl group, or an alkylene group. ), -0--C-, -8--3OZ-. ] It is also effective to add a phthalonitrile compound represented by: Specifically, it is a phthalonitrile compound whose general formula [ ] is represented by an 11th formula, for example,
The combined use of the following Ha Fa Ha Hs CHs CHs CHs 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 dieboxide, 3°4-epoxycyclohexylmethyl-(3,4-epoxy)cyclohexane carboxylate, vinylcyclohexane dioxide,
4,4'-di(1,2-epoxyethyl) dibiphenyl ether, 4,4'-(17,2-epoxyethyl)
biphenyl, 2,2-bis(3,4-epoxycyclohexyl)propane, diglycidyl ether of resorcinol, diglycidyl ether of phloroglucin, diglycidyl ether of methylphloroglucin, bis-(2,3-
epoxycyclopentyl)ether, 2-(3,4-
epoxy)cyclohexane-5,5-spiro(3,4-
epoxy) cyclohexane-m-dioxane, bis-(
Trifunctional epoxy compounds such as 3,4-epoxy-6-methylcyclohexyl)adipate, N,N'-m-phenylenebis(4,5-epoxy-1,2-cyclohexane)dicarboximide, triaminophenol Glycidyl ether, polyallyl glycidyl ether, 1,3.5-)-ly(1゜2-epoxyethyl)benzene, 2.2', 4゜4'-tetraglycidoxybenzophenone, tetraglycidoxytetraphenylethane , polyglycidyl ether of phenol formaldehyde novolak, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, or the following formula % formula % lower alkyl group, fluoro.

There are trifunctional or higher functional epoxy compounds represented by:

Furthermore, the following epoxy compounds have liquid crystal orientation in a molten state. It is highly effective in imparting heat resistance to cured products, improving mechanical strength, adhesion, and electrical properties.

Such compounds include, for example: and so on.

Also useful are epoxy compounds having at least one terminal vinyl group or terminal allyl group and at least one terminal epoxy group (ethylene oxide group) in the molecule. For example, - Shipman (in the formula, R14 is H or C
Typical examples include glycidyl acrylate, glycidyl methacrylate, β-methylglycidyl acrylate, and β-methylglycidyl methacrylate. Furthermore, it is a monomer having the structure -Funenin (in the formula, Rla, R18 is H or CH3), and (methyl)glycidyl (meth)acrylic ether is a typical example. Also, -Sailor (in the formula, SuRL7.Rla represents H or CHa.

Rx2 may be an ethylenically unsaturated f1 epoxy monomer having 6 to 12 carbon atoms such as -G-〇-CH2- ■ ○ or represented by the following formula, or an olefinically unsaturated monoepoxide. Also, -Sailor (in the formula, Rle is Hl
Or, a lower alkyl group having 1 to 4 carbon atoms, or
CHzC,+2, X is an integer from 1 to 9, and y
is an integer of 0 to 10), such as allyl glycidyl ether, (2-allyloxy)ethylene glycidyl ether, and 4-butenyl glycidyl ether.

Alternatively, there are compounds represented by the general formula (in the formula, - in Rzo'' R26 represents a hydrogen atom, methyl or allyl group, and the other R's represent a hydrogen atom).

Also, vinylcyclohexene monooxide.

Glycidyl ether of furfuryl alcohol or Ch-CH=CHz and so on. At least one of these is used.

In the present invention, the blending ratio of the etherimide compound represented by -Funenin CI) and the amino derivative having at least one fluorine-containing group in the molecule is 10% for the former.
The latter is generally in the range of 10 to 1000 parts by weight relative to 0 parts by weight. As the ratio of the latter decreases, the heat resistance increases, but the dielectric constant increases, and as the ratio increases, the opposite trend occurs.

Further, 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 obtained thereby has a glass transition point of 180°C or higher, and a bending strength of 150 kg/a at 180°C.
It is also possible to obtain a cured product having a strength retention rate of 80% or more after being left at 200° C. for 30 days. In addition, the elastic modulus of bending strength is 1.30 x 103 kg/m+++" or less, and the crack resistance when molded with a metal insert (70 φ x 4I111 thickness 0-shaped washer) is 40'C.
Even under a heat cycle of 2 hours to room temperature/2 hours to 140°C for 2 hours, no cracks were generated even after 20 hours or more.

In addition, depending on the purpose and use, the resin composition of the present invention may include:
It can be modified by adding monomers of the vinyl, allyl and acrylic type and containing at least one polymerizable CHz=C group.

Here, the monomer is, for example, styrene, vinyltoluene, α-methylstyrene, or divinylbenzene.

diallyl phthalate, diallyl phthalate prepolymer,
Chlorstyrene, dichlorostyrene, bromstyrene,
Dibromustyrene, diallylbenzene phosphonate, diallylaryl phosphylate, acrylic acid, methacrylic acid ester.

Examples include triallyl cyanurate, triallyl cyanurate prepolymer, tribromophenol allyl ether, or conventionally known N,N'-1-substituted bismaleimide compounds, and one or two of these can be used in combination. .

It is desirable to add a polymerization initiator to the resin composition of the present invention in order to complete its 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), hydroxyhebutyl peroxide, t-
Butyl hydroperoxide, p-menthane hydroperoxide, t-butyl perbenzoate, t-butyl peracetate, t-butyl peroctoate, t-butylperoxyisobutyrate, di-t-butylshiba-
Organic peroxides such as phthalates are useful, and one or more of them can be used.

In addition, tertiary amines such as triethylamine, tetramethylbutanediamine, tetramethylpentanediamine, tetramethylhexanediamine, triethylenediamine, dimethylaniline, oxyalkylamines such as dimethylaminoethanol, dimethylaminopentanol, and tris(dimethylaminomethyl) Phenol, amines such as N-methylmorpholine, cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, dotesyltrimethylammonium iodide, trimethyldodecylammonium chloride, benzyldimethyltetradecylammonium chloride,
benzyldimethylpalmitylammonium chloride,
Quaternary ammonium salts such as allyldotesyltrimethylammonium bromide, benzyldimethylstearylammonium bromide, stearyltrimethylammonium chloride, benzyldimethyltetradecylammonium acetate, furthermore, 2-methylimidazole,
2-ethylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, 2-methyl-4-ethylimidazole, 1-butylimidazole, 1-propyl-2-methylimidazole, 1-benzyl-2-methylimidazole, 1 -cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole,
1-Azine-2-methylimidazole, 1-Azine-2
- Imidazoles such as undecyl imidazole, triphenylphosphine tetraphenylborate, triethylamine tetraphenylborate, N-methylmorpholine tetraphenylborate, pyridine tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, 2-ethyl- Kalibol salts such as 1,4-dimethylimidazole tetraphenylborate are useful. It is preferable to use at least one of these catalysts in an amount of 0.01 to 10% by weight based on the above-mentioned blended composition. Moreover, these catalysts and the above-mentioned peroxide catalyst can also be used in combination.

In the present invention, the above-mentioned polymerization catalyst may include, for example, mercaptans, sulfides, β-diketones, metal chelates,
It is also possible to use a known accelerator such as metallparic acid. In addition, 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- Phenols such as t-butylhydroquinone, nitro compounds,
Known polymerization inhibitors such as metal salts can be used depending on the purpose.

Furthermore, the resin composition of the present invention may include, depending on its use,
Various materials can be blended.

For example, zircon, silica, alumina, aluminum hydroxide, titania, zinc white, calcium carbonate, magnesite, clay, kaolin, talc, silica sand, glass, fused silica glass, asbestos, and mica are suitable for use as molding materials. , various whiskers, carbon black,
At least one of inorganic fillers such as graphite and molybdenum disulfide, mold release agents such as higher fatty acids and wax, and coupling agents such as epoxy silane, vinyl silane, borane and alkoxy titanate compounds can be blended. Further, flame retardant imparting agents such as halogen-containing compounds, antimony oxide, and phosphorus compounds can be used as necessary.

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, dimethylsulfoxide, N-N-diethylacetamide, N-N-dimethylmethoxyacetamide, hexamethylphosphoramide, pyridine, dimethylsulfone, tetramethylsulfone, dimethyltetramethylenesulfone, etc. , and the phenolic solvent group includes phenol,
Examples include cresol and xylenol.

The above can be used alone or in combination of two or more.

By the way, the composition of the present invention can be used for element coating films such as glabella insulating films and delta-ray shielding films in multilayer wiring structures of semiconductor devices;
Wide range of applications including laminated materials for multilayer wiring boards for computers, LSI sealing materials, adhesives, liquid crystal alignment films, sealing materials for display devices, paints for various uses, sliding materials (surface coating materials) for magnetic recording disks, etc. There is.

For example, when applied to a semiconductor device, it is preferable that the solution containing the compounds represented by Ichiman CI) and -Senman (II) of the present invention is applied to the surface of a semiconductor element, etc., and the solvent is For example, aromatic hydrocarbons such as benzene, toluene, xylene, methanol, ethanol,
-In addition to alcohols such as propatool, methyl ethyl ketone.

Ketones such as acetone, cellosolve acetates such as ethyl cellosolve, chlorinated hydrocarbons, dimethylacetamide, dimethylpol-4amide, N-
Examples include polar solvents such as methyl-2-pyrrolidone.

Solutions of these compounds are applied to the surfaces of semiconductor elements, lead wires, and the like. Coating methods include dipping the element and lead wires into the solution, dropping the solution onto the element and lead wires, spraying, and spinner coating.

By such a method, the semiconductor elements and lead wires coated with the compound solution are first subjected to heat baking at a temperature of at least 100°C or higher, particularly preferably 120 to 250°C. Through this treatment, the compound has a higher molecular weight and is crosslinked to form a protective coating layer. Regarding the thickness of the coating layer,
There are no particular restrictions. Depending on the purpose and use, those with excellent effects are used as appropriate.

For example, the interlayer insulating film of a multilayer wiring type LSI requires 500 or more people.
The film thickness is several μm, and the δ-ray shielding film is 10 to 200 μm.
A film thickness of (Figure 1,
2 and 3) [Example] <Examples 1 to 20> Twenty types of blended compositions shown in Tables 1 and 2 were prepared.

After kneading a sufficient amount of each blended composition at 50 to 70°C,
It was cooled to obtain the desired heat-resistant resin composition.

Each composition was transfer molded under the conditions of 170° C., 70 kg/aJ, and 5 minutes to prepare specimens for measuring various characteristics. Tables 1 and 2 show the glass transition point, bending strength at 180°C, bending modulus, heat deterioration characteristics after being left at 200°C for 30 days, and storage stability of the material.

All cured products have a glass transition point of 180°C or higher.

Bending strength at 180℃, 450kg/cd or more, 200℃
, Strength retention after 30 days of storage: 80% or more 2 Flexural modulus: 1
, 30 x 10'kg/m" or more, and has excellent flexibility and heat resistance.

The following studies were conducted using the following fluorine-containing amino derivatives (A) to (F), which are essential components of the present invention.

Fluorine-containing amino derivative (A) Fluorine-containing amino derivative (C) Fluorine-containing amino derivative (E) Fluorine-containing amino derivative (F) <Examples 21 to 28> Five of the above-mentioned fluorine-containing amino derivatives (A) to (E) Selected types. In addition to these, bisphenol A type epoxy DER332 (manufactured by Dow Chemical Company), orthodiallyl bisphenol F, 2,2-bis(4-(4-maleimidophenoxy)phenyl]hexafluoropropane (abbreviated as DAPP-FMI) , triallyl isocyanurate (TAIC) were separately blended in the predetermined amounts (parts by weight) shown in Table 3 to make human-type formulations.

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

These formulations were then dissolved in an isostatic mixture of N-methyl-2-pyrrolidone (NMP) and methyl ethyl ketone (MEK) to form a varnish containing 45-48% solids by weight.

Using this varnish solution, apply a glass cloth (WE-made by Nittobo Co., Ltd.)
116P, BY-54), coated with resin and heated at 160°C.
, and dried for 15 minutes to prepare a coated cloth having a resin content of 45 to 48% by weight.

Next, apply a sheet to this coated cloth, and apply a layer of 35 μm above and below it.
Layer thick TAI-treated copper foil (manufactured by Furukawa Denki CFC),
Lamination and adhesion were carried out for 80 minutes under conditions of 170 to 185°C and 40 kg-f/- to produce a double-sided copper-clad laminate having a thickness of about 1.6 mm.

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

The method for measuring each characteristic is as follows.

(a) Copper foil peel strength After cutting a test piece into a size of 25 m x 100 mm from a copper-clad laminate, a copper foil with a width of 10 ai was left in the center, and the other copper foils were removed by etching. Next, the central copper foil was peeled off in the vertical direction at a speed of 5 m/win, and its strength was measured.

(b) A test piece was cut into a 25+s+ corner from a solder heat-resistant copper-clad laminate. This test piece was floated in a solder bath heated to 300°C, and the time required for abnormalities such as blistering to occur was measured.

(c) Anti-inflammatory tMeasured according to the JL-94 vertical method. A test piece was cut from the above copper-clad laminate to a width of 12 mm and a length of 125 m, and a copper foil was etched thereon.

The positive side of each test piece was measured and expressed as the average flame-out time.

In addition, an average flame-out time of 5 seconds or less and a maximum flame-out time of 10 seconds or less is UL-94, V-0, and an average flame-out time of 25 seconds or less and a maximum flame-out time of 30 seconds or less is UL-94, V-1.

<Examples 29-39. Comparative Example> As a polyfunctional epoxy compound, a fluorine-containing amino derivative (A ) and (B), as well as novolak type phenolic resin HP-60.
7N (manufactured by Hitachi Chemical Co., Ltd., softening point 78 to 82°C), p-hydroxy polymer M resin (manufactured by Maruzen Oil Co., Ltd., number average molecular weight 4800) + N,N'-bismaleimide diphenylmethane (DOM bismaleimide).

The prescribed amounts shown in Table 4 were blended.

To these compounds, 2.0 parts by weight of triphenylphosphine as a curing accelerator, 2.0 parts by weight of epoxysilane KBM303 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a coupling agent, and 0.8 parts by weight of an acylate titanate compound. 1.0 parts by weight of calcium stearate and 1.0 parts by weight of Hoechst Wax E (manufactured by Hoechst Javan) as a mold release agent, 5 parts by weight of addition type imide coated red phosphorus as a flame retardant,
As a filler, 50% by weight of spherical alumina with an average particle size of 1 μm (based on the entire blended composition) and 10 to 44 μm
30 weight percent of fused silica glass powder with m average particle size (based on the entire blended composition) and 2.0 parts by weight of carbon black (manufactured by Cabot) as a coloring agent were added separately to obtain m = type of fused silica powder. A blended composition was created.

These formulations were then heated to 75-85°C.
After heating and kneading for a minute using two inch diameter rolls, the mixture was cooled and coarsely ground to obtain a molding material composition for semiconductor encapsulation.

Using these compositions, IM bit D-RAM LSI
, 50 pieces were molded at 180"C using a transfer molding machine.
, 70 kg-f/al for 2 minutes to obtain a resin-sealed semiconductor device.

The temperature of the obtained resin-sealed semiconductor device was 121°C.

After placing the semiconductor device in a 2-atm supersaturated steam oven (preheat hookah oven) for a predetermined period of time, take it out and check whether the semiconductor device operates normally electrically.If it shows malfunction (broken wire), Destructive testing confirmed that the wiring on the device had broken 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 FIG.
3 are partial cross-sectional views of the 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 a wiring, 5 is a polyimide resin, 6 is a molding resin, and 7 is a thermal oxide film.

〔Effect of the invention〕

The etherimide composition of the present invention is heat resistant.

It is highly effective in imparting flexibility, moisture resistance, and low dielectric constant.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional view of a semiconductor device according to an embodiment of the present invention, and FIGS. 2 and 3 are partial cross-sectional views of elements of the semiconductor device according to the present invention. DESCRIPTION OF SYMBOLS 1...Lead wire, 2...Semiconductor element, 3...Protective coating resin, 3-I...-th layer protective coating resin, 3-■.
...Second layer protective coating resin, 4-1...Third layer wiring, 4
-11...Second layer wiring, 5...Polyimide resin, 6
...Mold resin, 7...Thermal oxidation film. Diagram

Claims (8)

[Claims] 1. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] [In the formula, R_1 to R_4 are H, a lower alkyl group, a fluoroalkyl group, or a halogen atom. Also,
R_5 and R_6 are CH_3, CF_3, H, ▲ formula,
There are chemical formulas, tables, etc. ▼. Also, D
_1 and D_2 are divalent organic groups having an ethylenically unsaturated double bond. ] An ether unsaturated bisimide compound represented by the general formula [II]
7 is one of the following: ▲There are mathematical formulas, chemical formulas, tables, etc.▼. ). Also, X has ▲mathematical formulas, chemical formulas, tables, etc.▼ (R', R'', R''' are any of F, CF_3, C_2F_5, C_3F_7, and they can be the same or different. ), and ▲Mathematical formulas, chemical formulas, tables, etc.▼ (m is 1 to 40). In addition, Y is either ▲ has a mathematical formula, chemical formula, table, etc. ▼ (D is a divalent organic group with an ethylenically unsaturated double bond), or ▲ has a mathematical formula, chemical formula, table, etc. ▼ It is. An etherimide composition comprising a fluorine-containing amino derivative represented by the following. 2. The general formula [II] becomes the following formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [III] [In the formula, R', R'', and R''' are the same as above. The etherimide composition according to claim 1, which is a fluorine-containing phenylmaleimide represented by the following formula. 3. The general formula [II] becomes the following formula [IV] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [IV] [m is the same as above. ] Patent claim 1 characterized in that it is a fluorine-containing phenylmaleimide represented by
The etherimide composition described in . 4. The general formula [II] is the following formula [V] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [V] [In the formula, R', R'', R''' and D are the same as above. Furthermore, R■ and R■ are any one of H, CH_3, and CF_3, and may be the same or different. The etherimide composition according to claim 1, which is a fluorine-containing unsaturated imide compound represented by the following. 5. The general formula [II] becomes the following formula [VI] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [VI] [In the formula, D, R■, R_9, and m are the same as above. The etherimide composition according to claim 1, which is a fluorine-containing unsaturated imide compound represented by the following. 6. A molding material for semiconductor encapsulation comprising the composition according to claim 1. 7. A semiconductor device characterized by being coated and/or encapsulated with the composition according to claim 1. 8. A material for a laminate comprising the composition according to claim 1 as a constituent component.