JPH02124930A - Glycidylamine compound having thioether bond, composition thereof and use thereof - Google Patents

Abstract

PURPOSE:To improve the mechanical strengths, heat resistance and humidity resistance of a cured product by reacting an arom. diamine compd. having thioether bonds with an epihalohydrin. CONSTITUTION:4-40mol of an epihalohydrin functioning as both a reactant and a solvent are added to 1mol of an arom. diamine compd. of formula I (wherein R1-4 are each H, a lower alkyl, a halogen or a perfluoroalkyl; R5-6 are each H, a lower alkyl, or a perfluoroalkyl) having thioether bonds and the mixture is stirred at 30 deg.C to reflux temp. of the epihalohydrin for 2-50hr in the presence of a catalyst (e.g., a quat. ammonium salt). Then, 4-8mol of an alkali (e.g., NaOH) based on 1mol of the diamine compd. is added thereto and, after the reaction is performed at 20-80 deg.C for 0.5-5hr, formed salts are filtered off and the solvent is distilled off under reduced pressure at 70-160 deg.C to obtain a tetraglycidylamine compd. of formula II having thioether bonds, which is reacted with a variety of curing agents (e.g., an aliph. polyamine).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to novel tetraglycidyl ether compounds having a thioether bond, compositions containing the same, and uses thereof.

[Conventional technology]

Epoxy compounds have thermal properties, mechanical strength, electrical properties,
Since it is easy to achieve a balance between adhesive properties and moldability, it is widely used in fields such as electrical equipment and electronic parts.

In particular, bisphenol A type diglycidyl ether compounds are extremely versatile and have become mainstream products. This is because the effect of imparting flexibility and adhesion to the cured product is large.

In recent years, as electrical equipment and electronic components have become smaller and lighter, have higher performance, and have become more reliable, products to which these are applied are required to have improved heat resistance.

[Problem to be solved by the invention]

In order to deal with this situation, there have been applications for bisphenol A type tetraglycidylamine compounds (Japanese Patent Laid-Open Nos. 62-477 and 62-114981).

However, with this compound, the effect of improving heat resistance can be achieved, but there is a decrease in moisture resistance and insert metal.

It has the disadvantage that it tends to cause corrosion of coated metals.

The object of the present invention is to provide a novel epoxy compound that has excellent cured product flexibility, heat resistance, and adhesiveness as well as excellent moldability, compositions using this compound, and uses thereof. Our goal is to provide the following.

([Means for Solving the Problem] The above object was achieved by the following tetrafunctional epoxy compound having a thioether bond. The summary is as follows.

(1), -Formula (1) %Formula%) In the formula C, R1''R4 is any one of hydrogen, a lower alkyl group, a halogen group, and a perfluoroalkyl group,
They may be the same or different. Also, R
5 and R6 are hydrogen, a lower alkyl group, or a perfluoroalkyl group, and may be the same or different. ] A tetraglycidylamine compound with a thioether bond.

(2) A resin composition comprising the tetraglycidylamine compound shown in (1).

(3) A varnish containing the tetraglycidylamine compound shown in (1).

(4) An adhesive containing the tetraglycidylamine compound shown in (1).

(5) A molding material containing the tetraglycidylamine compound shown in (1).

(6) A laminated material containing the tetraglycidylamine compound shown in (1).

(7) A semiconductor device, characterized in that at least a portion of a semiconductor element is coated with a coating material containing a tetraglycidylamine compound shown in (1).

[Effect]

General formula (1), which forms the basis of the present invention and is a tetrafunctional epoxy compound having a thioether bond (in the formula, R1-R4
is hydrogen, a lower alkyl group, a halogen group, or a perfluoroalkyl group, and may be the same or different and may be 11; Rg and Re are hydrogen, a lower alkyl group, or a perfluoroalkyl group; Tetraglycidylamine compounds having a thioether bond, which are any of the fluoroalkyl groups and may be the same or different from each other, are exemplified by the following compounds.

and so on.

The tetraglycidylamine compound having a thioether bond represented by the general formula (1) has the formula (II) [wherein R1 to R4 are hydrogen, a lower alkyl group, a halogen group, or a perfluoroalkyl group] It is
They may be the same or different. Also, R
5 and R8 are hydrogen, a lower alkyl group, or a perfluoroalkyl group, and may be the same or different. It can be obtained by reacting an aromatic diamine compound having a thioether bond represented by ] with shrimp halohydrin.

The reaction is carried out using epihalohydrin as a reactant and solvent in an amount of 4 to 40 mol, preferably 5 to 1 mol, per 1 mol of diamine.
It can be obtained by using 5 mol and stirring at a temperature of 30°C to epihalohydrin reflux temperature, preferably 50 to 100°C. The reaction time is usually 2 to 50 hours.

As the epihalohydrin, for example, epichlorohydrin, shrimp bromohydrin, shrimp iodohydrin, etc. can be used.

To complete this reaction, a dehydrohalogenation reaction proceeds after the addition reaction. Usually, this can be done by adding 4 to 8 moles of alkali per mole of aromatic diamine and stirring at a temperature of 20 to 80°C, preferably 30 to 60°C (7).

The reaction time is usually 0.5 to 5 hours. As the alkali, sodium hydroxide, potassium hydroxide, etc. can usually be used.

Further, both the addition reaction and the dehydrohalogenation reaction can be carried out at normal pressure, increased pressure, or reduced pressure.

In order to promote these reactions, quaternary ammonium salts, quaternary phosphonium salts, quaternary arsonium salts, crown ethers, and the like can be used as catalysts. After the completion of the dehydrohalogenation reaction, salts, catalysts, etc. in the reaction mixture are filtered (separated by filtration), and the solvent is removed under reduced pressure for 70 minutes.
By distilling off at a temperature of ~160°C, a tetraglycidylamine compound having a thioether bond represented by formula (1), which is the object of the present invention, is obtained.

The thioether bond represented by the above-mentioned formula (II),
Examples of the aromatic diamine compounds having the above-mentioned properties include those shown below.

Ha Ha Cz　Hs 4H11 Ha Hs Hs Fs zFa zFa s　Fy 4F9 aFs C4F@ aFs CM F? and so on.

In the present invention, a conventionally known polyfunctional epoxy compound may be used in combination with the composition containing the compound represented by the following formula [1].

For example, diglycidyl ether of bisphenol A, butadiene diepoxide, 3,4-epoxycyclohexylmethyl-(3,4-epoxy)cyclohexane carboxylate, vinylcyclohexane dioxide, 4,
4'-di(1,2-epoxyethyl) dibiphenyl ether, 4.4'-(1,2-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-(3,4-
Epoxy-6-methylcyclohexyl)adipate, N
.

87~m-phenylenebis(4,5-epoxy-1,2
-Trifunctional epoxy compounds such as dicarboximide (cyclohexane).

Triglycidyl ether of para-aminophenol, polyallyl glycidyl ether, 1,3.5-tri(1,2
-epoxyethyl)benzene, 2°2', 4,4'
- Tetraglycidoxybenzophenone, tetraglycidoxytetraphenylethane, polyglycidyl ether of phenol formaldehyde novolac, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, or the following formula (RIO, R11 is a H9 lower alkyl group) There are trifunctional or higher functional epoxy compounds represented by , fluoro, etc.

Further, the epoxy compound shown in the first order has liquid crystal orientation in a dissolved state. It is highly 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, a conventionally known curing agent can also be used in combination with the epoxy compound of the present invention. They are: Hiroshi Kakiuchi: Epoxy Resin (published September 1970) pages 109-149;
Written by Lee, Neville: EpoxyResin
s (Me Graw-Hllll Book Com
pany Inc: NetiYork, 1957
(Published in 2013) pages 63-141.

Written by P.E. Brunis: Epoxy Re5ins
Technology (Interscience)
Publishers, Now York, 196
8), pages 45 to 111, such as aliphatic polyamines, aromatic polyamines, amines including secondary and tertiary amines, carboxylic acids, carboxylic acid anhydrides, aliphatic, and , aromatic polyamide oligomers and polymers 5 boron trifluoride-amine complexes, synthetic resin initial condensates such as phenolic resins, melamine resins, urea resins, urethane resins, etc.
Examples include dicyandiamide, carboxylic acid hydrazide, various unsaturated bisimides, polyaminomaleimide, and P-hydroxystyrene resin.

One or more types of these curing agents can be used depending on the use and purpose.

A catalyst that promotes the curing reaction between the epoxy compound and the curing agent can be used in the resin composition of the present invention.

These catalysts include, for example, tertiary amines such as triethanolamine, tetramethylbutanediamine, tetramethylbutanediamine, tetramethylhexanediamine, triethylenediamine, dimethylaniline, oxyalkyl amines such as dimethylaminoethanol, dimethylaminopetanol, etc. There are amines such as amine, tris(dimethylaminomethyl)phenol, N-methylmorpholine, and N-ethylmorpholine.

Also, zetyltrimethylammonium bromide, cetyltrimethylammonium chloride, dodecyltrimethylammonium iodide.

Quaternary ammonium salts such as trimethyldodecyl ammonium chloride, benzyldimethyltetradecylammonium chloride, benzylmethylpalmitylammonium chloride, allyldodecyltrimethylammonium bromide, benzyldimethylstearylammonium bromide, stearyltrimethylammonium chloride, benzyldimethyltetradecylammonium acetate be.

Also, 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 undecylimidazole, triphenylphosphine tetraphenylborate, tetraphenylphosphonium tetraphenylborate, triethylamine tetraphenylborate, N-methylmorpholine tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, 2 -ethyl-1,
Examples include tetraphenylborate such as 4-dimethylimidazoletetraphenylborate.

Also, 25-diazabicyclo(4,2,O)octene-5,1,8-diaza-bicyclo(7゜2,O)undecene-8,1,4-diaza-bicyclo(3,3,O
) octene-4,3-methyl-1,4-diazabicyclo(3,3,O)octene-4,3,6,7,7-tetramethyl-1,4-diazadicyclo(3,3,O)octene- 4゜1.5-diaza-bicyclo(3,4,,O)
nonene-5,1,8-diaza-bicyclo(7,3,O
) Dodecene-8,1,7-diazabicyclo(4,3゜0
) Nonene-6,1,5-diazabicyclo (4°4.0)
Decene-5,1,8-diazabicyclo(7,4,O)
Tridecene-8,1,8-diazabicyclo(5,3,
O) Decene-7,9-methyl-1,8-diazabicyclo(5,3,0)Decene-7,1,8-diazabicyclo(
5,4,O) Undecene-7,1,6-diazabicyclo(5,5°O) Dodecene-6,1,7-diazabicyclo(6°5,O) Tridecene-7,1,8-diazabicyclo(7, 5,O) Tetradecene-8,1,10-diazabicyclo(7,3,O) Dodecene-9,1゜1
0-diazabicyclo(7,4,0) tridecene-9
,1,14-diazabicyclo(11,3,O)hexadecene-13,1,14-diazabicyclo(11,4,0
) Diazabicyclo-alkenes such as hebutadecene-13 are also useful. One or more of these compounds can be used in combination depending on the purpose and use. Among these compounds, 1°8-diazabicyclo(5,4,O)undecene-7 (DBU) and carboxylic acid salts of this compound are particularly effective in enhancing the effects of the present invention.

In the present invention, various inorganic substances and additives can be added to the resin composition depending on the purpose and use. Specific examples include zircon, silica, fused silica glass, alumina, aluminum hydroxide, glass, quartz glass, calcium silicate, gypsum, calcium carbonate, magnesite, clay kaolin, talc, iron powder, copper powder, mica. , fillers such as asbestos, silicon carbide, boron nitride, molybdenum disulfide, lead compounds, lead oxides, Ameika, titanium white, carbon black, higher fatty acids, mold release agents such as waxes, epoxy silane, These include coupling agents such as vinylsilane, aminosilane, borane compounds, alkoxytitanate compounds, and aluminum chelate compounds. Furthermore, known flame retardants containing antimony, phosphorus compounds, bromine and chlorine can be used.

The epoxy resin composition of the present invention has excellent heat resistance, low water absorption and moisture permeability, and good adhesion to metals, so it is useful as a sealant for semiconductor devices, and is useful for devices and devices. Used to cover and seal lead wires.

When the composition of the present invention is used to encapsulate a semiconductor device, the method is not particularly limited, and known methods such as casting and transfer molding can be applied.

Furthermore, since the epoxy resin composition of the present invention has excellent heat resistance and temperature resistance, it is also useful as a material for laminated boards.

The compound represented by the general formula (1) of the present invention is preferably applied to the surface of a semiconductor element, etc. as a solution,
Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, and xylene, methanol, ethanol, and 2-
In addition to alcohols such as propatool, ketones such as methyl ethyl ketone and acetone, cellosolve acetates such as ethyl cellosolve, chlorinated hydrocarbons, dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone, etc. Examples include polar solvents.

Solutions of these compounds are applied to the surfaces of semiconductor elements, lead wires, and the like. The coating method includes methods such as dipping the element and lead wires into the solution, dropping the solution onto the element and lead wires, and spray spinner coating.

By such a method, the semiconductor elements and lead wires coated with the compound solution are then heat-baked 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 limitations, and depending on the purpose and use, those with excellent effects may be used as appropriate.

For example, as an interlayer insulating film for a multilayer wiring type LSI, 50
The film thickness is from 0 to several μm, and the α-ray blocking film is from 10 to several μm.
A film thickness of 200 μm is effective in achieving the objective.

<Example 1> 10 equipped with a stirrer, reflux condenser, thermometer, and dropping funnel
2,2-bis(4-(4
-Aminothiophenoxy)phenyl]propane 221g
(0,5 mol), and.

364 mA (7.0 mol) of epichlorohydrin was charged and stirred at 90°C for 10 hours to carry out an addition reaction.

Next, the reaction solution was cooled to 50°C, 300g of sodium pentahydroxide and 3.7g (0,024 mol) of tetramethylammonium bromide were added, and the mixture was cooled to 50°C.
After 2 hours of reaction, the dehydrohalogenation reaction was completed. The formed salt, excess alkali, and catalyst are filtered off, and the solvent is distilled off from the filtrate under reduced pressure at 70°C and 2 nnHg.Then, the temperature is raised to 150°C and the solvent is completely distilled off to obtain the desired product. A tetraglycidylamine (A) having a thioether bond was obtained. Infrared absorption spectrum of this epoxy compound (I
As a result of measuring R), there is a characteristic absorption derived from thioether bonds, which is a gentle absorption around 680 to 7001''1, and a characteristic absorption derived from epoxy groups, which is 905.
an-” was confirmed.

Tetraglycidylamine (B
) to (D) were synthesized.

<Examples 2 to 10, Comparative Examples> As a polyfunctional epoxy compound, orthocresol novolak type epoxy resin EOCN-102S (manufactured by Hitachi Chemical Co., Ltd., epoxy equivalent weight 211, softening point 66.4°C) and the above-mentioned implementation of the present invention were used. Tetraglycidylamine compounds (A), (B), (C), (D
), a total of five types were selected. Further, as a curing agent, novolak type phenolic resin HP-607N (manufactured by Hitachi Chemical Co., Ltd., softening point 78 to 82°C), P-hydroxy polymer M resin (manufactured by Marukubi Sekiyu Co., Ltd., number average molecule t4800).

N-N'-bismaleimidiphenylmethane (DDM
Bismaleimide) was taken up and the predetermined amounts shown in Table 1 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 type titanate compound. Department,
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, and spherical particles with an average particle size of 1 μm as a filler. 50% by weight alumina (based on the total formulation) and 10-44 μm
30% by weight of fused silica glass powder with an average particle size (based on the entire blended composition) carbon black (
2.0 parts by weight (manufactured by Cabot Inc.) were added to each separately to prepare 11 types of blended compositions.

Next, the above-mentioned mixture was heated and kneaded with two rolls of 8-inch diameter heated to 75 to 85°C for about 1 minute, cooled, and coarsely ground to obtain a molding material composition for semiconductor encapsulation. .

Using this composition, IM bit D-RAM LSI.

Fifty pieces were heated to 180°C using a transfer molding machine.

Sealing molding was performed under conditions of 70 kg-f/cd for 2 minutes to obtain a resin-sealed semiconductor device.

The obtained resin-sealed semiconductor device was placed in a supersaturated steam pot (pressure hookah pot) at 121° C. and 2 atm for a predetermined period of time, and then taken out to check whether the semiconductor device operates normally electrically. Destructive inspection confirmed that those exhibiting defective operation (broken wire) were caused by broken wires due to corrosion in the wiring on the element. Table 1 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.
1 and 3 are partial cross-sectional views of the elements of the semiconductor device of the present invention. In FIG. 1, 1 is a lead wire, 2 is a semiconductor element, and 3
, 5 is protective wave yxta resin, 4 is wiring, 6 is sealing resin,
7 is a thermal oxide film.

〔Effect of the invention〕

According to the present invention, a tetraglycidylamine compound having a thioether bond can be crosslinked with various compounds. The resulting cured product has mechanical strength, heat resistance, and moisture resistance, and is particularly effective in suppressing corrosion of metals in high-temperature conditions.

[Brief explanation of drawings]

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. DESCRIPTION OF SYMBOLS 1...Lead wire, 2...Semiconductor element, 3...Protective coating resin, 3-1...-Second protection coating resin, 3-11
...Second layer protective coating resin, 4-! ... th layer wiring,
4-11... Second layer wiring, 5... Polyimide resin, 6... Mold resin, 7... Thermal oxidation film. Danzu

Claims (1)

[Claims] 1. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc.▼ [I] [In the formula, R_1 to R_4 are hydrogen, lower alkyl group, halogen group, perfluoroalkyl group They may be the same or different from each other. Further, R_5 and R_6 are any one of hydrogen, a lower alkyl group, and a perfluoroalkyl group, and may be the same or different. ] A tetraglycidylamine compound with a thioether bond. 2. A resin composition comprising the tetraglycidylamine compound according to claim 1. 3. A varnish containing the tetraglycidylamine compound according to claim 1. 4. An adhesive comprising the tetraglycidylamine compound according to claim 1. 5. A molding material containing the tetraglycidylamine compound according to claim 1. 6. A laminated material containing the tetraglycidylamine compound according to claim 1. 7. A semiconductor device, wherein at least a part of a semiconductor element is coated with a coating material containing the tetraglycidylamine compound according to claim 1.