JP2000119442A - Heat-resistant resin composition and electroconductive paste - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a novel resin composition having excellent heat resistance, low hygroscopicity, and excellent flexibility by selecting a composition essentially consisting of a cyclic Schiff compound obtained by reacting a diamine compound with a dialdehyde compound. SOLUTION: A heat-resistant resin composition is obtained which essentially consists of a cyclic Schiff compound obtained by reacting a diamine compound represented by formula III (wherein X is-CH = or -N; R1 is H, a lower alkyl, a lower alkoxide, a halogen, or a lower fluoroalkyl) with a dialdehyde compound represented by formula IV (wherein Y is -CH = or -N =; R2 is H, a lower alkyl, a lower alkoxide, a halogen, or a lower fluoroalkyl) and represented by at least either of formula I and II (wherein X, Y, R1, and R2 are each as defined in formula III or formula IV). This composition is polymerized by heating and/or irradiation with an electromagnetic wave at a wavelength of 300-10,000 nm to obtain a cured product having high crystallinity and excellent heat resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant resin composition having excellent heat resistance, thermal shock resistance (flexibility) and adhesiveness, which is useful as a material for laminated boards, molding materials for semiconductor encapsulation and the like. The present invention relates to a cured product of the composition and a conductive paste.

[0002]

2. Description of the Related Art In recent years, as electrical equipment has become smaller and lighter and the operating environment has become more severe, the heat resistance, mechanical properties, and the like required of electrical insulating materials used in these equipment have been further improved. It is desired to provide such properties.

[0003] Epoxy resins have excellent electrical insulation properties, mechanical properties, heat resistance, chemical resistance, and the like, and are widely used in the fields of laminates, molding materials, casting materials, paints, adhesives, and the like. In particular, for applications requiring heat resistance, polyfunctional epoxy resins such as novolak type and glycidylamine resins are used as epoxy resins. However, these epoxy resins are inferior in heat resistance to polyimide resins and the like,
There are problems with flexibility and water resistance.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel heat-resistant resin composition excellent in heat resistance, low moisture absorption and flexibility, and a compound of the resin composition.

[0005]

The gist of the present invention is as follows.

(1). General formula (chemical formula 1) and / or general formula (chemical formula 2)

[0007]

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[0008]

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(Wherein X and Y are -CH = or -N =
Is one of R ₁ and R ₂ are any of hydrogen, a lower alkyl group, a lower alkoxide group, a halogen atom and a lower fluoroalkyl group. A heat-resistant resin composition comprising at least the cyclic Schiff compound represented by the formula (1).

(2). General formula (Formula 3)

[0011]

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(Wherein X is either —CH ＝ or —NＮ; R ₁ is any _one of hydrogen, lower alkyl, lower alkoxide, halogen atom, and lower fluoroalkyl). A diamine compound represented by the general formula (Chemical Formula 4)

[0013]

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(Wherein, Y is either —CH 又 は or —N ＝; R ₂ is any one of hydrogen, lower alkyl, lower alkoxide, halogen atom and lower fluoroalkyl). General formula (Chemical formula 1) or / and General formula (Chemical formula 2) obtained by reacting with a dialdehyde compound

[0015]

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[0016]

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(Where X and Y are -CH = or -N =
Is one of R ₁ and R ₂ are any of hydrogen, lower alkyl, lower alkoxide, halogen atom and lower fluoroalkyl. A heat-resistant resin composition comprising at least the cyclic Schiff compound represented by the formula (1).

(3). General formula (Formula 3)

[0019]

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(Wherein X is either —CH ＝ or —NＮ; R ₁ is any _one of hydrogen, lower alkyl, lower alkoxide, halogen atom, and lower fluoroalkyl). A diamine compound represented by the general formula (Chemical Formula 4)

[0021]

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(Wherein, Y is either —CH ＝ or —N ＝; R ₂ is any one of hydrogen, lower alkyl, lower alkoxide, halogen atom, and lower fluoroalkyl). General formula (Chemical formula 1) or / and General formula (Chemical formula 2) obtained by reacting with a dialdehyde compound

[0023]

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[0024]

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(Wherein X and Y are -CH = or -N =
Is one of R ₁ and R ₂ are any of hydrogen, lower alkyl, lower alkoxide, halogen atom and lower fluoroalkyl. And at least one cyclic Schiff compound represented by the general formula (1) and a Schiff bond (-CH = N-) of the dialdehyde compound represented by the general formula (1) or (2). A heat-resistant resin composition comprising at least a possible component.

(4). Unsaturated imide compounds having at least one N-substituted unsaturated imide group as a polymerizable component with a Schiff bond (-CH = N-) of a dialdehyde compound, amide compounds having at least one amide bond The heat-resistant resin composition according to the above (3), which is selected from the group consisting of a compound having at least one carbon-carbon double bond, an isocyanate compound, a cyanate compound, a cyanamide compound, and a chelate compound. .

(5). General formula (Formula 3)

[0028]

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(Wherein X is either —CH ＝ or —N =; R ₁ is any _one of hydrogen, lower alkyl, lower alkoxide, halogen atom, and lower fluoroalkyl). A diamine compound represented by the general formula (Chemical Formula 4)

[0030]

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(Wherein, Y is either —CH ＝ or —N ＝; R ₂ is any one of hydrogen, lower alkyl, lower alkoxide, halogen atom and lower fluoroalkyl). General formula (Chemical formula 1) or / and General formula (Chemical formula 2) obtained by reacting with a dialdehyde compound

[0032]

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[0033]

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(Where X and Y are -CH = or -N =
Is one of R ₁ and R ₂ are any of hydrogen, lower alkyl, lower alkoxide, halogen atom and lower fluoroalkyl. ), At least one cyclic Schiff compound represented by the following formula, and a phenol resin, an epoxy resin, a melamine resin, a urea resin, an unsaturated polyester resin, a urethane resin, a p-hydroxystyrene resin,
A heat-resistant resin composition comprising at least a component selected from a siloxane resin and a fluoroethylene resin.

(6). The above-mentioned (1), (2), wherein the diamine compound represented by the general formula (Formula 3) is metaphenylenediamine and the dialdehyde compound represented by the general formula (Formula 4) is metaphenylenedialdehyde. And (4)
3. The heat-resistant resin composition according to item 1.

(7). General formula (chemical formula 1) and / or general formula (chemical formula 2)

[0037]

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[0038]

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(Where X and Y are -CH = or -N =
Is one of R ₁ and R ₂ are any of hydrogen, lower alkyl, lower alkoxide, halogen atom and lower fluoroalkyl. A cured product having excellent heat resistance, which is obtained by polymerizing a heat-resistant resin composition containing at least the cyclic Schiff-based compound represented by the formula (1) by heating or irradiating an electromagnetic wave.

(8). A cured product having excellent heat resistance obtained by polymerizing the heat-resistant resin composition according to any one of the above (1) to (7) by heating or irradiating an electromagnetic wave.

(9). The wavelength of the electromagnetic wave is 300 nm to 10
Item 8. The cured product according to the above items 6 and 7, which has a thickness of 000 nm.

(10). A semiconductor element is fixed to a support member via an adhesive layer, and at least one of the semiconductor elements
A semiconductor device in which a part is covered or / and sealed with a resin composition, wherein the adhesive layer is the heat-resistant resin composition according to the above item 1 or 2.

(11). Consisting of a semiconductor element on which an integrated circuit is formed, a plurality of electrode pads formed on the integrated circuit forming surface side of the semiconductor element, and a mounting base having an external connection bump electrode connected to the electrode pad. In a semiconductor device, at least one of the electrode pad and the external connection bump electrode is formed by using the conductive paste according to the present invention, and an integrated circuit forming surface of the semiconductor element is provided. Provided is a semiconductor device in which a formed electrode pad is electrically connected to an external connection bump electrode of the mounting substrate, and a stress relaxation layer is formed between the integrated circuit forming surface and the mounting substrate. .

[0044]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a compound represented by the general formula (Formula 3)
Examples of the cyclic Schiff compounds (dimers) represented by 7) and (Formula 38) include the following.

[0045]

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[0046]

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Among these, (a), (b),
(C) is preferred.

In the present invention, the compound represented by the general formula (Formula 39)

[0049]

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The cyclic Schiff compounds (trimers) represented by the following are, for example, the following.

[0051]

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[0052]

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[0053]

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Among these, (a), (b),
(C) is preferred.

The cyclic Schiff compound represented by the general formula (Chemical formula 1) and / or the general formula (Chemical formula 2) is polymerized by heating or / and irradiation of an electromagnetic wave to have high crystalline heat resistance. It becomes an excellent cured product.

In the present invention, the compound represented by the general formula (Chemical Formula 1) and / or the general formula (Chemical Formula 2)

[0057]

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[0058]

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(Wherein X and Y represent -CH = or -N =
Is one of R ₁ and R ₂ are any of hydrogen, lower alkyl, lower alkoxide, halogen atom and lower fluoroalkyl. The cyclic Schiff compound represented by the general formula (3)

[0060]

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(Wherein X is either —CH ＝ or —NＮ; R ₁ is any _one of hydrogen, lower alkyl, lower alkoxide, halogen atom, and lower fluoroalkyl). A diamine compound represented by the general formula (Chemical Formula 4)

[0062]

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(Wherein, Y is either —CH ＝ or —N ＝; R ₂ is any one of hydrogen, lower alkyl, lower alkoxide, halogen atom, and lower fluoroalkyl). Obtained by reacting with a dialdehyde-based compound. For example, the reaction of 1 mol of metaphenylenediamine with 1 mol of metaphenylenedialdehyde is represented by the following formula (Formula 47)

[0064]

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Is represented by

The diamine compound represented by the general formula (Chemical Formula 3) reacts with the dialdehyde compound represented by the general formula (Chemical Formula 4) to form a compound represented by the general formula (Chemical Formula 1) or (Chemical Formula 1). 2)
And a cyclic Schiff-based compound represented by If the reaction temperature is too high, the polymerization proceeds, and the oligomer production ratio increases.

The cyclic Schiff compound represented by the general formula (Chemical Formula 1) or the general formula (Chemical Formula 2) is a polymer having a high degree of regularity, excellent mechanical strength, and excellent heat resistance due to cyclopolymerization itself. Become.

Further, the compound represented by the general formula (Chemical Formula 1) or the general formula (Chemical Formula 2)
When at least one of X and Y of the cyclic Schiff compound represented by is a nitrogen atom, the obtained polymer is excellent in conductivity, mechanical strength, and heat resistance.

In particular, the cured product of the present invention has a viscosity of 600 to 3000.
By heating to ° C., an amorphous or crystalline carbide is obtained. The carbide is excellent in conductivity, mechanical strength, and heat resistance, and is used as an anode material for a lithium secondary battery, an electrolyte material for a sodium-sulfur battery, a molten carbonate fuel cell, a solar cell, or an electrolyte supporting material such as an electrode material. Useful as

The component capable of polymerizing with the Schiff bond (—CH ＝ N—) of the cyclic Schiff compound is an unsaturated imide compound having at least one N-substituted unsaturated imide group or an amide bond. Amide compounds having at least one or more, compounds having at least one carbon-carbon double bond, compounds having at least one ethynyl group, isocyanate compounds, cyanate compounds, cyanamide compounds, chelate compounds, etc. No.

In particular, an ethynyl group of a compound having at least one ethynyl group, an isocyanate group of an isocyanate compound, a cyanate group of a cyanate compound,
The cyanamide group of the cyanamide compound and the nitrile group of the nitrile compound react with a Schiff bond to polymerize while forming a cyclic structure shown below.

[0072]

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The obtained polymer has high regularity, high rigidity, and has excellent heat resistance comparable to light metals such as aluminum in the region of 400 to 600 ° C. in terms of mechanical strength. When the polymer is heated to 600 to 3000 ° C., an amorphous or crystalline carbide can be obtained. The carbide is excellent in conductivity, mechanical strength, and heat resistance, and is used as an anode material for a lithium secondary battery, an electrolyte material for a sodium-sulfur battery, a molten carbonate fuel cell, a solar cell, or an electrolyte supporting material such as an electrode material. Useful as

The N-substituted unsaturated imide compound includes, for example, maleimide, citraconimide, itaconimide and the like, and maleimide compounds such as mono-substituted maleimide, bis-substituted maleimide, tri-substituted maleimide and tetra-substituted maleimide are preferred. . Among these, an N-substituted unsaturated bisimide compound is particularly preferred.

Such compounds include, for example, N,
N'-diphenylmethanebismaleimide, N, N'-phenylenebismaleimide, N, N'-diphenyletherbismaleimide, N, N'-diphenylsulfonebismaleimide, N, N'-dicyclohexylmethanebismaleimide, N, N'- Xylene bismaleimide, N,
N'-tolylenebismaleimide, N, N'-xylylenebismaleimide, N, N'-diphenylcyclohexanebismaleimide, N, N'-dichlorodiphenylbismaleimide, N, N'-diphenylmethanebismethylmaleimide, N , N'-diphenylether bismethylmaleimide, N, N'-diphenylsulfonebismaleimide, 2,2-bis-4 [-4- [maleimidophenoxy] phenyl] propane (including isomers),
N, N'-bismaleimide compounds such as N, N'-ethylenebismaleimide, N, N'-hexamethylenebismaleimide, N, N'-hexamethylenebismethylmaleimide; these N, N'-bismaleimide compounds Examples thereof include a prepolymer having a terminal N, N'-bismaleimide skeleton obtained by adding a diamine, a maleimidated aniline and a formalin condensate, and a methylmaleimide. Among them, 2,2-bis-4 [-4
-[Maleimidophenoxy] phenyl] propane, 2,
2-bis-4 [-4- [maleimidophenoxy] phenyl] hexafluoropropane is preferred because of its large effects of imparting heat resistance, flexibility, adhesion and moisture resistance.

The N-substituted unsaturated bisimide compound is
It is derived from a diamino group-containing compound and an unsaturated dicarboxylic anhydride.

Examples of the diamino group-containing compound include 1,2-
Diaminoethane, 1,3-diaminopropane, 1,4-
Diaminobutane, 1,5-diaminopentane, 1,6-
Diaminohexane, 1,7-diaminoheptane, 1,8
-Diaminooctane, 1,9-diaminononane, 1,1
0-diaminodecane, 1,11-diaminoundecane,
Aliphatic diamines such as 1,12-diaminododecane, o-
Phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,
4'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3 '
-Diaminodiphenyldifluoromethane, 3,4'-diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diamino Diphenyl sulfone, 3,
3'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylketone, 3,4'-diaminodiphenylketone, 4 , 4'-
Diaminodiphenyl ketone, 2,2-bis (3-aminophenyl) propane, 2,2 '-(3,4'-diaminodiphenyl) propane, 2,2-bis (4-aminophenyl) propane, 2,2- Bis (3-aminophenyl)
Hexafluoropropane, 2,2- (3,4'-diaminodiphenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane,
3-bis (3-aminophenoxy) benzene, 1,4-
Bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 ′-(1,
4-phenylenebis (1-methylethylidene)) bisaniline, 3,4 '-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 4,4'-(1,4
-Phenylenebis (1-methylethylidene)) bisaniline, 2,2-bis (4- (3-aminophenoxy) phenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 2, 2-bis (4-
(3-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (4-aminophenoxy)
Phenyl) hexafluoropropane, bis (4- (3-
Aminophenoxy) phenyl) sulfide, bis (4-
(4-aminophenoxy) phenyl) sulfide, bis (4- (3-aminophenoxy) phenyl) sulfone,
There are aromatic diamines such as bis (4- (4-aminophenoxy) phenyl) sulfone.

The unsaturated dicarboxylic anhydrides include, for example, maleic anhydride, citraconic anhydride, itaconic anhydride, dichloromaleic anhydride and the like, or Diels-Alder of these compounds and dicyclogen. ) At least one of the adducts is used.

The reaction for obtaining the N-substituted unsaturated bisimide compound is not particularly limited, but a known method is applied. As a general method, a diamino group-containing compound and an unsaturated dicarboxylic anhydride are brought into contact with each other in an organic solvent to produce an amic acid in the first step,
A method of forming an imide ring by dehydration cyclization of the amide acid is disclosed in U.S. Patent Nos. 3,018,290 and 3,127,414.

Further, at least one carbon-carbon double bond is
Compounds having at least one polyhydric alcohol and α, β
Compounds obtained by condensation with unsaturated carboxylic acids, for example, ethylene glycol di (meth) acrylate (meaning diacrylate or dimethacrylate, the same applies hereinafter), triethylene glycol di (meth) acrylate, tetraethylene glycol di ( (Meth) acrylate, trimethylolpropanedi (meth) acrylate,
Trimethylolpropane tri (meth) acrylate,
1,2-propylene glycol di (meth) acrylate, di (1,2-propylene glycol) di (meth) acrylate, tri (1,2-propylene glycol) di (meth) acrylate, tetra (1,2-propylene glycol) ) Di (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, 1,4-butanediol di (meth) acrylate,
1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, etc.), styrene, divinylbenzene, 4-vinyltoluene, 4-
Vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl (meth) acrylate, 1,3- (meth) acryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide,
N-methylol acrylamide, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tetramethylolpropanetetra (meth) acrylate, and the like. Used in combination of more than one species.

The isocyanate compounds include, for example, o-, m- and p-phenylene diisocyanate, 2,3-tolylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane Diisocyanate, diphenyl ether diisocyanate, diphenylsulfone diisocyanate, dicyclohexylmethane diisocyanate, xylene diisocyanate, N, N'-tolylene diisocyanate, xylylene diisocyanate, diphenylcyclohexane diisocyanate, dichlorodiphenyl diisocyanate, diphenyl sulfone diisocyanate, 2,2-bis-4 [ -4- [isocyanatophenoxy] phenyl] propane, 2,2-bis-4
[-4- [isocyanatophenoxy] phenyl] hexafluoropropane (each of which includes an isomer), ethylene diisocyanate, hexamethylene diisocyanate and the like.

Examples of the cyanate-based compound include, for example, diphenylmethane biscyanate, phenylene biscyanate, diphenylether biscyanate, diphenylsulfone biscyanate, dicyclohexylmethanebiscyanate, xylene biscyanate, N, N '
-Tolylene biscyanate, xylylene biscyanate, diphenylcyclohexanebiscyanate, dichlorodiphenylbiscyanate, diphenylsulfonbiscyanate, 2,2-bis-4 [-4- [cyanatophenoxy] phenyl] Propane, 2,2-bis-4
[-4- [Cyanatophenoxy] phenyl] hexafluoropropane (each of the above includes isomers), ethylenebiscyanate, hexamethylenebiscyanate and the like.

Examples of the cyanamide compound include N, N'-diphenylmethanebiscyanamide and N, N'-diphenylmethanebiscyanamide.
N'-phenylenebiscyanamide, N, N'-diphenylether biscyanamide, N, N'-diphenylsulfonebiscyanamide, N, N'-dicyclohexylmethanebiscyanamide, N, N'-xylenebiscyanamide, N, N'- Tolylene biscyanamide, N, N'-xylylene biscyanamide, N, N'-diphenylcyclohexanebiscyanamide, N, N'-dichlorodiphenylbiscyanamide, N, N'-diphenylsulfonbiscyanamide, 2,2- Bis-4 [-4- [cyanamidophenoxy] phenyl] propane, 2,2-bis-4
[-4- [Cyanamidophenoxy] phenyl] hexafluoropropane (each of which includes an isomer), N, N'-ethylenebiscyanamide, N, N'-
Hexamethylene biscyanamide and the like.

Examples of chelating compounds include zirconium acetylacetonate, cobalt acetylacetonate, aluminum acetylacetonate, manganese acetylacetonate, titanium acetylacetonate, iron acetylacetonate, copper acetylacetonate, and lead acetyl. Acetonate, nickel acetylacetonate and the like can be mentioned.

In the present invention, a chelating agent may be added. The chelating agent is not particularly limited and may be any compound that can react with a metal salt to form a chelate compound, and examples thereof include salicylaldoxime, oxine, variamine-B base, and azo dyes. The metal salt is not particularly limited. For example, copper benzoate, zinc benzoate, manganese benzoate, nickel benzoate, iron (III) acetylacetone, chromium (III) acetylacetone, cobalt acetylacetone (I
I), zinc stearate, copper stearate, copper acetate, manganese acetate, and other organic metal salts, and FeCl ₂ , FeC
l ₃ , CuCl ₂ , Cu (OH) ₂ , Mg (OH) ₂ , Ca (O
H), NaVO ₃ , NiSO _{4 and} other inorganic metal salts.

Further, a conventionally known epoxy resin can be used in combination with the resin composition of the present invention. For example, an epoxy resin obtained by reacting a novolak resin obtained by a condensation reaction of a phenol and an aldehyde such as a phenol novolak type epoxy resin and an O-cresol novolak type epoxy resin with an acidic catalyst and epichlorohydrin, bisphenol A, Glycidyl ester type epoxy resins obtained by the reaction of glycidyl ethers such as bisphenol F, bisphenol S and hydrogenated bisphenol A, and polybasic acids such as phthalic acid and dimer acid with epichlorohydrin; polyamines such as p-phenylenediamine and diaminodiphenylmethane; There are glycidylamine type epoxy resin obtained by reaction with epichlorohydrin, linear aliphatic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid, etc., and one or more of these are used in combination. Rukoto can also. These epoxy resins are preferably sufficiently purified.

In the present invention, a conventionally known amine compound can be used in combination with the aromatic diamine compound. Such compounds include, for example,
1,2-diaminoethane, 1,3-diaminopropane,
1,4-diaminobutane, 1,5-diaminopentane,
Fats such as 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane Aromatic diamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3 '
-Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,
3,3'-diaminodiphenyldifluoromethane, 3,
4'-diaminodiphenyldifluoromethane, 4,4 '
-Diaminodiphenyldifluoromethane, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfide, 3,
4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylketone, 3,4'-diaminodiphenylketone,
4,4'-diaminodiphenyl ketone, 2,2-bis (3-aminophenyl) propane, 2,2 '-(3
4'-diaminodiphenyl) propane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-
Aminophenyl) hexafluoropropane, 2,2-
(3,4'-diaminodiphenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 1,3-bis (3-aminophenoxy)
Benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 '-(1,4-phenylenebis (1-methylethylidene)) bisaniline, , 4 '-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 4,4'-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 2,2-bis (4- ( 3
-Aminophenoxy) phenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 2,2-bis (4- (3-aminophenoxy) phenyl) hexafluoropropane, 2,2- Screw (4-
(4-aminophenoxy) phenyl) hexafluoropropane, bis (4- (3-aminophenoxy) phenyl) sulfide, bis (4- (4-aminophenoxy)
There are aromatic diamines such as phenyl) sulfide, bis (4- (3-aminophenoxy) phenyl) sulfone, and bis (4- (4-aminophenoxy) phenyl) sulfone.

In the present invention, when an epoxy resin is used, a curing agent may be further added and cured by heating, irradiation with light energy, or the like. The curing agent is not particularly limited as long as it shows a curing reaction with the epoxy resin, and a known curing agent can be used. For example, phthalic anhydride, methyltetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, maleic anhydride, Acid anhydrides such as citraconic acid and hytic methic anhydride, or 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-
Cyanoethyl-2-ethyl-4-methylimidazole,
1-cyanoethyl-2-undecylimidazole, 1-
Cyanoethyl-2-undecylimidazolium trimellitate, 2,4-diamino-6- [2-ethyl-4-
Methyl imidazolyl- (1)]-ethyl-S-triazine, 2-phenyl-4,5-dihydroxymethyl imidazole, imidazoles such as 1-dodecyl-2-methyl-3-benzylimidazolium chloride, or aniline, methyl Amines such as aniline, dimethylaniline, chloroaniline, bromoaniline, ortho, meta or para phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenylether, diaminobiphenyl, dicyandiamide, and the like, or triphenylphosphine tetraphenylborate, triethylamine Tetraphenylborate, N
Carbohydrate salts such as methylmorpholine tetraphenylborate and pyridinetetraphenylborate, or phenol novolak resins and cresol novolak resins;
Examples include, but are not limited to, phenols such as polyvinyl phenol, boron trifluoride-amine complex, organic acid hydrazide, and aromatic diazonium salt. These may be used alone or in combination of two or more. The amount of the curing agent is not particularly limited, but is preferably from 0.1 to 1.0 equivalent to 1 equivalent of the epoxy group in order to obtain a good cured product.

Among them, it is preferable to use a novolak phenol resin or an acid anhydride. Examples of the acid anhydride include hexahydrophthalic anhydride,
Tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, maleic anhydride, citraconic anhydride, dichloromaleic anhydride, etc.
Alternatively, at least one of Diels-Alder adducts of these compounds with dicyclogen is used.

Further, to the heat-resistant resin composition of the present invention, for example, amines, imidazoles, caribol salts, aromatic diazonium salts and the like can be added as a curing accelerator. Specific examples of the compound include tertiary amines such as 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine and tris (dimethylaminomethyl) phenol. , Imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and 1-benzyl-2-phenylimidazole, and organic phosphines such as tributylphosphine, triphenylphosphine and diphenylphosphine. And tetraphenylboron salts (caribole salts) such as tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, and 2-ethyl-4-methylimidazole tetraphenylborate. The compounding amount is appropriately determined according to the use conditions and applications.
It may be used in an amount of 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 00 parts by weight.

In the heat-resistant resin composition of the present invention, each component may be usually dissolved or dispersed in an organic solvent. Examples of the organic solvent used include acetone, methyl ethyl ketone, diethyl ketone, toluene, chloroform, methanol, ethanol, 1-propanol, 2-propanol.
Propanol, 1-butanol, 2-butanol, t-
Butanol, ethylene glycol monomethyl ether,
Xylene, tetrahydrofuran, dioxane, cyclopentanone, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N
-Acetyl-2-pyrrolidone, N-benzyl-2-pyrrolidone, γ-butyrolactone, dimethylsulfoxide,
Preferable examples include ethylene carbonate, propylene carbonate, sulfolane, hexamethylenephosphortriamide, N-acetyl-ε-caprolactam, dimethylimidazolidinone, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether. These may be used alone or as a mixed system.

The heat-resistant resin composition of the present invention may contain a sensitizer if necessary. As the sensitizer, for example,
7-N, N-diethylaminocoumarin, 7-diethylamino-3-thenonylcoumarin, 3,3'-carbonylbis (7-N, N-diethylamino) coumarin, 3,3 '
-Carbonylbis (7-N, N-dimethoxy) coumarin, 3-thienylcarbonyl-7-N, N-diethylaminocoumarin, 3-benzoylcoumarin, 3-benzoyl-7-methoxycoumarin, 3- (4'-methoxybenzoyl) ) Coumarin, 3,3'-carbonylbis-5,7
-(Dimethoxy) coumarin, benzalacetophenone,
4'-N, N-dimethylaminobenzalacetophenone, 4'-acetoaminobenza-4-methoxyacetophenone, 7-dimethylaminocyclopenta [c] coumarin, 7-diethylamino-4-methylcoumarin, 4,
Coumarin compounds such as 6-dimethyl-7-ethylaminocoumarin, 4,4'-bisdiaminobenzophenone,
And diaminobenzophenone derivatives such as 4'-bis (N, N-diethylamino) benzophenone.
The heat-resistant resin composition of the present invention may further contain other additives, for example, additives such as a plasticizer and an adhesion promoter.

Using the heat-resistant resin composition of the present invention, a cyclic Schiff polymer film composed of a cured product of the composition is formed by photolithography. The cyclic Schiff polymer film may be provided with conductivity.

According to the present invention, the pattern manufacturing method comprises:
A film made of the heat-resistant resin composition or the conductive paste of the present invention is formed on the surface of the supporting substrate. In the pattern manufacturing method of the present invention, the surface of the support substrate may be previously treated with an adhesion aid in order to improve the adhesion between the film or the cyclic Schiff polymer film after heat curing and the support substrate. .

The film made of the photosensitive resin composition or the conductive paste is formed, for example, by forming a varnish film of the photosensitive resin composition or the conductive paste and then drying the film. . The varnish film is formed by a means appropriately selected from means such as spin coating using a spinner, dipping, spray printing, screen printing, etc., according to the viscosity of the varnish.

The thickness of the film can be adjusted by the application conditions, the solid content concentration of the present composition and the like. Further, a film made of a heat-resistant resin composition is formed by peeling the film formed on the support in advance from the support, and the sheet is attached to the surface of the support substrate to form a film. Is also good.

Next, the coating film is irradiated with electromagnetic waves (ultraviolet rays or the like) through a photomask having a predetermined pattern, and then the unexposed portions are dissolved and removed with an organic solvent or a basic aqueous solution to form a desired relief pattern. obtain. The composition of the present invention has a wavelength of 300 nm to 300 as a light source used for exposure.
A good relief pattern can be obtained even with a 0 nm light beam, g-line and i-line. The developing step may be performed using a normal positive type photoresist developing device. As a solution used for development, a basic aqueous solution is preferable.

The resulting relief pattern is preferably subjected to a heat treatment at a temperature selected from the range of 150 ° C. to 450 ° C. to form a pattern comprising a cyclic Schiff polymer film. This pattern has high resolution, high heat resistance, and excellent mechanical properties.

A conductive paste can be provided by blending the resin composition of the present invention with a conductive material.

As the conductive material, for example, gold, silver,
Metals such as copper, iron, nickel, cobalt, manganese, chromium, and lead are preferred, and silver powder is particularly preferred. The metals can be used at a metal content of generally about 40% to less than 99% by weight, preferably 50% to less than 95% by weight based on the solid content of the resin.

Further, depending on the purpose and use, coloring pigments such as carbon black, titanium white, lead white, lead oxide and red iron oxide, antimony oxide, zinc oxide, basic lead carbonate, basic lead sulfate, barium carbonate, and carbonate Calcium, aluminum silica, magnesium carbonate, magnesium silica, clay, talc, etc., moisture resistant pigments, strontium chromate, lead chromate, basic lead chromate, leadtan, lead silicate, basic lead silicate, lead phosphate, Anticorrosive pigments such as basic lead phosphate, lead tripolyphosphate, lead silicochromate, graphite, cyanamide lead, calcium lead oxide, lead oxide and lead sulfate can also be used. Usually, the mixing ratio of the pigment and the resin is preferably in the range of 2: 1 to 7: 1 by weight of the solid content. Further, the conductive paste of the present invention is applied to a suitable conductive substrate (object to be coated), and the coating film is applied at, for example, 80 to 250 ° C., preferably 1 to 80 ° C.
It can be cured at a temperature of from 20 to 160C. In order to cure an electrodeposited coating film by electrodeposition at 160 ° C. or lower, a lead compound, a zirconium compound, a cobalt compound,
It is effective to add one or more catalysts selected from aluminum compounds, manganese compounds, copper compounds, zinc compounds, iron compounds, chromium compounds, nickel compounds, soot compounds and the like.

Specific examples of these compounds include chelating compounds such as zirconium acetylacetonate, cobalt acetylacetonate, aluminum acetylacetonate, manganese acetylacetonate, and titanium acetylacetonate, and have a β-hydroxyamino structure. Chelation reaction product of compound and metal oxide such as lead oxide, lead 2-ethylhexanoate, lead naphthenate, lead octylate, lead benzoate, lead acetate, lead lactate, lead formate, lead glycolate, octylate And carboxylate such as zirconium.

A diluent can be added to the conductive paste of the present invention, if necessary, in order to further improve the workability at the time of preparing the paste composition and the workability of application at the time of use. Examples of such a diluent include organic solvents such as butyl cellosolve, carbitol, butyl cellosolve acetate, carbitol acetate, ethylene glycol diethyl ether and α-terpineol, and a reactive diluent having 1-2 epoxy groups per molecule. And other known compounds.

The conductive paste of the present invention may contain, if necessary, a hygroscopic agent such as calcium oxide and magnesium oxide, an adhesion enhancer such as a silane coupling agent and a titanium coupling agent, a nonionic surfactant, and a fluorine-based agent. A wetting enhancer such as a surfactant, an antifoaming agent such as silicone oil, an ion trapping agent such as an inorganic ion exchanger, and the like can be appropriately added.

As the filler used in the conductive paste of the present invention, for example, a metal (layer) such as gold, silver, copper, nickel, iron, aluminum, stainless steel, silicon oxide, boron nitride, aluminum borate, etc. And the like. These include silica, alumina, titania, glass,
An inorganic insulator such as iron oxide can be added. The amount of the filler is 5 to 95% by weight based on the total amount of the conductive paste composition.
Is preferably 10 to 90% by weight, more preferably 20 to 90% by weight.
85% by weight is particularly preferred. The filler component may be used alone or 2
A mixture of more than one species can be used. Although the shape of the conductive material is not particularly specified, it is preferable that the conductive material has an average particle diameter of 10 μm or less when it is granular. When the average particle size exceeds 10 μm, the properties of the composition do not become paste-like, and the coating performance deteriorates.

The mixing ratio of the conductive material and the resin component [total amount of the cyclic Schiff represented by the general formula (Formula 1) and the cyclic Schiff type compound represented by the general formula (Formula 2)] is the former / the latter. It is desirable that the weight ratio be 40/60 to 95/5. If the amount of the conductive material is less than 40 parts by weight, good conductivity cannot be obtained, and if it exceeds 95 parts by weight, workability such as applicability deteriorates.

In the conductive paste of the present invention, an organic solvent can be used as needed for adjusting the viscosity. The organic solvents include dioxane, hexane, cellosolve acetate, ethyl cellosolve, butyl cellosolve, butyl cellosolve acetate, butyl carbitol acetate,
Isophorone and the like can be mentioned, and these can be used alone or in combination of two or more.

In order to produce the conductive paste of the present invention,
The composition containing at least each of the above-mentioned components, together with various additives, is collectively or separately combined with a dispersing / dissolving device such as a stirrer, a grinder, a three-roller, and a planetary mixer, and heated as necessary. The mixture may be mixed, dissolved, pulverized, kneaded or dispersed to form a uniform paste.

After covering the pad electrode portion on the circuit forming surface of the semiconductor element with the conductive paste of the present invention, the pad electrode portion and the external connection bump electrode terminal of the mounting base material are bonded to obtain a semiconductor device. be able to. Thereafter, the surface is covered with a sealing resin composition and / or resin-sealed to obtain a semiconductor device. Further, the external connection bump electrode terminal of the mounting substrate may be formed of the conductive paste of the present invention. When one of the pad electrode and the bump electrode for external connection is the conductive paste of the present invention, the other may be a metal such as gold, copper, or aluminum.

The reliability of the connection portion can be improved by forming a metal layer on the base of the pad electrode or the bump electrode for external connection, and forming a conductive layer on the surface with the conductive paste of the present invention. .

In order to adhere a semiconductor element to a support member such as a lead frame using the resin paste of the present invention, first, a resin paste composition is applied on the support member by a dispense method, a screen printing method, a stamping method or the like. ,
This can be performed by pressing the semiconductor element and then heating and curing it using a heating device such as an oven or a heat block. Furthermore, after a wire bonding step, at least a part of the semiconductor element can be covered and / or sealed with a normal resin (for example, an epoxy resin composition) or ceramics to obtain a semiconductor device.

A filler used in the heat-resistant resin composition of the present invention can be added. The filler is not particularly limited, and inorganic materials include silica, crushed stone, silica sand, calcium carbonate, barium hydroxide, alumina, aluminum hydroxide, talc, clay, kaolin, glass powder, glass fiber, and the like. Carbon or graphite,
Fibers or powders such as polyester and polyamide are used alone or in combination. The amount used is preferably 30 to 95% by weight based on the total amount of the epoxy resin composition. In addition, as long as the effects of the present invention are not impaired, diluents such as phenylglycidyl ether, diglycidyl ether, and diglycidyl aniline, polyglycidyl ether, polyol, carboxyl compound, etc.
A flexibility-imparting agent such as a urethane prepolymer, a silicone-based compound, or a fluorine-based compound can be blended. Antimony oxide, zinc oxide, basic lead carbonate, basic lead sulfate, barium carbonate, calcium carbonate, aluminum silica, magnesium carbonate, magnesium silica, clay, talc and other moisture-resistant pigments, strontium chromate, lead chromate, basic chromium Lead silicate, lead silicate, lead silicate, basic lead silicate, lead phosphate, basic lead phosphate, lead tripolyphosphate, lead silicate, lead, cyanamide, calcium lead, calcium suboxide, lead sulfate And the like. The ratio of these pigments to resin is usually 2: 1 to 1 by weight of solids.
A range of 7: 1 is preferred. Furthermore, various materials are blended in the heat-resistant resin composition of the present invention depending on the use.

The epoxy resin composition of the present invention is useful for coating and sealing semiconductor devices. Applications for semiconductor encapsulation include zircon, silica, alumina, aluminum hydroxide, calcium carbonate, clay, kaolin, talc, silica sand, fused quartz glass, asbestos, mica, various whiskers, carbon black, molybdenum disulfide, etc. , A release agent such as a higher aliphatic acid or a wax, and a coupling agent such as an epoxy silane, a vinyl silane, or an alkoxy titanate compound. If necessary, a flame retardant such as a halogen-containing compound, antimony oxide, or a phosphorus compound can be used. These are uniformly mixed with an epoxy resin composition using a roll, a kneader, or the like to form a molding material.

In this case, an epoxy compound represented by the general formula (Formula 1) and a glycidyl ether type epoxy resin such as bisphenol A type epoxy resin, phenol novolak type epoxy resin, allylphenol novolak type epoxy resin, etc. Triphenol alkane type epoxy resin and its polymer, naphthalene type epoxy resin,
Biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, phenol aralkyl type epoxy resin, glycidyl ester type epoxy resin, alicyclic epoxy resin, heterocyclic type epoxy resin, halogenated epoxy resin,
Further, an epoxy resin having at least one naphthalene ring having a substituted or unsubstituted allyl group in one molecule may be used in combination with part or all of the epoxy resin.

The semiconductor device of the present invention can be preferably provided by transfer molding a semiconductor element using the above-described epoxy resin composition. The transfer molding conditions include a molding temperature of 50 to 200 ° C., preferably 100 to 170 ° C., and more preferably 120 to 1 ° C.
50 ° C. The molding pressure is 100-5000kg
· F / cm, preferably 200 to 1000 kg · f / cm. The molding time is 30 to 600 seconds, preferably 4
It is 5 to 300 seconds, more preferably 60 to 180 seconds.

The semiconductor device sealed with resin by transfer molding may be subjected to after-cure if necessary. The after-cure condition is usually 100 to 200 ° C, preferably 120 to 180 ° C.

The materials for the laminated board include various glass cloths such as E glass, C glass, A glass, S glass, D glass and Q glass as inorganic fibers, and aramid fibers, carbon fibers, polyesters as organic fibers. A fiber, an aramid, an aromatic polyester nonwoven fabric, or the like is used. After dissolving the heat-resistant resin composition of the present invention in an organic solvent and applying it to each fiber, the organic solvent is dried by heating to obtain a laminate material. Examples of the organic solvent include acetone, xylene, methyl cellosolve, methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, quinoline, cyclopentanone, m-
At least one of cresol and chloroform is used.

Furthermore, the heat-resistant resin composition of the present invention includes:
Various materials are blended according to the use. For example, as a material for a laminated board, various glass cloths such as E glass, C glass, A glass, S glass, D glass, and Q glass as inorganic fibers, aramid fiber, carbon fiber, polyester fiber and the like as organic fibers. Aramid, aromatic polyester nonwoven fabric and the like are used. After dissolving the epoxy resin composition in an organic solvent and applying it to each fiber, the organic solvent is dried by heating to obtain a laminate material. Examples of the organic solvent include acetone, xylene, methyl cellosolve, methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, quinoline, cyclopentanone, m- At least one of cresol and chloroform is used.

The present invention will be specifically described with reference to examples.

(Examples 1 to 6) and (Comparative Example 1) << Preparation of Cyclic Schiff Compound (A) >>
In a 500 ml three-necked flask equipped with a thermometer, 108 parts by weight of metaphenylenediamine, 134 parts by weight of taphenylenedialdehyde, and 150 parts by weight of dimethyl sulfoxide are dissolved. Further, the mixture is heated and stirred at 80 ° C. for 4 hours. After lowering the solution temperature to 60 ° C., 25 parts by weight of sulfuric acid was added to 2 parts by weight.
It was added over time and left for another hour. Thereafter, dimethyl sulfoxide was distilled off under reduced pressure at a temperature of 130 ° C., 100 parts by weight of toluene was added to the residue, washing with water was repeated four times, and toluene was removed under heating and reduced pressure to further remove the target cyclic Schiff compound ( A) was obtained.

{Preparation of Cyclic Schiff Compound (B)} 107 parts by weight of 2,6-diaminopyridine, 2,6 parts in a 500 ml three-necked flask equipped with a stir bar, a condenser, and a thermometer.
Dissolve 132 parts by weight of dialdehyde pyridine and 150 parts by weight of N-methylpyrrolidone. Then, heat it to 8
Stir at 0 ° C. for 4 hours. After lowering the solution temperature to 60 ° C,
25 parts by weight of sulfuric acid were added over 2 hours, and the mixture was allowed to stand for 1 hour. Thereafter, dimethyl sulfoxide was distilled off under reduced pressure at a temperature of 130 ° C., 100 parts by weight of toluene was added to the residue, washing with water was repeated four times, and toluene was removed under heating and reduced pressure to further remove the target cyclic Schiff compound ( B) was obtained.

The cyclic Schiff compound (A) obtained above
And (B) using methylhexahydrophthalic anhydride (HN-5500, manufactured by Hitachi Chemical Co., Ltd.) as a curing agent and 1-cyanoethyl-2-ethyl-4-methylimidazole as a curing accelerator. Part), then mix
It was poured into a mold and cured at 100 ° C. for 2 hours and at 170 ° C. for 5 hours to obtain a test piece. Using these test pieces, the properties of bending properties, glass transition temperature, and water absorption were measured. Table 1 shows the results.

Comparative Example 1 A test piece was prepared in the same manner as in the example except that a bisphenol A type epoxy resin (EP-828, manufactured by Yuka Shell) was used, and the results of measuring each characteristic are shown in Table 1. Show.

[0124]

[Table 1]

Measurement conditions of properties Bending properties: Measurement in accordance with JIS K-6911 Glass transition temperature: Thermomechanical instrument (TMA) (manufactured by Vacuum Riko, TM-1500) Heating rate: 2 ° C./min Water absorption: Boiling water (Example 7) and (Comparative Example 2) 100 parts by weight of the cyclic Schiff compounds (A) and (B) obtained in Example 1 were separately dissolved in methyl ethyl ketone. A varnish having a solid content of 50% by weight was prepared. To the varnish, 4 parts by weight of 2-heptadecyl imidazole was added as a curing agent.

This varnish was applied to a glass cloth (E glass, thickness: 0.05 mm) and dried at 80 ° C. for 10 minutes to obtain a prepreg. Laminate 20 prepregs and apply pressure 3
The laminate was cured by heating at 0 kgf / cm, 130 ° C. for 40 minutes, and 170 ° C. for 2 hours. Table 2 shows a comparison of characteristics of a general epoxy resin laminate as Comparative Example 2.

[0127]

[Table 2]

(Example 8) and (Comparative Example 3) 70 parts by weight of cyclic Schiff compound (A), 2,2-bis-
30 parts by weight of 4 [-4- [maleimidophenoxy] phenyl] propane was dissolved in 100 ml of methyl ethyl ketone to prepare a varnish having a solid content of 50% by weight. To the varnish, 4 parts by weight of 2-heptadecyl imidazole was added as a curing agent. The varnish was applied to a glass cloth (E glass, thickness: 0.05 mm) and dried at 80 ° C. for 10 minutes to obtain a prepreg. Laminate 20 prepregs, pressure 30kg
The laminate was cured by heating at f / cm, 130 ° C. for 40 minutes and 170 ° C. for 2 hours. Table 3 shows, as Comparative Example 3, a comparison of the properties of the laminates when the epoxy resin was changed to bisphenol A type epoxy resin EP828 (manufactured by Yuka Shell Co., Ltd.).

[0129]

[Table 3]

Example 9 70 parts by weight of a cresol novolak resin (epoxy equivalent: 200) as an epoxy resin,
30 parts by weight of the cyclic Schiff compound (A), 45 parts by weight of phenol novolak resin, 2.0 parts by weight of triethylamine tetraphenylborate, 1.0 part by weight of γ-glycidoxypropyltrimethoxysilane as a coupling agent,
A mixture of 500 parts by weight of quartz powder, 1.5 parts by weight of stearic acid as a release agent and 1.0 part by weight of carbon black was uniformly mixed with two rolls at 70 ° C. to prepare a molding material. The molding material was subjected to transfer molding under the conditions of 180 ° C., 70 kg / cm, for 5 minutes to prepare test pieces for measuring various characteristics. Table 4
Shows characteristic values.

(Comparative Example 4) The cyclic shiff compound (A) was removed from the composition of Example 8, and 100 parts by weight of a cresol novolak resin (epoxy equivalent: 200) was used as an epoxy resin, and 60 parts by weight of a phenol novolak resin was used as a curing agent. Except for the above, a molding material and a test piece were produced in the same manner as in Example 8.

[0132]

[Table 4]

(Examples 10 to 13) and (Comparative Example 5) (1) Preparation of Epoxy Resin YDF-170 (manufactured by Toto Kasei Co., Ltd., bisphenol F type epoxy resin, epoxy equivalent = 170) 7.5 parts by weight and YL 7.5 parts by weight -980 (manufactured by Yuka Shell Epoxy Co., Ltd., bisphenol A type epoxy resin, epoxy equivalent = 185) was heated to 80 ° C. and stirred for 1 hour to obtain a uniform epoxy resin solution.

The solution was added with 1.0 part by weight of H-1 (manufactured by Meiwa Kasei Co., phenol novolak resin, OH equivalent = 106) and PP-101 (manufactured by Toto Kasei Co., alkylphenyl glycidyl ether, epoxy equivalent = 230) 2.
0 parts by weight was heated to 100 ° C., stirring was continued for 1 hour, and a uniform phenol resin solution, 2P4MHZ (imidazole-based curing accelerator manufactured by Shikoku Chemicals Co., Ltd.) was added.

Each material was mixed at the mixing ratio shown in Table 5 and
After kneading using this roll, 1
Defoaming treatment was performed for 0 minutes to obtain a resin paste composition.

The properties (viscosity, peel strength and reflow resistance) of this resin paste composition were examined by the following methods. Table 5 shows the results.

[0137]

[Table 5]

(1). Viscosity: The viscosity (Pa · s) at 25 ° C. was measured using an EHD type rotational viscometer (manufactured by Tokyo Keiki Co., Ltd.).

(2). Peel strength: Approximately 3.2 mg of the resin paste composition was applied to a copper lead frame, and an 8 mm × 8 mm Si chip (0.4 mm thick) was pressed thereon, and further heated in an oven to 150 ° C. for 30 minutes. Increase the temperature to 150 ° C for 1
Cured for hours. The peel strength (kg / chip) at 240 ° C. was measured using an automatic adhesive force device (manufactured by Hitachi Chemical Co., Ltd., in-house).

(3). Chip warpage: about 3.2 mg of the resin paste composition was applied on a copper lead frame, and a 5 mm × 13 mm Si chip (0.4 mm thick) was pressed thereon, and further heated in an oven to 150 ° C. for 30 minutes. The temperature was raised and cured at 150 ° C. for 1 hour. Use a surface roughness meter (Sloan, Dek
tuk 3030) was used to measure chip warpage (μm).

(4). Reflow resistance: Using the resin paste compositions obtained in Examples and Comparative Examples, the following lead frames and Si chips were cured and bonded under the following curing conditions. Afterwards, an epoxy encapsulant manufactured by Hitachi Chemical (product name C)
EL-4620) to obtain a package for a solder reflow test. The package was allowed to absorb moisture for 72 hours in a thermo-hygrostat set at a temperature and humidity of 85 ° C. and 85%, respectively. Thereafter, solder reflow was performed under reflow conditions of 240 ° C./10 seconds, and the number of external cracks generated in the package was observed with a microscope (magnification: 15 times). The number of cracked samples is shown for five samples.

Chip size: 8 mm × 10 mm Package: QFP, 14 mm × 20 mm × 2 mm Frame: Copper Curing conditions: Heat up to 150 ° C. in 30 minutes, cure at 150 ° C. for 1 hour From the results in Table 5, the resin paste of the present invention is shown. The compositions (Examples 1, 2 and 3) were different from the resin paste composition using epoxy resin (Comparative Example 1) and the resin paste composition using bismaleimide alone (Comparative Example 2) in peel strength and strength.
The chip warpage showed a good value, and the reflow resistance was also excellent. From this, it was confirmed that according to the resin paste composition of the present invention, occurrence of external cracks in the package was suppressed, and a highly reliable package was obtained even in a copper lead frame.

From the above results, Examples 1 to 5 are excellent in optical characteristics (light transmission) and adhesion to aluminum.
In addition, it has good releasability from the mold and continuous molding is possible by transfer molding.

On the other hand, in Comparative Examples 1 and 2, since the value of n / m in the general formula (Chemical Formula 1) of the internal release material exceeds the range of the present invention, the ratio of the hydrophilic group in one molecule is high. Optical transparency,
Although the adhesiveness is good, the releasability is poor and continuous molding cannot be performed. In Comparative Example 3, the value of n / m in the general formula (Chemical Formula 1) of the internal mold release material was 0, and no hydrophilic group was contained. Therefore, the compatibility with the resin was poor, and the light transmittance and adhesion were poor. It is difficult to put into practical use.

[0145]

When the resin paste composition of the present invention is used as a die bonding material for a semiconductor device, chip cracks, chip warpage, and peeling of the paste layer during solder reflow can be suppressed even in a copper lead frame. Reduces the occurrence of reflow cracks. As a result, the reliability of the semiconductor device can be improved.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C09J 179/04 C09J 179/04 B H05K 1/03 610 H05K 1/03 610N

Claims (16)

[Claims] 1. A compound of the general formula (1) and / or a compound of the general formula (2) Embedded image (Wherein X and Y are either —CH ＝ or —N =. R ₁ and R ₂ are any of hydrogen, a lower alkyl group, a lower alkoxide group, a halogen atom, and a lower fluoroalkyl group) A heat-resistant resin composition comprising at least a cyclic Schiff compound represented by the formula: 2. A compound of the general formula (3) (Wherein X is either -CH = or -N =. R
₁ is any _one of hydrogen, a lower alkyl group, a lower alkoxide group, a halogen atom and a lower fluoroalkyl group. And a diamine-based compound represented by the general formula (Chemical Formula 4) (Wherein Y is either -CH = or -N =. R
₂ is hydrogen, a lower alkyl group, a lower alkoxide group, a halogen atom, or a lower fluoroalkyl group. )) And / or a general formula (Chem. 2) obtained by reacting with a dialdehyde compound represented by the following formula: Embedded image (Wherein X and Y are either -CH = or -N =. R ₁ and R ₂ are any of hydrogen, lower alkyl, lower alkoxide, halogen atom, and lower fluoroalkyl. A heat-resistant resin composition comprising at least the cyclic Schiff compound represented by the formula (1). 3. A compound of the general formula (Chem. 3) (Wherein X is either -CH = or -N =. R
₁ is any of hydrogen, lower alkyl, lower alkoxide, halogen atom and lower fluoroalkyl. And a diamine compound represented by the general formula (Chemical Formula 4) (Wherein Y is either -CH = or -N =. R
₂ is hydrogen, lower alkyl, lower alkoxide, halogen atom, or lower fluoroalkyl. )) And / or a general formula (Chem. 2) obtained by reacting with a dialdehyde compound represented by the following formula: Embedded image (Wherein X and Y are either -CH = or -N =. R ₁ and R ₂ are any of hydrogen, lower alkyl, lower alkoxide, halogen atom, and lower fluoroalkyl. And at least one cyclic Schiff compound represented by the general formula (1) and a Schiff bond (-CH = N-) of the cyclic Schiff compound represented by the general formula (2). A heat-resistant resin composition comprising at least a possible component. 4. A Schiff bond (—CH) of a cyclic Schiff compound.
= N-), wherein the polymerizable component is an unsaturated imide compound having at least one N-substituted unsaturated imide group, an amide compound having at least one amide bond, and at least one carbon-carbon double bond. Compounds having at least one
The heat-resistant resin composition according to claim 3, wherein the heat-resistant resin composition is selected from a compound having at least one ethynyl group, an isocyanate compound, a cyanate compound, a cyanamide compound, and a chelate compound. 5. A compound of the general formula (3) (Wherein X is either -CH = or -N =. R
₁ is any of hydrogen, lower alkyl, lower alkoxide, halogen atom and lower fluoroalkyl. And a diamine compound represented by the general formula (Chemical Formula 4) (Wherein Y is either -CH = or -N =. R
₂ is hydrogen, lower alkyl, lower alkoxide, halogen atom, or lower fluoroalkyl. )) And / or a general formula (Chem. 2) obtained by reacting with a dialdehyde compound represented by the following formula: Embedded image (Wherein X and Y are either -CH = or -N =. R ₁ and R ₂ are any of hydrogen, lower alkyl, lower alkoxide, halogen atom, lower fluoroalkyl). And at least one cyclic Schiff compound represented by the following formula: phenolic resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, urethane resin, p-hydroxystyrene resin, siloxane resin, and fluoroethylene resin. A heat-resistant resin composition comprising at least a selected component. 6. The diamine compound represented by the general formula (Formula 3) is metaphenylenediamine, and the dialdehyde compound represented by the general formula (Formula 4) is metaphenylenedialdehyde. 5. The heat-resistant resin composition according to any one of items 2 and 4. 7. A compound of the general formula (1) or / and the general formula (2) Embedded image (Wherein X and Y are either -CH = or -N =. R ₁ and R ₂ are any of hydrogen, lower alkyl, lower alkoxide, halogen atom, and lower fluoroalkyl. A) a heat-resistant resin composition comprising at least a heat-resistant resin composition containing at least the cyclic Schiff-based compound represented by the formula (1), and a cured product having excellent heat resistance obtained by polymerization by irradiation with electromagnetic waves. Cured product of a conductive resin composition. 8. A cured product having excellent heat resistance obtained by polymerizing the heat-resistant resin composition according to claim 1 by heating or irradiating an electromagnetic wave. Cured product of heat resistant resin composition. 9. An electromagnetic wave having a wavelength of 300 nm to 10000 n.
The cured product of the heat-resistant resin composition according to claim 8, wherein m is m. 10. A compound of the general formula (3) (Wherein X is either -CH = or -N =. R
₁ is any of hydrogen, lower alkyl, lower alkoxide, halogen atom and lower fluoroalkyl. ) And a diamine compound represented by the general formula (Formula 4) (Wherein Y is either -CH = or -N =. R
₂ is hydrogen, lower alkyl, lower alkoxide, halogen atom, or lower fluoroalkyl. )) And / or a general formula (Chem. 2) obtained by reacting with a dialdehyde compound represented by the following formula: Embedded image (Wherein X and Y are either -CH = or -N =. R ₁ and R ₂ are any of hydrogen, lower alkyl, lower alkoxide, halogen atom, and lower fluoroalkyl. A conductive paste containing the cyclic Schiff compound represented by the formula (1) and a conductive material. 11. The conductive paste according to claim 4, wherein the conductive material is a metal powder and contains 30 to 99% by weight based on the total amount of the conductive paste. 12. A semiconductor device in which a semiconductor element is fixed to a supporting member via an adhesive layer, and at least a part of the semiconductor element is covered and / or sealed with a resin composition. The heat-resistant resin composition according to any one of claims 1 to 7, which is a heat-resistant resin composition. 13. A mounting substrate having a semiconductor element on which an integrated circuit is formed, a plurality of electrode pads formed on the integrated circuit forming surface side of the semiconductor element, and external connection bump electrodes connected to the electrode pad. The conductive paste according to claim 10, wherein at least one of the electrode pad and the external connection bump electrode is made of a conductive paste. 14. An electrode pad formed on an integrated circuit forming surface of said semiconductor element and an external connection bump electrode of said mounting substrate are electrically connected to each other. 14. The conductive paste according to claim 13, wherein the conductive paste is a semiconductor device having a stress relaxation layer formed thereon. 15. A circuit board having an electric circuit layer formed on a surface of an insulating base material and an external connection electrode formed on the electric circuit layer, wherein at least a part of the external connection electrode is formed. The conductive paste according to claim 11, wherein the circuit board is made of a conductive paste. 16. The conductive paste according to claim 15, wherein the insulating base is a circuit board formed of a polyimide film having a thickness of 1 to 500 μm.