JPH1180559A - Material for sealing gap between semiconductor chip and substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a material for sealing a gap between a semiconductor chip and a mounting substrate capable of exhibiting excellent low moisture absorption and resistance to heat cycle and useful for packaging of a highly reliable semiconductor for electronic.electric devices by adopting a polymer having a ring structure as a sealing material. SOLUTION: This material contains (A) a ring structure-containing polymer containing a repeating unit having a ring structure (e.g. a cyclic olefinic polymer or an aromatic condensation polymer having a repeating units of an aromatic ring in the main chain, occasionally having a functional group) and further, as necessary, (B) a hardener. The material is prepared as e.g. a solution or a film, and is utilized to form a semiconductor package, and in a case of using the solution, by joining a semiconductor chip (Z2 ) to a mounting substrate (Z1 ), covering the jointed part with the solution, removing a solvent and drying, while in a case of using the film, by laminating the film on the Z1 and then laminating the Z2 on the film and pressure welding the film by heating.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a device having excellent mechanical strength,
The present invention also relates to a semiconductor chip sealing material having excellent low moisture absorption and a semiconductor package sealed with the sealing material.

[0002]

2. Description of the Related Art In recent years, with the rapid progress of the highly information-oriented society, the processing capability of information processing devices such as computers and communication devices has been required to be improved, that is, the processing speed has been increased.
With the development of information communication networks, it is necessary to expand the communication wavelength range. In particular, the development of communication equipment that operates at a communication wavelength in the high frequency range of GHz (gigahertz) is urgent. Under these demands, in order to achieve higher information processing speeds and higher communication wavelength ranges, electronic components such as semiconductor chips have been shortened as much as possible by reducing the wiring distance between the mounting board and the transmission speed. Developments have been made to reduce transmission loss in the high frequency range. As a specific means, a method of directly connecting an electrode of a semiconductor chip or the like and an electrode of a mounting board directly via a gold wire or solder (bare chip mounting method) is exemplified. The electrodes connected by the above-described means and the wiring between them are sealed for the purpose of protecting them from moisture, impurities, etc. As the sealing material, a liquid sealing material or film made of a conventionally known epoxy resin is used. ing.

However, since the epoxy resin generally contains a liquid oligomer as a main component, there is a problem that the mechanical strength after curing is not sufficient and cracks easily occur in a heat cycle resistance test which is a long-term reliability test. In addition, since the water absorption rate is relatively large, there is a problem that the reliability is further reduced by the moisture absorbed. In recent years, it has been required to use a sealing material in the form of a sheet. However, it has been necessary to partially cure an epoxy resin so as to be tack-free when forming the sheet.

Under these circumstances, as a new sealing material, a cyclic olefin resin excellent in low moisture absorption and low impurity properties has been proposed. For example, Japanese Patent Application Laid-Open No. 62-2741
No. 2 discloses a method using a modified product obtained by graft-modifying an addition copolymer of tetracyclododecene and ethylene with allyl glycidyl ether or maleic anhydride,
JP-A-6-188336, JP-A-7-18161
Japanese Patent Application Laid-Open Publication No. H11-139,086 discloses a method of sealing an optical semiconductor device with a ring-opening polymer of methylmethoxycarbonyltetracyclododecene. Japanese Patent Application Laid-Open No. 6-318651 discloses a crosslinkable thermosetting resin obtained by modifying a thermoplastic norbornene resin by reacting it with an unsaturated silane and a radical generator in the presence of a silanol condensation catalyst such as dibutyltin laurate. There is disclosed a technique in which an electronic element is sealed with a plastic norbornene-based resin and treated with hot water at 100 ° C. for 2 hours to crosslink.

[0005] Such a polymer having a cyclic structure is excellent in low water absorption as compared with an epoxy resin. However, practically no attempt has been made to put it into practical use as a sealing material. However, only the technology of sealing or coating an optical semiconductor element having a simple shape such as an LED by injection molding is disclosed. Compared to general semiconductor devices, such materials are required to have high reliability, such as partially sealing between a high-performance semiconductor chip with highly integrated wiring and electrodes on a mounting board. When used, what properties were exhibited was not known at all.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a sealing material between a semiconductor chip and a mounting board which has low moisture absorption and excellent heat cycle resistance. Still another object is to provide a semiconductor package having a high degree of reliability and a method for efficiently manufacturing the same by a simple operation.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that it is effective to use a polymer having a ring structure as a sealing material. The present invention has been completed.

Thus, according to the present invention, as a first invention, there is provided a sealing material between a semiconductor chip and a mounting substrate, which comprises a ring structure-containing polymer containing a repeating unit having a ring structure. According to the present invention, as a second invention,
The sealing material according to the first invention is provided, wherein the ring structure-containing polymer is a cyclic olefin polymer or an aromatic condensed polymer having a repeating unit of an aromatic ring in a main chain. According to the present invention, there is provided, as a third invention, the sealing material according to the first or second invention, wherein the ring structure-containing polymer has a functional group. According to the present invention, as a fourth invention, there is provided the sealing material according to any one of the first to third inventions, further comprising a curing agent. According to the present invention,
As a fifth invention, there is provided a sealing material according to any one of the first to fourth inventions, which is a solution type or a film. According to the present invention, there is provided, as a sixth invention, a semiconductor package in which a semiconductor chip and a mounting substrate are sealed with the sealing material according to any one of the first to fifth inventions. According to the present invention, as a seventh invention, after bonding the semiconductor chip to the mounting substrate, the sealing material according to the fifth invention, which is a solution type, is applied so as to cover the bonding portion, and the solvent is removed and dried. A method for manufacturing a semiconductor package is provided. According to the present invention, as an eighth invention, the sealing material according to the fifth invention, which is a film, is laminated on a mounting substrate, and then, a semiconductor chip is laminated on the film, and heated and melt-pressed to form a mounting substrate. A method of manufacturing a semiconductor package by bonding a semiconductor chip is provided.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below by dividing them into items.

The sealing material used in the present invention comprises a polymer containing a cyclic structure containing a repeating unit having a cyclic structure as a main component, and optionally a curing agent and various compounding agents. Is blended.

[1] Ring structure-containing polymer containing repeating unit having a ring structure The polymer used in the present invention has a ring structure in a main chain and / or a side chain, and has a bonding mode of the polymer. Examples thereof include those obtained by ring-opening polymerization of carbon-carbon unsaturated bonds of the ring structure, those obtained by addition polymerization, those obtained by addition-polymerization of exocyclic carbon-carbon unsaturated bonds of the ring structure, and those other than the outer ring structure. Bonding modes such as condensation polymerization of groups are exemplified.

Specific examples of such a polymer include (1) a cyclic olefin polymer and a hydrogenated product thereof, (2) a cyclic conjugated diene polymer and a hydrogenated product thereof, and (3) a vinyl cyclic hydrocarbon polymer. And a hydrogenated product thereof, and (4) an aromatic condensed polymer having a repeating unit of an aromatic ring in the main chain. Among these, (1) a cyclic olefin polymer and a hydrogenated product thereof And (2) a cyclic conjugated diene-based polymer and a hydrogenated product thereof are preferred, and a cyclic olefin-based polymer and a hydrogenated product thereof are most preferred.

Examples of the ring structure of the polymer include an aromatic ring structure, a saturated cyclic hydrocarbon (cycloalkane structure), and an unsaturated cyclic hydrocarbon (cycloalkene) structure. From the viewpoints of strength characteristics, heat resistance and the like. Among them, those having a cycloalkane structure are most preferable. Further, from the viewpoints of strength characteristics, heat resistance, and the like, those having a ring structure in the main chain are preferable.

(Repeating Unit Having a Ring Structure) As described above, specific examples of the repeating unit having a ring structure include the following four types as typical examples. That is, (1) a cyclic olefin-based repeating unit, (2) a cyclic conjugated diene-based repeating unit, (3) a vinyl-based cyclic hydrocarbon repeating unit, and (4) an aromatic condensation-based repeating unit. Hereinafter, each will be described.

(1) Cyclic olefin-based repeating unit The cyclic olefin-based repeating unit is, for example, a repeating unit of norbornene-based monomer such as norbornene, ethylidene norbornene, dicyclopentadiene, tetracyclododecene and the like, and hydrogenated units thereof. Recurring unit: a repeating unit of a monocyclic cyclic olefin monomer such as cyclopentene and cyclohexene.

The cyclic olefin monomer used as a raw material for the cyclic olefin repeating unit is not particularly limited as long as it is a cyclic hydrocarbon compound having a carbon-carbon unsaturated bond. a) a norbornene-based monomer; and (b) a monocyclic cyclic olefin-based monomer.

(A) Norbornene monomer The norbornene monomer used in the present invention is disclosed in
20268 and JP-A-2-36224, which are alicyclic monomers having a norbornene ring. Representative examples of (a) norbornene, tetracyclododecene,
Monomers having no unsaturated bonds other than carbon-carbon unsaturated bonds involved in the polymerization reaction, such as these alkyl-substituted products; (b) ethylidene norbornene, vinyl norbornene, ethylidetetracyclododecene, dicyclo Monomers having an unsaturated bond other than the carbon-carbon unsaturated bond involved in the polymerization reaction, such as pentadiene; (c) monomers having an aromatic ring, such as dimethanotetrahydrofluorene and phenylnorbornene; d) Monomers having a polar group, such as methoxycarbonylnorbornene and methoxycarbonyltetracyclododecene. These alicyclic monomers having a norbornene ring can be used independently or in combination of two or more.

(B) Monocyclic Cyclic Olefin Monomer A monocyclic cycloolefin monomer has one carbon-carbon double bond in the ring, and is, for example, cyclobutene, cyclopentene, cyclohexene And monocyclic cycloolefin monomers such as cycloheptene and cyclooctene described in JP-A-64-66216. These monocyclic cycloolefin monomers can be used independently or in combination of two or more.

(2) Cyclic conjugated diene-based repeating unit As the cyclic conjugated diene-based repeating unit, a cyclic conjugated diene-based monomer such as cyclopentadiene or cyclohexadiene is subjected to 1,4-addition polymerization and hydrogenated. And repeating units.

The cyclic conjugated diene-based monomer used as a raw material of the cyclic conjugated diene-based repeating unit has a conjugated carbon-carbon double bond in the ring.
Cyclopentadiene, 1,3-cyclohexadiene,
It is a cyclic conjugated diene monomer such as 1,3-cycloheptadiene and 1,3-cyclooctadiene described in JP-A-7-258318. These cyclic conjugated diene monomers can be used independently or
More than one species can be used in combination.

(3) Vinyl-based cyclic hydrocarbon repeating unit Specific examples of the vinyl-based cyclic hydrocarbon repeating unit include:
For example, a vinylcyclopentene-based or vinylcyclopentane-based repeating unit or a hydrogenated repeating unit thereof, a vinylcyclohexene-based or vinylcyclohexane-based repeating unit or a hydrogenated repeating unit thereof, a vinylcycloheptene-based or vinylcycloheptane-based repeating unit, or a combination thereof Examples include a hydrogenated repeating unit, a vinylcyclooctene-based or vinylcyclooctane-based repeating unit or a hydrogenated repeating unit thereof, an aromatic vinyl-based repeating unit or a hydrogenated repeating unit thereof, and the like. Among these, the ring structure is 5 to 7 from the balance of heat resistance, moldability and strength properties.
A six-membered ring such as a vinylcyclohexene-based or vinylcyclohexane-based repeating unit or a hydrogenated repeating unit thereof, an aromatic vinyl-based repeating unit or a hydrogenated repeating unit is most preferable.
Further, it is preferable that the carbon-carbon unsaturated bond in the ring is hydrogenated.

Examples of the vinyl cyclic hydrocarbon monomer which is a raw material of the above-mentioned vinyl cyclic hydrocarbon repeating unit include styrene, α-methylstyrene, α-ethylstyrene, α-propylstyrene, α-propylstyrene, and the like. Isopropylstyrene, α-t-butylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4
-Styrene-based monomers such as diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, monochlorostyrene, dichlorostyrene, monofluorostyrene, and 4-phenylstyrene Vinylcyclohexane monomers such as vinylcyclohexane and 3-methylisopropenylcyclohexane; 4-vinylcyclohexene, 4-isopropenylcyclohexene, 1-methyl-4-vinylcyclohexene, 1-methyl-4-isopropenylcyclohexene, -Methyl-4-vinylcyclohexene,
Vinylcyclohexene monomers such as 2-methyl-4-isopropenylcyclohexene; d-terpene, 1-
Examples include vinylated six-membered ring hydrocarbon monomers such as terpene monomers such as terpenes and diterpenes, and substituted products thereof. When a styrene monomer containing an aromatic ring is used, the hydrogenation rate is preferably adjusted to 80% or more by a hydrogenation reaction.

(4) Aromatic condensed repeating unit having an aromatic ring in the main chain As the aromatic condensed repeating unit, an aromatic ring is contained in the main chain, and the aromatic rings are bonded in a unit structure containing a hetero atom. It is a repeating unit. The hetero atom is not particularly limited, but includes, for example, oxygen and sulfur, and has a bond form, for example, an ether bond or an ester bond.
Specific examples include, for example, polyphenylene sulfide,
Aromatic polyether repeating units such as polyphenylene ether, polyether sulfone, polysulfone, etc .; liquid crystal plastic, aromatic polyester, polyarylate, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyether ether ketone, polyether ketone, etc. An aromatic polyester-based repeating unit; Among them, in terms of heat resistance and low hygroscopicity, dielectric properties, etc., aromatic polyether-based repeating units such as polyphenylene sulfide, polyphenylene ether, which is composed of a simple ether bond of an aromatic ring and a hetero atom, are preferred. Among the aromatic polyester-based repeating units, liquid crystal plastic-based repeating units having a large content of aromatic ring with respect to the unit structure are preferable. In particular, the above three types of repeating units of a polyphenylene ether-based repeating unit, a polyphenylene sulfide-based repeating unit, and a liquid crystal plastic-based repeating unit are preferred, and a polyphenylene ether-based repeating unit which is easily modified as a curable resin is most preferred.

These repeating units having a ring structure may be used alone or in combination of two or more.

From the viewpoint of heat resistance, the content of the repeating unit having a ring structure used in the present invention in all the repeating units in the polymer is usually 50 mol% or more, preferably 70 mol% or more, more preferably. Is 80 mol% or more.

(Other Repeating Units) Examples of the copolymerizable monomer used as a raw material of other repeating units include those having 2 to 12 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene. Α-olefins;
Styrene, α-methylstyrene, p-methylstyrene,
Styrenes such as p-chlorostyrene; chain conjugated dienes such as 1,3-butadiene and isoprene; vinyl ethers such as ethyl vinyl ether and isobutyl vinyl ether; and carbon monoxide, provided that copolymerization is possible. However, the present invention is not particularly limited to these.

(Polymerization and Hydrogenation Method) Examples of the polymerization method of the polymer having a ring structure of the present invention include conventionally known polymerization methods. The method for obtaining a ring-opened polymer of a norbornene-based monomer is not particularly limited.
It can be obtained by a known method using a transition metal compound such as Ti, Mo, W or the like described in JP-A No. 26024 or JP-A-2-185520 as a metathesis polymerization catalyst. The method for obtaining the addition polymer of a norbornene monomer is not particularly limited.
No. 7, WO 95/14048, and a known method using a transition metal compound of Group VIII of the periodic table such as Ni or Pd as a polymerization catalyst. The method for obtaining the addition polymer of the monocyclic olefin-based monomer is not particularly limited.
/ 23010 can be obtained by a known method using a Ni, Pd complex as a polymerization catalyst. The method for obtaining a copolymer of a cyclic olefin monomer such as a monocyclic olefin monomer or a norbornene monomer and an α-olefin such as ethylene is not particularly limited.
For example, it can be obtained by a known method using a V-type Ziegler catalyst described in JP-A-60-168708 and a metallocene-based polymerization catalyst comprising a transition metal of Group IVb of the Periodic Table described in JP-A-3-45612. . The method for obtaining the polymer of the cyclic conjugated diene-based monomer is not particularly limited. For example, it can be obtained by a known method using an organic metal of Group Ia of the periodic table as a catalyst described in JP-A-7-247321. it can. A method for obtaining a polymer such as a vinyl compound having a cyclic hydrocarbon group, for example, styrenes and vinylcyclohexane derivatives, is not particularly limited,
It can be obtained by a known method using a suitable one among known radical polymerization catalysts, anion polymerization catalysts, cationic polymerization catalysts and Ziegler-Natta polymerization catalysts as a catalyst. These polymers may be copolymers with other copolymerizable monomers. Furthermore, when a carbon-carbon double bond is contained in the main chain portion and the side chain portion of the above polymer, the polymer may be hydrogenated by a known hydrogenation catalyst. Examples of the hydrogenation catalyst include a catalyst in which Ni and Pd are supported on alumina and silica, and a Ni, Pd-based Ziegler catalyst.

(Modification) The polymer of the present invention can be used as it is, but it is more preferable that the polymer into which a functional group is introduced for the purpose of improving the adhesion to a metal or the like.

The type of the functional group is a functional group having a polarity (polar group) composed of an organic group having a hetero atom. Examples of the hetero atom include oxygen, nitrogen, sulfur, silicon, and halogen. However, a polar group having oxygen and nitrogen is preferable from the viewpoints of adhesion, reactivity, and the like.

The kind of the polar group is preferably a polar group which has a function of mainly improving the adhesion to a semiconductor chip, a metal lead, a gold wire and a mounting substrate, and having a function of becoming a curing point during a curing reaction. There is no limitation, and specific examples thereof include an epoxy group, a carboxyl group, a hydroxyl group, an ester group, a silanol group, an amino group, a nitrile group, a halogen group, an acyl group, and a sulfone group. Among them, (a) the crosslink density and adhesion can be improved with a low modification rate, (b) the selection range of the curing agent is wide, and (c) the control of the curing speed with the curing agent is easy. From, a polar group containing an oxygen atom, such as an epoxy group, an acid anhydride group, a carboxyl group, a hydroxyl group and the like, which can react with an acidic curing agent such as a polyhydric phenol or an amine or a basic curing agent, is particularly preferable. A polar group that later generates a terminal -OH group such as a hydroxyl group or a carboxyl group, such as an epoxy group or an acid anhydride group, is preferred.

These polar groups may be used alone or in combination of two or more.

The introduction ratio of the polar group is appropriately selected according to the purpose of use, but is usually 0.1 to 100 mol%, preferably 2 to 80 mol%, more preferably 5 to 100 mol% in all the repeating units of the polymer. ５０50 mol%. When the polar group-containing cyclic olefin polymer has a polar group introduction rate in this range, the adhesive strength to metal, heat resistance, mechanical strength, water absorption, and dielectric properties are highly balanced, which is preferable.

The method for introducing a polar group may be any of a method of modifying the polymer and a method of copolymerizing a monomer having a polar group. A method of adding a contained unsaturated compound by graft modification, (2) a method of directly adding a polar group to the unsaturated bond when a carbon-carbon unsaturated bond is present in the polymer, and (3) a method of adding a polar group to the unsaturated bond. In the polymerization of the polymer, a case where a monomer having a polar group in advance is copolymerized is exemplified.

(1) Grafting reaction of a polar group-containing unsaturated compound A polar unit is introduced by reacting the polymer with a polar group-containing unsaturated compound in the presence of a radical generator such as an organic peroxide. be able to. The polar group-containing unsaturated compound is not particularly limited, but can impart photosensitivity in a small amount, and because of the improved adhesion, an epoxy group-containing unsaturated compound, a carboxyl group-containing unsaturated compound,
Examples include a hydroxyl group-containing unsaturated compound and a silyl group-containing unsaturated compound.

Examples of the unsaturated compound containing an epoxy group include glycidyl esters of unsaturated carboxylic acids such as glycidyl acrylate, glycidyl methacrylate and glycidyl p-styryl carboxylate; endo-cis-bicyclo [2,2,1] hepto Monoglycidyl of unsaturated polycarboxylic acids such as -5-ene-2,3-dicarboxylic acid and endo-cis-bicyclo [2,2,1] hept-5-ene-2-methyl-2,3-dicarboxylic acid Esters or polyglycidyl esters; unsaturated glycidyl ethers such as allyl glycidyl ether, 2-methylallyl glycidyl ether, glycidyl ether of o-allylphenol, glycidyl ether of m-allylphenol, and glycidyl ether of p-allylphenol; No. Among these, allyl glycidyl esters and allyl glycidyl ethers are preferable, and allyl glycidyl ethers are particularly preferable, since the epoxy group-containing unsaturated compound can be graft-added with a particularly high conversion. These epoxy group-containing unsaturated compounds can be used alone or in combination of two or more.

Examples of the unsaturated compound having a carboxyl group include compounds described in JP-A-5-271356, and examples thereof include unsaturated carboxylic acids such as acrylic acid, methacrylic acid and α-ethylacrylic acid; Fumaric acid, itaconic acid, endocis-bicyclo [2.
2.1] Hept-5-ene-2,3-dicarboxylic acid, methyl-endosis-bicyclo [2.2.1] hept-5
-Unsaturated dicarboxylic acids such as -ene-2,3-dicarboxylic acid and the like. Examples of the unsaturated carboxylic acid derivatives include, for example, acid anhydrides, esters, acid halides, amides, and imides of unsaturated carboxylic acids. Specific examples thereof include maleic anhydride, chloromaleic anhydride, and butenyl succinic anhydride. Acid anhydrides such as acid, tetrahydrophthalic anhydride and citraconic anhydride; esters such as monomethyl maleate, dimethyl maleate and glycidyl maleate; maleenyl chloride, maleimide and the like. Of these, unsaturated dicarboxylic acids or acid anhydrides thereof are preferable for the above reasons, and among them, acid anhydrides such as maleic anhydride and itaconic acid are particularly preferable.

Examples of the hydroxyl group-containing unsaturated compound include, for example, allyl alcohol, 2-allyl-6-methoxyphenol, 4-allyloxy-2-hydroxybenzophenone, 3-allyloxy-1,2-propanediol, and 2-allylphenol. , 3-buten-1-ol, 4-penten-1-ol, 5-hexen-1-ol and the like.

Examples of the silyl group-containing unsaturated compound include chlorodimethylvinylsilane, trimethylsilylacetylene, 5-trimethylsilyl-1,3-cyclopentadiene, 3-trimethylsilylallyl alcohol, trimethylsilyl methacrylate, and 1-trimethylsilyloxy-1,3- Butadiene, 1-trimethylsilyloxy-
Examples thereof include cyclopentene, 2-trimethylsilyloxyethyl methacrylate, 2-trimethylsilyloxyfuran, 2-trimethylsilyloxypropene, allyloxy-t-butyldimethylsilane, and allyloxytrimethylsilane.

As the radical generator, an organic peroxide is usually used, and as the organic peroxide, those similar to the organic peroxides in the section of the curing agent described later, and other azo compounds may be used. Can also. Specific examples of the azo compound include azobisisobutyronitrile and dimethylazoisobutyrate. Among these,
Dialkyl peroxide is preferably used as the organic peroxide. These organic peroxides can be used alone or in combination of two or more. The proportion of the organic peroxide used is 100 parts by weight of the unmodified cyclic olefin-based polymer in the proportion charged during the reaction.
Usually 0.001 to 10 parts by weight, preferably 0.01 to 5 parts
Parts by weight, more preferably 0.1 to 2.5 parts by weight. When the use range of the organic peroxide is within this range,
Various properties such as the reaction rate of the unsaturated compound having a polar group, the water absorption of the obtained polymer having a polar group, and the dielectric properties are highly balanced and are suitable.

The graft modification reaction is not particularly limited, and can be performed according to a conventional method. Reaction temperature is usually 0-4
The reaction time is usually from 1 minute to 24 hours, preferably from 30 minutes to 10 hours at 00 ° C, preferably from 60 to 350 ° C. After completion of the reaction, a large amount of a poor solvent such as methanol is added to the reaction system to precipitate a polymer, which can be obtained by filtration, washing, and drying under reduced pressure.

(2) Direct Modification of Carbon-Carbon Unsaturated Bond The polymer of the present invention may be modified by modifying the carbon-carbon unsaturated bond to add a polar group or by bonding a compound having a polar group. Polar groups can be introduced. The method of introducing a polar group is not particularly limited, but (a) a method by oxidation of an unsaturated bond, and (b) a method by addition reaction of a compound containing one or more polar groups in a molecule to the unsaturated bond. ,
And (c) a method described in JP-A-6-172423, represented by a method of introducing an epoxy group, a carboxyl group, a hydroxyl group, or the like by other methods.

(3) Copolymerization of Polar Group-Containing Monomer The polar group-containing monomer is not particularly limited. In the case of a cyclic olefin polymer, for example, 5-hydroxymethylnorbornene, 5-hydroxy-i-propylnorbornene , 5-methoxycarbonylnorbornene, 8-
For example, a monomer containing a hydroxy group, a carboxyl group, or an ester group, such as methoxycarbonyltetracyclododecene, 5,6-dicarboxynorbornene, or the like, may be used. Is preferred. As a polymerization catalyst and a polymerization method, a known polymerization catalyst and polymerization method for an alicyclic monomer having a norbornene ring can be used.

Among the above, as a method for introducing a polar group, it is possible to carry out the reaction under easily-reacting reaction conditions and to easily introduce a polar group at a high modification rate.
Graft modification of (1) is preferred, and the type of the unsaturated compound containing a polar group that undergoes a graft reaction includes a carbon-carbon unsaturated bond in a molecule such as an epoxy group, maleic anhydride, and itaconic anhydride for the reasons described above. An unsaturated compound having a dicarboxylic anhydride group is particularly preferred.

(Physical Properties of Polymer) The polymer having a ring structure of the present invention may be modified or unmodified, but the molecular weight before modification is determined by gel permeation.
When represented by a number average molecular weight (Mn) in terms of polystyrene measured by chromatography (GPC), it is 1,000.
~ 500,000, preferably 3,000 ~ 300,0
00, more preferably from 5,000 to 250,000, and most preferably from 10,000 to 200,000. If the number average molecular weight is excessively small, the strength of the sealing material is reduced, causing cracks and the like.On the contrary, if the number average molecular weight is excessively large, the viscosity of the polymer is too large, and the moldability is reduced. It is not good because it gets worse. Therefore, when the number average molecular weight is in the above range, the strength, viscosity, and processability of the molded product are appropriately balanced, which is particularly preferable. Even when modified, the physical properties of the polymer are preferably within the above range.

[2] Compounding agent As a compounding agent, for the purpose of improving the heat resistance and strength properties of the sealing material, it is more preferable to mix a curing agent into a curable polymer.

(Curing Agent) The sealing material of the present invention may contain a curing agent for the purpose of improving heat resistance and reducing the coefficient of linear expansion. Although the curing agent is not particularly limited, (1) an organic peroxide, (2) a curing agent that exhibits an effect by heat,
(3) A curing agent exhibiting an effect by light is used. (1) Organic peroxide Examples of the organic peroxide include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane. , 2,2-
Peroxy ketals such as bis (t-butylperoxy) butane; t-butyl hydroperoxide, 2,5
Hydroperoxides such as -dimethylhexane-2,5-dihydroperoxide; dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, α, α ' Dialkyl peroxides such as -bis (t-butylperoxy-m-isopropyl) benzene; diacyl peroxides such as octanoyl peroxide and isobutyryl peroxide; peroxyesters such as peroxydicarbonate. Can be Among them, dialkyl peroxide is preferable in view of the performance of the resin after curing, and the type of the alkyl group can be changed depending on the molding temperature.

(2) Curing agent exhibiting effect by heat The curing agent exhibiting effect by heat is not particularly limited as long as it is a curing agent capable of causing a crosslinking reaction by heating, but is preferably a diamine, a triamine or a higher aliphatic polyamine. , Alicyclic polyamines, aromatic polyamine bisazides, acid anhydrides, dicarboxylic acids, polyhydric phenols, polyamides and the like. Specific examples include aliphatic polyamines such as hexamethylenediamine, triethylenetetramine, diethylenetriamine, and tetraethylenepentamine; diaminocyclohexane, 3 (4), 8
(9) -Bis (aminomethyl) tricyclo [5.2.
1.0 ^{2, 6]} decane; 1,3- (diaminomethyl) cyclohexane, menthenediamine, isophoronediamine N
Alicyclic polyamines such as -aminoethylpiperazine, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) methane; 4,4'-
Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, α, α'-bis (4-aminophenyl)
Aromatic polyamines such as -1,3-diisopropylbenzene, α, α′-bis (4-aminophenyl) -1,4-diisopropylbenzene, 4,4′-diaminodiphenylsulfone, metaphenylenediamine, and metaxysilylenediamine And 4,4-bisazidobenzal (4-
Methyl) cyclohexanone, 4,4′-diazidochalcone, 2,6-bis (4′-azidobenzal) cyclohexanone, 2,6-bis (4′-azidobenzal) -4-
Methyl-cyclohexanone, 4,4′-diazidodiphenylsulfone, 4,4′-diazidodiphenylmethane,
Bisazides such as 2,2'-diazidostilbene; phthalic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, nadic anhydride, 1,2-cyclohexanedicarboxylic acid, maleic anhydride-modified polypropylene, maleic anhydride Acid anhydrides such as modified cyclic olefin resins; dicarboxylic acids such as fumaric acid, phthalic acid, maleic acid, trimellitic acid, and hymic acid; polyhydric phenols such as phenol novolak resins and cresol novolak resins; tricyclodecanediol; Polyhydric alcohols such as diphenylsilanediol, ethylene glycol and its derivatives, diethylene glycol and its derivatives, triethylene glycol and its derivatives; nylon-6, nylon-66, nylon-610, nylon-
11, nylon-612, nylon-12, nylon-
46, polyamides such as methoxymethylated polyamide, polyhexamethylenediamine terephthalamide, and polyhexamethyleneisophthalamide. These may be used alone or as a mixture of two or more. Among them, aromatic polyamines, acid anhydrides, polyhydric phenols, and the like, because of their excellent heat resistance, mechanical strength, adhesion to metals, and excellent dielectric properties (low dielectric constant and low dielectric loss tangent) , Polyhydric alcohols are preferred,
Among them, 4,4-diaminodiphenylmethane (aromatic polyamines), maleic anhydride-modified cyclic olefin resin (acid anhydride), polyhydric phenols and the like are particularly preferable.
It is also possible to increase the efficiency of the crosslinking reaction by adding a curing accelerator as required. The amount of the curing agent is not particularly limited, but the crosslinking reaction is performed efficiently, and from the viewpoint of improving the physical properties of the obtained cured product and economical efficiency, etc., based on 100 parts by weight of the polymer. 0.
It is used in the range of 1 to 30 parts by weight, preferably 1 to 20 parts by weight. If the amount of the curing agent is too small, crosslinking is unlikely to occur, and sufficient heat resistance and solvent resistance cannot be obtained. If the amount is too large, characteristics such as water absorption and dielectric properties of the crosslinked resin are undesirably reduced. Therefore, when the amount is within the above range, these characteristics are highly balanced and suitable.

Examples of the curing accelerator include amines such as pyridine, benzyldimethylamine, triethanolamine, triethylamine, imidazoles and the like. The curing speed is adjusted and the efficiency of the crosslinking reaction is further improved. It is added for the purpose. The amount of the curing accelerator is
Although not particularly limited, it is used in an amount of 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the above-described polymer. , Dielectric properties, water absorption, etc. are well balanced. In particular, imidazoles are preferable because of their excellent dielectric properties.

(3) Curing agent that exerts an effect by light Curing agent that exerts an effect by light is irradiated with actinic rays such as ultraviolet rays such as g-rays, h-rays, and i-rays, far ultraviolet rays, x-rays, and electron beams. Is not particularly limited as long as it is a photo-curing agent which reacts with the polymer to form a cross-linking compound. Examples thereof include an aromatic bis azide compound, a photo-amine generator, a photo-acid generator and the like.

Specific examples of the aromatic bisazide compound include 4,4′-diazidochalcone and 2,6-bis (4 ′
-Azidobenzal) cyclohexanone, 2,6-bis (4'-azidobenzal) 4-methylcyclohexanone, 4,4'-diazidodiphenylsulfone, 4,
Representative examples include 4'-diazidobenzophenone, 4,4'-diazidodiphenyl, 2,7-diazidofluorene, 4,4'-diazidophenylmethane, and the like. These can be used alone or in combination of two or more.

Specific examples of the photoamine generator include o-nitrobenzyloxycarbonylcarbamate, 2,6-dinitrobenzyloxycarbonylcarbamate and α, α-dimethyl-aromatic or aliphatic amine.
3,5-dimethoxybenzyloxycarbonyl carbamate and the like, and specifically, aniline, cyclohexylamine, piperidine, hexamethylenediamine, triethylenetetraamine, 1,3- (diaminomethyl)
O-Nitrobenzyloxycarbonyl carbamates such as cyclohexane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, and phenylenediamine. These can be used alone or in combination of two or more.

The photoacid generator is a substance that generates a Bronsted acid or a Lewis acid upon irradiation with actinic rays, such as an onium salt, a halogenated organic compound,
Examples include quinonediazide compounds, α, α-bis (sulfonyl) diazomethane compounds, α-carbonyl-α-sulfonyl-diazomethane compounds, sulfone compounds, organic acid ester compounds, organic acid amide compounds, and organic acid imide compounds. These compounds which can be cleaved by irradiation with actinic rays to generate an acid may be used alone or in combination of two or more.

The amount of the photocuring agent to be added is not particularly limited, however, from the viewpoints of efficiently performing the reaction with the polymer, not impairing the physical properties of the obtained crosslinked resin, and economical efficiency. 0.1 to 100 parts by weight of the polymer
It is used in an amount of 30 parts by weight, preferably 1 to 20 parts by weight. If the added amount of the photoreactive substance is too small, crosslinking is unlikely to occur, and sufficient heat resistance and solvent resistance cannot be obtained.If the added amount is too large, properties such as water absorption and dielectric properties of the crosslinked resin deteriorate. Therefore, it is not preferable. Therefore, when the amount is within the above range, these characteristics are highly balanced and suitable.

(Other Compounding Agents) The sealing material of the present invention comprises:
If necessary, other compounding agents may be added. Other compounding agents include fillers, flame retardants, other polymer components, other additives, and the like.

(1) Filler The sealing material of the present invention sometimes contains an inorganic or organic filler for the purpose of reducing the coefficient of linear expansion, and is used as a conventional sealing material. If it is not particularly limited, for example, silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, basic magnesium carbonate, domite, calcium sulfate,
Potassium titanate, barium sulfate, calcium sulfite,
Talc, clay, mica, asbestos, glass fiber, glass flake, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber, polyethylene fiber, polypropylene fiber, polyester fiber, polyamide Fiber and the like. Among these fillers, particularly, heat resistance, low water absorption, dielectric properties, inorganic fillers are preferable because of their excellent low impurity properties, etc.
Particularly, silica and the like are preferable.

(2) Flame Retardant The flame retardant is not an essential component, but it is preferable to add it especially when sealing LSI chips such as CPUs and DRAMs. The flame retardant is not particularly limited, but is preferably one that does not decompose, modify, or deteriorate with a curing agent, and a halogen-based flame retardant is usually used. As the halogen-based flame retardant, various chlorine-based and bromine-based flame retardants can be used, but the flame retardant effect, heat resistance at the time of molding, dispersibility in the resin, influence on the physical properties of the resin, etc. are considered. From, hexabromobenzene,
Pentabromoethylbenzene, hexabromobiphenyl, decabromodiphenyl, hexabromodiphenyloxide, octabromodiphenyloxide, decabromodiphenyloxide, pentabromocyclohexane, tetrabromobisphenol A, and derivatives thereof [for example, tetrabromobisphenol A-bis (hydroxy Ethyl ether), tetrabromobisphenol A-bis (2,3-dibromopropyl ether), tetrabromobisphenol A-bis (bromoethyl ether), tetrabromobisphenol A-bis (allyl ether), etc.], tetrabromobisphenol S, And derivatives thereof [eg, tetrabromobisphenol S-bis (hydroxyethyl ether), tetrabromobisphenol S-bis (2 3-dibromopropyl ether), etc.], tetrabromophthalic anhydride and derivatives thereof [for example, tetrabromophthalimide, ethylenebis tetrabromophthalimide, etc.], ethylenebis (5,6
Dibromonorbornene-2,3-dicarboximide), tris- (2,3-dibromopropyl-1) -isocyanurate, adduct of Diels-Alder reaction of hexachlorocyclopentadiene, tribromophenyl glycidyl ether, tribromophenyl acrylate , Ethylenebistribromophenylether, ethylenebispentabromophenylether, tetradecabromodiphenoxybenzene, brominated polystyrene, brominated polyphenylene oxide, brominated epoxy resin, brominated polycarbonate, polypentabromobenzyl acrylate, octabromonaphthalene, hexa Bromocyclododecane, bis (tribromophenyl) fumaramide,
It is preferable to use N-methylhexabromodiphenylamine and the like. The added amount of the flame retardant is usually 3 to 150 parts by weight, preferably 10 to 100 parts by weight of the cyclic polymer.
To 140 parts by weight, particularly preferably 15 to 120 parts by weight. As a flame retardant aid for more effectively exhibiting the flame retardant effect of the flame retardant, for example, it is possible to use an antimony flame retardant aid such as antimony trioxide, antimony pentoxide, sodium antimonate, and antimony trichloride. it can. These flame retardant aids are used in a proportion of usually 1 to 30 parts by weight, preferably 2 to 20 parts by weight, based on 100 parts by weight of the flame retardant.

(3) Other Polymer Components In the present invention, a rubbery polymer or another thermoplastic resin can be blended as required. The rubbery polymer is a polymer having a glass transition temperature of room temperature (25 ° C.) or less, and includes a usual rubbery polymer and a thermoplastic elastomer. The Mooney viscosity (ML1 + 4, 100 ° C.) of the rubbery polymer is appropriately selected depending on the purpose of use, and is usually 5 to 200. Examples of the rubbery polymer include ethylene-α-olefin-based rubbery polymers; ethylene-α-olefin-polyene copolymer rubber; ethylene and unsaturated carboxylic acid esters such as ethylene-methyl methacrylate and ethylene-butyl acrylate. Copolymer of ethylene and a fatty acid vinyl such as ethylene-vinyl acetate; ethyl acrylate, butyl acrylate, hexyl acrylate, and acrylic acid 2-
Polymers of alkyl acrylates such as ethylhexyl and lauryl acrylate; random copolymers of polybutadiene, polysoprene, styrene-butadiene or styrene-isoprene, acrylonitrile-butadiene copolymer, butadiene-isoprene copolymer, butadiene- (meta Diene rubbers such as alkyl acrylate copolymer, butadiene-alkyl (meth) acrylate-acrylonitrile copolymer, butadiene-alkyl (meth) acrylate-acrylonitrile-styrene copolymer; butylene-isoprene copolymer Polymers.

As the thermoplastic elastomer, for example,
Aromatic vinyl-conjugated diene block copolymers such as styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, styrene-isoprene block copolymer, hydrogenated styrene-isoprene block copolymer, low Crystalline polybutadiene resin, ethylene-
Propylene elastomer, styrene grafted ethylene
Propylene elastomer, thermoplastic polyester elastomer, ethylene ionomer resin and the like can be mentioned. Among these thermoplastic elastomers, preferred are hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-isoprene block copolymer, and the like. Specifically, JP-A-2-133406,
JP-A-2-305814, JP-A-3-72512
And Japanese Patent Application Laid-Open No. 3-74409. As other thermoplastic resins, for example, low-density polyethylene, high-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, polystyrene, polyphenylene sulfide , Polyphenylene ether, polyamide,
Examples include polyester, polycarbonate, and cellulose triacetate. These rubbery polymers and other thermoplastic resins can be used alone or in combination of two or more, and the amount thereof is appropriately selected within a range not to impair the object of the present invention. In order not to impair the properties of the insulating material, the amount is preferably 30 parts by weight or less.

(4) Other Additives As other additives, if necessary, a heat stabilizer,
Weathering stabilizer, leveling agent, antistatic agent, slip agent,
Antiblocking agents, antifogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes and the like can be added in appropriate amounts. Specifically, for example, tetrakis [methylene-3
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] methane, β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid alkyl ester, 2,2′-oxamidobis [ethyl-3 (3,3
5-di-t-butyl-4-hydroxyphenyl) propionate], and the like; trisnonylphenyl phosphite, tris (2,4-di-t-brylphenyl) phosphite, tris (2,4 -Di-t
Phosphorus-based stabilizers such as -butylphenyl) phosphite; fatty acid metal salts such as zinc stearate, calcium stearate and calcium 12-hydroxystearate; glycerin monostearate, glycerin monolaurate;
Glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate,
Polyhydric alcohol fatty acid esters such as pentaerythritol tristearate; synthetic hydrotalcite; amine-based antistatic agents; fluorine-based nonionic surfactants, leveling agents for paints such as specialty acrylic resin-based leveling agents, silicone-based leveling agents; silanes Coupling agents such as coupling agents, titanate coupling agents, aluminum-based coupling agents, and zircoaluminate coupling agents; plasticizers; coloring agents such as pigments and dyes;

[3] Encapsulating Material The encapsulating material of the present invention uses the above components, and is usually in the form of a liquid composition or a film. When used as a thermoplastic resin, it can be used for injection molding in a bulk pellet state.

(Liquid Composition) When used as a liquid composition, the above components are dissolved in a solvent before use. When a solvent is used, for example, aromatic hydrocarbons such as toluene, xylene, and ethylbenzene, aliphatic hydrocarbons such as n-pentane, hexane, heptane, alicyclic hydrocarbons such as cyclohexane, chlorobenzene, dichlorobenzene, and trichlorobenzene Examples thereof include halogenated hydrocarbons such as benzene. The solvent is used in an amount ratio sufficient to uniformly dissolve or disperse the cyclic polymer and, if necessary, each component to be blended, and usually has a solid content of 1 to 80% by weight, preferably 5 to 60% by weight, More preferably 10
It is adjusted to be に な る 50% by weight.

Further, a curable monomer can be used as a reactive diluent instead of the solvent. The reactive diluent is not particularly limited as long as it is a compound that causes a cross-linking reaction by conventional heat or light and is liquid at ordinary temperature, but includes an epoxy group-containing compound, an acrylic (methacrylic acid) ester compound, a vinyl ether compound, And vinyl compounds. Among these other reactive diluents, epoxy group-containing compounds are particularly preferred because of their excellent heat resistance, low water absorption, dielectric properties and the like.

When used as a liquid sealing material, the melt viscosity is preferably 50 poise or less, more preferably 20 poise or less in the range of 100 to 200 ° C. from the viewpoints of handling and process.

(Film) The sealing material of the present invention can also be used as a film, in which case there is an advantage that the sealing can be carried out efficiently by a method such as heat compression. To provide as a film, apply the polymer solution dissolved in the aforementioned solvent or reactive diluent on a flat substrate,
The solvent may be dried and removed to form a film by a casting method, or a film may be formed by an extrusion method using a film extruder. When the formed film contains a curing agent, it may be partially cured before use. The thickness of the film used is usually 30 to 200 μm, preferably 40 to 100 μm, more preferably 50 to 90 μm.

(Curing Method) When the sealing material used in the present invention is used as a cured resin, as described above, heat,
Light, may be cured using any method such as an electron beam, especially when sealing electronic components such as semiconductor components,
Except for the case of sealing in a thin film state such as an overcoat method, it is preferable to cure by heat. In the case of curing by heat, when the sealing material is a thick molded product, when it has a complicated shape such that light beams cannot partially reach,
It is suitable when a compounding agent that does not transmit light, such as a filler and an additive, is included.

(Sealing Method) The sealing material used in the present invention is mainly used to seal a portion of the above-described semiconductor bare chip mounting package or the like where a chip electrode and a mounting substrate electrode are directly connected. It is a material that can be used as a sealing method for mounting LSI bare chips in recent years. It can be applied as it is to the potting (medium-sized) sealing method and other special sealing methods that are commonly used when using liquid epoxy resin. Can be.

[4] Semiconductor Chip and Mounting Board The semiconductor chip and the mounting board to be sealed in the present invention, the connection method (mounting method) thereof, and the sealing method for each mounting method will be described.

(Mounting Board) The mounting board is not particularly limited as long as it has an insulating layer, a conductive layer, and an electrode, and can transmit an electric signal from the chip electrode to another electronic component or the like. Low dielectric constant printed wiring such as glass epoxy printed wiring board, glass polyimide printed wiring board, bismaleimide triazine resin printed circuit board, polyphenylene ether (polyphenylene oxide) printed circuit board, fluororesin printed circuit board, and other cyclic olefin resin printed circuit boards Printed circuit boards such as substrates; Flexible printed circuit boards (FPC) such as polyethylene terephthalate flexible printed circuit boards and polyimide flexible printed circuit boards; Silicon wafer substrates; Ceramic substrates; Resin coated metal film or dry film, high-density mounting substrate film laminated such adhesive insulating film; and a film circuit board, such as a thermoplastic Engineering A ring plastic film such as polyphenylene sulfide or liquid crystal polymer. In addition, a chip scale package (CS
A carrier film (such as a polyimide carrier film) or a single-layer substrate used for P) can also be exemplified as the mounting substrate.

(Semiconductor Chip Mounting Method and Sealing Method) Examples of the bare chip mounting method (connection technology) of a semiconductor chip include (1) a wire bonding technology, (2) a TAB technology, and (3) a flip chip bonding technology.

(1) Wire Bonding Technology In the wire bonding method, a semiconductor chip is placed on the above-mentioned mounting substrate with its electrodes facing away from the substrate surface, and the electrodes of the substrate and the electrodes of the chip are directly connected to a wire (gold). Line). In this case, sealing of the interelectrode connection portion is mainly performed by coating the above-mentioned diluted polymer solution so as to cover at least the above-mentioned wire connection portion, and removing the solvent and the like. In order to prevent the coated solution from flowing, a frame (dam) is set around the chip,
It is also possible to make only the chip mounting portion a concave portion.
Alternatively, the tip portion may be placed in a mold and insert-molded by an injection molding method.

(2) Tape Automated Bondin (Tape Automated Bondin)
g) Technology: TAB technology The TAB technology is basically composed of a carrier film, bumps (metal projections; electrodes), and a semiconductor chip. Carrier films are used for conveying members, package members,
It has a function as a mounting board, wiring patterns and leads are formed on a resin film, such as the above-mentioned polyimide flexible printed wiring board, and bumps are used as a medium for connecting the leads of the carrier film and the electrodes of the semiconductor chip. Has an important role. In this case, the sealing method between the electrodes is such that the carrier film is placed above the chip in a state where only the semiconductor chip portion is penetrated, so that the semiconductor chip surface actually forms the bottom surface. The carrier tape forms a frame.
Therefore, similarly to the method (1), the sealing between the electrodes can be performed by pouring the sealing material into the frame and drying it.

(3) Flip Chip Bonding Technology In a bare chip mounting method, a method of directly connecting a chip electrode and a substrate electrode without a gold wire (wire) is called flip chip bonding. Bumps (projections) or metal balls are formed, and electrodes (pads) are formed on the mounting substrate, and each is directly connected. In this case, the semiconductor chip is mounted on the mounting board in a face-down state with the electrode forming surface upside down. Accordingly, as an encapsulation method in this case, an underfill method of filling a gap between the mounting substrate surface and the semiconductor chip surface with an encapsulant is applied. In the underfill method, a solution of a sealing material similar to that used in (1) and (2) is poured into a gap between a substrate and a chip using a dispenser or the like, and dried and solidified to seal between electrodes. As another method, a method of sandwiching a sealing film such as an anisotropic conductive film between the electrodes and simultaneously bonding and sealing the electrodes has been recently developed as another method.

[5] Semiconductor Bare Chip Mounting Package The semiconductor chip encapsulated by the present invention has a highly integrated fine wiring such as used in CPU (Central Processing Unit) and memory (DRAM) among semiconductor components. Integrated circuit components and components.

In the present invention, a semiconductor package can be obtained by sealing at least the electrodes of the semiconductor chip and the tail connecting portions of the mounting substrate with the above-described sealing material. After the semiconductor chip is mainly mounted on a small printed circuit board with a bare chip, it is sealed with the aforementioned sealing material.
These are integrally used as a package. The above package, the thing that attached a connecting member such as solder ball for the purpose of connecting to the printed circuit board of the motherboard,
A package on which a plurality of semiconductor chips are mounted, called a ball grid array (BGA), can be used as a new semiconductor component package as a multi-chip package (multi-chip module) for a computer or a communication device.

Further, the sealing material of the present invention can be used for a chip scale package (CSP) as a recent form of a semiconductor bare chip mounting package. C
Specific forms of SP include μ-BGA, FBGA,
FLGA, SON, SOL, mold CSP, and the like.

[0076]

The present invention will be specifically described below with reference to examples and comparative examples. (1) The glass transition temperature was measured by the DSC method. (2) Unless otherwise specified, the molecular weight of gel permeation chromatography (G
(PC) as measured in terms of polystyrene. (3) The hydrogenation rate of the main chain and the modification rate of the polymer are ¹ H-N
Measured by MR. (4) Dielectric constant and dielectric loss tangent at 1 MHz are JIS C
It was measured according to 6481. (5) The flexural strength at normal temperature, tensile strength, tensile elongation, and water absorption under the conditions of 85 ° C. × 85% RH × 300 hours were measured in accordance with JIS K6911. (6) The glass transition temperature was measured by TMA. (7) Temperature cycle test (TCT) is -55 ° C (30m
in)-room temperature (5 min)-150 ° C (30 min)-
A temperature shock was applied by repeating a temperature cycle at room temperature (5 min) 500 times, and the presence or absence of cracks was examined. Pressure cooker test (PCT) is 100% humidity, 1
It was left in an environment of 05 ° C. for 300 hours and examined for occurrence of defects. (8) In Examples, "parts" and "%" refer to "parts by weight" and "% by weight", respectively, unless otherwise specified.

(Synthesis Example 1) Tungsten hexachloride, trii
Polymerization of sobutyl aluminum and isobutyl alcohol
8-ethyltetracycline by a known method.
B [4.4.1^2,5 . 1^7,10. 0] -3-dodecene (hereinafter referred to as
Lower abbreviated as ETD), and then nickel acetyl
Known using settonate and triisobutylaluminum
Ring-opened polymer hydride of ETD hydrogenated by the method of
(Hydrogenation rate ≧ 99%, Tg = 138 ° C., Mn = 18.5
(00, Mw = 31,600)
30 parts of maleic acid, 10 parts of dicumyl peroxide, ter
Mix 300 parts of t-butylbenzene and autoclave
After conducting the reaction at 150 ° C. for 4 hours in
Coagulate and dry in the same manner as in
-(A) was obtained. Tg of the obtained polymer (A) = 16
6 ° C., Mn = 16,400, Mw = 35,200, denatured
The rate was 28%.

Synthesis Example 2 Synthesis Example 1 except that 30 parts of maleic anhydride was changed to 30 parts of allyl glycidyl ether.
In the same manner as in the above, an epoxy-modified polymer (B) was obtained. Tg of the obtained polymer (B) = 160 ° C., Mn = 17,1
00, Mw = 36,900, and the modification rate was 24%.

Synthesis Example 3 Tetracyclo [4.4.1]
^2,5 . ^17,10 . 0] -3-dodecene (hereinafter abbreviated as TCD) and an ethylene copolymer obtained by a known method (TCD content 38 mol%, Tg = 135)
(C, Mn = 15,200, Mw = 35,600) in the same manner as in Synthesis Example 1 to obtain a maleic anhydride-modified polymer (C). Tg of the obtained polymer (C)
= 162 ° C, Mn = 14,200, Mw = 41,10
0, and the modification rate was 23%.

Synthesis Example 4 Synthesis Example 3 except that 30 parts of maleic anhydride was changed to 30 parts of allyl glycidyl ether.
In the same manner as in the above, an epoxy-modified polymer (D) was obtained. Tg of the obtained polymer (D) = 157 ° C., Mn = 13.3
00, Mw = 40,000, and the modification rate was 19%.

(Synthesis Example 5) Li-based living anion polymerization catalyst [n-BuLi / tetramethylenediamine (TMED) described in JP-A-7-258318
A: Living anion stabilizer) = 1/1 (molar ratio)]
A hydride of a 1,4-addition polymer shown in Table 1 obtained by polymerizing 1,3-cyclohexadiene (C-HD) using (hydrogenation rate ≧ 99%, Tg = 219 ° C., Mn = 5
3,400 (Mw = 78,000) except that maleic anhydride-modified polymer (E) was obtained in the same manner as in Synthesis Example 1. Tg of the obtained polymer (E) = 238
° C, Mn = 37,200, Mw = 94,800, and the modification rate was 22%.

Synthesis Example 6 Synthesis Example 5 except that 30 parts of maleic anhydride was changed to 30 parts of allyl glycidyl ether.
In the same manner as in the above, an epoxy-modified polymer (F) was obtained. Tg of the obtained polymer (E) = 230 ° C., Mn = 38.1
00, Mw = 89,900, and the modification rate was 18%.

(Synthesis Example 7) The number average molecular weight (Mn) is 92
100 parts of poly (2,6-dimethyl-1,4-phenylene ether), 6.0 parts of maleic anhydride, and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane ( After dry blending 2.0 parts of Nippon Oil & Fats Perhexa 25B) at room temperature, cylinder temperature 300
The mixture was extruded with a twin-screw extruder at a temperature of 230 ° C. and a screw rotation speed of 230 rpm to obtain maleic anhydride-modified polyphenylene ether (PPE) (G). Tg of the obtained polymer (G) = 183 ° C., Mn = 8,500, Mw = 1
5,400 and the modification rate was 20%.

(Examples 1 to 7)
100 parts of the polymers (A) to (G) are mixed with 30 parts of the polymer.
%, Dissolved in toluene to give
Add 6 parts of silicylenediamine, and as a flame retardant
Brominated bisphenol A type epoxy resin (EPI15
2: Dainippon Ink and Chemicals, Inc.) 20 parts, flame retardant aid
Sb as an agent_TwoO_Three 10 parts, fused silica 4 as a filler
00 parts, 2 parts of carbana wax as other compounding agents,
And add 1.5 parts of carbon black to form a liquid semiconductor encapsulant.
Created.

The obtained solution was thinned to 70 μm on a Teflon plate having a thickness of 3 mm using a spin coater.
The film was dried in nitrogen at 120 ° C. for 120 seconds to form a film.
The obtained film is placed on a glass bismaleimide triazine multilayer substrate having electrode pads for semiconductor flip chip bonding, and a semiconductor bare chip (100 μm pitch, 360 pins :) having electrode bumps based on silicon is placed thereon at 190 ° C. × Heating and pressing were performed for 5 seconds to bond the chip bumps and the substrate pads, and at the same time, sealed the bonded portions. After the film was completely cured by heating at 170 ° C. for 4 hours, the occurrence of defects in the temperature cycle test (TCT) and the pressure cooker test was examined. The evaluation results show excellent results for all samples,
The defective rate was 2% or less.

(Embodiment 8) In a tape carrier package in which a semiconductor bare chip similar to that in Embodiment 1 is mounted on a polyimide carrier film having a wiring pattern and leads by TAB, the semiconductor carrier is formed on a semiconductor chip surface on which a frame is formed with the carrier film. Then, the liquid sealing material using the polymer (A) obtained in Example 1 is applied so as to cover the connection portion between the chip electrode and the carrier film lead,
Drying was performed in nitrogen for 1 hour to form a coat film having a thickness of 70 μm. After the formed coating film was heated at 170 ° C. for 4 hours to completely cure it, the presence or absence of defects in a temperature cycle test (TCT) and a pressure cooker test was examined. The evaluation results of all the samples were excellent, and the defective rate was 2% or less.

(Comparative Example 1) As a main component of a sealing material component,
A bisphenol F type epoxy resin was used, 5 parts of 2-ethyl-4-methylimidazole was added thereto, and a brominated bisphenol A type epoxy resin (E
PI152: Dainippon Ink and Chemicals, Inc.) 20
Parts, Sb ₂ O ₃ as a flame retardant aid, 10 parts of fused silica as a filler, 2 parts of carbana wax as another compounding agent, and 1.5 parts of carbon black to prepare a liquid semiconductor sealing material. . The resulting solution was thinned to 70 μm on a 3 mm thick Teflon plate using a spin coater, reacted at 60 ° C. for 100 seconds, and partially cured to prepare a tack-free film. The obtained film was placed on the same multilayer substrate as in Example 1, and a semiconductor bare chip (1) having electrode bumps made of silicon as a base was placed thereon.
A 00 μm pitch, 360 pins :) was heated and pressure-bonded at 190 ° C. for 5 seconds to bond the chip bumps and the substrate pads, and at the same time, sealed the bonded portions. Film at 120 ° C, 3
After complete curing by heating for a time, a temperature cycle test (TC
T) and the occurrence of defects in the pressure cooker test. As a result of the evaluation, the defective rate was 30
%, 35%.

Comparative Example 2 Using the liquid sealing agent used in Comparative Example 1, the electrode joining portion of the tape carrier package was sealed in the same manner as in Example 8, and the coat film was heated at 120 ° C.
After complete curing in 3 hours, a temperature cycle test and a pressure cooker test were performed.
0% and 35%.

[0089]

According to the present invention, there is provided a sealing material between a semiconductor chip and a mounting substrate which is excellent in mechanical strength and low water absorption. Further, according to the present invention, a highly reliable semiconductor package can be obtained by sealing between a semiconductor chip and a mounting substrate using such a sealing material. INDUSTRIAL APPLICABILITY The sealing material of the present invention is useful in a wide range of fields as an encapsulating material for a semiconductor package that requires particularly high speed and high reliability in the field of electric and electronic devices.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI H01L 23/31

Claims (8)

[Claims] 1. A sealing material between a semiconductor chip and a mounting substrate, comprising a ring structure-containing polymer containing a repeating unit having a ring structure. 2. The encapsulating material according to claim 1, wherein the ring structure-containing polymer is a cyclic olefin polymer or an aromatic condensed polymer having a repeating unit of an aromatic ring in the main chain. 3. The sealing material according to claim 1, wherein the ring structure-containing polymer has a functional group. 4. The sealing material according to claim 1, further comprising a curing agent. 5. The sealing material according to claim 1, which is a solution type or a film. 6. A semiconductor package in which a space between a semiconductor chip and a mounting substrate is sealed with the sealing material according to claim 1. 7. A method of manufacturing a semiconductor package by bonding a semiconductor chip to a mounting substrate, applying a sealing material of a solution type so as to cover the bonded portion, removing a solvent, and drying. 8. The semiconductor device according to claim 5, wherein the sealing material according to claim 5 is a film on a mounting substrate, a semiconductor chip is laminated on the film, and the semiconductor chip is bonded by heating and fusion bonding. How to make a package.