KR20010013053A - Electronic component-protecting material - Google Patents

Abstract

Electronic component-protecting material excellent in mechanical properties, electric properties, heat resistance and chemical resistance and reduced in water absorption, made from a curable resin composition comprising (A) a cyclic olefinic polymer having a number-average molecular weight of 1,000 to 500,000 and (B) at least one curing agent selected from the group consisting of organic peroxides, curing agents which exhibit their effects upon heating and curing agents which exhibit their effects upon irradiation with a light.

Description

Electronic component protection material {ELECTRONIC COMPONENT-PROTECTING MATERIAL}

In recent years, with the rapid progress of the high-precision society, there is a demand for improving the processing capacity of information processing devices such as computers and communication devices, that is, increasing the speed. In addition, with the development of the information communication network, it is necessary to expand the communication wavelength region, and in particular, the development of a communication device that operates with the communication wavelength of the high frequency region of GHz (GHz) is rushing.

In order to meet such demands, in order to speed up the information processing speed and to increase the frequency of the communication wavelength range, for example, the operating frequency of electronic components such as semiconductor chips used in information processing equipment is increased to 400 MHz or more from the conventional 100 MHz. In addition, the wavelength range used for the communication equipment is also very high frequency, from the conventional tens of GHz to 50 GHz or more.

Such electronic components are required to have higher reliability in order to achieve sufficient performance in a state of high density or high frequency for realizing miniaturization and high speed. Therefore, high reliability is demanded also about various protective materials, such as the sealing material and overcoat material used for these electronic components.

More specifically, it is desired that mechanical strength, heat resistance, low hygroscopicity, dielectric properties, low impurity properties, etc. are remarkably and comprehensively improved in electronic component sealing materials and overcoat materials. There is also a lot of research and development.

Background Art Conventionally, a sealing material mainly composed of a cresol novolak type epoxy resin has been widely used as a sealing material for electronic components such as semiconductor devices such as a central processing unit of a computer, a memory, or the like. However, electronic components manufactured using this encapsulant have a problem in that moisture in the epoxy resin encapsulant absorbed during soldering flow at the time of mounting on a circuit board vaporizes and foams due to the high temperature of the solder. In addition, since the epoxy resin encapsulant lacks mechanical strength and heat resistance, cracking occurs at the interface between the encapsulant and the electronic device due to the foaming, which is a major problem to compromise the reliability of the part.

In such a situation, a technique for encapsulating a semiconductor device or an optical device using a thermoplastic norbornene-based resin having excellent heat resistance, low hygroscopicity, dielectric properties, and low impurity has been studied. For example, Japanese Laid-Open Patent Publication No. 62-27412 proposes a method of using a modified product obtained by graft-modifying an adduct copolymer of tetracyclododecene and ethylene with allyl glycidyl ether or maleic anhydride. JP-A-6-188336 and JP-A-7-18161 disclose a method of encapsulating an optical semiconductor device with a ring-opening polymer of methylmethoxycarbonyltetracyclododecene. However, the thermoplastic norbornene-based resin used in this encapsulation method is deformed to the soldering flow temperature (230 ° C or higher) when the encapsulated electronic component is surface mounted on a circuit board because it is thermoplastic and does not have a high heat deformation temperature. Since the thermal expansion coefficient is not large because it is not three-dimensional crosslinked (hardened), there is a problem that a package crack occurs due to a heat cycle test or the like due to the influence of the difference of the linear expansion coefficient between the semiconductor chip and the encapsulant.

JP-A-6-318651 discloses a crosslinkable thermoplastic norbor in which a thermoplastic norbornene-based resin is generated and modified in the presence of an unsaturated silane and a radical generator, and then formulated with a silanol condensation catalyst such as dibutyltin laurate. A technique is disclosed in which an electronic device is encapsulated with a nene resin, treated with 100 ° C hot water for 2 hours, and crosslinked. However, this crosslinking reaction is difficult to control moisture, and as a result, there is a problem that the crosslinking density does not sufficiently increase. In addition, this method has a problem in that corrosion of electronic devices is promoted by hydrothermal treatment.

On the other hand, as one of overcoat materials for electronic components such as semiconductor devices such as a central processing unit of a computer, a memory, or the like, there are a buffer coat film and a passivation film. In order to form these overcoat films, the material which has made polyimide resin the main component conventionally is used. However, since the conventional overcoat material is insufficient in chemical resistance and low hygroscopicity, double protection is further provided by a protective film mainly composed of an epoxy resin.

A technique in which a thermoplastic norbornene-based resin is crosslinked with an organic peroxide such as peroxide and used for a circuit board (Japanese Patent Laid-Open No. Hei 6-248164), and a thermoplastic norbornene-based resin having a polar group introduced therein may be an aromatic bisazide compound or a photoamine. A technique (Japanese Patent Application Laid-open No. Hei 8-259784) for curing using a photocuring agent such as a generator and using it for an interlayer insulating film of a circuit board is also proposed. However, it is not proposed to use these materials as the sealing material. In addition, when these materials are used as the sealing material as they are, it is difficult to effectively prevent the occurrence of cracks in the sealing material. And most of these materials do not have sufficient heat resistance as an overcoat film.

Background Art Conventionally, a number of methods using thermosetting polyphenylene ether resins as overcoat materials for electronic parts have been proposed. However, this resin is superior to epoxy resins especially in respect of hydrolysis resistance to acids, alkalis and the like, but it is not sufficient and has a problem that it is difficult to use alone.

Disclosure of the Invention

An object of the present invention is to provide an electronic component protective material excellent in mechanical strength, electrical properties, heat resistance, low absorption, chemical resistance and the like.

More specifically, an object of the present invention is to provide a material having sufficient mechanical strength as the electronic component encapsulation material, capable of thermal curing, and excellent in heat resistance, low water absorption, and dielectric properties.

It is also an object of the present invention to provide an overcoat material which is excellent in balance of chemical resistance, moisture resistance, heat resistance, mechanical strength, electrical properties, and the like, and in particular, heat resistance is remarkably improved.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly researched in order to solve the said subject, As a result, in the electronic component protective material which consists of curable resin composition containing the cyclic olefin type polymer of number average molecular weights 1,000-500,000, and a hardening | curing agent (except a water-based hardening | curing agent), It was overlaid.

The crosslinking density was sufficiently improved by crosslinking the cyclic olefin polymer with a curing agent, and the mechanical strength and the heat resistance were greatly improved, and it was found that the generation of cracks during reliability tests such as heat cycles and pressure cookers and the packaging could be greatly reduced. Since this curable resin composition can be cross-linked three-dimensionally, heat resistance and mechanical properties are remarkably improved compared with the thermoplastic resin whose glass transition temperature is equal. In addition, when a polymer having a high glass transition temperature is used as the cyclic olefin polymer, heat resistance can be further improved.

According to the present invention, at least one member selected from the group consisting of (A) a cyclic olefin polymer having a number average molecular weight of 1,000 to 500,000, (B) an organic peroxide, a curing agent that is effective by heat, and a curing agent that is effective by light The electronic component protective material which consists of curable resin composition containing a hardening | curing agent is provided.

As an electronic component protection material, sealing material and overcoat material are typical. And the protective material of this invention can provide the high characteristic suitable for each use by controlling each component of the curable resin composition to be used, especially the kind and physical property of a cyclic olefin polymer.

According to the present invention, there is provided an electronic component package in which an electronic component is sealed or overcoated by a protective material having such excellent properties. And according to this invention, the sealing method using such a protective material is provided.

The present invention has been completed based on these findings.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electronic component protection material, and more particularly, to an electronic component protection material excellent in mechanical properties, electrical properties, heat resistance, low absorption (moisture resistance), and chemical resistance. The electronic component protective material of the present invention is particularly preferable as a sealing material and overcoat material for electronic components.

The present invention also relates to an electronic component package and a sealing method encapsulated or overcoated by such an electronic component protective material.

The electronic component protective material of this invention is comprised from curable resin composition containing the cyclic olefin type polymer of number average molecular weights 1,000-500,000, and a hardening | curing agent. As an electronic component protective material, an electronic component sealing material and an electronic component overcoat material are typical.

The electronic component overcoat material according to the present invention is contained in (1) protection of micro wiring on a semiconductor bare chip [absorption of stress caused by the difference between the element (semiconductor) and external factors, such as the coefficient of linear expansion, or an encapsulant. A buffer coat film used for the purpose of shielding α rays emitted by the filler, (2) a protective film on the surface of the device (especially wiring) (e.g., from external contaminants (organic, acid, alkali, water), filler contact, etc.). (3) a passivation film as a protective layer, and (3) a semiconductor chip, a semiconductor package, or the like, on which the buffer coat film or the passivation film is formed, can be used as a sealing film or a protective film for further protecting from outside air.

Conventionally, although the overcoat material of said (1)-(3) was used combining two or more types of optimal materials, respectively, the overcoat material of this invention has all the functions of these (1)-(3), and is made of one kind of material The new overcoat material which can substitute.

[Cyclic olefin polymer]

The cyclic olefin polymer used in the present invention contains a repeating unit derived from a cyclic olefin monomer in all the repeating units of the polymer. Examples of the cyclic olefin monomers include alicyclic monomers having a norbornene ring, monocyclic cyclic olefins and cyclic conjugated dienes. These cyclic olefin monomers can be used individually or in combination of 2 or more types, respectively, Furthermore, it can copolymerize with the other copolymerizable monomer. Repeating units derived from cyclic olefin monomers include not only the repeating units of the cyclic olefin monomers but also those in which the repeating units are modified. Examples of the modification include hydrogenation and graft modification by a polar group-containing unsaturated compound.

The binding mode of the cyclic olefin monomer is not particularly limited as long as it can introduce a cyclic structure into the main chain, and may be any of addition polymerization and ring-opening polymerization. Examples of the cyclic olefin polymer include: (1) addition of a carbon-carbon unsaturated bond of an alicyclic monomer having a norbornene ring such as norbornene, ethylidene norbornene, dicyclopentadiene, and tetracyclododecene A carbon-carbon unsaturated bond of a polymer, (2) an additional copolymer obtained by addition copolymerization of an unsaturated monomer such as an alicyclic monomer having a norbornene ring and an α-olefin, and (3) a monocyclic cyclic olefin such as cyclopentene or cyclohexene. (B) ring-opening polymers obtained by ring-opening polymerization of an addition polymerized addition polymer, (4) a 1,4-addition polymerization product of cyclic conjugated dienes such as cyclohexadiene, (5) an alicyclic monomer having a norbornene ring, and (6) these Hydrogenated additives; and the like.

The cyclic olefin polymer used in the present invention preferably has good mechanical strength, electrical properties and low water absorption, and is excellent in heat resistance. Thermocyclic norbornene-based resins are preferred as the cyclic olefin polymers in view of these excellent properties, and in particular, addition (co) polymers and norbors mainly composed of alicyclic monomers (ie, norbornene-based monomers) having a norbornene ring Thermoplastic saturated norbornene-based resins such as hydrogenated products of the ring-opening polymer of the n-ene monomer are preferable. Moreover, the hydrogenated substance of the 1, 4- addition type polymer of cyclic conjugated diene, such as 1, 3- cyclohexadiene, is also preferable at the point which is excellent in various characteristics, such as heat resistance.

The ratio of the repeating unit derived from the cyclic olefinic monomer in the cyclic olefinic polymer can be appropriately determined according to the type of comonomer or the desired physical properties, and the mechanical strength and the electrical properties are usually 30 mol% or more based on the total repeating units of the polymer. It is preferable from the viewpoint of low water absorption, heat resistance and the like. The repeating unit derived from the cyclic olefin monomer in the cyclic olefin polymer is preferably 50 mol% or more, more preferably 70 mol% or more, and most preferably 80 mol% or more from the viewpoint of high heat resistance. In particular, when using a cyclic olefin polymer as an overcoat material, it is preferable that the repeating unit derived from the cyclic olefin monomer in a cyclic olefin polymer is 50 mol% or more. The upper limit is 100 mol%.

The cyclic olefin polymer preferably has a glass transition temperature (Tg) measured by a differential scanning calorimeter (DSC) of usually 100 ° C or higher, preferably 120 ° C or higher, and more preferably 140 ° C or higher. Even if Tg of a cyclic olefin type polymer is comparatively low, by hardening | curing with a hardening | curing agent, the heat resistance required in many cases can be obtained in the use of a sealing material. And when high heat resistance is calculated | required, Tg of a cyclic olefin type polymer is 150 degreeC or more normally, Preferably it is 160 degreeC or more, More preferably, it is preferable that it is 170 degreeC or more. In particular, when using a cyclic olefin polymer as an overcoat material, it is preferable that Tg is 160 degreeC or more, and it is more preferable that it is 170 degreeC or more. When high heat resistance is required for the cyclic olefin polymer, by adjusting the type of monomer, polymerization method, molecular weight, modification method, etc., a Tg of 200 ° C. or higher, in most cases 250 ° C. or higher, and even 300 ° C. or higher can be obtained. have. Since Tg of a cyclic olefin type polymer is high, when sealing of electronic components etc. using the said polymer can be performed, the sealing part and protective film which are excellent in heat resistance can be formed, and reliability of an electronic component improves significantly.

When the molecular weight of the cyclic olefin polymer used by this invention is represented by the number average molecular weight (Mn) of polystyrene conversion measured by the gel permeation chromatography (GPC), it is 1,000-500,000, Preferably it is 3,000-300,000, More Preferably it is 5,000-250,000, Most preferably, it is the range of 10,000-200,000.

If the number average molecular weight of the cyclic olefin polymer is too small, the strength of the encapsulation portion or the protective film is lowered, which causes cracking. On the contrary, if the number average molecular weight is too large, the viscosity of the polymer is too large and moldability deteriorates, which is not preferable. . Therefore, when a number average molecular weight exists in the said range, the strength, viscosity, and workability of a sealing part and a protective film are suitably balanced, and it is especially preferable.

It is preferable that a cyclic olefin type polymer contains a polar group (functional group) for the purpose of improving adhesiveness with metal wiring, etc. As a method of containing a polar group in a cyclic olefin polymer, the method of modifying a cyclic olefin polymer and the method of (co) polymerizing the cyclic olefin monomer which has a polar group are mentioned.

[Cyclic Olefin Monomer]

The cyclic olefin monomer which is the main component of the cyclic olefin polymer is not particularly limited as long as it is a cyclic hydrocarbon compound having a carbon-carbon unsaturated bond, but the main ones include (1) an alicyclic monomer having a norbornene ring (norbornene monomer) And (2) monocyclic cyclic olefin monomers and (3) cyclic conjugated diene monomers.

(1) alicyclic monomer having a norbornene ring

The alicyclic monomer having a norbornene ring is an alicyclic monomer having a norbornene ring described in JP-A-5-320268, JP-A 2-36224 and the like. The alicyclic monomers having these norbornene rings may be used alone or in combination of two or more thereof.

Examples of the alicyclic monomer having a norbornene ring include (a) monomers having no unsaturated bonds other than carbon-carbon unsaturated bonds involved in polymerization reactions such as norbornene, tetracyclododecene, and alkyl substituents thereof, and (b) ethyl Monomers having unsaturated bonds other than carbon-carbon unsaturated bonds involved in polymerization reactions such as lidene norbornene, vinyl norbornene, ethylidene tetracyclododecene, dicyclopentadiene, and (c) dimethanotetrahydroflu The monomer which has aromatic rings, such as orene and phenyl norbornene, (d) Monomer which has polar groups, such as methoxycarbonyl norbornene and methoxycarbonyl tetracyclo dodecene, etc. are mentioned. In more detail as follows.

(a) As a specific example of the monomer which does not have an unsaturated bond other than the carbon-carbon unsaturated bond which participates in a polymerization reaction, it is bicyclo [2.2.1] hept-2-ene, 5-methyl bicyclo [2.2.1] hept-, for example. 2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-butylbicyclo [2.2.1] hept-2-ene, 5-hexylbicyclo [2.2.1] hept-2- Bicyclo [2.2.1] hept-2-ene derivatives (norbornenes) such as N, 5-decylbicyclo [2.2.1] hept-2-ene; Tetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] -dodeca-3-ene, 8-methyltetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] -dodeca-3 -ene, 8-ethyl tetracyclo [4.4.1 ^2,5, 1 ^7,10 .0] - dodeca-3-ene, such as the tetracyclo [4.4.1 ^2,5, 1 ^7,10 .0] - Dodeca-3-ene derivatives (tetracyclododecenes); Tricyclo [4.3.1 ^2,5.0 ] -deca-3-ene; Bicyclo [2.2.1] hept-2- which has cyclic substituent, such as 5-cyclohexyl bicyclo [2.2.1] hept-2-ene and 5-cyclopentyl bicyclo [2.2.1] hept-2-ene Ene derivatives; and the like.

(b) Specific examples of the monomer having an unsaturated bond in addition to the carbon-carbon unsaturated bonds involved in the polymerization reaction include, for example, 5-ethylidenebicyclo [2.2.1] hept-2-ene and 5-vinylbicyclo [2.2.1 Bicyclo [2.2.1] hept-2-ene derivatives having an unsaturated bond in addition to rings such as] hept-2-ene and 5-propenylbicyclo [2.2.1] hept-2-ene; 8-methylidenetetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] -dodeca-3-ene, 8-ethylidenetetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] -Dodeca-3-ene, 8-vinyltetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] -dodeca-3-ene, 8-propenyltetracyclo [4.4.1 ^2,5 . 1 .0 ^7,10] - dodeca-3-en tetracyclo having an unsaturated bond in addition to the ring, such as [4.4.1 ^2,5 .1 ^7,10 .0] - dodeca-3-ene derivative; Tricyclo [4.3.1 ^2,5 .0] -deca-3,7-diene; Bicyclo [2.2.1 having a cyclic substituent having an unsaturated bond such as 5-cyclohexenylbicyclo [2.2.1] hept-2-ene and 5-cyclopentenylbicyclo [2.2.1] hept-2-ene ] Hept-2-ene derivative etc. are mentioned.

(c) Specific examples of the monomer having an aromatic ring, such as 5-phenyl-bicyclo [2.2.1] hept-2-ene, tetracyclo [6.5.1 ^2,5 .0 ^1,6 .0 ^8,13] Tree Deca-3,8,10,12-tetraene (also known as 1,4-methano-1,4,4a, 9a-tetrahydrofluorene), tetracyclo [6.6.1 ^2,5 .0 ^1,6 .0 ^8,13 ] tetradeca-3,8,10,12-tetraene (also called 1,4-methano-1,4,4a, 5,10,10a-hexahydroantracene), and the like. .

(d) As a specific example of the monomer which has a polar group (functional group), it is 5-methoxycarbonyl bicyclo [2.2.1] hept-2-ene, 5-ethoxycarbonyl bicyclo [2.2.1] hept-2, for example. -Ene, 5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-ethoxycarbonylbicyclo [2.2.1] hept-2-ene, ratio Cyclo [2.2.1] hept-5-enyl-2-methylpropionate, bicyclo [2.2.1] hept-5-enyl-2-methyloctanate, bicyclo [2.2.1] hept-2-ene -5,6-dicarboxylic acid anhydride, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2- A substituent containing an oxygen atom such as N, 5-hydroxy-i-propylbicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene Bicyclo [2.2.1] hept-2-ene derivative having; 8-methoxycarbonyltetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] -dodeca-3-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] -dodeca-3-ene, 8-hydroxymethyltetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] -dodeca-3-ene, 8-carboxytetra Tetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] having a substituent containing an oxygen atom such as cyclo [4.4.1 ^2,5 .1 ^7,10 .0] -dodeca-3-ene Dodeca-3-ene derivatives; Bicyclo which has a substituent containing nitrogen atoms, such as 5-cyanobicyclo [2.2.1] hept-2-ene and bicyclo [2.2.1] hept-2-ene-5, 6- dicarboxylic acid imide [2.2.1] hept-2-ene derivatives; and the like.

And the alicyclic monomer which has a norbornene ring which has a C4 or more alkyl substituent group in common to the alicyclic monomer which has all said norbornene rings is further mentioned.

(2) monocyclic cyclic olefin monomer

Monocyclic cyclic olefin monomers are cyclic compounds having one carbon-carbon double bond in the ring. Specific examples thereof include cyclobutene, cyclopentene, cyclohexene, cycloheptene and cyclooctene (Japanese Patent Laid-Open No. 64-66216). These monocyclic cyclic olefin monomers can be used individually or in combination of 2 or more types, respectively.

(3) Cyclic conjugated diene monomer

The cyclic conjugated diene monomer is a cyclic compound having a conjugated carbon-carbon double bond in a ring. Specific examples thereof include 1,3-dicyclopentadiene, 1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadiene and the like (Japanese Patent Laid-Open No. 7-258318). ). These cyclic conjugated diene type monomers can also be used individually or in combination of 2 or more types, respectively.

As an unsaturated monomer copolymerizable with a cyclic olefin type monomer, (alpha) -olefin which consists of C2-C12, such as ethylene, propylene, 1-butene, 4-methyl-1- pentene; Styrenes such as styrene, α-methylstyrene, p-methylstyrene, and 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 are mentioned. As such an unsaturated monomer, if copolymerization with a cyclic olefin monomer is possible, it will not specifically limit to what was mentioned above. When carrying out the addition copolymerization of the alicyclic monomer which has a norbornene ring, and other unsaturated monomer, as other unsaturated monomer, vinyl compounds, such as said alpha-olefin, are preferable, and ethylene is especially preferable.

[Polar group-containing cyclic olefin polymer]

Cyclic olefin polymers are intended to improve adhesion to metals, impart photosensitivity, impart variety to curing methods, increase crosslinking densities, improve compatibility with other compounding agents, resins, or improve heat resistance. It is preferable that the polar group (functional group) is contained.

The polar group of the polar group-containing cyclic olefin polymer used in the present invention is particularly a polar group having a function of improving adhesion to metals (semiconductor chips, metal lead frames, wires, metal wirings, etc.) or having a curing point during the curing reaction. It does not limit, For example, 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, a sulfone group, etc. are mentioned. Among these polar groups, ① it is possible to improve the crosslinking density and adhesiveness with a small modification rate, ② wide selection of curing agent, ③ easy to control the curing rate, and the like. Polar groups containing an oxygen atom capable of reacting, such as an epoxy group, an acid anhydride group, a carboxyl group, a hydroxyl group, and the like are preferable, and in particular, a polar group such as an epoxy group, an acid anhydride which generates terminal-OH groups such as a hydroxyl group or a carboxyl group after curing Group and the like are preferable.

The polar group-containing cyclic olefin polymer can be obtained by introducing a polar group into the cyclic olefin polymer, for example, by the following three kinds of methods.

(1) a method in which a polar group-containing unsaturated compound is added to a cyclic olefin polymer by a graft reaction,

(2) introducing a polar group directly to a carbon-carbon unsaturated bond in a cyclic olefin polymer,

(3) A method of copolymerizing a cyclic olefin monomer containing a polar group in a cyclic olefin polymer.

Hereinafter, the introduction method of each polar group is demonstrated in detail.

(1) Graft Reaction of Polar Group-Containing Unsaturated Compound

The polar group-containing cyclic olefin polymer can be obtained by reacting a cyclic olefin polymer with a polar group-containing unsaturated compound in the presence of an organic peroxide. Although it does not specifically limit as a polar group containing unsaturated compound, Since adhesiveness can be provided in small quantity and adhesiveness improves, an epoxy group containing unsaturated compound, a carboxyl group containing unsaturated compound, a hydroxyl group containing unsaturated compound, a silyl group containing unsaturated compound, etc. are preferable. .

As an epoxy-group-containing unsaturated compound, For example, glycidyl esters of unsaturated carboxylic acids, such as glycidyl acrylate, glycidyl methacrylate, and p-styryl carboxylic acid glycidyl; Endo-cis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid, endo-cis-bicyclo [2.2.1] hept-5-ene-2-methyl-2,3 Monoglycidyl esters or polyglycidyl esters of unsaturated polycarboxylic acids such as dicarboxylic acid; Unsaturated glycidyls 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 Ethers; 2- (o-vinylphenyl) ethylene oxide, 2- (p-vinylphenyl) ethylene oxide, 2- (o-allylphenyl) ethylene oxide, 2- (p-allylphenyl) ethylene oxide, 2- (o-vinylphenyl) propylene oxide, 2- (p-vinylphenyl) propylene oxide, 2- (o-allylphenyl) propylene oxide, 2- (p-allylphenyl) propylene oxide, p-glycid Dylstyrene, 3,4-Epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methyl-1-pentene And 5,6-epoxy-1-hexene, vinylcyclohexene monooxide, allyl-2,3-epoxycyclopentyl ether and the like. Among them, allylglycidyl esters and allylglycidyl ethers are preferable, and allylglycidyl ethers are particularly preferable in that graft addition of the epoxy group-containing unsaturated compound can be performed at a high reaction rate. These epoxy group containing unsaturated compounds can be used individually or in combination of 2 or more types, respectively.

As a carboxyl group-containing unsaturated compound, the compound of Unexamined-Japanese-Patent No. 5-271356, etc. are mentioned, For example, Unsaturated carboxylic acid, such as acrylic acid, methacrylic acid, (alpha)-ethylacrylic acid; Maleic acid, fumaric acid, itaconic acid, endocys-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid, methyl-endocys-bicyclo [2.2.1] hept-5-ene Unsaturated dicarboxylic acid, such as -2, 3- dicarboxylic acid, etc. are mentioned. The carboxyl group-containing unsaturated compound also includes an unsaturated carboxylic acid derivative. Examples of the unsaturated carboxylic acid derivatives include acid anhydrides, esters, acid halides, amides, imides, and the like of unsaturated carboxylic acids, and specific examples thereof include maleic anhydride, chloromaleic anhydride, butenyl anhydride and hydroxy acid. Acid anhydrides such as phthalic anhydride and citraconic anhydride; Esters such as monomethyl maleate, dimethyl maleate and glycidyl maleate; Maleyl chloride, maleimide, etc. are mentioned. Among these, unsaturated dicarboxylic acid or its acid anhydride is preferable for the said reason, and acid anhydrides, such as maleic anhydride and itaconic acid, are especially preferable.

Examples of the hydroxyl group-containing unsaturated compound include allyl alcohol, 2-allyl-6-methoxyphenol, 4-allyloxy-2-hydroxybenzophenone, 3-allyloxy-1,2-propanediol, and 2-allyldi. Phenol, 3-butene-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-cyclopentene, 2-trimethylsilyloxyethyl methacrylate, 2-trimethylsilyloxyfuran, 2-trimethylsilyloxypropene, allyloxy-t-butyldimethylsilane, allyloxy Trimethylsilane, etc. are mentioned.

As an organic peroxide, organic peroxide, organic perester, etc. are used preferably, for example. Specific examples of such organic peroxides include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxide benzoate) hexyne-3, 1,4-bis (tert-butylperoxyisopropyl) benzene, lauroylperoxide, tert-butylperacetate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butylperbenzoate, tert-butylperphenyl acetate, tert-butylperisobutylate, tert-butylper-sec-octo And tert-butylperpipalate, cumyl perpipalate and tert-butylperdiethyl acetate.

And in this invention, an azo compound can also be used as an organic peroxide. Specific examples of the azo compound include azobisisobutylonitrile and dimethyl azoisobutyrate.

Among these, as the organic peroxide, benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxide) hexine-3,2,5-dimethyl- Dialkyl peroxides such as 2,5-di (tert-butylperoxy) hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferably used.

These organic peroxides can be used individually or in combination of 2 or more types, respectively. The use ratio of the organic peroxide is usually 0.001 to 30 parts by weight, preferably 0.01 to 20 parts by weight, and more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the unmodified cyclic olefin polymer in the content ratio during the reaction. . When the usage-amount of an organic peroxide exists in this range, the physical property, such as the reaction rate of a polar group containing unsaturated compound, the water absorption of the obtained polar group containing polymer, and a dielectric property, is highly balanced and is preferable.

The graft modification reaction is not particularly limited and can be carried out according to a conventional method. Reaction temperature is 0-400 degreeC normally, Preferably it is 60-350 degreeC. The reaction time is usually in the range of 1 minute to 24 hours, preferably 30 minutes to 10 hours. After completion of the reaction, a poor solvent such as methanol (solvent to lower the solubility) is added in a large amount to the reaction system to precipitate the polymer, filtered off and washed, followed by drying under reduced pressure.

(2) Direct modification of carbon-carbon unsaturated bonds

The polar group-containing cyclic olefin polymer may introduce a polar group by modifying an olefinic carbon-carbon unsaturated bond in the cyclic olefin polymer to add a polar group, or by bonding a compound having a polar group to the olefinic carbon-carbon unsaturated bond. .

As for the method of introducing the polar group, a method as described in JP-A-6-172423 can be used. Specifically, an epoxy group, a carboxyl group, a hydroxyl group, or the like may be prepared by a method of oxidizing an olefinic unsaturated bond, a method of addition reaction of a compound containing at least one polar group in a molecule to an olefinic unsaturated bond, and other methods. A method of introducing is mentioned.

(3) Copolymerization of Polar Group-containing Cyclic Olefin Monomer

Although there is no restriction | limiting in particular as a polar group containing cyclic olefin monomer, The monomer which has a polar group of (d) in description of the weight mentioned above is mentioned. Among them, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-i-propylenecyclo [2.2.1] hept-2-ene, and 5-methoxycarbo which are easy to copolymerize. Nylbicyclo [2.2.1] hept-2-ene, 8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 .]-Dodeca-3-ene, 5,6-dicarboxy ratio The monomer containing a hydroxyl group, a carboxyl group, or ester group, such as cyclo [2.2.1] hept-2-ene, is preferable. As the polymerization catalyst and the polymerization method, a polymerization catalyst and a polymerization method of an alicyclic monomer having a norbornene ring can be used.

Among the above, as a method of introducing an acidic group, a graft modification method is preferable for the reason that the modification can be carried out under easy reaction conditions and the polar group is easily introduced at a high modification rate. As the kind of, an unsaturated compound having a dicarboxylic acid anhydride group having a carbon-carbon unsaturated bond in a molecule such as an epoxy group, maleic anhydride and itaconic anhydride is particularly preferable.

(4) Polar group introduction rate

The polar group introduction ratio (modification rate) of the polar group-containing cyclic olefin polymer is appropriately selected depending on the purpose of use, and is usually 0.1 to 100 mol%, preferably 0.5 to 70 mol%, based on the total number of monomer units in the polymer, More preferably, it is the range of 1-50 mol%. In the case where the use is an encapsulant, the higher the physical property and the higher the modification rate, the more preferably 5 to 100 mol%, more preferably 10 to 70 mol%, and most preferably 15 to 50 mol%. to be. When the polar group introduction ratio of the polar group-containing cyclic olefin polymer is within this range, the adhesion strength, heat resistance, mechanical strength, water absorption, and dielectric properties with the metal are highly balanced.

The polar group introduction ratio (modification rate: mol%) is represented by the following formula (1).

Polar group introduction rate = (X / Y) × 100 (1)

[X: total moles of (a) graft monomer-modified residues or (b) total moles of unsaturated bond-containing monomers x rate of polar group addition to unsaturated bonds or (c) total moles of polar group-containing monomers. (All measured by ¹ H-NMR)

Y: total number of monomer units of polymer (weight average molecular weight of polymer / average molecular weight of monomer)]

Curable Resin Composition

The cyclic olefin polymer used in the present invention is used as a curable cyclic olefin polymer composition (curable resin composition) by adding a curing agent. By making the cyclic olefin polymer a curable type, for example, (1) the difference in the coefficient of linear expansion between the metal and the resin (sealing resin, protective resin film) is reduced, and (2) sufficient heat resistance is shown at the time of mounting the electronic component and reliability test. This can be obtained. Although a hardening | curing agent does not have limitation in particular, (i) an organic peroxide, (ii) the hardening agent which exhibits an effect by heat, (i) the hardening agent which exhibits an effect by light, etc. are used.

There is no restriction | limiting in particular in the hardening means of curable resin composition, For example, it can carry out using heat, light, a radiation, etc., and the kind of hardening | curing agent is suitably selected according to these means. A curing aid, a flame retardant, other compounding agents, etc. can be mix | blended with curable resin composition as needed other than a hardening | curing agent.

Hardener

(1) organic peroxides

As an organic peroxide, For example, ketone peroxides, such as methyl ethyl ketone peroxide and cyclohexanone peroxide; Peroxy ketals such as 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane and 2,2-bis (t-butylperoxy) butane; hydroperoxides such as t-butylhydroperoxide and 2,5-dimethylhexane-2,5-dihydroperoxide; Dialkyls such as dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, α, α'-bis (t-butylperoxy-m-isopropyl) benzene Peroxides; Diacyl peroxides such as octanoyl peroxide and isobutyryl peroxide; Peroxy esters, such as a peroxydicarbonate, are mentioned. Among these, dialkyl peroxide is preferable in the performance of resin after hardening, and the kind of alkyl group can be changed with hardening temperature (molding temperature).

Although the compounding quantity of an organic peroxide does not have a restriction | limiting in particular, Usually, 0.1-30 weight part is preferable with respect to 100 weight part of cyclic olefin type polymers from the point of improving the physical property of the hardened | cured material obtained by carrying out a crosslinking reaction efficiently, and also from an economical viewpoint. Preferably it is used in the range of 1-20 weight part. If the amount is too small, crosslinking is unlikely to occur and sufficient heat resistance and solvent cannot be obtained. If the amount is too high, the water absorbency and dielectric properties of the crosslinked resin are lowered, which is not preferable. When the compounding quantity of an organic peroxide exists in the said range, these characteristics are highly balanced and it is preferable.

(2) Curing agent which exerts effect by heat

The curing agent which exerts the effect by heat is not particularly limited as long as it is a curing agent that can be crosslinked by heating, but is not limited to aliphatic polyamines, alicyclic polyamines, aromatic polyamine bisazides, acid anhydrides, dicarboxylic acids, polyhydric phenols, and polyamides. Can be mentioned.

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, mensendiamine, isophoronediamine N-aminoethylpiperazine, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) methane Alicyclic polyamines; 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, α-α'-bis (4-aminophenyl) -1,3-diisopropylbenzene, α, α'-bis Aromatic polyamines such as (4-aminophenyl) -1,4-diisopropylbenzene, 4,4'-diaminodiphenyl sulfone and metaphenylenediamine; 4,4-bisazidebenzal (4-methyl) cyclohexanone, 4,4'-diazidecalcon, 2,6-bis (4'-azidebenzal) cyclohexanone, 2,6-bis (4 Bis such as' -azidebenzal) -4-methyl-cyclohexanone, 4,4'-diazidediphenylsulfone, 4,4'-diazidediphenylmethane, 2,2'-diazidestilbene Jide; Acid anhydrides such as fumaric anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, nazix anhydride, 1,2-cyclohexanedicarboxylic acid, maleic anhydride modified polypropylene, maleic anhydride modified cyclic olefin resin logistics; Dicarboxylic acids such as fumaric acid, phthalic acid, maleic acid, trimellitic acid, and high mymic acid; Polyhydric phenols such as phenol novolak resin and cresol novolak resin; Nylon-6, nylon-66, nylon-610, nylon-11, nylon-612, nylon-12, nylon-46, methoxymethylated polyamide, polyhexamethylenediamine terephthalamide, polyhexamethylene isophthalamide, etc. Polyamides; and the like.

You may use these hardening | curing agents by 1 type or in mixture of 2 or more types. Among these, aromatic polyamines, acid anhydrides, polyhydric phenols, and polyhydric alcohols are preferable because of excellent heat resistance, mechanical strength, adhesion to metals, and excellent dielectric properties (low dielectric constant, low dielectric loss tangent). 4,4'- diamino diphenylmethane (aromatic polyamines), maleic anhydride modified cyclic olefin resin (acid anhydride), polyhydric phenols, etc. are especially preferable. If necessary, a curing accelerator may be added to increase the efficiency of the crosslinking reaction.

Although the compounding quantity of a hardening | curing agent does not have a restriction | limiting in particular, Usually, 0.1-30 weight part is preferable with respect to 100 weight part of cyclic olefin type polymers from the point of improving the physical property of the hardened | cured material obtained by carrying out a crosslinking reaction efficiently, and also from an economical viewpoint. Is used in the range of 1 to 20 parts by weight. If the amount of the curing agent is too small, crosslinking is unlikely to occur, so that sufficient heat resistance and solvent cannot be obtained. If the amount of the curing agent is too high, properties such as water absorption and dielectric properties of the crosslinked resin are lowered, which is not preferable. When the compounding quantity of a hardening | curing agent exists in the said range, these characteristics are highly balanced and it is preferable.

Examples of the curing accelerator include amines such as pyridine, benzyldimethylamine, trimethanolamine, triethylamine, and imidazole. A curing accelerator is added for the purpose of adjusting the curing rate or improving the efficiency of the crosslinking reaction. Although the compounding quantity of a hardening accelerator does not have a restriction | limiting in particular, Usually, it is 0.1-30 weight part with respect to 100 weight part of cyclic olefin polymers, Preferably it is used in the range of 1-20 weight part. When the compounding quantity of a hardening accelerator exists in this range, a crosslinking density, dielectric property, water absorption rate, etc. are highly balanced, and it is preferable. Among these, imidazoles are preferred because of their excellent dielectric properties.

(3) Curing agent which exerts effect by light

A curing agent that exerts an effect by light is photoreactive to react with cyclic olefin polymers to produce crosslinked compounds by irradiation with actinic rays such as ultraviolet rays such as g rays, h rays, and i rays, far ultraviolet rays, x rays, and electron rays. The substance is not particularly limited, and examples thereof include aromatic bisazide compounds, photoamine generators, and photoacid generators.

Specific examples of the aromatic bisazide compound include 4,4'-diazidechalcone, 2,6-bis (4'-azidebenzal) cyclohexanone, and 2,6-bis (4'-azidebenzal) 4-methyl Cyclohexanone, 4,4'-diazidediphenylsulfone, 4,4'-diazidebenzophenone, 4,4'-diazidediphenyl, 2,7-diazidefluorene, 4,4'-dia Zide phenylmethane etc. are mentioned. These can also be used 1 type or in combination of 2 or more types.

Specific examples of the photoamine generator include o-nitrobenzyloxycarbonylcarbamate, 2,6-dinitrobenzyloxycarbonylcarbamate or α, α-dimethyl-3,5-dimethoxybenzyl of aromatic amines or aliphatic amines. Oxycarbonyl carbamate and the like. More specifically, aniline, cyclohexylamine, piperidine, hexamethylenediamine, triethylenetetraamine, 1,3- (diaminomethyl) cyclohexane, 4,4'-diaminodiphenyl ether, 4,4 ' O-nitrobenzyloxycarbonylcarbamate bodies, such as -diaminodiphenylmethane and phenylenediamine, are mentioned. These can also be used 1 type or in combination of 2 or more types.

Photoacid generators are substances which generate norensedic acid or Lewis acid by irradiation with actinic light, for example, onium salts, halogenated organic compounds, quinonediazide compounds, α, α-bis (sulfonyl) diazomethanes The compound, the (alpha)-carbonyl (alpha)-sulfonyl- diazomethane type compound, a sulfone compound, an organic acid ester compound, an organic acid amide compound, an organic acid imide compound, etc. are mentioned. The compound which can dissociate by irradiation of these actinic rays and can generate an acid may be used individually or in mixture of 2 or more types.

Although the compounding quantity of a photoreactive compound does not have a restriction | limiting in particular, Usually 0.1-100 weight part with respect to the point which does not impair the physical property of the crosslinked resin obtained by carrying out reaction with the said polymer efficiently, and also economical efficiency etc. with respect to 100 weight part of cyclic olefin type polymers. It is used in 30 weight part, Preferably it is 1-20 weight part. If the amount of the photoreactive substance is too small, crosslinking is unlikely to occur, so that sufficient heat resistance and solvent cannot be obtained. If the amount of the photoreactive substance is too high, properties such as water absorption and dielectric properties of the crosslinked resin are deteriorated. When the compounding quantity is in the said range, these characteristics are highly balanced and it is preferable.

Hardening aid

In the present invention, a curing aid may be used in order to further increase the curability and dispersibility of the compounding agent.

Although it does not specifically limit as a hardening adjuvant, Well-known thing disclosed in Unexamined-Japanese-Patent No. 62-34924 etc. may be used, For example, oxime nitroso type hardening aids, such as quinone dioxime, benzoquinone dioxime, p-nitrosophenol, etc. ; Maleimide curing aids such as N, N-m-phenylenebismaleimide; Allyl curing aids such as diallyl phthalite, triallyl cyanurate and triallyl isocyanurate; Methacrylate-based curing aids such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; Vinyl curing aids such as vinyltoluene, ethylvinylbenzene and divinylbenzene; and the like. Among them, allyl curing aids and methacrylate curing aids are preferred because they are easy to disperse uniformly.

Although the compounding quantity of a hardening | curing agent is suitably selected according to the kind of hardening | curing agent, it is 0.1-10 weight part normally with respect to 1 weight part of hardening | curing agents, Preferably it is 0.2-5 weight part. If the amount of the curing aid is too small, curing hardly occurs. On the contrary, if the amount of the curing aid is too high, the electrical properties, moisture resistance, and the like of the cured resin may be lowered.

[Formulations]

Various compounding agents can be added to curable resin composition of this invention as needed.

Filler

The curable resin composition of this invention may mix | blend an inorganic or organic filler especially for the purpose of reducing a linear expansion coefficient. In particular, when using curable resin composition as a sealing material, it is often preferable to mix a filler. The filler is not particularly limited as long as it is conventionally used in a resin encapsulating material.

As the filler, for example, silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, basic magnesium carbonate, doromite, calcium sulfate, potassium titanate, valerium sulfate, calcium sulfite, talc, clay, mica, asbestos, Glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, glass fiber, boron fiber, silicon carbide fiber, polyethylene fiber, polypropylene fiber, polyester fiber, polyamide fiber and other powders , Flakes and fibrous fillers. Among these fillers, inorganic fillers are preferred, and silica and the like are particularly preferred because of their excellent heat resistance, low water absorption, dielectric properties, low impurity properties, and the like. It is preferable that these fillers are non-conductive, and it is preferable that they are excellent in thermal conductivity.

The blending amount of the filler can be appropriately determined according to the purpose of use, and is usually used in an amount of 1,000 parts by weight or less, preferably 0.1 to 1,000 parts by weight, and more preferably 5 to 800 parts by weight with respect to 100 parts by weight of the cyclic olefin polymer. . In the case where the curable resin composition is used as the encapsulant and the linear expansion coefficient needs to be particularly small, it is preferably 50 to 1,000 parts by weight, more preferably 100 to 800 parts by weight, based on 100 parts by weight of the cyclic olefin polymer, Most preferably, it is used in the ratio of 200-600 weight part.

In the sealing material of the present invention, the coefficient of linear expansion between the substrate, the electronic component, and the encapsulating portion can be reduced by adjusting the type and the amount of the filler.

Reactive diluent

Curable resin composition of this invention can mix | blend a low molecular weight reactive diluent for the purpose of adjusting a viscosity. Although the above-mentioned hardening | curing agent has a function as a reactive diluent, as another reactive diluent, the compound which causes a crosslinking reaction by conventional heat or light, and can use a liquid at normal temperature can be used. More specifically, an epoxy group containing compound, an acryl (methacrylic) acid ester type compound, a vinyl ether type compound, a vinyl compound, etc. are mentioned, for example. Among these other reactive diluents, epoxy group-containing compounds are particularly preferable for reasons of excellent heat resistance, low water absorption and dielectric properties.

Flame retardant

The flame retardant is not an essential component, but is preferably added when encapsulating an LSI chip such as a CPU or a DRAM or forming a protective film. Although there is no restriction | limiting in particular as a flame retardant, It is preferable that it does not decompose | disassemble, modify | denature, or deteriorate with a hardening | curing agent, A halogen type flame retardant is used normally.

As the halogen flame retardant, various flame retardants such as chlorine and bromine can be used. In terms of flame retardant effect, heat resistance during molding, dispersibility into resin, and influence on resin physical properties, hexabromobenzene and pentabromo Ethylbenzene, hexabromobiphenyl, decabromodiphenyl, hexabromodiphenyloxide, octabromodiphenyloxide, decabromodiphenyloxide, pentabromocyclohexane, tetrabromobisphenol A and derivatives thereof [e.g. tetrabromo Mobisphenol A-bis (hydroxyethyl ether), tetrabromobisphenol A-bis (2,3-dibromopropyl ether), tetrabromobisphenol A-bis (bromoethyl ether), tetrabromobisphenol A -Bis (allyl ether) and the like], tetrabromobisphenol S and its derivatives [for example, tetrabromobisphenol S-bis (hydroxyethyl ether), tetrabromobisphenol S-bis (2,3-dibro Mopropyl ether) and the like], tetrabromo phthalic anhydride and derivatives thereof [e.g., tetrabromophthalimide, ethylene bistetrabromophthalimide and the like], ethylenebis (5,6-dibromonorbornene- 2,3-dicarboxyimide), tris- (2,3-dibromopropyl-1) -isocyanurate, additive of Diels-Alder reaction of hexachlorocyclopentadiene, tribromophenyl glycidyl ether , Tribromophenyl acrylate, ethylene bistribromophenyl ether, ethylenebispentabromophenyl ether, tetradecabromodiphenoxybenzene, brominated polystyrene, brominated polyphenylene oxide, brominated epoxy resin, brominated polycarbonate, poly It is preferable to use pentabromobenzyl acrylate, octabromonaphthalene, hexabromocyclododecane, bis (tribromophenyl) fumaramide, N-methylhexabromodiphenylamine, and the like.

The addition amount of a flame retardant is 3-150 weight part normally with respect to 100 weight part of cyclic olefin polymers, Preferably it is 10-140 weight part, Especially preferably, it is 15-120 weight part.

As a flame retardant aid for exhibiting the flame retardant effect of a flame retardant more effectively, antimony flame retardant aids, such as antimony trioxide, antimony pentoxide, sodium antimonate, antimony trichloride, can be used, for example. These flame retardant aids are usually used in an amount of 1 to 30 parts by weight, preferably 2 to 20 parts by weight, relative to 100 parts by weight of the flame retardant.

The protective material of this invention can pass the combustion test in this technical field by adjusting the kind and compounding quantity of these flame retardants.

Curable resin

In this invention, the viscosity at the time of heat-melting processing, for example, mix | blending curable resin, such as an epoxy resin conventionally used for the purpose of the improvement of the viscosity characteristic at the time of heat-melting of a curable resin composition, can be controlled.

As a specific example of curable resin, conventionally well-known curable resins, such as a thermosetting epoxy resin, the photosensitive epoxy resin, polyimide resin, the photosensitive polyimide resin, bismaleimide triazine resin, a phenol resin, a phenol novolak resin, are mix | blended, for example. Can be.

Other polymer ingredients

In this invention, a rubbery polymer and other thermoplastic resin can be mix | blended with curable resin composition as needed.

The rubbery polymer is a polymer having a glass transition temperature of room temperature (25 ° C.) or less, and contains a conventional rubbery polymer and a thermoplastic elastomer. The Mooney viscosity (ML _{1 + 4} , 100 degreeC) of a rubbery polymer is suitably selected according to a use purpose, and is 5-200 normally.

As a rubbery polymer, For example, Ethylene-alpha-olefin type rubbery polymer; Ethylene-α-olefin-polyene copolymer rubbers; Copolymers of ethylene and unsaturated carboxylic acid esters such as ethylene-methyl methacrylate and ethylene-butyl acrylate; Copolymers of ethylene and fatty acid vinyl such as ethylene-vinyl acetate; Polymers of alkyl acrylates such as ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate and lauryl acrylate; Random copolymers of polybutadiene, polysoble, styrene-butadiene or styrene-isoprene, acrylonitrile-butadiene copolymer, butadiene-isoprene copolymer, butadiene- (meth) acrylic acid alkyl ester copolymer, butadiene- (meth) acrylic acid Diene rubbers such as alkyl ester-acrylonitrile copolymers and butadiene- (meth) acrylic acid alkyl ester-acrylonitrile-styrene copolymers; Butylene-isoprene copolymer etc. are mentioned.

Examples of the thermoplastic elastomers include aromatic vinyl-conjugated diene-based block copolymers such as styrene-butadiene block copolymers, styrene-butadiene block copolymers, styrene-isoprene block copolymers and styrene-isoprene block copolymers, and low crystals. Polybutadiene resin, ethylene-propylene elastomer, styrene graft ethylene-propylene elastomer, thermoplastic polyester elastomer, ethylene ionomer resin and the like. Among these thermoplastic elastomers, hydrogenated styrene-butadiene block copolymers, hydrogenated styrene-isoprene block copolymers, and the like are preferred, and more specifically, Japanese Patent Laid-Open Nos. 2-133406, 2-2305814, and What is described in Unexamined-Japanese-Patent No. 3-72512, Unexamined-Japanese-Patent No. 3-74409, etc. are mentioned.

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, poly Amide, polyester, polycarbonate, cellulose triacetate, etc. are mentioned.

These rubbery polymers and other thermoplastic resins may be used alone or in combination of two or more thereof, and the compounding amount thereof is appropriately selected within a range that does not impair the object of the present invention. It is preferable that it is 30 weight part or less with respect to 100 weight part of olefinic polymers.

Other compounding agents

In the curable resin composition of the present invention, other compounding agents such as heat stabilizers, weather stabilizers, leveling agents, antistatic agents, slip agents, anti blocking agents, antifog agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes, etc. An appropriate amount can be added.

Specifically, for example, tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, β- (3,5-di-t-butyl-4-hydrate Phenolic antioxidants such as hydroxyphenyl) propionic acid alkyl ester and 2,2'-oxamide bis [ethyl-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate]; Phosphorus stabilizers such as trisnonylphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite and tris (2,4-di-t-butylphenyl) phosphite; Fatty acid metal salts such as zinc stearate, calcium stearate and calcium 12-hydroxystearate; Polyhydric alcohol fatty acid esters such as glycerin monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate; Synthetic hydrotalcite; Amine antistatic agents; Leveling agents for paints such as fluorine-based nonionic surfactants, special acrylic resin leveling agents, and silicone leveling agents; Coupling agents such as a silane coupling agent, a titanate coupling agent, an aluminum coupling agent and a zirco aluminate coupling agent; Plasticizers; Pigments, such as carbon black, and coloring agents, such as dye, etc. are mentioned.

[Bag material]

Form of encapsulation material

The encapsulation material of the present invention is provided in a state in which a cyclic olefin polymer, a curing agent, and other compounding agents blended as desired are diluted with a reactive diluent, and without a diluent. You may melt | dissolve in.

When using a solvent, For example, aromatic hydrocarbons, such as toluene, xylene, ethylbenzene; alicyclic hydrocarbons such as aliphatic hydrocarbons such as n-pentane, hexane and heptane, and cyclohexane; Halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, and trichlorbenzene, etc. are mentioned.

The solvent is used in an amount sufficient to uniformly dissolve or disperse the cyclic olefin polymer, the curing agent and each component to be blended as necessary. The solid content concentration of the solution is usually adjusted to 1 to 80% by weight, preferably 5 to 60% by weight, more preferably 10 to 50% by weight.

As a sealing material, it is preferable that it is 50 poise or less and also 20 poise or less in the range of 100-200 degreeC especially in handling, process advantages, etc.

Curing method

The encapsulation material used in the present invention may be cured by any method of heat, light, electron beam, and the like as described above. Particularly, when encapsulating an electronic component such as a semiconductor component, the encapsulating material is encapsulated in a thin film such as an overcoat method. Except in the case, it is preferable to cure by heat. In the case of hardening by heat, when the sealing material is a thick molded article, when the light ray has a complicated shape which a part cannot reach, it is preferable when it contains the compounding agent which light rays, such as a filler and an additive, do not transmit.

Encapsulation method

The electronic component encapsulation material used in the present invention is a transfer method which is usually used in the case of using a method mainly used for encapsulating electronic components such as a semiconductor chip, such as (1) a conventional cresol novolak type epoxy resin encapsulant. The sealing method by the shaping | molding method, and (2) the sealing method by the potting (moulding) method normally used in the case of using liquid epoxy resin as a sealing method of the recent LSI bare chip mounting can be applied as it is.

The application method to each encapsulation method will be described below. For details of the encapsulation method, see, for example, "Hybrid Microelectronics Association: Basics of Electronics Manufacturing Technology, Vol. 4, Assembly Assembly Technology, Chapter 5: Semiconductors". The well-known literatures, such as the sealing technique and material of a device, pages 157-186, etc. can be referred to.

(1) Transfer molding method

A typical method of the transfer molding method is a low pressure transfer molding method, which is conventionally encapsulated using a sealing material of a cresol novolac epoxy resin main body. The process is briefly described below.

First, the semiconductor chip is connected to a central portion of the metal lead frame with a gold wire (wire) or the like and mounted on a preheated mold. The encapsulating resin is prepared in a tablet (solid) state, softened to an appropriate temperature, filled into a mold port, completely liquefied by heating, and injected into the cavity by plunger pressure. In this state, the resin is completely cured under pressure. When the mold cavity is injected, the tablet preheating temperature, mold mold temperature, transfer time, transfer pressure, curing time, etc. need to be optimized in order to obtain void-free molded parts without damaging the gold wire. The viscosity range described above is important because the viscosity of the material is an important condition.

(2) Potting method

The semiconductor package encapsulated by transfer molding as described above is generally called a quad flat package (QFP), and is mounted on a printed circuit board by soldering. In recent years, techniques for directly mounting a printed circuit board (bare chip mounting) before encapsulating a semiconductor chip have been advanced. In order to finally encapsulate these bare chip-mounted semiconductor chips, conventionally, a liquid epoxy encapsulating material mainly composed of the above-described bisphenol-type epoxy resin is used. However, according to the mounting type of the bare chip, conventional potting method, overcoat method, It is classified into the underfill method.

Particularly, in the case of the bare chip mounting method, when the chip electrode and the substrate electrode are connected by gold wires (wires), a method of covering the chip and gold wires with an encapsulant such as a potting method and an overcoat method is applied, and the chip is reversed from the front and rear surfaces. In the case of directly connecting the electrodes (flip chip mounting method), an underfill method for filling a gap between the chip and the substrate with a sealing material is applied.

Electronic parts

Electronic components to be encapsulated in the present invention includes an active component such as an integrated circuit component, hybrid integrated circuit component, individual semiconductor component; General electronic components, such as a passive component and a functional component, etc. are mentioned.

As an integrated circuit component, semiconductor (LSI) chips, such as a CPU (central processing unit) and DRAM (memory), etc. are mentioned, for example. As the hybrid integrated circuit component, for example, a multi-chip module (MCM) in which a plurality of integrated circuit components are mounted, a hybrid IC in which an integrated circuit component and an individual semiconductor component and a general electronic component are mixed and mounted. Examples of the individual semiconductor parts include diodes, transistors, light emitting elements (laser diodes, LEDs, and the like), light receiving elements (photodiodes and the like), and optical composite elements (photocouplers and the like). As a general electronic component, For example, passive components, such as a resistor, a capacitor, and an inductor; And functional parts such as oscillators, ceramic filters, SAW filters, NTC chip thermistors, ceramic varistors, and the like.

Electronic component package

In this invention, an electronic component package can be obtained by sealing such an electronic component using the sealing material mentioned above. In particular, the thing sealed by the above-mentioned transfer molding can be used as a package as a QFP as it is. After bare chip mounting of a semiconductor chip on a small printed circuit board, the semiconductor chip is sealed with the above-mentioned liquid sealing material, and these are used as a package. Attaching a connection member such as a solder ball to the package for connection to a printed circuit board of the motherboard is called a ball grid array (BGA), and can be used as a new semiconductor component package for a computer or a communication device.

[Overcoat Material]

Type of Overcoat Material

The overcoat material of this invention is provided in the state which diluted cyclic olefin type polymer, a hardening | curing agent, and the other compounding compound mix | blended as desired with an organic solvent or a reactive diluent. As the organic solvent, various organic solvents as described above can be used. The organic solvent is used in an amount sufficient to uniformly dissolve or disperse the cyclic olefin polymer, the curing agent and each component to be blended as necessary, and the solid content concentration is usually 1 to 80% by weight, preferably 5 to 60% by weight, more Preferably it is adjusted to 10 to 50% by weight.

The method of overcoat is not specifically limited, A conventionally well-known method can be employ | adopted. Specifically, for example, a roll coating method, a curtain coating method, a screen printing method, a spin coating method, a dipping method and the like are usually used.

As an overcoat material, it is preferable to perform viscosity adjustment suitable for a coating method from a handing, a process advantage, etc. For example, in spin coat, curtain coat, etc., it is preferable to set it as the viscosity of 10 cps or more and 3000 cps or more by 25 degreeC and an E-type viscosity meter measurement. If the viscosity is too low, it is difficult to obtain a sufficient film thickness. If the viscosity is too high, it is difficult to obtain a uniform film thickness. In roll coat, bar coat, etc., it is preferable to adjust to the viscosity of 1000 cps or more and 100000 cps or less. If the viscosity is too low, it is difficult to obtain a uniform film thickness. If the viscosity is too high, workability deteriorates. In screen printing, it is preferable to give the viscosity characteristic which has thixotropy.

The thickness of the overcoat film is preferably in the range of 1 to 10 μm when used as a buffer coat film or passivation film, and 30 to 60 μm when used as a protective film. A thickness of 30 μm or more is preferable when all of these are collectively overcoated. .

Curing method

The overcoat material used in the present invention may be cured by any method such as heat, light, electron beam, or the like. When overcoat in a relatively thick film state, it is preferable to harden by heat. In the case of hardening by heat, it is suitable for the case where the electronic component to overcoat is a complicated three-dimensional shape, when it contains the compounding agent which light rays, such as a filler and an additive, cannot transmit.

Electronic parts

Examples of the electronic component to be overcoated in the present invention include active components such as integrated circuit components, hybrid integrated circuit components, and individual semiconductor components, which are the same as those described above for the encapsulation material; General electronic components, such as a passive part and a functional part, are mentioned. Moreover, the thing similar to the above is mentioned also in an electronic component package.

Hereinafter, an Example, a comparative example, and a synthesis example are given and this invention is concretely demonstrated. In these examples, "part" and "%" are based on weight unless there is particular problem.

The measuring method of various physical properties is as follows.

(1) The glass transition temperature (Tg) is measured by differential scanning calorimetry (DSC method).

(2) The number average molecular weight (Mn) and the weight average molecular weight (Mw) are measured as polystyrene conversion values by gel permeation chromatography (GPC) using toluene as a solvent unless otherwise specified.

(3) The hydrogenation rate of the main chain, the modification rate and the copolymerization ratio of the polymer are measured by ¹ H-NMR. Modification rate is computed by said formula (1).

(4) Dielectric constant and dielectric loss tangent are measured at 1 MHz according to JIS C6481.

(5) Bending strength at room temperature, tensile strength, tensile elongation, and water absorption under the conditions of 85 ° C x relative humidity (RH) 85% x 300 hours are measured according to JIS K6911.

(6) Glass transition temperature is measured by TMA.

(7) The sample was added to the pressure cooker test PCT (160 ° C. × 20 hours, 4 atmospheres) as an indicator of purity, and then the amount of chlorine and metal ions was measured by an ion chromatography meter using the extracted water, and the total amount thereof. Calculate the value of Residual Ion.

(8) The temperature cycle test (TCT) generates cracks by applying a temperature shock by repeating the temperature cycle of -55 ° C (30 min) → room temperature (5 min) → 150 ° C (30 min) → room temperature (5 min) 500 times. Investigate the presence of The pressure cooker test (PCT) is carried out in an environment of 100% humidity and 105 ° C for 300 hours to investigate the occurrence of defects.

(9) To evaluate the moisture resistance of the protective film and the like, the sample was left to stand for 1,000 hours at a temperature of 85 ° C. and a relative humidity of 85%, and then a 1 ㎸ voltage was applied between the layers to measure the defective rate.

Synthesis Example 1

Using tungsten hexachloride, triisobutylaluminum and isobutyl alcohol as a polymerization catalyst, 8-ethyl tetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] -3-dodecene ( Hereinafter, ETD) is ring-opened polymerization. The obtained ring-opened polymer was hydrogenated using a known method using nickel acetylacetonate and triisobutylaluminum to give hydrogenated ring-opened polymer hydrogenated ETD (hydrogenation rate ≥ 99%, Tg = 138 ° C, Mn = 18,500, Mw = 31,600). Get 30 parts of maleic anhydride, 10 parts of dicumyl peroxide, and 300 parts of tert-butylbenzene were mixed with respect to 100 parts of the hydrogenated substance, and the reaction solution was poured into 300 parts of methanol after reacting at 150 DEG C for 4 hours in an autoclave. Solidify. The coagulum is dried to obtain maleic anhydride modified polymer (A). The synthesis results are shown in Table 1.

Synthesis Example 2

An epoxy modified polymer (B) is obtained in the same manner as in Synthesis example 1 except that 30 parts of maleic anhydride was changed to 30 parts of allylglycidyl ether. The synthesis results are shown in Table 1.

Synthesis Example 3

Tetracyclo [4.4.1 ^2,5 , 1 ^7,10 .0] -3-dodecene (hereinafter referred to as TCD) and ethylene by addition copolymerization by addition method to add copolymer (TCD content 38 mol%, Tg = 135 ° C, Mn = 15,200, Mw = 35,600). A maleic anhydride modified polymer (C) is obtained in the same manner as in Synthesis example 1 except using this addition type copolymer. The synthesis results are shown in Table 1.

Synthesis Example 4

An epoxy modified polymer (D) was obtained in the same manner as in Synthesis Example 3 except that 30 parts of maleic anhydride was changed to 30 parts of allylglycidyl ether. The synthesis results are shown in Table 1.

Synthesis Example 5

1,3- using Li-based living anion polymerization catalyst [n-BuLi / tetramethylenediamine (TMEDA: living anion stabilizer) = 1/1 (molar ratio)] described in JP-A-7-258318 Cyclohexadiene (C-HD) is polymerized to obtain a 1,4-addition polymer. This addition polymer is then hydrogenated to obtain a hydrogenated product (hydrogenation rate> 99%, Tg = 219 占 폚, Mn = 53,400, Mw = 78,000). A maleic anhydride modified polymer (E) is obtained in the same manner as in Synthesis example 1 except that this hydrogenated substance is used. The synthesis results are shown in Table 1.

Synthesis Example 6

An epoxy modified polymer (F) was obtained in the same manner as in Synthesis Example 5 except that 30 parts of maleic anhydride was changed to 30 parts of allylglycidyl ether. The synthesis results are shown in Table 1.

Synthesis Example 7

100 parts of poly (2,6-dimethyl-1,4-phenylene ether) having a number average molecular weight (Mn) of 9,200, 6.0 parts of maleic anhydride and 2,5-dimethyl-2,5-di (t-butyl) 2.0 parts of peroxy) hexane (Nippon Yushi Co., Ltd. perhexa 25B) were dry blended at room temperature, and it extruded with a twin screw extruder on the conditions of a cylinder temperature of 300 degreeC, and a screw speed of 230 rpm, and a maleic anhydride modified polyphenylene. Ether (PPE) (G) is obtained. The synthesis results are shown in Table 1.

Synthesis Example 8

To 100 parts of the ring-opened polymer hydrogenated compound obtained in Synthesis Example 1, 1.0 part of dicumyl peroxide and 3.0 parts of vinyltrimethoxysilane were added, and the mixture was heated and kneaded at a resin temperature of 240 ° C. using a twin screw extruder to produce the silane-modified polymer (H). Get The synthesis results are shown in Table 1.

(1) ETD: ethyl tetracyclododecene ring-opening polymer (hydrogen)

(2) TCD / ethylene: tetracyclododecene / ethylene copolymer

(3) C-HD: 1,3-cyclohexadiene addition polymer (hydride)

(4) PPE: polyphenylene ether

(5) MAAH: maleic anhydride

(6) AGE: allyl glycidyl ether

(7) BTMS: vinyltrimethoxysilane

[Examples 1 to 6]

Hereinafter, the Example and comparative example regarding hardened | cured material of resin only and a semiconductor sealing material are demonstrated.

First, in order to prepare a test piece of a cured product of a resin alone, phenol novolac resin (TD-2131: Dainippon Ink & Chemicals Co., Ltd.) as a modified polymer (A) to (F) synthesized in Synthesis Examples 1 to 6 and a curing agent ( Note) The composition, the softening point of 80 ° C.), and triphenylphosphine (TPP) as a curing accelerator were mixed in the composition shown in Table 2 to prepare a curable resin composition.

These resin compositions were cured under conditions of 2 hours at 100 ° C, 2 hours at 160 ° C, and 2 hours at 180 ° C to form test pieces, and were subjected to bending strength, tensile strength, tensile elongation, and 85 ° C x 85% RH at room temperature. The water absorption under the conditions of x300 hours is measured. The glass transition temperature, residual ions and electrical characteristics are measured. These results are shown in Table 32.

Comparative Example 1

The same procedure as in Example 1 was carried out except that maleic anhydride-modified polyphenylene ether (PPE) (G) synthesized in Synthesis Example 7 was used, and the curing agent and curing accelerator were changed to Table 2. The compositions and results are shown in Tables 2 and 3.

Comparative Example 2

The silane modified polymer (H) synthesized in Synthesis Example 8 was used, and instead of adding a curing agent and a curing accelerator, dibutyltin laurate, a silanol condensation catalyst, was used, and the curing reaction was carried out in hot water at 100 ° C. for 2 hours. A test piece was created and evaluated in the same manner as in Example 1 except that the test piece was made. The results are shown in Tables 2 and 3.

(1) PNR: Phenol novolac resin (Dainippon Ink Chemical Co., Ltd. make, TD-2131, softening point 80 ℃)

(2) PBH: 2,5-dimethyl-2,5-di-t-butylperoxyhexine-3

(3) TPP: triphenylphosphine

(4) TAIC: triallyl isocyanurate

As can be seen from the results in Table 3, when maleic anhydride-modified PPE is used (Comparative Example 1), the absorption rate is high and the amount of residual ions is large. In the case of water crosslinking using a silane-modified polymer (Comparative Example 2), the curing reaction does not proceed sufficiently, the crosslinking density decreases, and mechanical properties such as bending strength are insufficient.

[Examples 7 to 14]

The hardening | curing agent and hardening accelerator of Table 4 are added to 100 parts of polymers (A)-(F) obtained by the synthesis examples 1-6, and a brominated bisphenol-A epoxy resin (EPI 152: Dainippon Ink & Chemicals Co., Ltd. Note) 20 parts of manufacture), 10 parts of Sb ₂ O ₃ as a flame retardant aid, 400 parts of fused silica as a filler, 2 parts of carnauba wax and 1.5 parts of carbon black as a compounding agent are added to prepare a semiconductor encapsulating material. The composition is collectively shown in Table 4.

The semiconductor encapsulating material prepared as described above was kneaded with a heat roll at 100 ° C. for 8 minutes, and thereafter, a tablet was prepared at a pressure of 1200 to 1400 kg / cm 2, and the plunger pressure was 80 kg / using a transfer molding machine. A test piece for evaluation (a package encapsulating a semiconductor element) was prepared under the conditions of cm 2, mold temperature of 175 ° C. and molding time of 100 seconds. Thereafter, postcure for 8 hours at 175 ° C. Using this, the temperature cycle test (TCT) and pressure cooker test (PCT) are carried out. The number of test pieces shall be 20 pieces (n = 20), and the crack generation rate at the time of these tests is investigated. These results are shown in Table 5.

Comparative Example 3

The same procedure as in Example 7 was carried out except that maleic anhydride-modified polyphenylene ether (PPE) (G) synthesized in Synthesis Example 7 was used, and the curing agent and curing accelerator were changed to those in Table 4. The compositions and results are shown in Tables 4 and 5.

[Comparative Example 4]

The silane-modified polymer (H) synthesized in Synthesis Example 8 was used, and dibutyltin laurate as a silanol condensation catalyst was used instead of the curing agent and the curing accelerator, and the curing reaction was carried out in hot water at 100 ° C. for 2 hours. Test pieces are prepared and evaluated in the same manner as in Example 7. The results are shown in Tables 4 and 5.

(1) PNR: Phenol novolac resin (Dainippon Ink Chemical Co., Ltd. make, TD-2131, softening point 80 ℃)

(2) TPP: triphenylphosphine

(3) DADPM: 4,4'-diaminodiphenylmethane

(4) MAAH: maleic anhydride

(5) PBH: 2,5-dimethyl-2,5-di-t-butylperoxyhexine-3

(6) TAIC: triallyl isocyanurate

(7) BPAE: brominated bisphenol A epoxy resin (manufactured by Dainippon Ink & Chemicals Co., Ltd., EPI152)

As can be seen from the results of Table 5, when maleic anhydride-modified PPE was used (Comparative Example 3), cracks were observed in both the PCT test and the TCT test. In addition, in the case of water crosslinking using a silane-modified polymer (Comparative Example 4), the generation of cracks was remarkable.

As can be seen from the above results, when the ratio of polar group introduction at the time of denaturation is small, when the combination of the polar group and the curing agent is not suitable, the crosslinking density at the time of hardening of the encapsulating material is lowered and the mechanical strength is lowered. It can be seen that the number of cracks greatly increased in reliability tests such as PCT.

Synthesis Example 9

(Preparation of epoxy modified norbornene-based copolymer)

<polymerization>

Adduct copolymer of 2-norbornene (NB) and 5-decyl-2-norbornene (DNB) by the known method described in US Patent No. 5,468,819 [Number average molecular weight (Mn) = 69,200, weight average molecular weight (Mw) = 132,100, copolymerization composition ratio = NB / DNB = 76/24 (molar ratio), Tg = 260 ° C].

<Epoxy degeneration>

28 parts of norbornene-based copolymers obtained above, 10 parts of 5,6-epoxy-1-hexene and 2 parts of dicumylperoxide are dissolved in 130 parts of t-butylbenzene, and the reaction is carried out at 140 ° C for 6 hours. The reaction product solution obtained is poured into 300 parts of methanol to solidify the reaction product. The coagulated epoxy modified polymer was vacuum dried at 100 ° C. for 20 hours to obtain 26 parts of epoxy modified norbornene-based copolymer. The molecular weight of this resin was Mn = 72,600, Mw = 198,400, and Tg was 265 degreeC. The epoxy group content rate measured by <^1> H-NMR of this epoxy modified norbornene-type copolymer was 2.4% per repeating structural unit of a polymer. 15 parts of the epoxy-modified norbornene-based copolymer and 0.6 parts of 4,4'-bisazidebenzal (4-methyl) cyclohexanone as 45 parts of xylene as a photoreactive substance (photocuring agent) were dissolved to cause precipitation. It became a homogeneous solution without.

Synthesis Example 10

(Preparation of epoxy modified norbornene / ethylene copolymer)

<polymerization>

Addition copolymer of NB and ethylene [Mn = 66,200, Mw = 142,400, copolymer composition ratio = NB / ethylene = 63/37 (molar ratio), Tg = by a known method described in JP-A-7-292020 184 ° C.] is obtained.

<Epoxy degeneration>

30 parts of norbornene / ethylene copolymers obtained above, 10 parts of 5,6-epoxy-1-hexene and 2 parts of dicumylperoxide are dissolved in 130 parts of t-butylbenzene, and the reaction is carried out at 140 ° C for 6 hours. The reaction product solution obtained is poured into 300 parts of methanol to solidify the reaction product. The coagulated epoxy modified polymer is vacuum dried at 100 ° C. for 20 hours to obtain 29 parts of epoxy modified norbornene / ethylene copolymer. The molecular weight of this resin was Mn = 82,400, Mw = 192,300 and Tg was 185 ° C. The epoxy group content rate measured by <^1> H-NMR of this epoxy modified norbornene-type copolymer was 2.4% per repeating structural unit of a polymer. As a result of dissolving 15 parts of this epoxy-modified norbornene-based copolymer and 0.6 parts of 4,4'-bisazidebenzal (4-methyl) cyclohexanone in 45 parts of xylene as a photoreactive substance, a uniform solution without causing precipitation It became.

Synthesis Example 11

(Preparation of epoxy modified norbornene-based copolymer)

<polymerization>

18 parts of 5-hexyl-2-norbornene (HNB) were used instead of 26 parts of 5-decyl-2-norbornene and 3 parts of 5-ethylidene-2-norbornene (ENB) were added, The polymerization is carried out in the same manner as in Production Example 1. 21 parts of norbornene-based copolymer [Mn = 71,100, Mw = 107,000, copolymerization composition ratio = NB / HNB / ENB = 74/23/3 (molar ratio), Tg = 323 ° C] is obtained.

<Epoxy degeneration>

30 parts of norbornene-based copolymers obtained above are added to 120 parts of toluene, heated to 120 ° C to dissolve, and 1.2 parts of t-butylhydroperoxide and 0.09 parts of hexacarbonyl molybdenum are added to reflux for 2 hours. This is poured into 100 parts of cold methanol to solidify the reaction product. The solidified epoxy-modified polymer is vacuum dried at 80 ° C. for 20 hours to obtain 30 parts of epoxy-modified norbornene-based copolymer. Mn = 85,200, Mw = 154,600, Tg = 328 ° C of the epoxy-modified norbornene-based copolymer, the epoxy modification ratio of the unsaturated bond measured by ¹ H-NMR is 100%, and the epoxy group content per repeat structural unit of the polymer is 3.0%. As a result of dissolving 15 parts of this epoxy-modified norbornene-based copolymer and 0.6 parts of 4,4'-bisazidebenzal (4-methyl) cyclohexanone in 45 parts of xylene as a photoreactive substance, a uniform solution without causing precipitation It became.

Synthesis Example 12 (Maleic Acid Modified Norbornene Copolymer)

<Maleic acid degeneration>

30 parts of norbornene-based copolymer obtained in Production Example 9 was added to 150 parts of toluene, heated to 120 ° C to dissolve, toluene solution of maleic anhydride (3 parts / 100 parts) and toluene solution of dicumylperoxide (0.3 Parts / 45 parts) is added slowly and reacted for 4 hours. This is poured into 600 parts of cold methanol to solidify the reaction product. The solidified epoxy modified polymer is vacuum dried at 80 ° C. for 20 hours to obtain 30 parts of maleic acid-modified norbornene-based copolymer. Mn = 73,100, Mw = 162,400 and Tg = 266 ° C of this resin, and the maleic acid content per repeating structural unit of the polymer measured by ¹ H-NMR was 2.5%. 15 parts of this maleic acid-modified norbornene-based copolymer, 9 parts of triallyl cyanurate as a crosslinking aid, and 1.2 parts of 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 as a peroxide As a result of dissolving in 45 parts of xylene, a uniform solution was obtained without causing precipitation.

Synthesis Example 13 (hydroxy-modified NB / HNB / ENB copolymer)

<Hydroxy modification>

30 parts of norbornene-based copolymers obtained in Synthesis Example 11 are added to 300 parts of toluene, heated to 120 ° C to dissolve, and 50 parts of 90% formic acid and 7.5 parts of 30% hydrogen peroxide are slowly added dropwise to reflux for 2 hours. Subsequently, after neutralizing with sodium hydroxide solution methanol, the mixture was poured into 700 parts of acetone to solidify the reaction product. The coagulated modified polymer is vacuum dried at 80 ° C. for 20 hours to obtain 30 parts of hydroxy-modified norbornene-based copolymer. The resin had a Mn of 82,100, Mw = 133,400 and Tg = 328 ° C. The hydroxy modification rate of the unsaturated bond measured by ¹ H-NMR was 100%, and the hydroxy group content per repeat structural unit of the polymer was 3.0%. 15 parts of this hydroxy-modified norbornene-based copolymer, 9 parts of 9 parts of triallyl cyanurate, and 1.2 parts of 2,5'-dimethyl-2,5-di (t-butylperoxy) hexine-3 were xylene 45 As a result of dissolving in a portion, a uniform solution was obtained without causing precipitation.

Synthesis Example 14

<polymerization>

The ring-opening polymerization and hydrogenation reaction of methylmethoxytetracyclododecene were carried out by the known method described in JP-A-477520, and the number average molecular weight (Mn) in terms of hydrogenation rate of 100% and polystyrene was 16,400. The ring-opened polymer hydrogenated substance with weight average molecular weight (Mw) = 58,100, Tg = 172 degreeC is obtained.

As a result of dissolving 15 parts of the obtained ring-opened polymer hydrogenated substance and 9 parts of triallyl cyanurate and 1.2 parts of 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 in 45 parts of xylene as a curing aid It became a uniform solution without causing precipitation.

Synthesis Example 15

<polymerization>

Cyclohexadiene addition polymerization and hydrogenation were carried out by a known method described in JP-A-7-258318, and the number average molecular weight (Mn) = 48,300, weight average molecular weight (Mw) = 72,200, in terms of polystyrene. A polymer of Tg = 218 ° C. is obtained. The hydrogenation rate by ¹ H-NMR of the obtained cyclic conjugated diene type polymer hydrogenated substance was 85%.

<Epoxy degeneration>

30 parts of the cyclic conjugated diene polymer hydrogenated additive obtained above is added to 120 parts of toluene, it is heated and dissolved at 120 degreeC, 1.2 parts of t-butyl hydroperoxides, and 0.09 parts of hexacarbonyl molybdenum are refluxed for 2 hours. This is poured into 300 parts of cold methanol to solidify the reaction product. The solidified epoxy-modified polymer is vacuum dried at 80 ° C. for 20 hours to obtain 30 parts of an epoxy-modified cyclic conjugated diene polymer hydrogenated product. The epoxy-modified cyclic conjugated diene-based polymer hydrogenated product of Mn = 68,200, Mw = 122,100, Tg = 220 ℃, epoxy group modification rate to 100% unsaturated bond measured by ¹ H-NMR, epoxy group per repeat structural unit of the polymer The content rate was 15%. As a result of dissolving 15 parts of the obtained cyclic conjugated diene-based polymer hydrogenated additive and 0.6 parts of 4,4'-bisazidebenzal (4-methyl) cyclohexanone in 45 parts of xylene as a photoreactive substance, a uniform solution without causing precipitation It became.

Synthesis Example 16 (Opening Polymer Hydrogen Additive)

<polymerization>

Ring-opening polymerization and hydrogenation of tetracyclododecene and 8-methyltetracyclododecene by the known method described in JP-A-4363312, number average molecular weight (Mn) = 31,200, weight average in terms of polystyrene The ring-opening copolymer hydrogenated substance of molecular weight (Mw) = 55,800 and Tg = 158 degreeC is obtained. The hydrogenation rate by ¹ H-NMR of the obtained polymer was 99% or more.

<Epoxy degeneration>

28 parts of the ring-opened copolymer hydrogenated compounds obtained above, 10 parts of 5,6-epoxy-1-hexene and 2 parts by weight of dicumylperoxide are dissolved in 130 parts of t-butylbenzene, and the reaction is carried out at 140 ° C for 6 hours. The reaction product solution obtained is poured into 300 parts of methanol to solidify the reaction product. The coagulated epoxy modified polymer is vacuum dried at 100 ° C. for 20 hours to obtain 28 parts of epoxy modified ring-opening copolymer hydrogenated product. The molecular weight of this epoxy modified ring-opening copolymer hydrogenated product was Mn = 38,600, Mw = 85,100, and Tg was 165 degreeC. The epoxy group content rate measured by <^1> H-NMR of this epoxy modified ring-opening copolymer hydrogenated substance was 2.0% per repeating structural unit of a polymer. As a result of dissolving 15 parts of epoxy-modified ring-opening copolymer hydrogenated product and 0.6 parts of 4,4'-bisazidebenzal (4-methyl) cyclohexanone as 45 parts of xylene as a photoreactive substance, a uniform solution was obtained without causing precipitation. It became.

Table 6 shows the results of these Synthesis Examples 9-16.

(1) NB / DNB: 2-norbornene / 5-decyl-2-norbornene secondary copolymer

(2) NB / ethylene: 2-norbornene / ethylene copolymer

(3) NB / HNB / ENB: 2-norbornene / 5-hexyl-2-norbornene / 5-ethylidene-2-norbornene secondary copolymer

(4) MMTCD: Methylmethoxytetracyclododecene ring-opening polymer (Hydrated)

(5) C-HD: 1,3-cyclohexadiene addition polymer (hydride)

(6) TCD / MTCD: tetracyclododecene / 8-methyltetracyclododecene ring-opening copolymer (hydrogen)

Example 15

<Formation of Overcoat Film>

The homogeneous solution obtained in the synthesis example 9 is filtered with the tetrafluoroethylene (PTFE) fine filter of 0.22 micrometers of pore diameters, and the solution of curable resin composition is obtained. After overcoating this solution on the micro bare wiring chip | tip formed by using a spinner, it prebakes at 80 degreeC for 90 second, and post-bakes at 180 degreeC for 1 hour, and forms a buffer coat film and a protective film with a film thickness of 40 micrometers.

〈Formation of Semiconductor Packages〉

The obtained semiconductor chip after film formation is mounted on a high-density mounting substrate by wire bonding, and subjected to flux cleaning, and then the chip portion is sealed with a liquid epoxy resin encapsulant to form a semiconductor package. The moisture resistance test of the obtained semiconductor package showed that the defective rate was 5% or less.

[Examples 16-22]

The overcoat film and the semiconductor package were formed in the same manner as in Example 15 except that the uniform solutions obtained in Synthesis Examples 10 to 16 were used, respectively. As a result of the evaluation, the defective rate in the evaluation of moisture resistance was excellent in 1% or less.

[Comparative Example 5]

Polyimide (manufactured by Toray Co., Ltd., semicofine SP-230) is applied on a semiconductor bare chip on which fine wiring is formed using a spinner, and then baked at 300 ° C. for 1 hour to form a polyimide buffer coat film. A solution prepared from 45 parts of bisphenol-type epoxy resin (epicoat 828, molecular weight 380, epoxy equivalent 185 to 195), 65 parts of xylene, and 4 parts of ethylenediamine was filtered on a buffer coat film of the obtained semiconductor chip with a 0.22 μm PTFE fine filter. To obtain a curable resin composition. After overcoating this solution on the semiconductor bare chip | tip with a micro wiring using a spinner, it pre-bakes at 80 degreeC for 120 second, and post-bakes at 180 degreeC for 4 hours, and forms a protective film with a film thickness of 40 micrometers. When the moisture resistance test was done with respect to the obtained semiconductor package, the defective rate was 12%.

Comparative Example 6

Synthesis of Maleic Anhydride Modified PPE Polymer

100 parts of poly (2,6-dimethyl-1,4-phenylene ether) having a number average molecular weight (Mn) of 9,200, 1.5 parts of maleic anhydride and 2,5-dimethyl-2,5-di (t-butyl) 1.0 part of peroxy) hexane (Per Hexa 25B manufactured by Nippon Yushi Co., Ltd.) was dry blended at room temperature, and then extruded with a twin screw extruder at a cylinder temperature of 300 ° C. and a screw rotation speed of 230 rpm to modify maleic anhydride-modified polyphenylene. Obtain ether (PPE).

15 parts of obtained maleic anhydride modified PPE polymer, 9 parts of triallyl cyanurate as a hardening adjuvant, and 1.2 parts of 2, 5- dimethyl- 2, 5- di (t-butylperoxy) hexyn-3 to 45 parts of thermal toluene As a result of dissolution, a uniform solution was obtained without causing precipitation.

Preparation of Thermoset PPE Resin Overcoat Film

Except for using the PPE resin composition synthesize | combined above, the semiconductor bare chip is overcoat by the method similar to Example 15, and a semiconductor package is created and evaluated. As a result, hydrolysis slightly occurred by the chemical treatment at the time of flux cleaning, and the reliability by moisture resistance test drastically decreased by migration. Defective rate was more than 20%.

(1) BABC: 4,4'-bisazidebenzal (4-methyl) cyclohexanone

(2) peroxide: 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3

(3) TAC: triallyl cyanurate

(4) Modified PPE: Maleic anhydride modified polyphenylene ether

According to the present invention, a protective material for an electronic component excellent in mechanical strength, chemical resistance, heat resistance, low water absorption, electrical characteristics, and the like is provided.

More specifically, according to the present invention, there is provided an electronic component sealing material composed of a curable resin composition excellent in strength characteristics and heat resistance, particularly suitable for sealing electronic components such as semiconductor chips. Moreover, according to this invention, electronic component packages, such as a semiconductor chip using the said sealing material, are provided. The encapsulation material of the present invention is excellent in electrical properties such as dielectric constant and dielectric loss tangent and moisture resistance, and also excellent in adhesion to metal lead frames, LSI chips and the like. The electronic component sealing material of the present invention is useful in a wide range of fields as a sealing material for semiconductor packages requiring high speed and high reliability, particularly in the field of electric and electronic devices.

Moreover, according to this invention, the electronic component overcoat material excellent in chemical-resistance, low hygroscopicity, and heat resistance especially suitable for buffer coating films, passivation films, protective films, etc. of electronic components, such as a semiconductor chip, is provided. And according to this invention, electronic components, such as a semiconductor chip using the said overcoat material, are provided. The overcoat material of the present invention is excellent in electrical properties such as dielectric constant and dielectric loss tangent, low powder properties, and excellent adhesion to an LSI chip or metal wiring. The electronic component overcoat material of the present invention is useful in a wide range of fields as the overcoat material for semiconductor components and the like, which requires high speed and high reliability, particularly in the field of electric and electronic devices.

Claims (31)

(A) A cyclic olefin polymer having a number average molecular weight of 1,000 to 500,000, (B) an organic peroxide, a curing agent exerting an effect by heat, and a curing agent selected from the group consisting of curing agents exerting an effect by light. Electronic component protective material which consists of curable resin composition. The electronic component protective material according to claim 1, wherein the cyclic olefin polymer (A) has a polar group of 5 to 100 mol% based on the total number of monomer units of the polymer. The electronic component protective material according to claim 2, wherein the polar group is an epoxy group, a carboxyl group, an acid anhydride group, a hydroxyl group or a carbonyl group. The addition (co) polymer of the alicyclic monomer which has a cyclic olefin type polymer (A) which has a norbornene ring, (2) The addition copolymer of the alicyclic monomer and vinyl compound which have a norbornene ring At least one thermoplastic nord selected from the group consisting of (3) a ring-opening (co) polymer of an alicyclic monomer having a norbornene ring and (4) a hydrogenated compound of a ring-opening (co) polymer of an alicyclic monomer having a norbornene ring Electronic component protection material which is a borenic resin. The electronic component protective material according to claim 1, wherein the cyclic olefin polymer (A) is at least one member selected from the group consisting of an addition polymer of a cyclic conjugated diene and a hydrogenated product of the addition polymer. The electronic component protective material according to claim 1, wherein the number average molecular weight of the cyclic olefin polymer (A) is in the range of 10,000 to 200,000. The electronic component protective material of Claim 1 containing 0.1-30 weight part of hardening | curing agents (B) with respect to 100 weight part of cyclic olefin type polymers (A). The electronic component protective material according to claim 1, further comprising a filler (C). The electronic component protective material according to claim 1, further comprising a flame retardant (D). The electronic component protection material according to any one of claims 1 to 9, wherein the electronic component protection material is an electronic component sealing material. The electronic component protective material according to claim 10, wherein the cyclic olefin polymer (A) contains a repeating unit derived from a cyclic olefin monomer in the range of 30 to 100 mol% based on the total repeating units of the polymer. The electronic component protective material of Claim 10 whose glass transition temperature of a cyclic olefin type polymer (A) is 100 degreeC or more. The electronic component protective material according to claim 10, wherein the curable resin composition further contains a flame retardant (C) and a filler (D). The curable resin composition according to claim 10, wherein the curable resin composition contains 0.1 to 30 parts by weight of the curing agent (B), 50 to 1,000 parts by weight of the filler (C) and 3 to 150 parts by weight of the flame retardant (D) based on 100 parts by weight of the cyclic olefin polymer (A). An electronic component protective material containing a part. The cyclic olefin polymer (A) is a hydrogenated product of a ring-opening copolymer of tetracyclododecenes, an addition copolymer of tetracyclododecene and a vinyl compound, or hydrogen of an addition polymer of 1,3-cyclohexadiene. An electronic component protective material which is a modified polymer in which an additive is grafted with a polar group-containing unsaturated compound to introduce a polar group. The electronic component protective material according to claim 14, wherein the filler (C) is an inorganic filler. 17. The electronic component protective material according to claim 16, wherein the inorganic filler is silica. The electronic component protective material according to claim 14, wherein the flame retardant (D) is a bromine flame retardant. The electronic component protection material according to any one of claims 1 to 9, wherein the electronic component protection material is an electronic component overcoat material. The electronic component protective material according to claim 19, wherein the cyclic olefin polymer (A) contains a repeating unit derived from a cyclic olefin monomer in a range of 50 to 100 mol% based on the total repeating units of the polymer. The electronic component protective material according to claim 19, wherein the glass transition temperature of the cyclic olefin polymer (A) is 160 ° C or higher. 20. The cyclic olefin polymer (A) according to claim 19, wherein the cyclic olefin polymer (A) is an addition (co) polymer of norbornenes, a hydrogenated product of a ring-opening (co) polymer of tetracyclododecenes, or an addition polymer of 1,3-cyclohexadiene. Electronic component protective material which is a polymer in which a polar group was introduce | transduced as a hydrogenated substance. 20. The electronic component protective material according to claim 19, wherein the electronic component overcoat material is a buffer coat film, a passivation film or a protective film. The electronic component package formed by sealing an electronic component with the electronic component protection material as described in any one of Claims 10-19. 25. The electronic component package of claim 24 wherein the electronic component is mounted directly on a substrate. The electronic component package according to claim 24 or 25, wherein the electronic component is a semiconductor element. Using the electronic component protection material as described in any one of Claims 10-19. A method of encapsulating an electronic component, in which an electronic component mounted directly on a substrate is sealed by a transfer molding method, a potting method, or an overcoat method. 28. The method of claim 27, wherein the electronic component is a semiconductor element. The electronic component package formed by overcoat an electronic component with the electronic component protection material as described in any one of Claims 20-23. 30. The electronic component package of claim 29, wherein the electronic component is mounted directly on the substrate. The electronic component package according to claim 29 or 30, wherein the electronic component is a semiconductor element.