JPH11106597A - Flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a compsn. excellent in flame retardance and heat resistance while retaining the characteristics, such as low water absorption and dielectric properties, inherent in a cycloolefin polymer by compounding a cycloolefin addition polymer with a flame retardant. SOLUTION: This compsn. is prepd. by compounding 100 pts.wt. cycloolefin addition polymer contg. at least 50 mol.% repeating cycloolefin monomer units with 1-200 pts.wt. at least one flame retardant selected from among halogenated epoxy resin flame retardants, halogenated arom. flame retardants. halogenated alicyclic flame retardants, phosphoric ester flame retardants, and antimony oxide flame retardants. Pref., the cycloolefin addition polymer has functional groups for improving the compatibility with the flame retardant and for improving the adhesiveness required as an electronic part, pref. functional groups being epoxy groups. acid anhydride groups, etc., which form terminal OH groups such as hydroxyl groups or carboxyl groups after the compsn. is cured.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant resin composition having excellent heat resistance.

[0002]

2. Description of the Related Art Conventionally, cyclic olefin polymers are known to be suitable as sealing materials for various molded articles, electronic components, insulating materials, etc. due to their low moisture absorption and excellent dielectric properties. A technique has been disclosed in which an addition copolymer of cyclododecene and ethylene or a hydrogenated product of a ring-opening polymer of methylmethoxycarbonyltetracyclododecene is used as an insulating material for circuit boards or a sealing material for electronic components. I have. However, in recent years, with the increase in the density of circuit boards and electronic components, high heat is generated when a semiconductor chip is sealed or mounted on a circuit board, so that resin is required to have higher heat resistance. In response to this requirement, the norbornene-based addition polymer obtained by addition polymerization without opening the ring of the monocyclic olefin-based monomer, the cyclic diene-based monomer, and the norbornene-based monomer has the heat resistance of the conventional cyclic olefin. Since it is even better than a system polymer, it is suitable as an encapsulating material, an insulating material, and the like for electronic components with higher density. However, since such a cyclic olefin-based addition polymer easily burns, its use is restricted from the viewpoint of safety in applications where flame retardancy is strongly required, such as electric parts.

[0003] On the other hand, as a method for imparting flame retardancy to a resin, it is generally well known to add a flame retardant.
A composition comprising a norbornene-based monomer, an addition copolymer of ethylene, and a flame retardant has already been reported (JP-A-2-255848, JP-A-5-239284). However, the heat distortion temperature of the cyclic olefin addition polymer shown in the examples is as low as 115 ° C. or less,
There was a problem with heat resistance. Further, since the flame retardant used generally has low heat resistance, the use of a resin composition further reduces the heat resistance, and is used as an encapsulating material, an insulating material, and the like for electronic components that require higher heat resistance than before. That was difficult. Furthermore, the evaluation of the flame retardancy of a resin is affected by the degree to which it is melted by the heat of the flame, as well as the fire extinguishing properties of the flame in a combustion test. Therefore, when it is attempted to satisfy the requirement of flame retardancy by increasing the amount of the flame retardant added, there arises a problem that heat resistance, electric characteristics and the like are reduced.

As described above, no resin composition having excellent flame retardancy without impairing the characteristics of the resin, such as electrical properties and heat resistance, has not been found.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin composition having excellent flame retardancy and heat resistance without impairing the characteristics of the conventional cyclic olefin polymer itself.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, by combining a flame retardant with a polymer having a structure excellent in heat resistance among cyclic olefins. It has been found that excellent flame retardancy can be imparted as long as the characteristics of the cyclic olefin polymer are not impaired, and the present invention has been completed.

Thus, according to the present invention, (1) 100 parts by weight of a cyclic olefin-based addition polymer (A) containing 50 mol% or more of a cyclic olefin-based monomer repeating unit,
There is provided a flame-retardant resin composition comprising 1 to 200 parts by weight of a flame retardant (B). According to the present invention, (2) the flame retardant is a halogenated epoxy resin flame retardant, a halogenated aromatic flame retardant, a halogenated alicyclic flame retardant, a phosphate ester flame retardant, an antimony oxide flame retardant The resin composition according to (1), which is at least one member selected from the group consisting of: According to the present invention, (3) the resin composition according to (1), wherein the cyclic olefin-based addition polymer has a functional group.

[0008]

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

(Cyclic Olefin Addition Polymer) The cyclic olefin addition polymer used in the present invention comprises a cyclic olefin monomer repeating unit in an amount of 5% of the total repeating units of the polymer.
0 mol% or more, characterized in that the bonding mode of the monomer is an addition polymerization type repeating unit involving a carbon-carbon unsaturated bond in the ring. Further, it also contains a cyclic olefin polymer obtained by hydrogenating the above addition polymer.

Examples of the cyclic olefin monomer repeating unit include norbornene monomer repeating units such as norbornene and tetracyclododecene; monocyclic olefin monomer repeating units such as cyclopentene and cyclohexene; cyclopentadiene and cyclohexadiene And cyclic conjugated diene-based monomer repeating units.

Specific examples of the monomer as a raw material of the above-mentioned cyclic olefin-based repeating unit will be described below.

Specific examples of the norbornene monomer include:
For example, (a) a norbornene monomer having no unsaturated bond other than the carbon-carbon unsaturated bond involved in the polymerization reaction,
(B) a norbornene monomer having an unsaturated bond other than a carbon-carbon unsaturated bond involved in the polymerization reaction; (c) a norbornene monomer having an aromatic ring; and (d) a norbornene monomer having a polar group. And the like.

(A) As a specific example of a norbornene-based monomer having no unsaturated bond other than the carbon-carbon unsaturated bond involved in the polymerization reaction, for example, bicyclo [2.2.1]
Hept-2-ene, 5-methylbicyclo [2.2.1]
Hept-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-ene, 5-decylbicyclo [2.2.
1] bicyclo [2.2.1] such as hept-2-ene
Hept-2-ene derivative; tetracyclo [4.4.1
^2,5 . ^17,10 . 0] -dodec-3-ene, 8-methyltetracyclo [4.4.1 ^2,5 . ^17,10 . 0] -dodeca
3-ene, 8-ethyltetracyclo [4.4.1 ^2,5 .
^17,10 . 0] -dodec-3-ene and the like tetracyclo [4.4.1 ^2,5 . ^17,10 . 0] -dodec-3-ene derivative; tricyclo [4.3.1 ^2,5 . 0] -Deca-3-
Ene; 5-cyclohexylbicyclo [2.2.1] hept-2-ene, 5-cyclopentylbicyclo [2.2.
1] bicyclo [2.2.1] hept-2-ene derivatives having a cyclic substituent such as hept-2-ene;

(B) Specific examples of norbornene monomers having an unsaturated bond other than the carbon-carbon unsaturated bond involved in the polymerization reaction include, for example, 5-ethylidenebicyclo [2.
2.1] Hept-2-ene, 5-vinylbicyclo [2.
2.1] Hept-2-ene, 5-propenylbicyclo [2.2.1] hept-2-ene, etc., and bicyclo [2.2.1] hept-2- having an exocyclic unsaturated bond. Ene derivative; 8-methylidenetetracyclo [4.4.
^12.5 . ^17,10 . 0] -dodec-3-ene, 8-ethylidenetetracyclo [4.4.1 ^2,5 . ^17,10 . 0] -dodec-3-ene, 8-vinyltetracyclo [4.4.1
^2,5 . ^17,10 . 0] -dodec-3-ene, 8-propenyltetracyclo [4.4.1 ^2,5 . ^17,10 . 0] - dodeca-3-tetracyclo with ene, the exocyclic unsaturated bond such as [4.4.1 ^{2,5. 17,10} . 0] -dodec-3-ene derivative; tricyclo [4.3.1 ^2,5 . 0] -deca
3,7-diene; 5-cyclohexenylbicyclo [2.
2.1] Bicyclo [2.2.1] hept-2 having a cyclic substituent having an unsaturated bond, such as hept-2-ene and 5-cyclopentenylbicyclo [2.2.1] hept-2-ene. -Ene derivatives, and the like.

(C) Specific examples of the norbornene-based monomer having an aromatic ring include, for example, 5-phenylbicyclo [2.2.1] hept-2-ene and tetracyclo [6.
5.1 ^2,5 . 0 ^1,6 . 0 ^8,13] trideca -3,8,10,
12-tetraene (1,4-methano-1,4,4a, 9
a- also referred tetrahydrofluorene), tetracyclo [6.6.1 ^2,5. 0 ^1,6 . 0 ^8,13] tetradeca -3,
8,10,12-tetraene (1,4-methano-1,
4,4a, 5,10,10a-hexahydroanthracene), and the like.

(D) Specific examples of the norbornene monomer having a polar group include, for example, 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene and 5-ethoxycarbonylbicyclo [2.2 .1] Hept-2-ene, 5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-ethoxycarbonylbicyclo [2.2.1] hept-2 −
Ene, bicyclo [2.2.1] hept-5-enyl-2
-Methylpropionate, bicyclo [2.2.1] hept-5-enyl-2-methyloctanoate, bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride, 5 -Hydroxymethylbicyclo [2.2.
1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5-hydroxy-i-propylbicyclo [2.2.1] hept-2- Ene, 5,6-dicarboxybicyclo [2.2.
1] bicyclo [2.2.1] hept-2-ene derivative having a substituent containing an oxygen atom such as hept-2-ene; 8-methoxycarbonyltetracyclo [4.4.1]
^2,5 . 1 ^{7,1 0.} 0] -dodec-3-ene, 8-methyl-
8-methoxycarbonyltetracyclo [4.4.
^12.5 . ^17,10 . 0] -dodec-3-ene, 8-hydroxymethyltetracyclo [4.4.1 ^2,5 . ^17,10 .
0] -dodec-3-ene, 8-carboxytetracyclo [4.4.1 ^2,5 . ^17,10 . 0] -dodec-3-ene,
And tetracyclo having a substituent containing an oxygen atom such as [4.4.1 ^2,5 . ^17,10 . 0] -dodec-3-ene derivative; 5-cyanobicyclo [2.2.1] hept-2-
Ene, bicyclo [2.2.1] hept-2-ene-5,
Bicyclo [2.2.1] hept-2-ene derivatives having a substituent containing a nitrogen atom, such as 6-dicarboxylic imide, and the like. When it is desired to improve the compatibility with the flame retardant, 5 to 100 mol% of norbornene having an aromatic ring or norbornene monomer having a polar group is used.
It is preferred to (co) polymerize.

(2) Monocyclic Olefin Monomer Repeating Unit The monomer constituting the monocyclic olefin monomer repeating unit of the present invention has one carbon-carbon double bond in the ring. And monocyclic cycloolefin monomers such as cyclobutene, cyclopentene, cyclohexene, cycloheptene and cyclooctene described in JP-A-64-66216. These monocyclic cycloolefin monomers can be used independently or in combination of two or more.

(3) Cyclic conjugated diene monomer The monomer constituting the cyclic conjugated diene monomer repeating unit of the present invention has a conjugated carbon-carbon double bond in the ring, For example, 1,3-cyclopentadiene,
JP-A-7-cyclohexadiene, 1,3-cycloheptadiene and 1,3-cyclooctadiene;
258318 and the like. These cyclic conjugated diene monomers can be used independently or in combination of two or more.

Among the above cyclic olefin-based monomer repeating units, a norbornene-based monomer repeating unit is preferred in view of the balance of strength properties, moldability, flow properties, and the like.

Other copolymerizable monomers include α-olefins having 2 to 12 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene;
Styrene, α-methylstyrene, p-methylstyrene,
styrenes such as p-chlorostyrene and divinylbenzene; chain conjugated dienes such as 1,3-butadiene and isoprene; vinyl ethers such as ethyl vinyl ether and isobutyl vinyl ether; and carbon monoxide, but copolymerization is possible. Is not particularly limited to these. Above all, when it is desired to improve the compatibility with the flame retardant, 5 to 50 mol% of styrenes is used.
It is preferred to (co) polymerize.

In the present invention, the glass transition temperature is usually from 120 to 400 ° C., preferably from 150 to 350 ° C., in order to obtain excellent heat resistance when a resin composition is prepared by blending a flame retardant. More preferably 180 to 300
A cyclic olefin polymer in the range of ° C is used.
Since the glass transition temperature depends on the content of the cyclic olefin-based monomer repeating unit (particularly, norbornene-based monomer repeating unit) in the total repeating units of the polymer, the content is usually 50 mol% or more, preferably It is at least 70 mol%, more preferably at least 80%.

Specific examples of the preferable polymer as described above include a norbornene-based monomer repeating unit of 80 mol%.
The norbornene-based addition (co) polymer contained above is preferred.

Further, the cyclic olefin polymer used in the present invention may be used as an insulating material and a sealing material as a film.
In order to improve the flexibility when molded, etc., at least a part of the cyclic olefin monomer repeating unit preferably has a long-chain substituent bonded to the ring. Specific examples of the monomer include the aforementioned 5-butylbicyclo [2.2.
1] Hept-2-ene, 5-hexylbicyclo [2.
2.1] Hept-2-ene, 5-decylbicyclo [2.
2.1] Bicyclo [2.2.1] hept-2-ene having a long-chain substituent having 4 or more carbon atoms, such as hept-2-ene.
And ene derivatives.

The molecular weight of the cyclic olefin polymer of the present invention can be determined by gel permeation chromatography (G
When represented by a number average molecular weight (Mn) in terms of polystyrene measured by PC), it is 1,000 to 500,000, preferably 3,000 to 300,000, more preferably 5,000 to 250,000, and most preferably. 10,0
The range is from 00 to 200,000. If the number average molecular weight is too small, the mechanical strength will decrease. Conversely, if the number average molecular weight is too large, the viscosity of the polymer will be too large to mix with the flame retardant.

(Functional Group) The cyclic olefin polymer of the present invention preferably has a functional group for the purpose of improving the compatibility with the flame retardant and the adhesion as an electronic component.
The type of the functional group is not particularly limited as long as it meets the above purpose, and specific examples thereof include an epoxy group, a carboxyl group, a hydroxyl group, an ester group, a silanol group, an amino group, a nitrile group, a halogen group, and an acyl group. , A sulfone group, and a vinyl group. Among them, compatibility with a small modification rate, for the reason that it is possible to improve adhesion, for example, an oxygen atom-containing polar group capable of reacting with an acidic curing agent such as a polyhydric phenol or an amine or a basic curing agent, for example, An epoxy group, an acid anhydride group, a carboxyl group, a hydroxyl group and the like are preferable, and a polar group which generates a terminal -OH group such as a hydroxyl group or a carboxyl group after curing, such as an epoxy group and an acid anhydride group, is particularly preferable.

[Method of introducing a functional group] The method of introducing a functional group may be either a method of modifying the polymer or a method of copolymerizing a monomer having a polar group. (1) a method of adding a functional group-containing unsaturated compound by graft modification, and (2) a method of adding a functional group directly to the unsaturated bond when a carbon-carbon unsaturated bond is present in the polymer. And (3) a case where a monomer having a functional group in advance is copolymerized during the polymerization of the polymer.

(1) Grafting reaction of a functional group-containing unsaturated compound Introduction of a functional group can be obtained by reacting the polymer with a functional group-containing unsaturated compound in the presence of an organic peroxide. The functional group-containing unsaturated compound is not particularly limited, but is preferably an epoxy group-containing unsaturated compound, a carboxyl group-containing unsaturated compound, a hydroxyl group-containing unsaturated compound, or a silyl group-containing unsaturated compound because of its excellent compatibility and adhesion. And the like.

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

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

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

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

As the organic peroxide, those similar to the organic peroxides in the section of the curing agent to be described later and other azo compounds can be used. Specific examples of the azo compound include:
Azobisisobutyronitrile and dimethylazoisobutyrate can be mentioned. Among them, dialkyl peroxide is preferably used as the organic peroxide. These organic peroxides can be used alone or in combination of two or more. The ratio of the organic peroxide to be used is usually 0.1 to 100 parts by weight of the unmodified cyclic olefin-based polymer in the charged ratio at the time of the reaction.
001 to 10 parts by weight, preferably 0.01 to 5 parts by weight,
More preferably, it is in the range of 0.1 to 2.5 parts by weight. When the use range of the organic peroxide is within this range, the reactivity of the polar group-containing unsaturated compound, the water absorption of the obtained polar group-containing polymer, various properties such as dielectric properties are highly balanced and suitable. .

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

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

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

Among the methods described above, the polar group can be introduced under such conditions that the modification can be easily performed under a reaction condition and the polar group can be easily introduced at a high modification rate.
Graft modification of (1) is preferred, and the type of the unsaturated compound containing a polar group that undergoes a graft reaction includes a carbon-carbon unsaturated bond in a molecule such as an epoxy group, maleic anhydride, and itaconic anhydride for the reasons described above. An unsaturated compound having a dicarboxylic anhydride group is particularly preferred.

The functional group introduction ratio of the cyclic olefin polymer of the present invention is appropriately selected according to the purpose of use, and is usually 0.1 to 50 based on the total number of monomer units in the polymer.
Mol%, preferably 0.5 to 40 mol%, more preferably 1 to 30 mol%. When the polar group-introducing ratio of the polar group-containing cyclic olefin polymer is within this range, compatibility with the flame retardant, adhesion, and dielectric properties are highly balanced, which is preferable.

(Flame Retardant) The flame retardant used in the present invention is not particularly limited as long as it is a flame retardant added to a resin conventionally used in electric equipment, but a flame retardant which is not decomposed, denatured or deteriorated by a curing agent is preferable. . Types of flame retardants include additive flame retardants and reactive flame retardants. Additive flame retardants include antimony oxide, antimony flame retardants, inorganic flame retardants such as aluminum hydroxide and zinc borate; phosphorus flame retardants such as phosphate esters and phosphorus compounds; chlorine flame retardants, and bromine flame retardants. Halogen flame retardants such as, and reactive flame retardants include those having a functional group such as hydroxyl group, epoxy group, unsaturated bond, chlorendic anhydride, halogenated phthalic anhydride, tetrabromobisphenol A, Halogen-based flame retardants such as brominated aromatic compounds; phosphate ester-based flame retardants; halogen, phosphorus-containing polyols, and anhydrous chlorides.

Among the above flame retardants, halogen-based flame retardants, phosphorus-based flame retardants, and antimony-based flame retardants are preferred from the viewpoints of compatibility with the polymer and heat resistance.

Specific examples will be described below.

(1) Halogen-based flame retardant As the halogen-based flame retardant, various chlorine-based and bromine-based flame retardants can be used. The flame-retardant effect, heat resistance during molding, and dispersibility in resin In terms of the effect on the physical properties of the resin,
Hexabromobenzene, pentabromoethylbenzene,
Hexabromobiphenyl, decabromodiphenyl, hexabromodiphenyl oxide, octabromodiphenyl oxide, decabromodiphenyl oxide, tribromophenyl glycidyl ether, tribromophenyl acrylate, ethylene bistribromophenyl ether, ethylene bispentabromophenyl ether, tetradecabromo Diphenoxybenzene, octabromonaphthalene, bis (tribromophenyl) fumaramide,
Halogenated aromatic compounds such as N-methylhexabromodiphenylamine; tetrabromobisphenol A, and derivatives thereof [for example, tetrabromobisphenol A
-Bis (hydroxyethyl ether), tetrabromobisphenol A-bis (2,3-dibromopropyl ether), tetrabromobisphenol A-bis (bromoethyl ether), tetrabromobisphenol A-bis (allyl ether), etc.], tetra Halogenated bisphenols such as bromobisphenol S and derivatives thereof [for example, tetrabromobisphenol S-bis (hydroxyethyl ether), tetrabromobisphenol S-bis (2,3-dibromopropyl ether) and the like]; brominated polystyrene, Brominated polyphenylene oxide, brominated epoxy resin, brominated polycarbonate,
Halogenated aromatic polymers such as polypentabromobenzyl acrylate; adducts of the Diels-Alder reaction of ethylenebis (5,6-dibromonorbornene-2,3-dicarboximide), pentabromocyclohexanone, and hexachlorocyclopentadiene; Halogen-based alicyclic compounds such as hexabromocyclododecane; tetrabromophthalic anhydride and derivatives thereof (eg, tetrabromophthalimide, ethylenebistetrabromophthalimide and the like), tris- (2,3-dibromopropyl-
1) -isocyanurate and the like.

Among these halogen-based flame retardants, from the viewpoints of compatibility with the polymer, solvent solubility, heat resistance, etc.
Halogenated aromatic flame retardants such as tetrabromobisphenol A derivatives, tetrabromobusphenol A
Halogenated epoxy resin-based flame retardants such as type epoxy resins and halogen-based alicyclic flame retardants are preferred.

(2) Phosphorus Flame Retardants Phosphorus flame retardants include tris (chloroethyl) phosphate, tris (2,3-dichloropropyl) phosphate, tris (2-chloropropyl) phosphate, tris (2,3-bromo) Propyl) phosphate, tris (bromochloropropyl) phosphate, 2,3-dibromopropyl-2,3-chloropropyl phosphate,
Halogen-containing phosphate flame retardants such as tris (tribromophenyl) phosphate, tris (dibromophenyl) phosphate, and tris (tribromoneopentyl) phosphate; trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl Aliphatic phosphates such as phosphates; triphenyl phosphate,
Cresyl diphenyl phosphate, dicresyl phenyl phosphate, tricresyl phosphite, trixylenyl phosphate, xylenyl diphenyl phosphate, tri (isopropylphenyl) phosphate, isopropylphenyl diphenyl phosphate, diisopropylphenyl phenyl phosphate, tri (trimethylphenyl) phosphate, Tri (t-butylphenyl)
Non-halogen phosphate ester flame retardants such as aromatic phosphate esters such as phosphate, hydroxyphenyldiphenyl phosphate, octyl diphenyl phosphate and the like.

Among these phosphorus-based flame retardants, similarly, phosphate ester-based flame retardants are preferable from the viewpoints of compatibility with a polymer, solvent solubility, heat resistance and the like.

(3) Antimony-based flame retardant Examples of the antimony-based flame retardant include antimony oxide-based flame retardants such as antimony trioxide and antimony pentoxide, and sodium antimonate.

These flame retardants may be used alone, but when two or more are used in combination, a synergistic effect can be obtained and the amount of addition can be reduced. The use of a reactive flame retardant is preferable since the heat resistance of the resin composition is not reduced.

As the flame retardant, it is usually preferable to use a halogen-based flame retardant as a main component, and it is preferable to use a phosphorus-based flame retardant or an antimony-based flame retardant in combination.

The amount of the flame retardant to be added is generally 1 to 200 parts by weight, preferably 3 to 1 part by weight, per 100 parts by weight of the resin composition.
It is 50 parts by weight, more preferably 10 to 140 parts by weight, and most preferably 15 to 120 parts by weight. When the addition amount of the flame retardant is in the above range, the heat resistance, the electrical characteristics, and the flame retardancy of the resin composition are highly balanced and suitable. The above-mentioned antimony-based flame retardant can be used alone. However, as a flame retardant auxiliary for more effectively exhibiting the flame retardant effect of the flame retardant, 1 to 30 parts by weight of the flame retardant is usually used. It is effective to use it in a ratio of 2 parts by weight, preferably 2 to 20 parts by weight.

(Compounding Agent) The compounding agent required for each application can be added to the resin composition of the present invention.
The compounding agents are exemplified below.

[Curing Agent] When used as an electronic component, it is preferable to add a curing agent for the purpose of improving heat resistance and solvent resistance and reducing the coefficient of linear expansion. The curing agent used in the present invention is generally used as a crosslinking agent for crosslinking an organic compound such as a polymer compound, and as a curing agent, used for curing a curable resin such as an epoxy resin or a urethane resin. There is no particular limitation as long as it is present.
Acids and bases can be classified into those that generate an effect by generating ions, and those in which crosslinking and curing reactions are initiated by energy such as heat, light such as ultraviolet rays, and electron beams. Examples of the curing agent that produces an effect by generating a radical include organic peroxides, quinone and quinone dioxime derivatives, and azo compounds. Examples of the effect agent that generates an effect by generating ions include a phenol resin and an amino resin, a halogen compound, an amine and an aziridine compound, an isocyanate compound, carboxylic acid and an acid anhydride, an aldehyde, an alcohol, an epoxy compound,
Examples include metal oxides, peroxides, sulfides, metal halides and organic metal halides, metal salts of organic acids, metal alkoxides, organic metal compounds, silane compounds, and epoxy resin curing agents.

Among the above-mentioned curing agents, an effect agent which generates an ion and exerts an effect is preferred for reasons such as improvement in crosslinking reaction efficiency and crosslinking density, and amines and aziridine compounds, isocyanate compounds, carboxylic acid and acid Anhydrides, aldehydes and alcohols are particularly preferred.

The following is an example of grouping.

[Curing Agent Expressing Effect by Heat] A hardening agent mainly expressing an effect by thermal energy is (1) one that generates an effect by generating a radical, and (2) an ion generates an effect. Can be classified. (1) Curing agent that generates an effect by generating a radical a) Organic peroxide The organic peroxide generates a radical particularly by thermal energy to crosslink an organic compound. Specific examples include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide;
Peroxy ketals such as bis (t-butylperoxy) 3,3,5-trimethylcyclohexane and 2,2-bis (t-butylperoxy) butane; t-butyl hydroperoxide, 2,5-dimethylhexane −2,
Hydroperoxides such as 5-dihydroperoxide; dicumyl peroxide, 2,5-dimethyl-2,
5-di (t-butylperoxy) hexyne-3, α,
dialkyl peroxides such as α'-bis (t-butylperoxy-m-isopropyl) benzene; diacyl peroxides such as octanoyl peroxide and isobutyryl peroxide; peroxyesters such as peroxydicarbonate; Is mentioned. Among them, dialkyl peroxide is preferable in view of the performance of the resin after curing, and the type of the alkyl group can be changed depending on the molding temperature.

B) Quinone and quinone dioxime derivatives Quinone and quinone dioxime crosslink vinyl groups, vinylidene groups and other organic compounds having a carbon-carbon unsaturated bond. Specific examples include p-quinone and its derivatives; p-quinone dioxime and p-quinone dioxime dibenzoate; and nitroso compounds such as p-nitrosophenol and p-nitrosoaniline.

C) Azo compound Examples of the azo compound include diazoaminobenzene, bisazidoformate, bisazoester, bis (dioxotriazoline) derivative, difluorodiazine and the like.

(2) Curing Agents that Generate Ions to Express Hardening There are many types of curing agents that generate ions to exhibit effects.
d) a phenolic resin such as a di- or polymethylophenol resin; a polyhydric phenolic resin such as a phenol novolak resin and a cresol novolak resin; A) monohalogen compounds; dihalogen compounds; α, ω-dihaloalkanes; halogen compounds such as polyhalides such as trichloromelamine, hexachlorocyclopentadiene, octachlorocyclopentadiene, trichloromethanesulfochloride and benzotrichloride;
Amines such as di- and triethanolamine, N- (2-aminoethyl) piperazine, hexamethylenediamine, polyamine; aziridine compounds; g) diisocyanates such as hexamethylene diisocyanate and toluylene diisocyanate; diisocyanates Body, 3
Polyisocyanates such as adducts of diisocyanates to diols and triols; blocked isocyanates in which the isocyanate portion is protected by a blocking agent; h) phthalic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride Anhydrides, nadic anhydride, 1,2-cyclohexanedicarboxylic acid, maleic anhydride-modified polypropylene, maleic anhydride-modified cyclic olefin resin, etc .; fumaric acid, phthalic acid, maleic acid, trimellitic acid, high-mic acid I) aldehydes such as formaldehyde and dialdehydes; j) alcohols such as diols, polyols and bisphenols; 1,3′-butanediol;
Diols such as 4′-butanediol, hydroquinone dihydroxydiethyl ether, tricyclodecanediol and diphenylsilanediol; triols such as 1,1,1-trimethylolpropane; ethylene glycol and its derivatives, diethylene glycol and its derivatives,
Polyhydric alcohols such as triethylene glycol and derivatives thereof; k) diepoxy compounds; l) metal oxides such as zinc oxide, zinc peroxide, and lead oxide; and peroxides such as zinc, lead, calcium, and manganese; ) Zinc chloride, ferric chloride, dicyclopentadiene metal (Ti, Zr, Hf)
Metal halides and organometallic halides such as dihalides, stannous chloride, stannic chloride and ferric chloride as Louisic acid; n) metal alkoxides such as alkoxides of Ti, Zr and Al, and aluminum trialkoxides;
Organic metal salts such as copper acetylacetone, aluminum stearate, and chromium stearate; organic metal compounds such as dibutyltin oxide; o) silane compounds such as acetoxysilane, alkoxysilane, ketoximesilane, aminosilane, aminoxysilane, and silane coupling agent; p) curing agent for epoxy resin; q) nylon-6, nylon-66, nylon-610, nylon-11, nylon-612, nylon-12, nylon-46, methoxymethylated polyamide, polyhexamethylenediamine terephthalamide, Polyamides such as polyhexamethylene isophthalamide; r) 4,4-bisazidobenza (4-methyl) cyclohexanone, 4,4′-diazidochalcone, 2,6-bis (4′-azidobenzal)
Bisazides such as cyclohexanone, 2,6-bis (4'-azidobenzal) -4-methyl-cyclohexanone, 4,4'-diazidodiphenylsulfone, 4,4'-diazidodiphenylmethane, and 2,2'-diazidostilbene And the like.

Among them, p) epoxy resin curing agents are of various types, and include diethylenetriamine (DETA), triethylenetetramine (TEDA), tetraethylenepentamine (TEPA), and diethylaminopropylamine (D
EAPA), aliphatic polyamines such as hexamethylenediamine (HMDA); modified aliphatic polyamines;
-Diaminodiphenyl ether, 4,4′-diaminodiphenylmethane (DDM), α, α′-bis (4-aminophenyl) -1,3-diisopropylbenzene, α,
α'-bis (4-aminophenyl) -1,4-diisopropylbenzene, metaphenylenediamine, diaminodiphenylsulfone (DDS), metaxylenediamine (MXDA), metaaminobenzylamine (MAB
A), benzidine, 4-chloro-o-phenylenediamine (CPDA), bis (3,4-diaminophenyl) sulfone (DAPS), 4,4′-diaminodiphenylsulfone, 2,6 diaminopyridine (DAPy) and the like. Aromatic polyamine; modified aromatic polyamine; 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, 3,
Alicyclic polyamines such as 3′-dimethyl-4,4′-diamino-dicyclohexylmethane, N-aminoethylpiperazine; modified alicyclic polyamines; polyamidoamines; modified polyamidoamines;
Tertiary amines such as 2,4,6 trisdimethylaminomethylphenol; urea melamine formaldehyde condensate;
Aliphatic acids such as dodecenyl succinic anhydride (DDS) and its anhydrides; alicyclic acids and anhydrides thereof such as tetrahydrophthalic anhydride, hexahydrophthalic anhydride and methylendmethylenetetrahydrophthalic anhydride; phthalic anhydride Aromatic acids and their anhydrides; halogenated acids and their anhydrides; dicyandiamide and its derivatives; boron halide complex salts (BF ₃ -amine complex compounds); organometallic compounds; polythiols; Isocyanates such as functional aromatic isocyanates, aromatic diisocyanates, polyfunctional aromatic polyisocyanates, polyfunctional aliphatic isocyanates; block isocyanates; ketimines; 2-methylimidazole, 2-ethyl-4-methyl Imidazole, 2-ethylimidazole, , Such as imidazole and its derivatives such as 4-dimethyl imidazole it can be exemplified.

These may be used alone or as a mixture of two or more. Among these, aromatic polyamines, acid anhydrides, etc., because of their excellent solvent resistance, heat resistance, mechanical strength, adhesion to metals, and dielectric properties (low dielectric constant, low dielectric loss tangent), etc. , Polyhydric phenols and polyhydric alcohols are preferable, and among them, 4,4-diaminodiphenylmethane (aromatic polyamines), maleic anhydride-modified cyclic olefin resin (acid anhydride), polyhydric phenols and the like are particularly preferable. It is also possible to increase the efficiency of the crosslinking reaction by adding a curing accelerator as required. Although the amount of the curing agent is not particularly limited, the polymer 1 is used in order to efficiently perform a cross-linking reaction, to improve the physical properties of the obtained cured product, and to reduce the cost.
0.1 to 30 parts by weight, preferably 1 to 100 parts by weight
Used in the range of ２０20 parts by weight. If the amount of the curing agent is too small, crosslinking is unlikely to occur, and sufficient heat resistance and solvent resistance cannot be obtained. If the amount is too large, characteristics such as water absorption and dielectric properties of the crosslinked resin are undesirably reduced.
Therefore, when the amount is within the above range, these characteristics are highly balanced and suitable.

Examples of curing accelerators include pyridine, benzyldimethylamine, triethanolamine, triethylamine, tributylamine, tribenzylamine,
Examples thereof include amines such as dimethylformamide and imidazole, and are added for the purpose of adjusting the curing speed or further improving the efficiency of the crosslinking reaction. The amount of the curing accelerator is not particularly limited.
0.1-30 parts by weight, preferably 1-2
It is used in a range of 0 parts by weight, and when the compounding amount is in this range, the crosslinking density, the dielectric properties, the water absorption and the like are highly balanced, which is preferable. In particular, imidazoles are preferable because of their excellent dielectric properties.

[Curing Agent Expressing Effect by Light] A curing agent exhibiting an effect by light is obtained by irradiation with ultraviolet rays such as g-rays, h-rays and i-rays, far ultraviolet rays, x-rays and electron rays. There is no particular limitation as long as it is a photoreactive substance that reacts with the polymer to generate a cross-linking compound, and similarly, (1) a substance which generates an effect by generating a radical, and (2) generates an ion. And (3) a mixture thereof. For example, an aromatic bis azide compound, a photo amine generator, a photo acid generator and the like can be mentioned.

(1) A curing agent which generates radicals and exerts an effect A radical which mainly generates radicals by light energy such as ultraviolet rays to exert curing is a photo-radical polymerization initiator. Radicals are generated by being excited in the near ultraviolet region of 300 to 450 nm. Specifically, for example, benzoin compounds such as benzoin, benzyl, and benzoin ethers (eg, methyl, ethyl, isopropyl, and n-butyl) are used. Compounds: azobisisobutyronitrile (AIBN), 2,2′-azobispropane,
azo compounds such as m, m'-azoxystyrene and hydrazone; diphenyl disulfide compounds such as diphenyl-mono-disulfide, dibenzyl-mono-disulfide and dibenzoyl-di-sulfide; benzoyl peroxide, di-t-butyl par Organic peroxide compounds such as oxide, cyclic peroxide, 1 or 2-naphthoyl peroxide; organic dye compounds such as acetyl-peroxide-anthracene or naphthalene, fluorenone peroxide-fluorene, benzoyl peroxide-chlorophyll An iron-phthalocyanine compound;

(2) Curing Agent that Generates an Effect by Generating Ions A curing agent that generates ions to exhibit curing includes a photobase (amine) generator and a photoacid generator.

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

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

Further, as a complex type curing agent of the above (1) and (2), a (base) amine is generated once via a radical, or a base (amine) is generated by absorbing moisture in the system. Aromatic bisazide compounds may be mentioned as those which exhibit the effect as described above. Specifically, 4,4′-diazidochalcone,
2,6-bis (4′-azidobenzal) cyclohexanone, 2,6-bis (4′-azidobenzal) 4-methylcyclohexanone, 4,4′-diazidodiphenylsulfone, 4,4′-diazidobenzophenone, 4, 4 '
-Diazidodiphenyl, 2,7-diazidofluorene,
4,4'-diazidophenylmethane is a typical example. These can be used alone or in combination of two or more.

The amount of the photoreactive compound to be added is not particularly limited, however, from the viewpoint that the reaction with the polymer is carried out efficiently, the physical properties of the obtained crosslinked resin are not impaired, and the economy is low. 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the polymer. If the added amount of the photoreactive substance is too small, crosslinking is unlikely to occur, and sufficient heat resistance and solvent resistance cannot be obtained.If the added amount is too large, properties such as water absorption and dielectric properties of the crosslinked resin deteriorate. Therefore, it is not preferable. Therefore, when the amount is within the above range, these characteristics are highly balanced and suitable.

[Other Polymer Components] In the present invention, a rubbery polymer or other thermoplastic resin can be blended as necessary for the purpose of imparting flexibility or the like to the resin composition. The rubbery polymer is a polymer having a glass transition temperature of room temperature (25 ° C.) or less, and includes a usual rubbery polymer and a thermoplastic elastomer. Mooney viscosity of rubbery polymer (ML1 + 4,100 ° C)
It is appropriately selected according to the purpose of use, and is usually 5 to 200. Examples of the rubbery polymer include an ethylene-α-olefin rubbery polymer; ethylene-α-olefin-
Polyene copolymer rubber; a copolymer of ethylene and an unsaturated carboxylic acid ester such as ethylene-methyl methacrylate and ethylene-butyl acrylate; a copolymer of ethylene and a fatty acid vinyl such as ethylene-vinyl acetate; ethyl acrylate; Polymers of alkyl acrylates such as butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate; random copolymers of polybutadiene, polysoprene, styrene-butadiene or styrene-isoprene, acrylonitrile-butadiene copolymer Butadiene-isoprene copolymer, butadiene- (meth) acrylic acid alkyl ester copolymer, butadiene- (meth) acrylic acid alkyl ester-acrylonitrile copolymer, butadiene- (meth) acrylic acid Acid alkyl ester - - acrylonitrile diene rubber such as styrene copolymers; butylene - like isoprene copolymer.

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

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

(Applications) The resin composition of the present invention can be used for various applications by utilizing its excellent flame retardancy, heat resistance, and dielectric properties. It is useful as a material for a protective film. In particular,
For example, insulating varnishes for copper-clad laminates of printed wiring boards, interlayer insulating films for build-up multilayer wiring layers (sequential lamination) of high-density mounting boards, insulating materials for electronic components such as insulating materials for semiconductor package substrates; LSI, IC, etc. Encapsulation materials such as encapsulation materials for transfer molding of semiconductor components, liquid encapsulation materials, and underfill encapsulation materials; buffer coat films, passivation films, α-ray shielding protective films, solder resists, cover coat films, over coats Examples include a protective film such as a coat film.

[0071]

The present invention will be described more specifically below with reference to examples and comparative examples. (1) The glass transfer temperature is determined by the differential scanning calorimetry (DSC method).
Was measured by (2) Unless otherwise specified, the molecular weight was measured as a value in terms of polystyrene by gel permeation chromatography (GPC) using toluene as a solvent. (3) The copolymerization ratio was measured by ¹ H-NMR. (4) The epoxy group content was measured by ¹ H-NMR. (5) The carboxy group content was measured by ¹ H-NMR. (6) The hydroxyl group content was measured by ¹ H-NMR. (7) The dielectric constant and the dielectric loss tangent were measured at 1 MHz according to JIS K6911. (8) Flame retardancy was measured according to the US UL-94 test standard. (9) Pressure cooker test PCT (160 ° C x 2)
(0 hours, 4 atmospheres) to evaluate the reliability under high temperature. (If a deformation, crack, or the like occurs during the process, it becomes defective in the reliability test, so the defect rate was measured.) (10) The temperature cycle test (TCT) was performed at -55 ° C (30
min)-room temperature (5 min)-160 ° C (30 min)
A temperature shock was applied by repeating a temperature cycle from to room temperature (5 min) 500 times, and the occurrence of cracks was examined.
(If a deformation, a fine crack or the like occurs during the process, the crack increases in the reliability test and becomes defective, so the defect rate was measured.)

[Production Example 1] (Production of Epoxy-Modified Norbornene Copolymer) [Polymerization] 2-norbornene (NB) and 5-norbornene were prepared by a known method described in US Pat. No. 5,468,819.
Decyl-2-norbornene (DNB) addition copolymer (number average molecular weight (Mn) = 69,2 in terms of polystyrene)
00, weight average molecular weight (Mw) = 132,100, monomer composition ratio NB / DNB = 76/24 (molar ratio), Tg
= 260 ° C). [Epoxy modification] 28 parts by weight of the obtained polynorbornene-based resin, 5,6-epoxy 1-
Hexene (10 parts by weight) and dicumyl peroxide (2 parts by weight) were dissolved in t-butylbenzene (130 parts by weight).
For 6 hours. The obtained reaction product solution was added to 30
The reaction product was solidified by pouring into 0 parts by weight of methanol. The coagulated epoxy-modified polymer was vacuum dried at 100 ° C. for 20 hours to obtain 26 parts by weight of epoxy-modified polynorbornene. The molecular weight of this resin is Mn = 72,600, M
Tg was 265 ° C. at w = 198,400. The epoxy group content of the resin measured by ¹ H-NMR was 2.4% per repeating structural unit of the polymer.
15 parts by weight of an epoxy-modified polynorbornene resin and 4,4'-bisazidobenzal (4-methyl) as a curing agent
When 0.6 parts by weight of cyclohexanone was dissolved in 45 parts by weight of xylene, a homogeneous solution was obtained without precipitation.

[Production Example 2] (Production of Epoxy-Modified Norbornene / Ethylene Copolymer) [Polymerization] An addition copolymer of NB and ethylene (NB) was obtained by a known method described in JP-A-7-2922020. Composition 63 mol%, Mn = 66,200, Mw = 1
42,400, Tg = 184 ° C). [Epoxy modification] 30 parts by weight of the obtained norbornene / ethylene copolymer, 5,6-epoxy-1-hexene 10
Parts by weight and 2 parts by weight of dicumyl peroxide were dissolved in 130 parts by weight of t-butylbenzene and reacted at 140 ° C. for 6 hours. The obtained reaction product solution was poured into 300 parts by weight of methanol to coagulate the reaction product. The coagulated epoxy-modified polymer was vacuum dried at 100 ° C. for 20 hours,
29 parts by weight of the epoxy-modified polymer was obtained. The molecular weight of the resin was Mn = 82,400, Mw = 192,300, and Tg was 185 ° C. The epoxy group content of the resin measured by ¹ H-NMR was 2.4% per repeating structural unit of the polymer. When 15 parts by weight of the epoxy-modified polymer and 0.6 parts by weight of 4,4′-bisazidobenzal (4-methyl) cyclohexanone as a curing agent were dissolved in 45 parts by weight of xylene, a homogeneous solution without precipitation was obtained. became.

[Production Example 3] (Production of Epoxy-Modified Norbornene Copolymer) [Polymerization] 5-hexyl-2-norbornene (HNB) 18 instead of 26 parts by weight of 5-decyl-2-norbornene
Parts by weight, 5-ethylidene-2-norbornene (ENB)
Polymerization was carried out in the same manner as in Production Example 1 except that 3 parts by weight was added. 21 parts by weight of a polymer (number average molecular weight (Mn) = 51,100 in terms of polystyrene, weight average molecular weight (Mw) = 117,000, and copolymer composition ratio is NB / HN
B / ENB = 74/23/3 (molar ratio), Tg = 323
° C). [Epoxy modification] The obtained norbornene-based polymer 30
The weight part was added to 120 parts by weight of toluene, dissolved by heating to 120 ° C., 1.2 parts by weight of t-butyl hydroperoxide and 0.09 part by weight of hexacarbonylmolybdenum were added, and the mixture was refluxed for 2 hours. This was poured into 100 parts by weight of cold methanol to coagulate the reaction product. The coagulated epoxy-modified polymer was vacuum dried at 80 ° C. for 20 hours to obtain 30 parts by weight of an epoxy-modified norbornene-based polymer. Mn = 57,200, Mw = 134,600 of this polymer,
At Tg = 326 ° C., the degree of epoxy modification to unsaturated bonds measured by ¹ H-NMR was 100%, and the epoxy group content per repeating structural unit of the polymer was 3.0%.
Met. When 15 parts by weight of the epoxy-modified polymer and 0.6 parts by weight of 4,4′-bisazidobenzal (4-methyl) cyclohexanone as a curing agent were dissolved in 45 parts by weight of xylene, a homogeneous solution without precipitation was obtained. became.

[Production Example 4] (Maleic acid modification) [Maleic acid modification] 30 parts by weight of the norbornene-based polymer obtained in Production Example 1 was added to 150 parts by weight of toluene.
The mixture was dissolved by heating to 120 ° C., and a toluene solution of maleic anhydride (3 parts by weight / 100 parts by weight) and a toluene solution of dicumyl peroxide (0.3 parts by weight / 45 parts by weight) were gradually added. The reaction was performed for 4 hours. This was poured into 600 parts by weight of cold methanol to coagulate the reaction product. The solidified modified polymer was vacuum dried at 80 ° C. for 20 hours to obtain 30 parts by weight of a maleic acid-modified norbornene-based polymer.
Mn = 73,100, Mw = 162,4 of this polymer
The maleic acid content per repeating structural unit of the polymer measured by 00H, Tg = 266 ° C and ¹ H-NMR was 2.5%. When 15 parts by weight of the obtained polymer and 1.1 parts by weight of hexamethylene diisocyanate as a crosslinking agent were dissolved in 45 parts by weight of xylene, a homogeneous solution was obtained without precipitation.

[Production Example 5] (Hydroxy-modified NB / HN
B / ENB copolymer) [Hydroxy-modified] 30 parts by weight of the norbornene-based polymer obtained in Production Example 3 was added to 300 parts by weight of toluene.
The mixture was heated and dissolved at 120 ° C., and 50 parts by weight of 90% by weight formic acid and 7.5 parts by weight of 30% by weight aqueous hydrogen peroxide were gradually added dropwise and refluxed for 2 hours. Next, the mixture was neutralized with methanol dissolved in sodium hydroxide, and then poured into 700 parts by weight of acetone to coagulate the reaction product. The coagulated modified polymer was vacuum dried at 80 ° C. for 20 hours to obtain 30 parts by weight of a hydroxy-modified norbornene-based polymer. M of this polymer
n = 56,100, Mw = 133,400, Tg = 32
At 8 ° C., the hydroxy modification of the unsaturated bond measured by ¹ H-NMR was 100%, and the hydroxy group content per repeating structural unit of the polymer was 3.0%.
When 15 parts by weight of the obtained polymer and 1.5 parts by weight of tolylene diisocyanate as a crosslinking agent were dissolved in 45 parts by weight of xylene, a homogeneous solution was obtained without precipitation.

[Example 1] [Formation of cast film] A tetrabromobisphenol A type epoxy resin (TBA) as a halogen-based flame retardant and a phosphate ester-based flame retardant were added to the uniform solution obtained in Production Example 1. Cresyl diphenyl phosphate (CD
P) and 60 parts and 20 parts, respectively, of 100 parts of the polymer (based on weight, the same applies hereinafter). The resulting formulation is applied on a fluorine-coated silicon wafer substrate by spin coating,
Heat for 120 min to remove the solvent and dry, 15 cm x
A uniform cast film having a thickness of 15 cm and a thickness of 60 μm was formed. When the physical properties of the obtained cast film were evaluated, the flame retardancy was V-0, the dielectric constant was 3.1, and the dielectric loss tangent was 0.0.
05, the water absorption was 0.09%. [Manufacture of multilayer wiring board]
It was laminated on a mm-glass epoxy multilayer substrate using a vacuum laminator, heated and melt-pressed by a heating press, and then completely cured at 170 ° C. for 4 hours. An interlayer connection via having a diameter of 50 μm was formed in the laminated film using a carbon dioxide laser, and a wiring layer was formed by a conventionally known method.
Using another cast film, lamination, via formation, and wiring layer formation were performed in the same manner to produce a multilayer substrate having two layers of high-density wiring. After mounting a semiconductor chip for DRAM on the obtained multilayer substrate by a wire bonding method, the chip portion is sealed using a liquid epoxy resin sealing agent to manufacture a semiconductor package, and the above-mentioned (9), ( As a result of performing the reliability test of 10) and evaluating the results, the defective rate was 3% or less in each case.

Example 2 Using the homogeneous solution obtained in Production Example 2, the addition amount of TBA was 25 parts, and antimony pentoxide was used as an antimony pentaoxide instead of the phosphate ester flame retardant CDP. As a result of evaluation using a cast film in the same manner as in Example 1 except that
0, dielectric constant 2.9, dielectric loss tangent 0.004), and water absorption was 0.08%. Further, as a result of manufacturing and evaluating a semiconductor package in the same manner as in Example 1, the defect rate was 5%.
It was below.

Example 3 The procedure of Example 3 was repeated except that the homogeneous solution obtained in Production Example 3 was used and 22 parts of tricresyl phosphate (TCP) was added instead of CDP as the phosphate ester flame retardant. 1 As a result of evaluation using a cast film, the flame retardancy was V-0, the dielectric constant was 3.2, the dielectric loss tangent was 0.005, and the water absorption was 0.10%. Further, a semiconductor package was manufactured and evaluated in the same manner as in Example 1, and as a result, the defect rate was 3% or less.

[Example 4] Using the uniform solution obtained in Production Example 4, the addition amount of TBA was 30 parts, and antimony pentoxide was used as an antimony-based flame retardant in place of the phosphate-based flame retardant, and 5 parts of antimony pentoxide was used. Except for the addition, evaluation was performed using a cast film in the same manner as in Example 1. As a result, the flame retardancy was V-0, the dielectric constant was 3.0, the dielectric loss tangent was 0.004, and the water absorption was 0.08%.
Met. Further, a semiconductor package was manufactured and evaluated in the same manner as in Example 1, and as a result, the defect rate was 3% or less.

Example 5 Using the uniform solution obtained in Production Example 4, replacing the phosphate ester-based flame retardant with CDP and using T
Except for adding 24 parts of CP, the evaluation was performed using a cast film in the same manner as in Example 1. As a result, the flame retardancy was V-0, the dielectric constant was 3.2, the dielectric loss tangent was 0.005, and the water absorption was 0.10%. Met. Further, a semiconductor package was manufactured and evaluated in the same manner as in Example 1, and as a result, the defect rate was 3% or less.

[Production Example 6] (Production of Epoxy-Modified Norbornene / Ethylene Copolymer) [Polymerization] 2-norbornene, 5-hexyl-2-norbornene by a known method described in JP-A-7-2922020. (HNB) and ethylene terpolymer (copolymer composition ratio: NB / HNB / ethylene = 40)
/ 15/45 (mol%), Mn = 43,200, Mw =
122,400, Tg = 145 ° C.). [Epoxy modification] 30 parts by weight of the obtained norbornene / ethylene copolymer, 5,6-epoxy-1-hexene 10
Parts by weight and 2 parts by weight of dicumyl peroxide were dissolved in 130 parts by weight of t-butylbenzene and reacted at 140 ° C. for 6 hours. The obtained reaction product solution was poured into 300 parts by weight of methanol to coagulate the reaction product. The coagulated epoxy-modified polymer was vacuum dried at 100 ° C. for 20 hours,
29 parts by weight of the epoxy-modified polymer was obtained. The molecular weight of the resin was Mn = 48,400, Mw = 142,100, and Tg was 146 ° C. The epoxy group content of the resin measured by ¹ H-NMR was 2.1% per repeating structural unit of the polymer. When 15 parts by weight of the epoxy-modified polymer and 0.6 parts by weight of 4,4′-bisazidobenzal (4-methyl) cyclohexanone as a curing agent were dissolved in 45 parts by weight of xylene, a homogeneous solution without precipitation was obtained. became.

Example 6 The homogeneous solution obtained in Production Example 6 was used, and 25% of CDP was used as a phosphate-based flame retardant.
Except for the addition of a part, as a result of evaluation using a cast film in the same manner as in Example 1, the flame retardancy was V-0, the dielectric constant was 3.2,
The dielectric loss tangent was 0.005, and the water absorption was 0.10%. Further, as a result of manufacturing and evaluating a semiconductor package in the same manner as in Example 1, the defective rate was 7%.

[Production Example 7] (Production of Epoxy-Modified Norbornene / Ethylene Copolymer) [Polymerization] An addition copolymer of NB and ethylene (NB) was obtained by a known method described in JP-A-3-45612. Composition 38 mol%, Mn = 68,200, Mw = 1
40,100, Tg = 124 ° C.). [Epoxy modification] 30 parts by weight of the obtained norbornene / ethylene copolymer, 5,6-epoxy-1-hexene 10
Parts by weight and 2 parts by weight of dicumyl peroxide were dissolved in 130 parts by weight of t-butylbenzene and reacted at 140 ° C. for 6 hours. The obtained reaction product solution was poured into 300 parts by weight of methanol to coagulate the reaction product. The coagulated epoxy-modified polymer was vacuum dried at 100 ° C. for 20 hours,
29 parts by weight of the epoxy-modified polymer was obtained. The molecular weight of the resin is Mn = 72,400, Mw = 152,300 and T
g was 125 ° C. The epoxy group content of the resin measured by ¹ H-NMR was 2.4% per repeating structural unit of the polymer. Epoxy-modified polymer 1
When 5 parts by weight and 0.6 parts by weight of 4,4′-bisazidobenzal (4-methyl) cyclohexanone as a curing agent were dissolved in 45 parts by weight of xylene, a homogeneous solution was obtained without precipitation.

[Comparative Example 1] The uniform solution obtained in Production Example 7 was evaluated using a cast film as in Example 1. As a result, the flame retardancy was HB.

Comparative Example 2 Same as Example 1 except that the uniform solution obtained in Production Example 7 was used, the amount of TBA was 100 parts, and 30 parts of CDP was added as a phosphate-based flame retardant. As a result of evaluation using a cast film,
Flame retardancy is V-0, dielectric constant 4.2, dielectric loss tangent 0.009,
The water absorption was 0.12%. Further, a semiconductor package was manufactured and evaluated in the same manner as in Example 1, and as a result, the defect rate was 25%.

From the above Examples and Comparative Examples, the cast film produced by using the resin composition of the present invention is excellent in the balance between low water absorption, dielectric properties, heat resistance and flame retardancy. Compared to the manufactured semiconductor package, which is also excellent in reliability, the resin composition used in the comparative example has insufficient heat resistance of the polymer. It can be confirmed that a large amount is required, low water absorption and dielectric properties are reduced, and that the added flame retardant further reduces heat resistance and reliability of the semiconductor package.

[0088]

According to the present invention, there is provided a resin composition having sufficient heat resistance and flame retardancy without deteriorating properties such as low water absorption and dielectric properties. The resin composition of the present invention is useful in a wide range of fields such as molded articles such as films having excellent flame retardancy and heat resistance, electronic component insulating materials, sealing materials, overcoat materials, and other molding materials using the molded articles. It is.

Claims (3)

[Claims] 1. A cyclic olefin addition polymer (A) containing at least 50 mol% of a cyclic olefin monomer repeating unit.
A flame-retardant resin composition comprising 1 to 200 parts by weight of a flame retardant (B) per 100 parts by weight. 2. The flame retardant is at least one selected from a halogenated epoxy resin flame retardant, a halogenated aromatic flame retardant, a halogenated alicyclic flame retardant, a phosphate ester flame retardant, and an antimony oxide flame retardant. Claim 1 which is of one kind
The resin composition as described in the above. 3. The resin composition according to claim 1, wherein the cyclic olefin-based addition polymer has a functional group.