JP2006152148A - Thermosetting resin composition, thermosetting film and cured products thereof, and electronic component - Google Patents

Abstract

Kind Code: A1 To obtain a cured product excellent in mechanical properties, electrical properties, insulation, heat resistance, thermal shock resistance, reliability, and such a cured product, with very little change in physical properties during a reliability test. A thermosetting resin composition that can be produced is provided.
A thermosetting resin composition includes (A) an epoxy resin, (B) a diene-based crosslinked rubber having an amount of bonded acrylonitrile of less than 10% by weight, (C) an anti-aging agent, (D) a curing agent, (E ) Contains a curing catalyst. (B) The diene-based crosslinked rubber is preferably a copolymer of a crosslinkable monomer having at least two polymerizable unsaturated bonds and does not contain acrylonitrile.
[Selection figure] None

Description

  The present invention relates to a thermosetting resin composition, a thermosetting film and a cured product thereof, and an electronic component. More specifically, a thermosetting resin composition capable of obtaining a cured product having excellent properties such as electrical insulation, thermal shock resistance, and heat resistance, a thermosetting film using the composition, and a cured product thereof. And an electronic component having an insulating layer formed using the composition.

In recent years, electronic components mounted on precision devices such as electronic devices and communication devices have been increasingly required to have higher speed, smaller size, thinner thickness, lighter weight, higher density, and higher reliability.
Such electronic components tend to be multilayered as the density, accuracy, and miniaturization increase, and an interlayer insulating film or a planarizing film used for such a multilayer circuit board is required. ing. Such a resin material for an interlayer insulating film or planarizing film is required to have excellent electrical insulation between conductors and excellent heat resistance to cope with high heat generation or high-temperature solder. ing.

  Conventionally, as a resin material such as an insulating film used for a circuit board of such an electronic component, a thermosetting resin such as polyimide, phenol resin, or epoxy resin has been used. However, since these resins generally have a dielectric constant of 3.5 or higher and their electrical characteristics are not sufficient, there is a problem that it is difficult to speed up the arithmetic processing with electronic parts using these materials. In addition, even if excellent electrical characteristics are exhibited, there is a problem that heat resistance is poor. In addition, these resins have sufficient initial physical properties, but changes in physical properties such as an increase in elastic modulus were observed during reliability tests such as thermal shock tests and insulation durability tests, and cracking and This may cause disconnection. The appearance of a resin material having a good balance of these characteristics has been desired.

  A method using a cross-linked acrylonitrile rubber with a small particle size is disclosed for an insulating material for the purpose of preventing the occurrence of cracks and achieving both (thermal) impact resistance, heat resistance and electrical insulation (patent) Reference 1). Similarly, a method using a crosslinked acrylonitrile rubber having an average secondary particle diameter of 0.5 to 2 μm is disclosed (see Patent Document 2). However, the technology disclosed here usually uses an elastic body containing 20% or more of acrylonitrile and has excellent compatibility with an epoxy resin or the like, but the electrical characteristics such as dielectric constant or dielectric loss tangent of the insulating resin, Alternatively, the insulation reliability tends to decrease, which is not preferable. In addition, these diene rubbers are generally easily deteriorated by heat, etc., and often undergo chemical changes during reliability tests such as thermal shock properties, and may show changes in physical properties such as reduced rubber elasticity. There is a risk of problems such as shortening of the life of electronic parts using this insulating resin layer.

  Accordingly, the present inventors have intensively studied to solve the above problems, and a thermosetting resin composition comprising an epoxy resin, a diene rubber having an amount of bound acrylonitrile of less than 10% by weight, an anti-aging agent, a curing agent, and a curing catalyst. It has been found that when a product is used, a change in physical properties during a reliability test is extremely small, and a cured product having excellent mechanical properties, electrical properties, insulation properties, heat resistance, thermal shock resistance, and reliability can be obtained. It came to complete.

In addition, as a composition which forms an insulating layer, the epoxy resin composition containing the hardening | curing agent which has the epoxy resin which has a polyfunctional epoxy resin as an essential component, the rubber elastic fine particle which is incompatible with an epoxy resin, and a phenol novolak resin as an essential component (Patent Document 3), an epoxy resin as a main agent, a phenol novolac resin as a curing agent, and a resin composition (Patent Document 4) prepared using imidazole silane as a coupling agent are known. The problem is to keep thermal expansion small, and the latter is to improve the adhesion between the inner circuit and the insulating layer while maintaining high heat resistance.
JP-A-8-139457 JP 2003-113205 A JP 2003-246849 A JP 2003-318499 A

  The present invention has a very small change in physical properties during a reliability test, and has excellent properties such as electrical insulation, electrical properties, thermal shock properties, and heat resistance, and thermosetting capable of obtaining such a cured product. It is an object to provide a functional resin composition. Another object of the present invention is to provide a highly reliable electronic component that uses such a thermosetting resin composition and does not generate cracks or breakage due to thermal stress.

  According to the present invention, there are provided the following thermosetting resin composition, thermosetting films using the composition and cured products thereof, and an electronic component having an insulating layer formed using the composition. The above problems of the present invention are solved.

  (1) It contains (A) an epoxy resin, (B) a diene-based crosslinked rubber having an amount of bonded acrylonitrile of less than 10% by weight, (C) an anti-aging agent, (D) a curing agent, and (E) a curing catalyst. A thermosetting resin composition.

  (2) The diene-based crosslinked rubber (B) is a copolymer having one or more glass transition temperatures, the at least one glass transition temperature being 0 ° C. or less, and at least a polymerizable unsaturated bond The thermosetting resin composition as described in (1) above, which is a copolymer of two crosslinkable monomers and does not contain acrylonitrile.

(3) A cured product obtained by thermosetting the thermosetting resin composition according to (1) or (2).
(4) A thermosetting film formed using the thermosetting resin composition according to (1) or (2).

(5) A cured film obtained by thermosetting the thermosetting film according to (4).
(6) An electronic component comprising an insulating layer formed using the thermosetting resin composition according to (1) or (2).

  By using the thermosetting resin composition according to the present invention, changes in physical properties during the reliability test are extremely small, and excellent mechanical properties, insulation properties, electrical properties (dielectric constant, dielectric loss), heat resistance, thermal shock A cured product having reliability and reliability can be obtained.

  Hereinafter, the thermosetting resin composition according to the present invention, thermosetting films using the composition and cured products thereof, and electronic components having an insulating layer formed using the composition will be specifically described. To do.

<Thermosetting resin composition>
The thermosetting resin composition according to the present invention comprises an epoxy resin (A), a diene cross-linked rubber (B) having an amount of bound acrylonitrile of less than 10% by weight, an anti-aging agent (C), a curing agent (D), and a curing catalyst. (E) is contained. Moreover, the said thermosetting resin composition can also contain another polymer, an organic solvent, an inorganic filler, a close_contact | adherence adjuvant, surfactant other additives, etc. as needed.

First, the components used in the present invention will be described.
(A) Epoxy resin:
The epoxy resin (A) used in the present invention is not particularly limited as long as it is an epoxy resin used for an interlayer insulating film or planarizing film of a multilayer circuit board, a protective film or an electric insulating film of an electronic component, etc. In
Bisphenol A type epoxy, bisphenol F type epoxy, hydrogenated bisphenol A type epoxy, hydrogenated bisphenol F type epoxy, bisphenol S type epoxy, brominated bisphenol A type epoxy, biphenyl type epoxy, naphthalene type epoxy, fluorene type epoxy, spiro ring Type epoxy, bisphenol alkane type epoxy, phenol novolak type epoxy, orthocresol novolak type epoxy, brominated cresol novolak type epoxy, trishydroxymethane type epoxy, tetraphenylolethane type epoxy, alicyclic epoxy, alcohol type epoxy, butylglycidyl Ether, phenyl glycidyl ether, cresyl glycidyl ether, nonyl glycidyl ether, diethylene glycol diglycidyl ether Polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin polyglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, hexahydrophthalic acid diglycidyl ether, Fatty acid-modified epoxy, toluidine type epoxy, aniline type epoxy, aminophenol type epoxy, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, hindered-in type epoxy, triglycidyl isocyanurate, tetraglycidyl diaminodiphenylmethane, diphenyl ether type Epoxy, dicyclopentadiene type epoxy, dimer acid diglycidyl ester, hexahydrophthalic acid Glycidyl ester, dimer acid diglycidyl ether, silicone modified epoxy, silicon-containing epoxy, urethane modified epoxy, NBR modified epoxy, CTBN modified epoxy, epoxidized polybutadiene, glycidyl (meth) acrylate (co) polymer, allyl glycidyl ether (co) A polymer etc. are mentioned.

(B) Diene-based crosslinked rubber having a bound acrylonitrile amount of less than 10% by weight:
The diene type crosslinked rubber (B) used in the present invention has a bound acrylonitrile amount of less than 10% by weight, preferably less than 8% by weight, particularly preferably 0% by weight. The diene-based crosslinked rubber (B) used in the present invention is a copolymer having one or more glass transition temperatures (Tg), and at least one glass transition temperature thereof is 0 ° C. or lower, preferably −100 ° C. to It is desirable to be in the range of 0 ° C, more preferably -80 ° C to -20 ° C. When the Tg of the diene-based crosslinked rubber (B) is within the above range, the cured product (cured film) of the thermosetting resin composition exhibits excellent flexibility (crack resistance). On the other hand, when Tg exceeds the above upper limit, the cured product is inferior in crack resistance, and a large number of cracks may be generated on the substrate surface in an environment where the temperature change is large.

Such a diene-based crosslinked rubber (B) includes, for example, a crosslinkable monomer having at least two polymerizable unsaturated bonds (hereinafter simply referred to as “crosslinkable monomer”) and a monomer other than the crosslinkable monomer (hereinafter referred to as “crosslinkable monomer”). A copolymer with “other monomer”), wherein the other monomer is at least one other monomer selected such that the Tg of the copolymer is −100 ° C. to 0 ° C. Certain copolymers are preferred. Further preferable other monomers include a functional group having no polymerizable unsaturated bond, such as a carboxyl group, an epoxy group,
Examples thereof include monomers having a functional group such as an amino group, an isocyanate group, and a hydroxyl group.

  Specific examples of the crosslinkable monomer include divinylbenzene, diallyl phthalate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Examples thereof include compounds having at least two polymerizable unsaturated bonds such as polyethylene glycol di (meth) acrylate and polypropylene glycol di (meth) acrylate. Of these, divinylbenzene is preferably used.

Specifically, as other monomers,
Vinyl compounds such as butadiene, isoprene, dimethylbutadiene, chloroprene;
1,3-pentadiene, (meth) acrylonitrile, α-chloroacrylonitrile, α-chloromethylacrylonitrile, α-methoxyacrylonitrile, α-ethoxyacrylonitrile, crotonic acid nitrile, cinnamic acid nitrile, itaconic acid dinitrile, maleic acid dinitrile, fumarate Unsaturated nitrile compounds such as acid dinitriles;
(Meth) acrylamide, N, N′-methylenebis (meth) acrylamide, N, N′-ethylenebis (meth) acrylamide, N, N′-hexamethylenebis (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, Unsaturated amides such as N- (2-hydroxyethyl) (meth) acrylamide, N, N′-bis (2-hydroxyethyl) (meth) acrylamide, crotonic acid amide, cinnamic acid amide;
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene (Meth) acrylic acid esters such as glycol (meth) acrylate;
Aromatic vinyl compounds such as styrene, α-methylstyrene, o-methoxystyrene, p-hydroxystyrene, p-isopropenylphenol;
Epoxy (meth) acrylates obtained by reaction of diglycidyl ether of bisphenol A or diglycidyl ether of glycol with (meth) acrylic acid or hydroxyalkyl (meth) acrylate;
Urethane (meth) acrylates obtained by reaction of hydroxyalkyl (meth) acrylates with polyisocyanates;
Epoxy group-containing unsaturated compounds such as glycidyl (meth) acrylate and (meth) allyl glycidyl ether;
(Meth) acrylic acid, itaconic acid, succinic acid-β- (meth) acryloxyethyl, maleic acid-β- (meth) acryloxyethyl, phthalic acid-β- (meth) acryloxyethyl, hexahydrophthalic acid- unsaturated acid compounds such as β- (meth) acryloxyethyl;
Amino group-containing unsaturated compounds such as dimethylamino (meth) acrylate and diethylamino (meth) acrylate;
Amide group-containing unsaturated compounds such as (meth) acrylamide and dimethyl (meth) acrylamide;
Examples thereof include hydroxyl group-containing unsaturated compounds such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate.

  Of these, butadiene, isoprene, (meth) acrylonitrile, (meth) acrylic acid alkyl esters, styrene, p-hydroxystyrene, p-isopropenylphenol, glycidyl (meth) acrylate, (meth) acrylic acid, hydroxyalkyl ( Meth) acrylates and the like are preferred.

The diene-based crosslinked rubber (B) used in the present invention includes a crosslinked rubber obtained from a vinyl compound, an aromatic vinyl compound, an unsaturated acid compound, and a crosslinking monomer, and contains a vinyl compound, an aromatic vinyl compound, and a hydroxyl group. A crosslinked rubber obtained from an unsaturated acid compound and a crosslinking monomer, and a crosslinked rubber obtained from a vinyl compound, an unsaturated nitrile compound, an unsaturated acid compound, a hydroxyl group-containing aromatic vinyl compound and a crosslinking monomer are preferred.

  In the present invention, the crosslinkable monomer used in the production of the diene-based crosslinked rubber is preferably used in an amount of 1 to 20% by weight, more preferably 2 to 10% by weight, based on the total amount of monomers.

The manufacturing method of diene type crosslinked rubber (B) is not specifically limited, For example, an emulsion polymerization method can be used. In the emulsion polymerization method, a monomer containing a crosslinkable monomer in water is emulsified using a surfactant, and a radical polymerization initiator such as a peroxide catalyst or a redox catalyst is added as a polymerization initiator. Then, a molecular weight regulator such as a mercaptan compound or a halogenated hydrocarbon is added. Next, polymerization is performed at 0 to 50 ° C., and after reaching a predetermined polymerization conversion rate, a polymerization stopper is added to stop the polymerization reaction such as N, N-diethylhydroxylamine.
Thereafter, the diene-based crosslinked rubber (B) can be synthesized by removing the unreacted monomer in the polymerization system by steam distillation or the like.

  The surfactant is not particularly limited as long as it can produce the diene-based crosslinked rubber (B) by emulsion polymerization. For example, anionic surfactants such as alkyl naphthalene sulfonate and alkyl benzene sulfonate; Cationic surfactants such as alkyltrimethylammonium salts and dialkyldimethylammonium salts; nonionic interfaces such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and fatty acid monoglycerides Activators; amphoteric surfactants; reactive emulsifiers. These surfactants can be used alone or in admixture of two or more.

  The latex containing the diene-based crosslinked rubber (B) obtained by the emulsion polymerization is coagulated by a method such as salting out, washed with water, and dried to obtain a solid diene-based crosslinked rubber (B). . In addition to solidifying by salting out, the diene-based crosslinked rubber (B) is solidified by heating the latex above the cloud point of the nonionic surfactant when a nonionic surfactant is used as the surfactant. You can also Even in the case of polymerization using a surfactant other than the nonionic surfactant, a nonionic surfactant is added after the polymerization, and the latex is heated to a cloud point or higher to solidify the diene-based crosslinked rubber (B). You can also

  In addition, as a method for producing the diene-based crosslinked rubber (B) without using a crosslinking monomer, a method of crosslinking a latex particle by adding a crosslinking agent such as a peroxide to the latex, or increasing the polymerization conversion rate. And a method of gelling in latex particles, and a method of crosslinking in latex particles by adding a crosslinking agent such as a metal salt using a functional group such as a carboxy group.

  The particle size of the diene-based crosslinked rubber (B) used in the present invention is usually 30 to 500 nm, preferably 40 to 200 nm. When the particle size of the diene-based crosslinked rubber (B) is within the above range, the cured film is excellent in mechanical properties, thermal shock resistance and other properties.

  The method for controlling the particle size of the diene-based crosslinked rubber (B) is not particularly limited. For example, when the crosslinked rubber particles are synthesized by emulsion polymerization, the number of micelles during emulsion polymerization is adjusted by adjusting the amount of the emulsifier used. And the particle size can be controlled.

In the present invention, the diene-based crosslinked rubber (B) is preferably blended in an amount of 5 to 200 parts by weight, preferably 10 to 150 parts by weight, based on 100 parts by weight of the epoxy resin (A). If the blending amount is less than the above lower limit, the thermal shock resistance of the cured film obtained by thermosetting the thermosetting resin composition is lowered, and if it exceeds the upper limit, the heat resistance of the cured film is lowered or the thermosetting resin is reduced. The compatibility with other components in the composition may decrease.

(C) Anti-aging agent Examples of the anti-aging agent used in the present invention include phenol-based anti-aging agents, sulfur-based anti-aging agents and amine-based anti-aging agents, and phenol-based anti-aging agents are particularly preferable. By using an anti-aging agent, the physical property change during the reliability test is extremely small, and the product life of the electronic component can be extended.

Specific examples of the phenolic anti-aging agent include 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-p-ethylphenol, 2,4,6-triphenol. -T-butylphenol, butylhydroxyanisole, 1-hydroxy-3-methyl-4-isopropylbenzene, mono-t-butyl-p-cresol, mono-t-butyl-m-cresol, 2,4-dimethyl-6 t-butylphenol, triethylene glycol-bis [
3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,
6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5 -Di-t-butylanilino) -1,3,5-triazine, 2,2-thio-diethylenebis [
3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythrityl tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2, 2'-methylene-bis- (4-methyl-6-tert-butylphenol), 2,2'methylene-bis- (4-ethyl-6-tert-butylphenol), 2,2'-methylene-bis (4- Methyl-6-t-nonylphenol), 2,2'-isobutylidene-bis- (4,6-dimethylphenol), 4,4'-butylidene-bis- (3-methyl-6-t-
Butylphenol), 4,4'-methylene-bis- (2,6-di-t-butylphenol)
2,2-thio-bis- (4-methyl-6-tert-butylphenol), 4,4′-thio-bis- (3-methyl-6-tert-butylphenol), 4,4′-thio-bis -(2-Methyl-6-butylphenol), 4,4'-thio-bis- (6-tert-butyl-3-methylphenol), bis (3-methyl-4-hydroxy-5-tert-butylbenzene) Sulfide, 2,
2-thio [diethyl-bis-3- (3,5-di-t-butyl-4-hydroxyphenol) propionate], bis [3,3-bis (4′-hydroxy-3′-t-butylphenol) buty Rick acid] glycol ester, bis [2- (2-hydroxy-5-methyl-3-tert-butylbenzene) -4-methyl-6-tert-butylphenyl] terephthalate, 1,3,5-tris (3 ′ , 5′-di-t-butyl-4′-hydroxybenzyl) isocyanurate, N, N′-hexamethylene-bis (3,5-di-t-butyl-4-hydroxy-hydroxyamide), N-octadecyl -3- (4′-hydroxy-3 ′, 5′-di-t-butylphenol) propionate, tetrakis [methylene- (3 ′, 5′-di-t-butyl-
4-hydroxyphenyl) propionate] methane, 1,1′-bis (4-hydroxyphenyl) cyclohexane, mono (α-methylbenzene) phenol, di (α-methylbenzyl) phenol, tri (α-methylbenzyl) phenol, Bis (2′-hydroxy-3′-t-butyl-5′-methylbenzyl) 4-methyl-phenol, 2,5-di-t-amylhydroquinone, 2,6-di-butyl-α-dimethylamino- Examples include p-cresol, 2,5-di-t-butylhydroquinone, diethyl ester of 3,5-di-t-butyl-4-hydroxybenzyl phosphate, and the like.

Specific examples of amine-based antioxidants include bis (2,2,6,6-tetramethyl-4-
Piperidyl) sebacate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6-tetramethyl-4- Piperidyl) 1,2,3,4-butanetetracarboxylate, 1,2,2,6,6-
Pentamethyl-4-piperidyl / tridecyl 1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5.5] undecane) diethanol condensate, dimethyl succinate 1- (2-hydroxy Ethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine- 2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]] and the like It is done. Preferably, a tertiary> N—R type hindered amine anti-aging agent tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1, 2,
2,6,6-pentamethyl-4-piperidyl / tridecyl 1,2,3,4-butanetetracarboxylate.

Specific examples of the sulfur-based antiaging agent include dilauryl thiopropionate.
These anti-aging agents can be used alone or in combination of two or more.
The blending amount of the anti-aging agent is preferably 0.1 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight per 100 parts by weight of the component (A).

(D) Curing agent:
The curing agent (D) used in the present invention is not particularly limited as long as it causes a curing reaction with the epoxy group in the resin, and examples thereof include amines, phenols, and acid anhydrides.

  Examples of amines include diethylamine, diethylenetriamine, triethylenetetramine, diethylaminopropylamine, aminoethylpiperazine, mensendiamine, metaxylylenediamine, dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone, methylenedianiline, and metaphenylenediamine. .

  The phenol is not particularly limited as long as it has a phenolic hydroxyl group. Co) polymers and their halides, alkyl group-substituted products and the like.

Acid anhydrides include hexahydrophthalic anhydride (HPA), tetrahydrophthalic anhydride (THPA), pyromellitic anhydride (PMDA), chlorendic anhydride (HET), nadic anhydride (NA), and methyl nadic anhydride (MNA), dodecynyl succinic anhydride (DDSA), phthalic anhydride (PA), methylhexahydrophthalic anhydride (MeHPA), maleic anhydride and the like.
These curing agents can be used singly or in combination of two or more.

The curing agent (D) is preferably added in an amount of 1 to 100 parts by weight, preferably 10 to 70 parts by weight, based on 100 parts by weight of the epoxy resin (A).
(E) Curing catalyst:
The curing catalyst (E) used in the present invention is not particularly limited, but examples thereof include amines, carboxylic acids, acid anhydrides, dicyandiamide, dibasic acid dihydrazide, imidazoles, organic boron, organic phosphine, guanidines and the like. A salt etc. are mentioned, These can be used individually by 1 type or in combination of 2 or more types.

It is preferable that the curing catalyst (E) is added in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the epoxy resin (A). Moreover, a curing accelerator can be used in combination with the curing catalyst (E) as needed for the purpose of accelerating the curing reaction.

(F) Organic solvent:
In this invention, in order to improve the handleability of a thermosetting resin composition, or to adjust a viscosity or storage stability, an organic solvent can be used as needed. The organic solvent (F) used in the present invention is not particularly limited.
Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate;
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether;
Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate;
Cellosolves such as ethyl cellosolve and butyl cellosolve;
Carbitols such as butyl carbitol;
Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate and isopropyl lactate;
Aliphatic carboxylic acid esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, isobutyl propionate;
Other esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate;
Aromatic hydrocarbons such as toluene and xylene;
Ketones such as 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, methyl amyl ketone, cyclohexanone;
Amides such as N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone;
Examples include lactones such as γ-butyrolacun.

These organic solvents can be used individually by 1 type or in mixture of 2 or more types.
(G) Other resins:
The thermosetting resin composition according to the present invention includes a diisocyanate compound such as polyimide, acrylic polymer, polystyrene resin, phenoxy resin, polyolefin elastomer, styrene butadiene elastomer, silicon elastomer, tolylene diisocyanate, or a block thereof as necessary. , High density polyethylene, medium density polyethylene, polypropylene, polycarbonate, polyarylate, polyamide, polyamideimide, polysulfone, polyethersulfone, polyetherketone, polyphenylene sulfide, (modified) polycarbodiimide, polyetherimide, polyesterimide, modified polyphenylene A thermoplastic or thermosetting resin such as a resin having an oxide or oxetane group can be contained. These resins can be used as long as the effects of the present invention are not impaired.

(H) Other additives:
The thermosetting resin composition according to the present invention includes an inorganic filler, an adhesion assistant, a polymer additive, a reactive diluent, a leveling agent, a wettability improver, a surfactant, a plasticizer, and a charge as necessary. An inhibitor, an inorganic filler, an antifungal agent, a humidity control agent, a flame retardant, and the like may be included. These additives can be used as long as the effects of the present invention are not impaired.

(Preparation of thermosetting resin composition)
For preparing the thermosetting resin composition of the present invention, for example, the epoxy resin (A), the diene-based crosslinked rubber (B), the anti-aging agent (C), the curing agent (D), and the curing catalyst (E). It can manufacture by mixing each component and a solvent other component as needed. As a method for producing the thermosetting resin composition, a conventionally known method can be used as appropriate, and each component may be added at once or in any order and stirred, mixed, and dispersed.

(Thermosetting resin composition)
The thermosetting resin composition according to the present invention includes at least an epoxy resin (A), a diene-based crosslinked rubber (B), an anti-aging agent (C), a curing agent (D), and a curing catalyst (E). By thermosetting the thermosetting resin composition, a change in physical properties before and after the reliability test is extremely small, and a cured product excellent in mechanical properties, electrical properties, insulation properties, thermal shock properties, and heat resistance can be obtained. .

  The thermosetting resin composition according to the present invention is particularly suitable for an interlayer insulating film or planarizing film of a multilayer circuit board of a semiconductor element, a protective film or an electric insulating film of various electric devices and electronic parts, a capacitor film, and the like. Can be used. Also, it can be suitably used as a semiconductor sealing material, an underfill material, a liquid crystal sealing material, or the like.

Moreover, the thermosetting resin composition according to the present invention can be prepared in the form of powder, pellets, etc., and used as a thermosetting molding material.
Furthermore, the thermosetting resin composition according to the present invention can be impregnated into a glass cloth or the like to prepare a prepreg and used as a laminate material such as a copper-clad laminate. The prepreg can be prepared by impregnating the thermosetting resin composition of the present invention into glass cloth or the like as it is, and preparing the solution by mixing the thermosetting resin composition of the present invention with a solvent. It can also be prepared by impregnating the solution with glass cloth or the like.

The thermosetting resin composition according to the present invention can also be used as an insulating adhesive layer for flexible printed wiring boards by applying it to a copper foil to form a thermosetting thin film.
<Thermosetting film>
The thermosetting film according to the present invention is formed by applying the thermosetting resin composition to, for example, a suitable support that has been subjected to a release treatment in advance to form a thermosetting thin film, and without thermosetting the thin film. It can be obtained by peeling from the support. The obtained thermosetting film can be used as an electronic component such as a printed wiring board or an (insulating) adhesive film of an electric device.

  The support is not particularly limited, and examples thereof include metals such as iron, nickel, stainless steel, titanium, aluminum, copper, and various alloys; silicon nitride, silicon carbide, sialon, aluminum nitride, boron nitride, boron carbide, and oxidation. Ceramics such as zirconium, titanium oxide, alumina, silica, and mixtures thereof; semiconductors such as Si, Ge, SiC, SiGe, and GaAs; ceramic materials such as glass and ceramics; aromatic polyamides, polyamideimides, polyimides, aromatic polyesters And heat resistant resins. If necessary, the support may be subjected to a release treatment in advance, chemical treatment with a silane coupling agent, a titanium coupling agent, etc., plasma treatment, ion plating, sputtering, gas phase reaction method, Pretreatment such as vacuum deposition may be performed as appropriate.

As a method for applying the thermosetting resin composition to a support, a known application method can be used. For example, a coating method such as a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a silk screen method, or an inkjet method can be used.
The thickness of the coating film is adjusted by appropriately controlling the solid content concentration and viscosity of the coating means and the composition solution.

<Hardened thermosetting resin>
The thermosetting resin cured product according to the present invention can be produced, for example, by the following method using the thermosetting resin composition, and changes in physical properties before and after a reliability test are small. Excellent in heat resistance, thermal shock resistance and heat resistance.

  A cured film of a thermosetting resin composition, which is one of the cured products, can be produced by thermosetting the thermosetting film. In addition, the cured film is formed by applying the thermosetting resin composition to an appropriate support that has been subjected to a release treatment in advance to form a thermosetting film layer, and the thermosetting film layer is heated to be cured. Then, a cured film can also be manufactured by peeling the obtained cured film layer from a support body. The support used at this time can be the same as the support used in the production of the aforementioned thermosetting film.

  The curing conditions of the thermosetting resin composition are not particularly limited, but may be heated for about 10 minutes to 48 hours at a temperature in the range of 50 to 200 ° C., for example, depending on the use of the resulting cured product. it can. Moreover, in order to fully advance hardening and to prevent generation | occurrence | production of a bubble, it can also heat in two steps, for example, at the temperature of the range of 50-100 degreeC at a 1st step, about 10 minutes-10 hours In the second stage, it may be heated and cured at a temperature in the range of 80 to 200 ° C. for about 30 minutes to 12 hours. Such heating can be performed using a general oven or heating equipment such as an infrared furnace.

  The thermosetting resin cured product according to the present invention has a very small change in physical properties before and after a reliability test and is excellent in electrical characteristics, electrical insulation, thermal shock resistance, and heat resistance. It can be made to act as an insulating layer by forming a cured film of a thermosetting resin composition on an electronic component such as a printed wiring board. This insulating layer is excellent not only in electrical insulation but also in electrical characteristics, thermal shock resistance, and heat resistance.

[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by this Example. In the following examples and comparative examples, “parts” represents parts by weight unless otherwise specified.

First, the raw material used in the Example etc. and the physical property evaluation method of the obtained hardened | cured material are demonstrated.
(A) Epoxy resin:
A-1: Phenol-biphenylene glycol condensation type epoxy resin
(Nippon Kayaku Co., Ltd., trade name: NC-3000P)
A-2: Phenol-naphthol / formaldehyde condensation type epoxy resin
(Nippon Kayaku Co., Ltd., trade name: NC-7000L)
A-3: Phenol / dicyclopentadiene type epoxy resin
(Nippon Kayaku Co., Ltd., trade name: XD-1000)
(B) Diene rubber:
B-1: Butadiene / styrene / methacrylic acid / divinylbenzene
= 75/20/2/3 (weight ratio)
(Tg = −48 ° C., average particle size = 70 nm)
B-2: Butadiene / styrene / hydroxybutyl methacrylate / methacrylic acid /
Divinylbenzene = 50/10/32/6/2 (weight ratio)
(Tg = −45 ° C., average particle size = 65 nm)
B-3: Butadiene / acrylonitrile / methacrylic acid / hydroxybutylmeta
Chrylate / divinylbenzene = 78/5/5/10/2 (weight ratio)
(Tg = −40 ° C., average particle size = 70 nm, amount of bound nitrile 4.8%)
B-4: Butadiene / styrene / hydroxybutyl methacrylate / methacrylic acid /
Pentaerythritol triacrylate = 68/10/20/3 (weight ratio)
(Tg = −45 ° C., average particle diameter 75 nm)
B-5: Butadiene / acrylonitrile / methacrylic acid / divinylbenzene
= 62/30/5/3 (weight ratio)
(Tg = −45 ° C., average particle diameter 70 nm)
(C) Anti-aging agent C-1: Nonflex RD (trade name, manufactured by Seiko Chemical Co., Ltd.)
C-2: Antage SP (trade name, manufactured by Kawaguchi Chemical Industry Co., Ltd.)
C-3: Nocrac G1 (trade name, manufactured by Ouchi Shinsei Chemical Co., Ltd.)
C-4: Irganox # 1010 (trade name, manufactured by Ciba Specialty Chemicals)
(D) Curing agent:
D-1: Phenol-xylylene glycol condensation resin (manufactured by Mitsui Chemicals, Inc.
(Product name: XLC-LL)
D-2: Phenol novolac resin (made by Showa Polymer Co., Ltd., trade name: CRG-951)
D-3: Dicyandiamide (E) curing catalyst:
E-1: 2-ethylimidazole E-2: 1-cyanoethyl-2-ethyl-4-methylimidazole (F) organic solvent:
F-1: 2-Heptanone F-2: Ethyl lactate F-3: Propylene glycol monomethyl ether acetate <Physical property evaluation method>
(1) Amount of bound acrylonitrile The diene rubber latex was precipitated and purified with methanol, vacuum-dried, and then subjected to elemental analysis and determined from the nitrogen content.

(2) Glass transition temperature The resin composition was applied to a PET film and heated in a convection oven at 80 ° C for 30 minutes. Further, after heating at 170 ° C. for 2 hours, the PET film was peeled off to prepare a cured film having a thickness of 50 μm. A test piece (thickness 50 μm) of 3 mm × 20 mm was produced from this cured film, and the glass transition temperature (Tg) was determined by DSC method using this test piece.

(3) Elastic modulus The resin composition was applied to a PET film and heated in a convection oven at 80 ° C. for 30 minutes. Further, after heating at 170 ° C. for 2 hours, the PET film was peeled off to prepare a cured film having a thickness of 50 μm. A test piece (thickness 50 μm) of 3 mm × 20 mm was produced from this cured film, and measurement was performed by the TMA method using this test piece.

(4) Electrical insulation (volume resistivity)
The resin composition was applied to a SUS substrate and heated in a convection oven at 80 ° C. for 30 minutes to prepare a uniform resin film having a thickness of 50 μm. Furthermore, it heated at 170 degreeC for 2 hours, and obtained the cured film. The cured film was subjected to a resistance test for 500 hours under the conditions of a temperature of 85 ° C. and a humidity of 85% using a constant temperature and constant chamber test apparatus (manufactured by Tabai Espec). The volume resistivity between the cured film layers was measured before and after the test in accordance with JIS C6481.

(5) Thermal shock property The resin composition was applied to a release-treated PET film and heated in a convection oven at 80 ° C. for 30 minutes to prepare a uniform resin film having a thickness of 50 μm. Furthermore, it heated at 170 degreeC for 2 hours, and obtained the cured film. This cured film was subjected to a 1000 cycle test with a thermal shock tester (TSA-40L, manufactured by Tabai Espec Co., Ltd.), with -65 ° C / 30 minutes to 150 ° C / 30 minutes as one cycle.

(6) Dielectric constant, dielectric loss The thermosetting resin composition was applied to a mirror-finished plate-like SUS and heated in a convection oven at 80 ° C for 30 minutes. Furthermore, it heated at 170 degreeC * 2 hours, and produced the 10-micrometer-thick cured film on plate-shaped SUS. An aluminum electrode was formed on the cured film, and the dielectric constant and dielectric loss were measured with a dielectric constant / dielectric loss measuring machine (manufactured by Hewlett Packard: LCR meter HP4248) under the condition of a frequency of 1 MHz.

<Example 1>
As shown in Table 1, epoxy resin (A-1) 100 parts by weight, diene rubber (B-1) 30 parts by weight, anti-aging agent (C-1) 5 parts by weight, curing agent (D-1) 70 Part by weight and the curing catalyst (E-1) were dissolved in 200 parts by weight of the organic solvent (F-1). Using this solution, the glass transition temperature, the elastic modulus, the electrical properties, the electrical insulation properties, and the glass transition temperature after the thermal shock test and the elastic modulus of the cured product were measured according to the property evaluation method. The obtained results are shown in Table 1.

<Examples 2 to 6>
The characteristics of the cured product were measured in the same manner as in Example 1 except that the resin composition was prepared with the composition shown in Table 1. The obtained results are shown in Tables 1 and 2.

<Comparative Examples 1-2>
The characteristics of the cured product were measured in the same manner as in Example 1 except that the resin composition was prepared with the composition shown in Table 2. The obtained results are shown in Table 2.

  When the thermosetting resin composition according to the present invention and the cured product thereof are used to form, for example, an interlayer insulating film of a multilayer circuit board, there is no occurrence of cracking or disconnection due to thermal stress, and high reliability. A circuit board can be produced.

FIG. 1 is a cross-sectional view of the base material used in the thermal shock test of the example. FIG. 2 is a top view of the base material used in the thermal shock test of the example.

Explanation of symbols

1 Base material (silicon wafer)
2 Metal pads (copper)

Claims (6)

  It contains (A) an epoxy resin, (B) a diene-based crosslinked rubber having an amount of bonded acrylonitrile of less than 10% by weight, (C) an anti-aging agent, (D) a curing agent, and (E) a curing catalyst. A thermosetting resin composition.   The diene-based crosslinked rubber (B) is a copolymer having one or more glass transition temperatures, the at least one glass transition temperature being 0 ° C. or less, and having at least two polymerizable unsaturated bonds. The thermosetting resin composition according to claim 1, which is a copolymer of a crosslinkable monomer and does not contain acrylonitrile.   A cured product obtained by thermosetting the thermosetting resin composition according to claim 1.   A thermosetting film formed using the thermosetting resin composition according to claim 1.   A cured film obtained by thermally curing the thermosetting film according to claim 4. An electronic component comprising an insulating layer formed using the thermosetting resin composition according to claim 1.

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