JP2003026766A - Epoxy-based reactive diluent and liquid epoxy resin composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid epoxy resin composition which contains an epoxy- based reactive diluent and is useful as a sealing material for semiconductor package, a sealing material for a photoelectric conversion element, a conductive adhesive, a die-bonding paste, an anisotropic conductive paste, and a joint filler for viaholes, through holes, etc. SOLUTION: This epoxy resin composition contains (A) an epoxy resin, (B) a reactive diluent, (C) a curing agent, and optionally (D) a filler. Ingredient B is a nuclear hydrogenation product of bisphenol A diglycidyl ether, has a content (obtained by GPC) of a compound represented by formula (1) of 5 wt.% or lower, a degree of nuclear hydrogenation of 80% or higher, a chlorine content of 0.2 wt.% or lower, an epoxy equivalent of 210 or lower, and a viscosity of 1,000 mPa s or lower.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an epoxy-based reactive diluent and a liquid epoxy resin composition containing the diluent. The epoxy resin composition is a sealing material for semiconductor packages, a conductive adhesive, a die bonding paste, an anisotropic conductive paste, and a joint material for via holes and through holes, and a sealing material for photoelectric conversion elements such as LEDs. It is suitable as a sealing material for surface-mounting type semiconductor packages.

[0002]

2. Description of the Related Art In recent years, as typified by the development of portable electronic devices such as mobile phones, digital cameras, and notebook personal computers, electronic parts have a tendency toward higher density and higher integration. For high integration without taking up the mounting area, BGA (ball grid array), CSP (chip size package), COG (chip on glass), COB
Techniques such as (chip on board) or MCM (multi-chip module) have been developed. As a sealing material for these elements, a liquid epoxy resin composition is usually used because of its good workability and excellent electrical properties, mechanical properties, heat resistance, adhesiveness, water resistance, and solvent resistance of the cured product. Is used.

In recent years, light emitting elements such as LEDs and semiconductor lasers, photoconductive elements, photodiodes, solar cells,
Light receiving elements such as phototransistors and photothyristors,
A miniaturized surface-mount type photoelectric conversion device represented by an optical coupling element such as a photocoupler and a photointerrupter is also on the market. Workability for these sealing materials,
A liquid epoxy resin composition is used because it has excellent electrical properties, mechanical properties, adhesiveness, water resistance, solvent resistance, and transparency.

Further, a liquid epoxy resin composition may be used as a binder such as a conductive adhesive, a die bonding paste, an anisotropic conductive paste, a joint material for via holes and through holes.

In the case of a liquid epoxy resin composition used as an encapsulant for semiconductor packages, in order to prevent cracks, warpage and peeling, a large amount of an inorganic filler is blended to improve the linear expansion coefficient of the epoxy resin cured product. The curing shrinkage rate is reduced. Further, in the case of a conductive adhesive, a die bonding paste, or an anisotropic conductive paste, it is necessary to mix a large amount of a conductive filler with an epoxy resin in order to impart conductivity. In order to mix such an inorganic filler or a conductive filler in a large amount in an epoxy resin composition, it is necessary to use a low-viscosity epoxy resin binder. Further, also in the case of a sealing material for photoelectric conversion elements, it is necessary to use a low-viscosity epoxy resin composition in order to improve workability such as casting and coating. Various reactive diluents have been studied for the purpose of reducing the viscosity.

[0006] In recent years, as the density and integration of semiconductor packages, photoelectric conversion elements, etc. have advanced, the requirements for reactive diluents have become stricter year by year. That is, since it is directly surface-mounted on the substrate, if the total chlorine content of the composition is high, corrosion and migration of Cu wiring and aluminum wiring on the substrate become a problem. In order to prevent these, the reactive diluent is required to have a low total chlorine content in the diluent, have a diluting effect, and prevent physical properties of the cured product such as Tg from being deteriorated as much as possible.

Distilled purified products of low molecular weight monoglycidyl ethers such as butyl glycidyl ether, phenyl glycidyl ether and cresyl glycidyl ether have been known as diluents having a diluting effect and a low total chlorine content. Since molecular weight monoglycidyl ether has very strong skin irritation and mutagenicity, its use tends to be avoided.

On the other hand, lauryl glycidyl ether, 1,
Diluents with a large molecular weight such as 6-hexanediol diglycidyl ether and hydrogenated bisphenol A diglycidyl ether are known to have low skin irritation and mutagenicity, but aliphatic alcohols or hydrogenated bisphenol A and epichlorohydrin are known. Is obtained by an addition reaction in the presence of an acid catalyst to obtain a chlorohydrin ether compound, and then cyclized with an alkali such as sodium hydroxide to obtain a product having a total chlorine content of 2 to 5% by weight. Inevitably, it was not suitable for the above applications. Further, an epoxy diluent having a cyclo ring skeleton such as hydrogenated bisphenol A diglycidyl ether obtained by this production method was known to have a small decrease in Tg, but a viscosity of 2000 mP
Since it was a.s or more, the dilution effect was low and it was not suitable as a diluent for the above-mentioned use.

For this reason, many semiconductor peripheral materials for surface mounting are highly densified and highly integrated, and it is necessary to obtain highly reliable products. Therefore, the total chlorine content as a diluent is low. A liquid epoxy resin composition that is excellent in the diluting effect and that does not deteriorate the physical properties such as Tg is required.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide an epoxy-based reactive diluent having a low chlorine content, an excellent diluting effect, and less deterioration in physical properties such as Tg, and further containing the reactive diluent. Another object of the present invention is to provide a liquid epoxy resin composition useful as a liquid sealing material for semiconductor packages, a sealing material for photoelectric conversion elements, a conductive adhesive, a die bonding paste, an anisotropic conductive paste, a via hole joint material, and the like.

[0011]

As a result of intensive studies to solve the above problems, the present inventors have found that a bisphenol A diglycidyl ether nuclear hydride in which the amount of specific impurities is kept below a certain amount. By blending as a reactive diluent, (1) low viscosity, good workability and impregnability, and being able to maintain a liquid state even if a large amount of a filler such as an inorganic filler or a conductive filler is blended, (2) Cu with low chlorine content
It was found that corrosion and migration of wiring such as aluminum and aluminum did not occur, and (3) physical properties such as Tg were not deteriorated. The present invention has been completed based on such findings.

That is, the present invention provides the following epoxy-based reactive diluent and a liquid epoxy resin containing the diluent.

Item 1 A nuclear hydride of bisphenol A diglycidyl ether, wherein the content of the compound represented by the formula (1) in GPC analysis is 5% or less, the nuclear hydrogenation rate is 80% or more, and the total chlorine content is Is 0.2 wt% or less, epoxy equivalent is 210 or less, and viscosity at 25 ° C. is 1000 mP
An epoxy-based reactive diluent having a content of a · s or less.

Item 2 In the liquid epoxy resin composition containing the epoxy resin (A), the epoxy-based reactive diluent (B), the curing agent (C) and, if necessary, the filler (D), the component (B). Is a reactive diluent according to item 1 above, which is a liquid epoxy resin composition.

Item 3. A semiconductor package encapsulating material comprising the liquid epoxy resin composition according to item 2.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Component (A): Epoxy Resin As the epoxy resin of the component (A) according to the present invention, a liquid epoxy resin containing two or more epoxy groups in the molecule is preferable. For example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol AD diglycidyl ether, naphthalene diol diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, vinylcyclohexene diepoxide, etc. Cycloaliphatic epoxy resin, diglycidyl ether of bisphenol A ethylene oxide adduct, diglycidyl ether of bisphenol A propylene oxide adduct, cyclohexanedimethanol diglycidyl ether, polyglycidyl ether of polyhydric alcohol, dihydrohexahydrophthalic anhydride Examples thereof include polyglycidyl esters of polybasic acids such as glycidyl ether. These epoxy resins may be used alone or in admixture of two or more, as long as the effects of the present invention are not impaired.

Among these, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, naphthalene diol diglycidyl ether, 3,4
-Epoxycyclohexylmethyl-3 ', 4'-cyclohexanecarboxylate is preferably used alone or in admixture of two or more in an amount within a range that does not impair the effects of the present invention, in order to obtain a liquid epoxy resin composition. .

In order to prevent corrosion and migration of Cu wiring and aluminum wiring, the total chlorine content is 10%.
Is less than 00 ppm and the content of hydrolyzable chlorine is 40
It is preferable to use the low chlorine type epoxy resin of 0 ppm or less.

If necessary, bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin, hydroquinone type epoxy resin,
Naphthalene skeleton type epoxy resin, tetraphenylolethane type epoxy resin, DPP type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadiene phenol type epoxy resin and other solid epoxy resins at room temperature, and butyl glycidyl ether, lauryl Alkyl glycidyl ether such as glycidyl ether,
Diluents such as glycidyl ether having one epoxy group such as phenyl glycidyl ether and cresyl glycidyl ether can be used. These are single or 2
One or more kinds may be appropriately mixed and used in an amount within a range that does not impair the effects of the present invention.

Component (B): Reactive Diluent The reactive diluent of the component (B) according to the present invention (hereinafter abbreviated as “the diluent”) is a nuclear hydride of bisphenol A diglycidyl ether. In gel permeation chromatography analysis (hereinafter abbreviated as "GPC analysis"), the content of the compound represented by the formula (1) is 5
% Or less, nuclear hydrogenation rate is 80% or more, total chlorine content is 0.2
It is an epoxy-based reactive diluent having a weight% or less, an epoxy equivalent of 210 or less, and a viscosity at 25 ° C. of 1000 mPa · s or less. The content of the compound represented by the formula (1) in the diluent is 5% or less, preferably 2% or less. If it exceeds 5%, the viscosity increases and the diluting effect decreases, which is not preferable. The total chlorine content of the diluent is 0.2 wt% or less,
It is preferably 0.1% by weight or less. Total chlorine content is 0.
If it exceeds 2% by weight, problems such as corrosion and migration of Cu wiring and aluminum wiring occur, which is not preferable.
The epoxy equivalent of the diluent is 210 or less. 210
If it exceeds, physical properties of the cured product Tg and the like are deteriorated, which is not preferable.
The nuclear hydrogenation rate of the diluent is 80% or more, preferably 9
It is 0% or more. When the nuclear hydrogenation rate is less than 80%, there is a problem that the viscosity increases, the dilution effect decreases, and the weather resistance decreases, which is not preferable. The viscosity of the diluent at 25 ° C. is 1000 mPa · s or less, preferably 800 mP
It is a · s or less. When the viscosity exceeds 1000 mPa · s, the diluting effect is lowered, and a large amount of compound is required to obtain the necessary diluting effect, so that Tg is lowered and moisture resistance, strength and the like are lowered, which is not preferable.

The diluent can be produced, for example, by the following method. Bisphenol A diglycidyl ether is subjected to post-distillation by a method such as molecular distillation to reduce the content of the compound represented by formula (2) to 5% or less and then nuclear hydrogenation, or represented by formula (2). The bisphenol A diglycidyl ether containing 5% or more of the compound described above is subjected to nuclear hydrogenation, and then the post-distillation is cut off by a method such as molecular distillation to reduce the content of the compound represented by the formula (1) to 5%.
It can be manufactured by the following method. The method of nuclear hydrogenation is not particularly limited and, for example, using a rhodium and / or ruthenium catalyst proposed by the present inventors, in the presence of a specific ether group-containing alcohol, under a hydrogen pressure of 1 to 20 MPa, and from 30 to It is possible to carry out nuclear hydrogenation at 100 ° C. (Japanese Patent Application No. 2000-287238). Here, in the present specification, the content of the compounds represented by the formulas (1) and (2) is defined as the peak area% of the compounds represented by the formulas (1) and (2) in the GPC analysis.

The blending amount of the component (B) is preferably in the range of 5 to 50 parts by weight, more preferably 100 parts by weight of the epoxy resin of the component (A) and the reactive diluent of the component (B). Is 10 to 30 parts by weight. If it is less than 5 parts by weight, the dilution effect is insufficient, and if it exceeds 50 parts by weight, Tg, strength and the like are lowered, which is not preferable.

Component (C): Curing Agent As the curing agent for the component (C) according to the present invention, any of those used in this field can be used, but generally an acid anhydride-based curing agent and a phenol-based curing agent are used. Examples of the curing agent, polyamine-based curing agent, cationic polymerization catalyst and the like are preferable, and those which are liquid at room temperature are particularly preferable. Among them, acid anhydride type curing agents are preferable when lower viscosity is required, and phenol type curing agents are preferable when higher humidity resistance and hydrolysis resistance are required, and low temperature curing is preferable. If necessary, an amine curing agent or a cationic polymerization catalyst which is liquid at room temperature is preferable.

Specific examples of the acid anhydride-based curing agent include hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride and 4 -Methyl tetrahydrophthalic anhydride, methyl nadic acid anhydride, methyl norbornane-2,3-dicarboxylic acid anhydride, norbornane-2,3-dicarboxylic acid anhydride, dodecenyl succinic anhydride, decatriene such as α-terpinene and aloocimene and anhydride Examples include Diels-Alder reaction products with maleic acid and hydrogenated products thereof, and structural isomers or geometric isomers of these acid anhydrides, as well as mixtures and modified products thereof. Of these, acid anhydride curing agents that are liquid at room temperature by a method such as structural isomerization, geometric isomerization of these acid anhydrides, or a mixture of two or more acid anhydrides are preferable. Also, if necessary, tetrahydrophthalic anhydride, phthalic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, ethylene glycol bisanhydrotrimellitate, deacetic acid condensation product of triacetin and trimellitic anhydride. Such acid anhydrides that are solid at room temperature can be mixed and used as long as the effects of the present invention are not impaired.

Among such acid anhydride type curing agents, (1)
When a low-viscosity epoxy resin binder is required for the purpose of blending a large amount of filler or for the purpose of placing importance on workability such as injection, impregnation and coating, (2) attach importance to electrical characteristics, heat resistance and transparency. In this case, a liquid acid anhydride curing agent is preferable, and it is appropriately selected according to its application. For example, acid anhydride curing agents used for epoxy resin encapsulants for semiconductor packages include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylnorbornene-2,3-dicarboxylic anhydride. , Trialkyltetrahydrophthalic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, norbornane-
2,3-dicarboxylic acid anhydride and a liquid mixture thereof are preferable. Further, when transparency of a cured product is required for a sealing material for a photoelectric conversion element such as a chip type LED, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylnorbornane-2,3-dicarboxylic acid anhydride is used. , Norbornane-2,3-dicarboxylic acid anhydride, and liquid anhydrides thereof, such as acid anhydrides having no double bond, are preferable.

The amount of the acid anhydride curing agent blended is not particularly limited as long as a predetermined effect can be obtained,
Usually, the equivalent ratio of the acid anhydride group to 1 mol of the epoxy group is 0.7 to 1.3, preferably about 0.8 to 1.2,
The amount is preferably 65 to 120 parts by weight based on 100 parts by weight of the total of the epoxy resin as the component (A) and the reactive diluent as the component (B).

As the acid anhydride-based curing agent, a curing accelerator for an epoxy resin generally used in this field can be used. For example, tertiary amines such as benzyldimethylamine, tris (dimethylaminomethyl) phenol, dimethylcyclohexylamine, 1-cyanoethyl-
2-Ethyl-4-methylimidazole, 2-ethyl-4
-Imidazoles such as methyl imidazole and 1-benzyl-2-methyl imidazole, organic phosphorus compounds such as triphenylphosphine and triphenyl phosphite, quaternary phosphonium such as tetraphenylphosphonium bromide and tetra-n-butylphosphonium bromide salts,
1,8-diazabicyclo [5.4.0] undecene-7
Etc. and their organic acid salts and other diazabicycloalkenes, zinc octylate, organometallic compounds such as tin octylate and aluminum acetylacetone complex, quaternary ammonium salts such as tetraethylammonium bromide and tetrabutylammonium bromide, trifluoride Examples thereof include boron compounds such as boron and triphenylborate, and metal halides such as zinc chloride and stannic chloride. Furthermore, high melting point imidazole compounds, dicyandiamide, high melting point dispersion type latent accelerators such as amine addition type accelerators in which amines are added to epoxy resins, imidazole type, phosphorus type and phosphine type accelerators are coated with a polymer surface. Curing represented by microcapsule type latent accelerators, amine salt type latent curing accelerators, high temperature dissociative thermal cationic polymerization type latent curing accelerators such as Lewis acid salts and Bronsted acid salts Accelerators can also be used. These curing accelerators can be used alone or in admixture of two or more.

Among these curing accelerators, imidazoles, quaternary phosphonium salts and diazabicycloalkenes are preferable in order to obtain a cured product having a high Tg. For applications such as photoelectric conversion element encapsulants where transparency of the cured product is required, quaternary phosphonium salts, diazabicycloalkenes, organometallic compounds, and quaternary ammonium salts are cured with good transparency. It is preferable in that a product can be obtained. In addition, in applications such as liquid encapsulating materials for semiconductor packages, conductive adhesives, die bonding pastes, anisotropic conductive pastes, via hole joint materials, etc., when one liquid is required, the latent curing acceleration described above is promoted. It is preferable to use an agent.

The compounding amount of the curing accelerator is 10 in total of the epoxy resin as the component (A) and the reactive diluent as the component (B).
The amount is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 6 parts by weight, based on 0 parts by weight. (C)
If the compounding amount of the component curing accelerator is less than 0.1 part by weight, the curing rate will be reduced, and if it exceeds 10 parts by weight, the hue will be deteriorated and the mechanical strength will be reduced, such being undesirable.

As the phenol-based curing agent, catechol, resorcin, hydroquinone, bisphenol F,
Bisphenol A, phenol novolacs, cresol novolacs, t-butylphenol novolacs,
Nonylphenol novolaks, bisphenol A novolaks, trishydroxyphenylmethanes, aralkyl polyphenols, polyparaoxystyrene, dicyclopentadiene polyphenols, naphthol novolaks, allylphenol compounds, etc. are exemplified, and they may be used alone or in combination of two or more. It can be used by appropriately mixing.
Among these, a liquid phenol-based curing agent is particularly preferable, and specific examples thereof include low molecular weight compounds and allylphenol which are liquid at room temperature.

The amount of the phenol-based curing agent is not particularly limited as long as the desired effect can be obtained, but usually, the equivalent ratio of phenol group to 1 mol of epoxy group is 0.5 to 1.5, preferably. Is about 0.8 to 1.2.

Specific examples of the polyamine curing agent include 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole and 2-methylimidazole. Aromatic polyamines such as imidazoles, xylylenediamine, diaminodiphenylmethane, etc., ethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine , Pentaethylenehexamine, 1,3,6-trisaminomethylhexane, N-benzylethylenediamine, trimethylhexamethylenediamine, dimethylaminopropylamine,
Diethylaminopropylamine, aminoethylethanolamine, diethylene glycol / bispropylenediamine, menthenediamine, isophoronediamine, N-
Aminoethylpiperazine, diaminodicyclohexylmethane, bis (4-amino-3-methylcyclohexyl)
Methane, 1,3-bis (aminomethyl) cyclohexane, 3,9-bis (3-aminopyropyr) -2,4
8,10-tetraoxaspiro [5.5] undecane,
Examples thereof include aliphatic polyamines such as dicyandiamide and mixtures thereof, and modified products of carboxylic acids, epoxy compounds, methyl methacrylate, phenol / formaldehyde, acrylonitrile and the like. Further, high melting point imidazole compound, dicyandiamide, high melting point latent curing agent such as amine adduct obtained by adding amine to epoxy resin, microcapsule type latent curing agent coated with polymer on the surface of imidazole type curing agent, A latent curing agent such as an amine salt type latent curing agent can also be used.

The compounding amount of the polyamine-based curing agent is not particularly limited as long as a predetermined effect can be obtained, but usually, the equivalent ratio of active hydrogen in the curing agent to 1 mol of the epoxy group is 0.5 to 1. 0.2, preferably about 0.7 to 1.0.

As the cationic polymerization catalyst, it is possible to use a Lewis acid, for example, BF ₃ , PF ₅ , As.
Examples include F ₅ and SbF ₆ , and BF ₃ is preferably recommended. Further, it is also possible to use complexes of these Lewis acids with organic primary amines such as methylamine, ethylamine and n-butylamine, preferably BF ₃ complexes with ethylamine, and triphenylphosphine. Further, an aromatic diazonium salt, as a thermal cationic polymerization catalyst or a photocationic polymerization catalyst in which the catalyst is decomposed by heating or irradiation with ultraviolet rays or visible light and acts as a curing agent.
Examples thereof include diaryl iodonium salts, triaryl sulfonium salts, triaryl selenium salts and the like. Specifically, aromatic diazonium salts such as p-chlorobenzenediazonium hexafluorophosphate, p-methoxybenzenediazonium hexafluorophosphate, diphenyliodonium hexafluorophosphate, 4,4-di-t-butylphenyliodonium hexafluoro. Diaryl iodonium salts such as phosphates, triphenylsulfonium hexafluorophosphates, triarylsulfonium salts such as bis- [4- (diphenylsulfonio) phenyl] sulfide-bis-hexafluorophosphates, triphenyl selenium hexafluorophosphates It is also possible to use triaryl selenium salts such as ferrates.

The amount of the cationic polymerization catalyst used is 0.1 to 20 parts by weight, preferably 0.5 to 1 per 100 parts by weight of the total of the epoxy resin (A) and the reactive diluent (B).
An example is 0 part by weight.

In the present invention, in addition to acid anhydride type curing agents, phenol type curing agents, amine type curing agents, cationic polymerization catalysts, other known curing agents such as dicyandiamides, adipic acid organic hydrazides and Organic acid hydrazides such as phthalic acid hydrazide are applied.

Component (D): Filler In the epoxy resin composition according to the present invention, if necessary,
A filler as the component (D) can be added. Examples of the component (D) include inorganic fillers and conductive fillers. Epoxy resin compositions containing no fillers are preferred for applications requiring transparency such as encapsulants for photoelectric conversion elements, and epoxy resin compositions containing inorganic fillers are liquid encapsulants for semiconductor packages and via holes. Suitable for applications requiring low internal stress such as joint material such as through holes, epoxy resin composition containing conductive filler has high conductivity such as conductive adhesive, die bonding paste, anisotropic conductive paste, etc. Is preferred for applications where

As the inorganic filler in the component (D), either a particulate filler or a fibrous filler can be used. Examples of the particulate filler include crystalline silica, fused silica, alumina, talc, calcium carbonate, silicon nitride, aluminum hydroxide, magnesium hydroxide, kaolin, clay, dolomide, zinc oxide, mica powder, silicon carbide, glass powder. , Carbon, graphite, barium sulfate, titanium dioxide, boron nitride and the like. Examples of the fibrous filler include wollastonite, potassium titanate whiskers, glass fibers, alumina fibers, silicon carbide fibers, boron fibers, carbon fibers, aramid fibers, phenol fibers, and metal whiskers. These inorganic fillers can be used alone or in combination of two or more. Further, as these inorganic fillers, those treated with a coupling agent or a surface treatment agent may be used. Of these, crushed or spherical fused silica is preferable because it is necessary to reduce the linear expansion coefficient and internal stress particularly when used in a semiconductor device package, and a low α-ray type is used depending on the application. It is preferable. As the conductive filler, Ag, Cu,
Examples thereof include metal powders of Ni, Ag-Pd and the like, and fillers in which the surface of the above-mentioned inorganic filler is coated with these metals. These conductive fillers can be used alone or in combination of two or more.

The blending amount of the component (D) is
Although it can be appropriately selected depending on the purpose, it is usually 100 parts by weight to 9 parts by weight based on 100 parts by weight of the total of the epoxy resin as the component (A), the reactive diluent as the component (B), and the curing agent as the component (C).
00 parts by weight is preferred. If the blending amount exceeds 900 parts by weight, the viscosity will remarkably increase and the work during casting, coating or impregnation by a dispenser or screen printing will become difficult. If the amount is less than 100 parts by weight, the curing shrinkage reduction effect and linear expansion coefficient reduction effect that can be expected by compounding an inorganic filler are low. Without
When it is used as a conductive adhesive, an anisotropic conductive paste, or a die bonding paste, the conductivity decreases, which is not preferable.

The average particle size of the component (D) is 0.1 to 100.
μm is preferable, and more preferably 0.5 to 80 μm. When the average particle size is less than 0.1 μm, the viscosity of the epoxy resin composition becomes high, and when it exceeds 100 μm, there is a problem that mechanical strength is lowered and sedimentation occurs to deteriorate workability, which is not preferable. In order to keep the viscosity of the liquid epoxy resin composition low, it is preferable to use spherical inorganic fillers, and it is also effective to mix and use two or more fillers having different average particle diameters.

Liquid Epoxy Resin Composition The liquid epoxy resin composition according to the present invention contains, if necessary, an aliphatic polyol such as ethylene glycol and propylene glycol, a carbon dioxide gas such as an aliphatic or aromatic carboxylic acid compound and a phenol compound. Anti-generation agent, flexibility-imparting agent such as polyalkylene glycol, antioxidant, plasticizer,
Lubricants, coupling agents such as silanes, surface treatment agents for inorganic fillers, flame retardants, antistatic agents, colorants, antistatic agents, leveling agents, ion trap agents, slidability improvers, various rubbers, organic polymers Impact resistance improver such as beads, thixotropic agent, surfactant, surface tension lowering agent, antifoaming agent, anti-settling agent, light diffusing agent, ultraviolet absorber, antioxidant, release agent, fluorescent agent, Additives such as conductive fillers can be added.

The method for producing the liquid epoxy resin composition according to the present invention is not particularly limited, and the epoxy resin as the component (A), the reactive diluent as the component (B), the curing agent as the component (C),
If necessary, the filler of the component (D) and other additives may be blended and mixed by a roll, a mixer, a kneader, or the like, and the production can be performed by a conventionally known method. Furthermore, an epoxy resin liquid containing (A) component, (B) component and, if necessary, (D) component as a main component, and (C) component and, if necessary, a curing accelerator and a filler as main components. It is also possible to prepare two liquids of a curing agent liquid and mix the epoxy resin liquid and the curing agent liquid before use to produce a liquid epoxy resin composition.
The component (A), the component (B), the component (C), and optionally the component (D) and other additives may all be mixed to produce a liquid epoxy resin composition in the form of one liquid. . When the acid anhydride type curing agent is used to form a one-pack type, it is preferable to use the latent curing accelerator as the curing accelerator for the purpose of improving the storage stability of the liquid epoxy resin composition. preferable.

The method of coating, potting or impregnating the liquid epoxy resin composition is not particularly limited, and coating or potting with a dispenser, coating by vacuum or atmospheric pressure screen printing, spin coating, reaction injection molding, etc. are conventionally known. The method can be adopted.

The method for curing the liquid epoxy resin composition includes
There is no particular limitation, and a conventionally known curing device such as a closed type curing furnace or a tunnel furnace capable of continuous curing can be adopted.
The heating source is not particularly limited, and it can be performed by a conventionally known method such as hot air circulation, infrared heating, and high frequency heating. The curing temperature and the curing time are 30 at 80 ° C to 250 ° C.
The range of seconds to 15 hours is preferred. If you want to reduce the internal stress of the cured product, pre-cure under the conditions of 80 to 130 ° C for 0.5 hours to 5 hours, and then post-cure under the conditions of 130 to 180 ° C for 0.1 hours to 15 hours. Is preferred, and for the purpose of short-time curing, 150 to 250 ° C., 30 seconds to 3
It is preferable to cure under the condition of 0 minutes. When a photo-curing catalyst is used as the curing agent of the component (C), it can be cured in the range of room temperature to 150 ° C. by irradiating it with ultraviolet rays, visible light, electron beams and the like.

The thus obtained liquid epoxy resin composition of the present invention has a low chlorine content, an excellent diluting effect, and contains an epoxy-based reactive diluent with less deterioration of physical properties such as Tg. It has good workability such as coating and impregnation, and can maintain a liquid state even if a large amount of fillers such as inorganic fillers and conductive fillers are mixed, without causing corrosion or migration of Cu wiring or Al wiring. , Tg is high and heat resistance is excellent, so epoxy for liquid sealing material for semiconductor package, photoelectric conversion element sealing material, conductive adhesive, die bonding paste, anisotropic conductive paste, joint material such as via hole, through hole, etc. It can be used as a resin composition.

Concretely, a BGA (ball grid array), which is exemplified by a liquid epoxy resin composition such as an underfill agent for a semiconductor flip chip, a grab top material for wire bonding, and a TAB sealing material, C
Insulation sealing material for surface mounting type semiconductor packages such as SP (chip size package), COG (chip on glass), COB (chip on board) or MCM (multi-chip module), and LE
D, a light emitting element such as a semiconductor laser, a photoconductive element, a photodiode, a solar cell, a light receiving element such as a phototransistor and a photothyristor, and an insulation seal of a photoelectric conversion element represented by an optical coupling element such as a photocoupler and a photointerrupter. It can be used as a stop material. Furthermore, it can also be used as anisotropic conductive adhesive, die bonding paste, anisotropic conductive paste, die bonding paste, printed circuit board, multi-layer printed circuit board adhesive, through hole joint material, build-up base via hole joint material, etc. it can.

The liquid epoxy resin composition according to the present invention is
The present invention is not limited to the above-mentioned applications, and can be applied to conventionally known epoxy resin applications such as potting, casting, filament winding, insulation sealing such as lamination, and moldings. Specifically, mold transformers, mold transformers (current transformers (CT), zero-layer current transformers (ZCT), instrument transformers (PT), stationary instrument transformers (ZPT), gas switch parts) (Insulating spacers, support insulators, operating rods, sealed terminals, bushings, insulating columns, etc.), solid insulated switchgear parts, overhead distribution line automation equipment parts (rotating insulators, voltage detection elements, integrated capacitors, etc.), underground distribution line equipment Parts (molded discs, power transformers, etc.), power capacitors, resin insulators,
It can also be used as a heavy electric insulating sealant such as a coil for a linear motor car, and an impregnating varnish (a generator, a motor, etc.) of a coil for various rotating devices. Also, it can be used as a potting resin such as a flyback transformer, an ignition coil, an AC capacitor, a film capacitor, an insulating sealing resin used in a weak electric field such as an impregnating resin for various coils. In addition, it can also be used for various FRP molded products, various coating materials, decorative materials, and the like, which are not necessarily required to have a laminated plate or insulating properties.

[0048]

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples. The GPC analysis of the reactive diluent and the physical properties of the cured epoxy resin product obtained in each example were measured and evaluated by the following methods.

GPC Analysis of Reactive Diluent GPC analysis was performed under the following conditions using an LC-6A (trade name) device manufactured by Shimadzu Corporation. In the following production examples, the content of the compound represented by the formula (1) and the content of the compound represented by the general formula (2) represents the area% of the peak obtained as a result of the GPC analysis. Column: Shimazu Shim-Pack80M
(Inner diameter 8 mm x length 30 cm) + TOSOH TSKg
el G2000H _XL (inner diameter 7.8mm x length 30
cm) + TOSOH TSKgel G1000H _XL
(Inner diameter 7.8 mm x length 30 cm) x 3 Flow rate: 1.0 ml / min Temperature: 40 ° C Detector: RI

Formulation Viscosity The liquid epoxy resin composition used as a sample has a viscosity at 25 ° C.
It was measured with a B-type viscometer. The lower the compound viscosity, the better the workability of casting, coating, impregnation and the like.

Cured product Tg A glass transition temperature (Tg) of a cured product obtained by pouring an epoxy resin composition as a sample into a plastic test tube having an inner diameter of 6 mm so as to have a thickness of 7 mm and curing it under predetermined conditions.
According to the method described in ASTM D3418-82.
It was measured by the SC method. The higher the cured product Tg, the better the heat resistance.

Chlorine Extraction A liquid epoxy resin composition as a sample is poured into a metal dish having an inner diameter of 68 mm so as to have a thickness of 2 mm and cured under predetermined conditions to obtain a cured product. 10 g of a sample obtained by crushing this cured product was dispersed in 100 g of distilled water, and the temperature was 121 ° C. × 0.1.
After heating under the condition of 21 MPa × 24 hours, the chlorine concentration in distilled water was measured by ion chromatography.
The lower the chlorine extraction amount, the lower the migration of the corrosiveness of Cu wiring and Al wiring.

Production Example 1 Bisphenol A diglycidyl ether ("Epototo YD-8125" (trade name), epoxy equivalent 1) was added to 500 ml of stainless steel autoclave equipped with a magnetic stirrer.
72, total chlorine content 690 ppm, manufactured by Tohto Kasei Co., Ltd.) 40
g, 120 g of propylene glycol monomethyl ether
(Abbreviated as “MFG”) and 1.0 g of commercially available 5% Ru—C catalyst (manufactured by NE Chemcat) are charged.
After replacing the inside of the system with hydrogen, hydrogenation was carried out for 5 hours under conditions of 50 ° C. and a hydrogen pressure of 4.9 MPa while stirring. After the reaction, the catalyst was filtered off and the solvent was distilled off at 150 ° C. at 266 Pa to obtain hydrogenated bisphenol A diglycidyl ether (abbreviated as “reactive diluent A”). The obtained reactive diluent A had a nuclear hydrogenation rate of 99.9%, an epoxy equivalent of 191, and a content of the compound represented by the formula (1) was 0%.
The viscosity at 25 ° C. was 680 mPa · s, and the total chlorine content was 690 ppm.

Production Example 2 Bisphenol A diglycidyl ether ("R-140
S "(trade name), epoxy equivalent 185, total chlorine content 1
Hydrogenated bisphenol A diglycidyl ether was obtained by carrying out the reaction under the same conditions as in Production Example 1 except that the hydrogen pressure was set to 15 MPa using 600 ppm (Mitsui Petrochemical Co., Ltd.) 40 g (abbreviated as "reactive diluent B"). Yes.). The reactive diluent B thus obtained had a nuclear hydrogenation rate of 99.8%, an epoxy equivalent of 202, and a content of the compound represented by the formula (1) was 1
The viscosity was 3.0%, the viscosity at 25 ° C. was 1600 mPa · s, and the total chlorine content was 1600 ppm.

Example 1 Bisphenol A diglycidyl ether (“Epototo YD-128” (trade name), epoxy equivalent 185.5,
25 ° C viscosity 12700 mPa · s, manufactured by Tohto Kasei Co., Ltd., “DG
EBA "is abbreviated. ) 75 parts by weight, reactive diluent A
25 parts by weight were mixed at room temperature to obtain an epoxy resin solution. Next, 4-methylhexahydrophthalic anhydride (“Ricacid MH-700” (trade name), acid anhydride equivalent 164.8, so that the acid anhydride group / epoxy group equivalent ratio is 1.0).
Abbreviated as "Me-HHPA" manufactured by Shin Nippon Rika Co., Ltd. ) 8
8.2 parts by weight, 1,8-diazabicyclo [5.4.0]
Undecene-7 2-ethylhexanoate ("U-CA
"TSA102" (trade name), manufactured by San-Apro, "U-
CAT SA102 ". ) 0.5 parts by weight to 7
After mixing at 0 ° C for 30 minutes, the mixture was cooled to room temperature to obtain a curing agent liquid. The epoxy resin solution and the curing agent solution were mixed at room temperature and then degassed in vacuum to obtain an epoxy resin composition. The formulation viscosity, cured product Tg and chlorine extraction of the obtained epoxy resin composition were measured. The measurement results are shown in Table 1. The curing conditions were 100 ° C., 2 hours pre-curing, 130 ° C., 2 hours post-curing.

Example 2 An epoxy resin composition was obtained in the same manner as in Example 1 except that 50 parts by weight of DGEBA and 50 parts by weight of reactive diluent A were used. The blending amount of Me-HHPA was calculated with an acid anhydride group / epoxy group equivalent ratio of 1.0. The compounding ratio, the compounding viscosity of the obtained epoxy resin composition, the cured product Tg, and the chlorine extraction amount were measured. The measurement results are shown in Table 1.

Comparative Example 1 An epoxy resin composition was obtained in the same manner as in Example 1 except that the reactive diluent A was not used. Me-HHP
The compounding amount of A was calculated at an acid anhydride group / epoxy group equivalent ratio of 1.0. The compounding ratio, the compounding viscosity of the obtained epoxy resin composition, the cured product Tg, and the chlorine extraction amount were measured. The measurement results are shown in Table 1.

Comparative Examples 2-5 Hydrogenated bisphenol A diglycidyl ether produced by reaction of reactive diluent B in place of reactive diluent A or hydrogenated bisphenol A with epichlorohydrin (lycaredine "HBE-100" (commercial product Name), epoxy equivalent 214, total chlorine content 4.5%, viscosity at 25 ° C 2200
It is abbreviated as "HBE-100" manufactured by Shin Nippon Rika Co., Ltd. in mPa · s. ) Was used, and the same operation as in Example 1 was carried out except that the compounding ratio of DGEBA and these reactive diluents was changed to obtain an epoxy resin composition. The blending amount of Me-HHPA was calculated with an acid anhydride group / epoxy group equivalent ratio of 1.0.
The compounding ratio, the compounding viscosity of the obtained epoxy resin composition, the cured product Tg, and the chlorine extraction amount were measured. The results are shown in Table 1.

Example 3 75 parts by weight of DGEBA, 25 parts by weight of epoxy resin A, and 283 parts by weight of crushed fused silica (average particle size 10 μm) were mixed with a universal stirrer at 60 ° C. for 30 minutes to obtain an epoxy resin solution. Next, the acid anhydride group / epoxy group equivalent ratio is 1.0
88.2 parts by weight of Me-HHPA and 2-ethyl-4-methylimidazole (“Cureazole 2E4M
Z "(trade name), manufactured by Shikoku Kasei Kogyo Co., Ltd., and abbreviated as" 2E4MZ ". ) 0.5 part by weight was mixed and dissolved at 70 ° C. for 30 minutes and cooled to room temperature to obtain a curing agent liquid. The epoxy resin solution and the curing agent solution were mixed at room temperature and then degassed in vacuum to obtain an epoxy resin composition. The formulation viscosity, cured product Tg, and chlorine extraction of this epoxy resin composition were measured. The results are shown in Table 2. The curing conditions are 100 ° C. and 2 hours before pre-curing 15
The post-curing was performed at 0 ° C. for 5 hours.

Example 4 An epoxy resin composition was obtained in the same manner as in Example 3 except that DGEBA was 50 parts by weight and reactive diluent A was 50 parts by weight. The blending amount of Me-HHPA was calculated with an acid anhydride group / epoxy group equivalent ratio of 1.0. The formulation viscosity, cured product Tg and chlorine extraction of the obtained epoxy resin composition were measured. The measurement results are shown in Table 2.

Comparative Example 6 An epoxy resin composition was obtained by the same procedure as in Example 3 except that the reactive diluent A was not used. Me-HHP
The compounding amount of A was calculated at an acid anhydride group / epoxy group equivalent ratio of 1.0. The compounding ratio, the compounding viscosity of the obtained epoxy resin composition, the cured product Tg, and the chlorine extraction amount were measured. The measurement results are shown in Table 2.

Comparative Examples 7-10 Reactive diluent B or HBE-1 in place of reactive diluent A
No. 00 was used, and the same operation as in Example 3 was carried out except that the compounding ratio of DGEBA and these reactive diluents was changed to obtain an epoxy resin composition. The blending amount of Me-HHPA was calculated with an acid anhydride group / epoxy group equivalent ratio of 1.0. The compounding ratio, the compounding viscosity of the obtained epoxy resin composition, the cured product Tg, and the chlorine extraction amount were measured. The measurement results are shown in Table 1.

[0063]

[0064]

Examples 1 to 4 using reactive diluent A
Compared with Comparative Example 1 and Comparative Example 6 in which no diluent was used, the viscosity of the blend was low, and the workability of casting, coating, impregnation and the like was excellent. In addition, in Examples 1 to 4, the amount of chlorine extracted was smaller than that of HBE-100 produced by a conventionally known production method and Cu was used.
The corrosiveness of wiring and Al wiring indicates that migration is low. Comparative Examples 2 to 3 and Comparative Examples 7 to 7 in which the reactive diluent B containing 13% of the compound represented by the formula (1) was blended.
In Comparative Examples 4 to 5 and Comparative Examples 9 to 10 in which 8 and HBE-100 were blended, the viscosity of the blends was less decreased, and workability such as casting, coating and impregnation could not be improved. Further, Examples 1 to 4 using the reactive diluent A are HBE-100.
In comparison with Comparative Examples 4 to 5 and Comparative Examples 9 to 10 in which
Excellent heat resistance with little decrease in Tg.

[0066]

The liquid epoxy resin composition of the present invention is
Since it contains an epoxy-based reactive diluent with a low total chlorine content, excellent dilution effect, and less deterioration of physical properties such as Tg, it has low viscosity and good workability such as casting, coating and impregnation, and an inorganic filler, Even if a large amount of a filler such as a conductive filler is mixed, the liquid state can be maintained, the wiring such as aluminum is not corroded or migrated, and the Tg is high and the heat resistance is excellent. Therefore, liquid encapsulant for semiconductor package, photoelectric conversion element,
It can be used in a wide range of industrial fields including epoxy resin compositions such as conductive adhesives, die bonding pastes, anisotropic conductive pastes and via hole joint materials.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Tsutomu Fujitani             13 Yakura-cho, Yashimajima, Fushimi-ku, Kyoto-shi, Kyoto New             Within Nippon Rika Co., Ltd. F term (reference) 4J036 AA01 AA05 AB01 AC01 AC08                       AD01 AD07 AD08 AG06 AJ08                       AJ09 AJ11 AJ14 BA04 DB05                       DB15 DB17 DB18 DB21 DC02                       DC19 DC31 DC40 DC46 DD07                       FA01 FA03 FA04 FA05 FA06                       FA11 FB07 FB13 FB14 GA01                       GA03 GA04 GA06 GA19 GA20                       JA07                 4M109 AA01 EA02 EB02

Claims (3)

[Claims] 1. A nuclear hydride of bisphenol A diglycidyl ether, wherein the content of the compound represented by formula (1) in GPC analysis is 5% or less and the nuclear hydrogenation rate is 80.
% Or more, the total chlorine content is 0.2% by weight or less, the epoxy equivalent is 210 or less, and the viscosity at 25 ° C. is 1000 mPa · s.
An epoxy-based reactive diluent characterized in that: 2. A liquid epoxy resin composition containing an epoxy resin (A), an epoxy-based reactive diluent (B), a curing agent (C) and optionally a filler (D),
A liquid epoxy resin composition, wherein the component (B) is the epoxy-based reactive diluent according to claim 1. 3. A semiconductor package encapsulating material comprising the liquid epoxy resin composition according to claim 2.