WO2015125760A1

WO2015125760A1 - Resin-modified filler, epoxy resin composition, and cured product thereof

Info

Publication number: WO2015125760A1
Application number: PCT/JP2015/054217
Authority: WO
Inventors: 政隆中西
Original assignee: 日本化薬株式会社
Priority date: 2014-02-19
Filing date: 2015-02-17
Publication date: 2015-08-27
Also published as: TWI663220B; TW201544553A; JPWO2015125760A1; JP6521942B2

Abstract

The purpose of the present invention is to provide: a resin-modified filler exhibiting excellent anti-blocking properties, and contributing fluidity to an epoxy resin composition; an epoxy resin composition using the same; and a cured product thereof. This resin-modified filler is one containing an inorganic filler (a) and an epoxy resin (b) having an average of 2-10 epoxy groups in each molecule, wherein the weight ratio of (a) to (b) is (a):(b)=70:30-98:2, and the lengthwise diameter thereof is 5cm or less.

Description

Resin-modified filler, epoxy resin composition, and cured product thereof

The present invention relates to a resin-modified filler that gives an epoxy resin composition excellent in fluidity and handling characteristics, an epoxy resin composition using the same, and a cured product thereof.

The present invention relates to electrical and electronic material applications that require high functionality, and particularly to a resin-modified filler, an epoxy resin composition, and a cured product thereof suitable as a semiconductor sealant and a thin film substrate material.

Epoxy resin compositions are widely used in the fields of electrical and electronic parts, structural materials, adhesives, paints, etc. due to their workability and excellent electrical properties, heat resistance, adhesion, moisture resistance (water resistance), etc. It has been.

However, in recent years, with the development in the electric / electronic field, moisture resistance, adhesion, dielectric properties, low viscosity for high filling of filler (inorganic or organic filler) as well as high purity of resin composition, There is a need for further improvements in various properties such as increased reactivity to shorten the molding cycle. Further, as a structural material, there is a demand for a material that is lightweight and has excellent mechanical properties in applications such as aerospace materials and leisure / sports equipment. Especially in the field of semiconductor encapsulation, substrates (substrate itself or its peripheral materials), the complexity of thinning, stacking, systematization, and three-dimensionalization has become more complex as the semiconductor has changed. Pitching and thinning are progressing more and more, and if there is no high fluidity, a wire sweep is induced. Furthermore, it has come to have a bad influence on the connection part of a wire.
Furthermore, in the flip chip type package, a technique called MUF is attracting attention because it does not use an underfill from the aspect of a low cost manufacturing method and seals at a stretch. In this application, the resin needs to pass through a very narrow gap between the chip and the package substrate, and miniaturization of the filler is important. This miniaturization increases the viscosity of the system and causes voids.
Furthermore, in the sealing resin used for the rewiring layer such as wafer level package and the correlation insulating film used for the build-up layer, etc., the thickness of the layer is thin and the filler is filled with fine filler to reduce the linear expansion coefficient. Necessary. Therefore, the low viscosity of the system is necessary in this application as well (Non-Patent Document 1).

In general, as a method for reducing the viscosity of an epoxy resin composition, lowering the molecular weight of the resin used is used. However, if the molecular weight is lowered, the softening point decreases, and the shape at room temperature tends to have fluidity. Problems such as difficulty in handling at room temperature and stickiness when used as a composition make storage and handling difficult.
Thus, although provision of a crystalline epoxy resin is being studied for such applications, even if the handling characteristics of the resin itself are good, crystallization does not proceed after melt-kneading and may be sticky. Even if this is intended to be uniform at the time of kneading, the clearance of kneading is large in industrial production, and since uniform kneading is difficult, resin lumps remain on the surface, thereby promoting blocking, etc. This is because the problem arises.
In view of such conventional problems, the present invention provides a resin-modified filler that contributes to the fluidity of an epoxy resin composition and has excellent blocking resistance, an epoxy resin composition using the resin-modified filler, and a cured product thereof. Is an issue.

As a result of intensive studies in view of the actual situation as described above, the present inventors have completed the present invention.
That is, the present invention relates to the following [1] to [4].
[1] A resin-modified filler comprising an inorganic filler (a) and an epoxy resin (b) having an average of 2 to 10 epoxy groups in one molecule,
A resin-modified filler having a weight ratio of (a) to (b) of (a) :( b) = 70: 30 to 98: 2 and a major axis of 5 cm or less.
[2] The resin-modified filler according to [1], wherein the softening point of the epoxy resin (b) is 35 to 75 ° C.
[3] An epoxy resin composition comprising the resin-modified filler according to [1] or [2] and a curing agent for epoxy resin and / or a polymerization catalyst.
[4] A cured product obtained by curing the epoxy resin composition according to [3].

The resin-modified filler of the present invention is a filler that contributes to the fluidity of the epoxy resin composition, and the curable epoxy resin composition containing the filler includes an insulating material for electrical and electronic parts and a laminate (printed wiring board, build It is useful for various composite materials such as up-substrates) and CFRP, adhesives and paints. In particular, it is extremely useful for a semiconductor sealing material for protecting a semiconductor element.

FIG. 1 is an enlarged photograph of the massive resin-modified filler of the present invention. FIG. 2 is an enlarged photograph of the powdery resin-modified filler of the present invention. FIG. 3 is an enlarged photograph of a mixture of an epoxy resin and an inorganic filler. FIG. 4 is an enlarged photograph (magnification 200 times) of the resin-modified filler obtained in Example 8. FIG. 5 is an enlarged photograph of the resin-modified filler obtained in Example 8 (magnification rate 800 times). FIG. 6 is an enlarged photograph (magnification rate 50000 times) of the resin-modified filler obtained in Example 8. FIG. 7 is an enlarged photograph (magnification 200 times) of the resin-modified filler obtained in Example 9. FIG. 8 is an enlarged photograph (magnification rate 800 times) of the resin-modified filler obtained in Example 9. FIG. 9 is an enlarged photograph (magnification rate 50000 times) of the resin-modified filler obtained in Example 9.

The resin-modified filler of the present invention contains an inorganic filler (a) and an epoxy resin (b) having an average of 2 to 10 epoxy groups in one molecule.

In the present invention, the inorganic filler (a) is silica gel (crystalline silica, fused silica, nano silica, sol-gel silicon oxide polymer, etc.), alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, Examples include, but are not limited to, powders such as fosterite, steatite, spinel, titania, and talc, or beads obtained by spheroidizing these. These may be used alone or in combination of two or more. In the present invention, silica gel, alumina, boron nitride, aluminum nitride and the like are particularly preferable, and silica gel and alumina are particularly preferable.
There are various particle sizes, but the average particle size is preferably 0.1 to 100 μm, more preferably 0.1 to 60 μm, and particularly preferably 0.1 to 30 μm. The average particle size can be measured using, for example, a laser diffraction / scattering type particle size distribution analyzer (dry type) (manufactured by Seishin Co., Ltd .: LMS-30).
The average particle size is preferably selected according to the package shape. In the case of a flip chip type, 0.1 to 10 μm is preferable, and 0.1 to 5 μm is more preferable. In the case of a wire bonding type, 1 to 30 μm is preferable, and 1 to 25 μm is particularly preferable.

Specific examples of the epoxy resin (b) used in the present invention include novolac type epoxy resin, bisphenol A type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol aralkyl type epoxy resin and the like. Specifically, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetate Enone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1, Glycidyl ethers derived from polycondensates with 4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene and the like, modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, and alcohols , Cycloaliphatic epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, silsesquioxane epoxy resin (chain structure, cyclic structure, ladder structure, or a mixed structure of at least two of them) Glycidyl group and / or epoxycyclohexane structure Epoxy resin) epoxy resin and the like having, but not limited thereto. Among these, biphenyl type phenol aralkyl type epoxy resins, phenyl type phenol aralkyl type epoxy resins, polycondensates of phenols with dicyclopentadiene, modified products thereof, and novolac type epoxy resins are preferred.

However, in the present invention, the softening point of the resin is particularly preferably 35 to 75 ° C, and particularly preferably 35 to 60 ° C. In general, an epoxy resin can be kept in a solid state while suppressing blocking in the epoxy resin when used in an environment lower by 30 ° C. than the softening point. Epoxy resins are preferably used at a temperature lower by 50 ° C. than the softening point. In that case, when the temperature exceeds 75 ° C., it usually becomes solid, and it is not necessary to use this method. There is a risk that it may end up. Further, a compound having a softening point of 35 to 75 ° C. tends to have an excellent balance between melt viscosity and curing characteristics such as heat resistance.
Moreover, the preferable melt viscosity in 150 degreeC is 0.2 Pa.s or less. If the melt viscosity is higher than 150 ° C., there is a risk of problems in moldability. Since the lower the viscosity, the more useful it is, the lower limit is not set in the present invention (measurement is difficult with a normal viscometer).

The epoxy resin used in the present invention has an average of 2 to 10 epoxy groups in one molecule. If the average number of epoxy groups contained in one molecule is less than 2, the curing properties such as heat resistance will be adversely affected. If the average number of epoxy groups contained in one molecule exceeds 10, the viscosity will be very high. However, there is a problem in handling characteristics.
The epoxy equivalent of the epoxy resin used in the present invention is 150 to 750 g / eq. And particularly preferably 150 to 500 g / eq. It is. By being in this range, the composition tends to have good fluidity and curability, and the cured product tends to have excellent heat resistance, thermal decomposition characteristics, water absorption characteristics, and mechanical strength. It can be suitably used for manufacturing a semiconductor device.

In the present invention, the weight ratio of the inorganic filler (a) to the epoxy resin (b) is (a) :( b) = 70: 30 to 98: 2, more preferably 70:30 to 95: 5. It is.
When the proportion of the filler amount is reduced compared to the ratio of (a) :( b) = 70: 30, particularly when an epoxy resin having a softening point of 60 ° C. or lower is used, blocking is likely to occur in handling at room temperature. , Handling becomes very difficult. For example, when an epoxy resin having a softening point of 50 ° C. or lower is used, it becomes difficult to finely pulverize, granulate, flakes or small blocks. That is, from the viewpoint of characteristics such as fluidity and handling, (a) :( b) = 70: 30 to 98: 2.

The resin-modified filler of the present invention can further contain additives such as a coupling agent. The coupling agent is preferably added during mixing in order to improve the familiarity between the resin and the filler.
Preferred coupling agents include, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Methoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxy Silane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloro Silane coupling agents such as propyltrimethoxysilane; isopropyl (N-ethylaminoethylamino) titanate, isopropyl triisostearoyl titanate, titanium di (dioctyl pyrophosphate) oxyacetate, tetraisopropyl di (dioctyl phosphite) titanate Titanium coupling agents such as neoalkoxytri (pN- (β-aminoethyl) aminophenyl) titanate; Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neoalkoxyzirconate, neoalkoxytrisneo Decanoyl zirconate, neoalkoxytris (dodecanoyl) benzenesulfonyl zirconate, neoalkoxytris (ethylenediaminoethyl) zirconate, neoalkoxy Examples thereof include zirconium such as citris (m-aminophenyl) zirconate, ammonium zirconium carbonate, Al-acetylacetonate, Al-methacrylate, and Al-propionate, or an aluminum coupling agent.
These coupling agents may be used alone or in combination of two or more.
In the epoxy resin composition of the present invention, the coupling agent is usually contained in an amount of 0.05 to 20 parts by weight, preferably 0.1 to 10 parts by weight, if necessary.

The method for producing the resin-modified filler of the present invention is not particularly specified, but a method using a solvent is preferable. Although there is a modification method by melt-kneading, in consideration of uniformly coating and / or impregnating the epoxy resin with the filler, it is preferable that the filler be sufficiently familiar with the filler. Specifically, the resin-modified filler of the present invention is obtained by mixing a solvent, a resin and a filler, and then distilling off the solvent under reduced pressure. At this time, the resin may be dissolved in the solvent in advance, and then the filler may be added and mixed, or the resin may be added and mixed in a place where the filler is dispersed in the solvent, or may be added simultaneously. The mixing temperature is not particularly limited, but is preferably 0 ° C. to 100 ° C., particularly preferably 10 ° C. to 80 ° C. In addition, you may use the method of cooling after heating and making it uniform.
The solvent is distilled off under reduced pressure. The distillation temperature of the solvent is usually 50 to 200 ° C, particularly preferably 50 to 180 ° C. At this time, the residual solvent is preferably 1% or less, and if it exceeds this, voids and peeling may occur during molding.

Solvents that can be used in the present invention include aromatic hydrocarbons represented by toluene, xylene, naphtha, ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetone, cyclohexanone, cyclopentanone, ethyl acetate, butyl acetate, ethyl lactate, Examples include carbitol acetate, propylene glycol monomethyl ether acetate, esters such as γ-butyrolactone, alcohols such as methanol, ethanol, and pronol butanol, and ethers such as diglyme, triglyme, dioxane, and tetrahydrofuran. Hydrogens, ketones, and esters are preferable from the solubility of the resin, and it is particularly preferable to use ketones and esters. Two or more kinds of solvents can be combined, and the dispersibility of the resin soluble filler and the volatility at the time of distillation can be adjusted. For example, it is possible to adjust solubility with a combination of ketones and alcohols, and to adjust volatility with ketones and aromatic hydrocarbons.
In the present invention, those having a boiling point of 150 ° C. or lower are preferable, and particularly preferably 130 ° C. or lower. If the boiling point is too high, residual solvent tends to remain, which is not preferable.

In the present invention, the method for distilling off the solvent is not particularly limited, but it is preferable to distill off the solvent while stirring. Specifically, a nauter mixer, ribocorn, conical dryer, a planetary mixer under reduced pressure, an evaporator, A structure such as a vacuum dryer (a chopper that can be used under reduced pressure) is preferable, and a structure that can be stirred in an environment capable of reducing the pressure at 200 torr or less is preferable. However, in the case of a metal pulverizer that is crushed vigorously, the possibility of metal contamination is high, which is not preferable.
In the present invention, the number of magnetized foreign metal particles of 100 μm or more is preferably 1 or less per 10 g, more preferably 1 or less per 30 g, and particularly preferably 1 or less per 50 g. When one or more magnetized foreign substances are mixed per 100 g, there is a risk of giving a fatal problem to the completed semiconductor device.

The resin-modified filler thus obtained is in the form of granules, lumps, or powders, and even if it is piled up at 1 cm or more at 20 ° C., it does not become a single lumps for more than one week. 5 cm) or powder (major axis: 0.1 μm to 0.1 mm). In addition, the lump and the powder remain as a guideline for separating both. Here, the fact that it is not a single lump indicates that it is a sticking to the extent that it can be loosened by the power of human hands, even if there is a little sticking. When blocking that normally occurs when a general epoxy resin is stacked, the shape becomes almost single and does not become a shape that can be loosened by human hands. A particularly preferable shape is one that does not become a single lump even when stored at 100 ° C. for 1 hour or longer.
The resin-modified filler of the present invention exists, for example, in a state in which an inorganic resin is impregnated with a filler in which inorganic fillers are bound together by an epoxy resin or an inorganic filler. The major axis of the resin-modified filler is 5 cm or less, preferably 0.1 μm to 1 cm, and more preferably 0.3 μm to 5 mm. Here, the major axis indicates the diameter of the longest diameter of granular, massive or powdery particles, and the measurement method is to use a ruler or have a mesh of a certain size to be measured. It can be measured by passing the mesh and confirming the presence or absence of the passage. It is also possible to measure the major axis using a microscope. The average particle size is usually 5 cm or less, preferably 0.1 μm to 1 cm, and more preferably 0.3 μm to 5 mm. The measurement method is the same.
As an example of the shape of the resin-modified filler of the present invention, each of FIGS. 1 and 2 is compared with a conventional mixture of an epoxy resin and an inorganic filler (integrated in a plate shape as a whole: FIG. 3). It is the shape shown in.

Hereinafter, it describes about the epoxy resin composition of this invention containing the resin modified filler of this invention.
In the epoxy resin composition of the present invention, a curing agent and / or a polymerization catalyst are used as essential components. In addition, it is also conceivable to add an epoxy resin separately. In that case, the epoxy resin that can be used is not particularly limited, but for example, the above-described epoxy resin can be used.

Specific examples of the curing agent contained in the epoxy resin composition of the present invention include, for example, phenol resins, phenol compounds, amine compounds, acid anhydride compounds, amide compounds, carboxylic acid compounds, and the like. Specific examples of the curing agent that can be used include phenol resin, phenol compound; bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 '. , 5,5'-tetramethyl- [1,1'-biphenyl] -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2- Tetrakis (4-hydroxyphenyl) ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1'-biphenyl, 4,4'-bis (methoxymethyl)- Polycondensates with 1,1′-biphenyl, 1,4′-bis (chloromethyl) benzene, 1,4′-bis (methoxymethyl) benzene, etc., and their modified products, halogenated tetrabromobisphenol A, etc. Polyphenols such as bisphenols and condensates of terpenes and phenols are exemplified, but the invention is not limited to these. These may be used alone or in combination of two or more.

Preferable phenol resins include phenol aralkyl resins (resins having an aromatic alkylene structure), particularly preferably a structure having at least one selected from phenol, naphthol, and cresol, and the alkylene portion serving as the linker is benzene. A resin characterized by at least one selected from a structure, a biphenyl structure, and a naphthalene structure (specific examples include zylock, naphthol zylock, phenol biphenylene novolak resin, cresol-biphenylene novolak resin, phenol-naphthalene novolak resin, etc.) Is.)
Amine compounds, amide compounds; nitrogen-containing compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, linolenic acid and polyamide resins synthesized from ethylenediamine;
Acid anhydride compounds, carboxylic acid compounds; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydro Phthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2.2.1] heptane-2, Acid anhydrides such as 3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, etc .; by addition reaction of various alcohols, carbinol-modified silicone, and the above-mentioned acid anhydrides Resulting carboxylic acid resin;
Others: Examples include, but are not limited to, imidazole, trifluoroborane-amine complexes, guanidine derivative compounds, and the like. These may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a phenol resin from the viewpoint of reliability.

In the epoxy resin composition of the present invention, the amount of curing agent used is preferably 0.7 to 1.2 equivalents relative to 1 equivalent of the epoxy groups of all epoxy resins. When less than 0.7 equivalent or more than 1.2 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.

In the epoxy resin composition of the present invention, the polymerization catalyst may be used in combination with a curing agent or without a curing agent. Specific examples of the polymerization catalyst that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo. Tertiary amines such as (5,4,0) undecene-7, phosphines such as tolylphosphine and triphenylphosphine, tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium Quaternary ammonium salts such as salts, quaternary phosphonium salts such as triphenylbenzylphosphonium salts, triphenylethylphosphonium salts, and tetrabutylphosphonium salts. (The counter ion of the quaternary salt is not particularly specified, such as halogen, organic acid ion, hydroxide ion, etc., but organic acid ion and hydroxide ion are particularly preferable), metal compounds such as tin octylate, etc. It is done. When a curing accelerator is used, 0.01 to 5.0 parts by weight is used as necessary with respect to 100 parts by weight of the epoxy resin.
In the present invention, tertiary amines, phosphines, quaternary phosphonium salts and the like are particularly preferable.
When amine-based compounds such as tertiary amines are used as the polymerization catalyst, the curing agent may be cured without using a curing agent, or the curing agent amount may be smaller than a predetermined amount, and may be cured by anionic polymerization. It doesn't matter.

In the epoxy resin composition, other epoxy resins may be used in combination with the epoxy resin used for the resin-modified filler of the present invention. When used in combination, the proportion of the epoxy resin used in the resin-modified filler of the present invention in the total epoxy resin is preferably 15% by weight or more, particularly preferably 20% by weight or more.

Specific examples of other epoxy resins include novolac type epoxy resins, bisphenol A type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, phenol aralkyl type epoxy resins, and the like. Specifically, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetate Enone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1, Glycidyl ethers derived from polycondensates with 4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene and the like, modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, and alcohols , Cycloaliphatic epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, silsesquioxane epoxy resin (chain structure, cyclic structure, ladder structure, or a mixed structure of at least two of them) Glycidyl group and / or epoxycyclohexane structure Epoxy resin) epoxy resin and the like having, but not limited thereto.

The epoxy resin composition of the present invention can contain a phosphorus-containing compound as a flame retardant component. The phosphorus-containing compound may be a reactive type or an additive type. Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis ( Phosphoric esters such as dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9-oxa Phosphanes such as -10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide; epoxy resin and active hydrogen of the phosphanes Contains phosphorus obtained by reacting with Poxy compounds, red phosphorus and the like can be mentioned. Phosphate esters, phosphanes or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylenebis (dixylylenyl phosphate), 1,4-phenylenebis (dixylylene). Nyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred. The phosphorus-containing compound content is preferably phosphorus-containing compound / total epoxy resin = 0.1 to 0.6 (weight ratio). If it is 0.1 or less, the flame retardancy is insufficient, and if it is 0.6 or more, there is a concern that it may adversely affect the hygroscopicity and dielectric properties of the cured product.

Furthermore, an antioxidant may be added to the epoxy resin composition of the present invention as necessary. Antioxidants that can be used include phenol-based, sulfur-based, and phosphorus-based antioxidants. Antioxidants can be used alone or in combination of two or more. The amount of the antioxidant used is usually 0.008 to 1 part by weight, preferably 0.01 to 0.5 part by weight, per 100 parts by weight of the resin component in the epoxy resin composition of the present invention.

Examples of the antioxidant include a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant. Specific examples of phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,4-bis- (n-octylthio)- Monophenols such as 6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,4-bis [(octylthio) methyl] -o-cresol; 2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-thiobis (3- Til-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) ) Propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t -Butyl-4-hydroxy-hydrocinnamamide), 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,5-di-t -Butyl-4-hydroxybenzyl phosphonate-diethyl ester, 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl-4-hydroxy-5- Bisphenols such as (tilphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, bis (3,5-di-t-butyl-4-hydroxybenzylsulfonate ethyl) calcium 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t- Butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, bis [3,3′-bis- (4 '-Hydroxy-3'-tert-butylphenyl) butyric acid] glycol ester, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -iso Anureate, 1,3,5-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol And the like.

Specific examples of the sulfur antioxidant include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyll-3,3′-thiodipropionate, and the like. .

Specific examples of phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2,4-di-t- Butylphenyl) phosphite, cyclic neopentanetetraylbis (octadecyl) phosphite, cyclic neopentanetetraylbi (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbi (2,4 -Phosphites such as -di-t-butyl-4-methylphenyl) phosphite, bis [2-tert-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] hydrogen phosphite ; 9,10-dihydride -9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene- Examples thereof include oxaphosphaphenanthrene oxides such as 10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the like.

These antioxidants can be used alone, but two or more kinds may be used in combination. In the present invention, a phosphorus-based antioxidant is particularly preferable.

Furthermore, you may add a light stabilizer to the epoxy resin composition of this invention as needed.
As the light stabilizer, hindered amine-based light stabilizers, particularly HALS and the like are suitable. HALS is not particularly limited, but representative examples include dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4- Polycondensate of piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, dimethyl-1- (2-hydroxyethyl) -4-hydroxy succinate -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}], bis (1,2,2, 6,6-Pentamethyl-4-pi Peridyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2- (3,5-di -T-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), etc. Only one HALS is used. Two or more types may be used in combination.

Furthermore, the epoxy resin composition of the present invention can be blended with a binder resin as necessary. Examples of the binder resin include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, and silicone resins. However, it is not limited to these. The blending amount of the binder resin is preferably within a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 50 parts by weight, preferably 0.05 to 20 parts per 100 parts by weight of the resin component. Part by weight is used as needed.

The epoxy resin composition of the present invention further includes various combinations of a silane coupling agent, a release agent such as stearic acid, palmitic acid, zinc stearate, calcium stearate, a surfactant, a dye, a pigment, and an ultraviolet absorber. An agent and various thermosetting resins can be added.

The epoxy resin composition of the present invention can be obtained by uniformly mixing each component. The epoxy resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, until the resin-modified filler of the present invention, a curing agent, and if necessary, a curing accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, and a compounding agent are uniform using an extruder, a kneader, a roll, or the like as necessary Mix thoroughly to obtain an epoxy resin composition, pot the epoxy resin composition, and after melting (without melting in the case of liquid), mold using a casting or transfer molding machine, and further at 80 to 200 ° C. The cured product of the present invention can be obtained by heating for 2 to 10 hours.

The cured product obtained by curing the epoxy resin composition of the present invention can be used for various applications. Preferably used as a sealing material for semiconductors, but other than that, for example, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials (including printed circuit boards, wire coatings, etc.) ), Additives to other resins and the like in addition to the sealant. Examples of the adhesive include civil engineering, architectural, automotive, general office, and medical adhesives, and electronic material adhesives. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).

As sealing agents, potting, dipping, transfer mold sealing for capacitors, transistors, diodes, light-emitting diodes, ICs, LSIs, potting sealings for ICs, LSIs such as COB, COF, TAB, flip chip It is suitable for underfill for such as, and for sealing (including reinforcing underfill) when mounting IC packages such as QFP, BGA, and CSP.

EXAMPLES Next, the present invention will be described more specifically with reference to examples. In the following, parts are parts by weight unless otherwise specified. The present invention is not limited to these examples.
The various analysis methods used in the examples are described below.
・ Epoxy equivalent: Conforms to JIS K 7236 (ISO 3001) ・ ICI melt viscosity: Conforms to JIS K 7117-2 (ISO 3219) ・ Softening point: Conforms to JIS K 7234

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

Examples 1-7, Comparative Examples 1-4
Methyl ethyl ketone (MEK) as a solvent, orthocresol novolak type epoxy resin having a softening point of 52 ° C. as an epoxy resin (EP1: Nippon Kayaku EOCN-1020-52), orthocresol novolak type epoxy resin having a softening point of 55 ° (EP2: Nippon Kayaku EOCN-1020-55), softening point 52 ° C. biphenyl novolac type epoxy resin (EP3: Nippon Kayaku NC-3000-L), softening point 45 ° C. trisphenol methane type epoxy resin ( EP4: Trisphenolmethane (TrisP-M made by Honshu Chemical Industry) glycidyl ether, epoxidized bisphenolfluorene ethylene oxide adduct (EP5: Osaka Gas Chemical Co., Ltd.) with a softening point of 40 ° C, fused silica as inorganic filler (MSR made by Sasamori 2122) The following procedure was performed with the composition of Table 1 using.

A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with methyl ethyl ketone (MEK) and each epoxy resin shown in Table 1 as a solvent while purging with nitrogen, and then stirred at 25 ° C. for 1 hour. Thereafter, the solvent was distilled off by a rotary evaporator, and finally, the solvent was distilled off at 120 ° C. under a reduced pressure of 20 torr until no solvent was left.
The obtained resin-modified filler was taken out, the sample was embedded in resin after platinum sputtering, a cross-sectional sample was prepared at CP 3.5 kV, and the sample was observed with SEM (non-deposition low vacuum acceleration voltage 10 kV). Was a particle size of 5.0 cm or less, and it was confirmed that the resin and the filler had a collected shape. Moreover, the blocking test was done over one week at 25 degreeC. The results are shown in Table 1.

As described in Table 1, the resin-modified filler of the present invention maintained the powdery or granular shape both immediately after production and after the stability test, and the result of the blocking test was also good. On the other hand, the mixture of the epoxy resin and the inorganic filler of the comparative example could only be obtained in the form of blocking immediately after production or after the stability test, or in the form of a plate and inferior in handleability.

Examples 8 and 9
Acetone and methyl isobutyl ketone (1: 1) solution as solvent, biphenyl novolac type epoxy resin (EP6: Nippon Kayaku NC-3000) having a softening point of 58 ° C as epoxy resin, and spherical silica (Admafine 1030 Admatechs) as inorganic filler Co., Ltd. (average particle size: 0.3 μm) using solution 150, epoxy resin 10, spherical silica 90 composition (Example 8), and solution 150, epoxy resin 20, spherical silica 80 composition (Example 9) The following operations were performed.
Each of the flasks equipped with a stirrer, a reflux condenser, and a stirrer was charged with the above composition, and then stirred at 25 ° C. for 30 minutes. Thereafter, the solvent was distilled off with a rotary evaporator, and finally, the solvent was distilled off at 120 ° C. under a reduced pressure of 20 torr until no solvent was left.
The obtained resin-modified filler was taken out, the sample was embedded in resin after platinum sputtering, a cross-sectional sample was prepared at CP 3.5 kV, and the sample was observed with SEM (non-deposition low vacuum acceleration voltage 10 kV). Is a particle diameter of 1 mm or less, and it has been confirmed that the resin and filler are in a collected shape. 4 to 9, it can be seen that the resin and filler are mixed and the outermost surface is covered with the filler. In addition, when a blocking test was performed at 25 ° C. over 1 week, no blocking (a state in which many resins were in contact with each other) was observed.

Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
The present application is based on a Japanese patent application (Japanese Patent Application No. 2014-029097) filed on February 19, 2014, and is incorporated by reference in its entirety. Also, all references cited herein are incorporated as a whole.

Claims

A resin-modified filler comprising an inorganic filler (a) and an epoxy resin (b) having an average of 2 to 10 epoxy groups in one molecule,
A resin-modified filler having a weight ratio of (a) to (b) of (a) :( b) = 70: 30 to 98: 2 and a major axis of 5 cm or less.
The resin-modified filler according to claim 1, wherein the softening point of the epoxy resin (b) is 35 to 75 ° C.
An epoxy resin composition comprising the resin-modified filler according to claim 1 and a curing agent for epoxy resin and / or a polymerization catalyst.
A cured product obtained by curing the epoxy resin composition according to claim 3.