TWI663220B - Method for manufacturing resin modified concrete - Google Patents

Abstract

An object of the present invention is to provide a resin-modified filler which imparts fluidity to an epoxy resin composition and is excellent in blocking resistance, an epoxy resin composition using the filler, and a cured product thereof.

The modified resin 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, and the weight ratio of (a) to (b) is (a ): (B) = 70: 30 ~ 98: 2, and the long axis is 5 cm or less.

Description

Manufacturing method of resin modified filler

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

The present invention relates to an application of electrical and electronic materials that require high functions, especially a resin modified filler, a epoxy resin composition, and a cured product thereof, which are preferred as semiconductor sealants, film substrate materials.

Epoxy resin compositions are widely used in electrical and electronic parts, structural materials, adhesives, and coatings because of their excellent electrical properties, heat resistance, adhesion, and moisture resistance (water resistance). And other fields.

However, in recent years in the electrical and electronic fields, along with its development, it is required to be represented by the high purity of the resin composition, moisture resistance, adhesion, electrical properties, and high filling fillers (inorganic or organic fillers). Various properties such as lower viscosity and improved reactivity to shorten the molding cycle have been further improved. In addition, as a structural material, materials that are lightweight and excellent in mechanical properties are required for aerospace materials, leisure, and sports equipment applications. Especially in the field of semiconductor sealing and the substrate (the substrate itself or its surrounding materials), with the change of its semiconductor, thinning, stacking, systematization, and three-dimensionalization become complicated, and the narrow pitch of its metal wire wiring 3. Thinning continues to develop. Without high fluidity, wire sweep is induced. Further, it adversely affects the connection portion of the metal wire.

Furthermore, in the flip-chip type package, a method of performing MUF sealing without using under filling in terms of a so-called inexpensive manufacturing method has attracted much attention. In this application, the resin must pass through a very narrow gap between the wafer and the package substrate, and the miniaturization of the filler becomes important. Due to the miniaturization, the viscosity of the system increases and becomes a cause of voids.

Furthermore, in sealing resins used in redistribution layers such as wafer-level packaging, or related insulating films used in build up layer layers, the thickness of the layers is thinner, and the linear expansion rate is reduced, so they must be filled. Fine filler. Therefore, also in this application, the same as the above, a low viscosity of the system becomes necessary (Non-Patent Document 1).

Non-Patent Document 1: "2008 Annual Report of the Special Committee on Semiconductor Road Map of the 2008 STRJ Report", Chapter 8, p1-17, [online], March 2009, JEITA (Company) Electronics and Information Technology Industry Association Semiconductors Technical Blueprint Special Committee, [Retrieved on May 30, 2012], Internet <URL: http: //strj-jeita.elisasp.net/strj/nenjihoukoku-2008.cfm>

As a method for reducing the viscosity of a general epoxy resin composition, the molecular weight of the resin used can be reduced. However, if the molecular weight is reduced, the softening point is reduced, and the shape at room temperature becomes easy to have fluidity. Operation at room temperature also causes stickiness when used as a composition, causing discomfort such as difficulty in storage and handling.

Therefore, for this application, the provision of a crystalline epoxy resin has been studied, but even if the resin itself has good processing characteristics, it is difficult to crystallize after melt-kneading, and it may be sticky. Although it is uniform at the time of kneading, since the clearance of kneading is large in industrial manufacturing, it is difficult to knead uniformly to leave a resin block on the surface, which causes problems such as blocking promotion.

In view of such a previous problem, an object of the present invention is to provide a resin-modified filler that imparts fluidity to an epoxy resin composition and is excellent in end-capping resistance, an epoxy resin composition using the filler, and a cured product thereof.

The present inventors have made intensive studies in view of the above-mentioned actual situation, and as a result, have completed the present invention.

That is, the present invention relates to the following [1] to [4].

[1] A resin modified filler containing an inorganic filler (a) and an epoxy resin (b) having an average of 2 to 10 epoxy groups in one molecule, and a weight ratio of (a) to (b) (A) :( b) = 70: 30 ~ 98: 2, and the long axis is 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 containing the resin-modified filler of [1] or [2], a hardener for epoxy resin, and / or a polymerization catalyst.

[4] A cured product obtained by curing the epoxy resin composition of [3].

The resin-modified filler of the present invention imparts fluidity to an epoxy resin composition, and the hardening epoxy resin composition containing the filler is suitable for insulating materials for electric and electronic parts and laminated boards (printed wiring boards, laminated layers). Boards, etc.) or CFRP is useful for a variety of composite materials, adhesives, coatings, etc. It is particularly useful for semiconductor sealing materials for protecting semiconductor elements.

FIG. 1 is an enlarged photograph of a block-shaped resin-modified filler of the present invention.

FIG. 2 is an enlarged photograph of the powdery resin-modified filler of the present invention.

Figure 3 is an enlarged photograph of a mixture of an epoxy resin and an inorganic filler.

FIG. 4 is an enlarged photograph (200x magnification) of the resin-modified filler obtained in Example 8. FIG.

FIG. 5 is an enlarged photograph (800 times magnification) of the resin-modified filler obtained in Example 8. FIG.

FIG. 6 is an enlarged photograph (50,000 times magnification) of the resin-modified filler obtained in Example 8. FIG.

FIG. 7 is an enlarged photograph (200 times magnification) of the resin-modified filler obtained in Example 9. FIG.

FIG. 8 is an enlarged photograph (800 times magnification) of the resin-modified filler obtained in Example 9. FIG.

FIG. 9 is an enlarged photograph (50,000 magnifications) of the resin-modified filler obtained in Example 9. FIG.

The modified resin 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.

Examples of the inorganic filler (a) in the present invention include: silica gel (from crystalline silica, fused silica, nano-silica, sol-gel silica polymer, etc.), alumina, zircon , Calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, forsterite, talc, spinel, titanium oxide, talc, etc. Etc., but not limited to them. These can be used alone or in combination of two or more. Particularly preferred in the present invention are silica gel or alumina, boron nitride, aluminum nitride, and the like, and particularly preferred are silica gel and alumina.

There are various types of particle diameters, but the average particle diameter is preferably 0.1 to 100 μm, more preferably 0.1 to 60 μm, and particularly preferably 0.1 to 30 μm. The measurement of the average particle diameter can be performed using, for example, laser diffraction, a scattering-type particle size distribution measuring device (dry type) (manufactured by SEISHIN ENTERPRISE CO., LTD: LMS-30), and the like.

The average particle diameter is preferably selected based on the package. If it is a flip chip type, it is preferably 0.1 to 10 μm, and more preferably 0.1 to 5 μm. If it is a metal wire bonding type, it is preferably 1 to 30 μm, particularly preferably 1 to 25 μm.

Specific examples of the epoxy resin (b) used in the present invention include novolac epoxy resin, bisphenol A epoxy resin, biphenyl epoxy resin, triphenylmethane epoxy resin, Phenol aralkyl type epoxy resin and the like. Specific examples include: bisphenol A, bisphenol S, thiobiphenol, pyrene bisphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'-tetramethyl- [1,1'-biphenyl] -4,4'-diol, hydroquinone, resorcinol, 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) -1,1'-biphenyl, 1,4-bis (chloromethyl) benzene, 1,4-bis (methoxy) Polymethyl condensates such as benzene, etc. and their modifications, epoxypropyl etherates derived from halogenated bisphenols such as tetrabromobisphenol A, alcohols, alicyclic epoxy resins, and propylene oxide Silsesquioxane based epoxy resins (chain, cyclic, ladder, or a mixture of at least two or more of these) Structural silicon oxide An epoxy resin such as an epoxy group having an epoxy group structure and / or an epoxy cyclohexane structure in the alkane structure is not limited thereto. Here, among them, biphenyl-type phenol aralkyl-type epoxy resin, phenyl-type phenol aralkyl-type epoxy resin, polycondensates of phenols and dicyclopentadiene, and modifications thereof, Novolac epoxy resin.

However, in the present invention, especially the softening point of the resin is preferably 35 to 75 ° C, and particularly preferably 35 to 60 ° C. Generally speaking, when the epoxy resin is used in an environment where the softening point is lower than 30 ° C, the epoxy resin can keep the solid shape while suppressing the end-capping. In epoxy resin, especially good in soft If it is used at a temperature lower than 50 ° C, it usually becomes a solid shape if it usually exceeds 75 ° C. It is necessary to use this method in a small way, but it may not only have a small effect but also a high viscosity. A compound having a softening point of 35 to 75 ° C tends to have an excellent balance of melt viscosity and heat resistance such as heat resistance.

The preferred melt viscosity at 150 ° C is 0.2Pa. s or less. If the melt viscosity is higher than 150 ° C, there may be a problem in the formability. Since the lower the viscosity, the more useful it is. In the present invention, no lower limit is set (it is also difficult to measure with a general viscosity meter).

Moreover, the epoxy resin used in the present invention has an average of 2 to 10 epoxy groups in one molecule. If the number of epoxy groups contained in one molecule is less than 2 on average, it has an adverse effect on hardening properties such as heat resistance. If the number of epoxy groups contained in one molecule exceeds 10 on average, the viscosity becomes Very high and causes problems with processing characteristics.

The epoxy equivalent of the epoxy resin used in the present invention is preferably 150 to 750 g / eq., And particularly preferably 150 to 500 g / eq. With this range, the composition tends to have good fluidity and hardenability, and the hardened material tends to be excellent in heat resistance, thermal decomposition characteristics, water absorption characteristics, and mechanical strength, and can be suitably used. In good semiconductor device manufacturing.

In the present invention, the ratio of the inorganic filler (a) to the epoxy resin (b) is a weight ratio (a): (b) = 70: 30 to 98: 2, and more preferably 70:30 to 95: 5.

Compared with the ratio of (a) :( b) = 70: 30, if the ratio of the filler amount is reduced, especially when using an epoxy resin with a softening point of 60 ° C or less, the possibility of capping may occur during room temperature operation. High and 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 form a fine chipped, granular, or sheet or small block. That is, (a): (b) = 70: 30 to 98: 2 in terms of characteristics of fluidity and processing.

The resin-modified filler of the present invention may further contain additives such as a coupling agent. I The mixture is preferably added during mixing to make the resin and the filler compact.

Preferred coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropylmethyl Dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane , N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxy Silane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3- Silane-based coupling agents such as chloropropylmethyldimethoxysilane and 3-chloropropyltrimethoxysilane; isopropyl (N-ethylaminoethylamino) titanate, isopropyltriisostearate Acid titanate, titanium di (dioctyl pyrophosphate) oxyacetate, tetra-isopropyldi (dioctyl phosphite) ) titanate), neoalkoxytris (pN (β-aminoethyl) aminophenyl) titanate Mixture; zirconium acetoacetone, zirconium methacrylate, zirconium propionate, neoalkoxy zirconate, neoalkoxy tris neodecanoyl zirconate, neoalkoxy tris (ten Difluorenyl) benzenesulfonyl zirconate, neoalkoxytris (ethylenediamineethyl) zirconate, neoalkoxytris (m-aminophenyl) zirconate, ammonium zirconium carbonate, acetamidine Zirconium or aluminum-based coupling agents such as aluminum acetone, aluminum methacrylate, and aluminum propionate.

These coupling agents may be used in combination of one kind or two or more kinds.

The coupling agent is usually 0.05 to 20 parts by weight in the epoxy resin composition of the present invention, preferably 0.1 to 10 parts by weight as needed.

The method for producing the resin-modified filler of the present invention is not particularly specified, and a method using a solvent is preferred. There are also modification methods using melt-kneading, but consider the epoxy resin When the filler is uniformly applied and / or impregnated, it is preferred that the filler is sufficiently bonded to the filler by a solvent. Specifically, a solvent, a resin, and a filler are mixed, and then the solvent is distilled off under reduced pressure, thereby obtaining a resin-modified filler of the present invention. In this case, it is not necessary to dissolve the resin in a solvent first, and then mix the filler, or to mix the resin when the filler is dispersed in the solvent, or it may be added at the same time. In addition, the mixing temperature is not particularly limited, but is preferably 0 ° C to 100 ° C, and particularly preferably 10 ° C to 80 ° C. It is also possible to use a method of heating to uniformity and then cooling.

The solvent is removed by distillation under reduced pressure. The solvent removal temperature is usually 50 ~ 200 ° C, particularly preferably 50 ~ 180 ° C. At this time, the residual solvent is preferably 1% or less, and if it exceeds this, it may cause gaps and peeling during molding.

Examples of the solvent usable in the present invention include aromatic hydrocarbons typified by toluene, xylene, and petroleum naphtha, methyl ethyl ketone, methyl isobutyl ketone, acetone, cyclohexanone, and cyclo Ketones such as pentanone, ethyl acetate, butyl acetate, ethyl lactate, carbitol acetate, propylene glycol monomethyl ether acetate, gamma butyrolactone and other esters, methanol, ethanol, propanol , Alcohols such as butanol, diglyme, diglyme, In particular, ethers such as alkane and tetrahydrofuran are aromatic hydrocarbons, ketones, and esters, and particularly preferred are ketones and esters in terms of solubility of the resin. Furthermore, two or more types of solvents can be combined, and the solubility of the resin, the dispersibility of the filler, and the volatility during distillation can be adjusted. For example, the solubility can be adjusted by combining ketones and alcohols, and the volatility can be adjusted by ketones and aromatic hydrocarbons.

Furthermore, in the present invention, the boiling point is preferably 150 ° C or lower, and particularly preferably 130 ° C or lower. If the boiling point is too high, residual solvents tend to remain, which is not preferable.

The method for distilling and removing the solvent in the present invention is not particularly limited, but it is preferable to distill and remove the solvent while stirring, and specifically, a Nauta mixer (Nauta- Mixer), ribocone, cone dryer, planetary mixer under reduced pressure, evaporator, vacuum dryer (chopper that can be used under reduced pressure), etc. It can be stirred in a reduced pressure environment below 200torr. Among them, a crusher made of a metal that is severely cracked is not preferable because the possibility of metal contamination is high.

In the present invention, the magnetized metal foreign matter 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 more than one magnetized foreign substance is mixed per 100 g, there is a possibility that a fatal problem may be caused to a completed semiconductor device.

The resin-modified filler obtained in this way is granular, lumpy, or powdery, and does not become a single lumpy at 20 ° C even if it is overlapped by more than 1cm for more than a week. It is expressed as lumpy or lumpy (long axis: 0.1mm ~ 5cm) , Or powdery (major axis: 0.1μm ~ 0.1mm) shape. Furthermore, the lump and powder are limited to the criterion for distinguishing the two. It does not mean a single piece here means that even a small amount of cake is a cake that can be removed by human hands. Generally, when the epoxy resin overlaps, it usually gradually forms agglomerates, and often becomes a single shape that cannot be pulled out by human hands. A particularly good shape is one that does not become a single piece even if stored at 100 ° C for more than one hour.

The resin-modified filler of the present invention exists, for example, in a state in which an epoxy resin is impregnated between inorganic fillers and the epoxy resin is a filler or an inorganic filler. Therefore, the major axis of the particle diameter of such a 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 long axis indicates the diameter of the long part of the longest diameter of the granular, lump, or powder particles. As a measuring method, a ruler can be used for measurement, or it can be confirmed through a sieve with a certain size of the mesh to be measured. Whether to use this to determine. The long axis can also be measured using a microscope. The average particle diameter 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, as compared with the previous mixture of epoxy resin and inorganic filler (a plate-like shape integrated as a whole: FIG. 3), it is shown in FIGS. 1 to 2 respectively. The shape shown.

Hereinafter, the epoxy resin composition of this invention containing the resin modified filler of this invention is described.

In the epoxy resin composition of the present invention, a hardener and / or a polymerization catalyst are used as essential components. Furthermore, it may be further considered that it contains other epoxy resins. In this case, the epoxy resins that can be used are not particularly limited, and for example, the aforementioned epoxy resins 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-based compounds, amine-based compounds, acid anhydride-based compounds, amidine-based compounds, and carboxylic acid-based compounds. Specific examples of usable hardeners include phenol resins and phenol compounds; bisphenol A, bisphenol F, bisphenol S, bisphenol, terpene diphenol, 4,4'-biphenol, 2, 2'-biphenol, 3,3 ', 5,5'-tetramethyl- [1,1'-biphenyl] -4,4'-diol, hydroquinone, resorcinol, naphthalenedi Phenol, tri- (4-hydroxyphenyl) methane, 1,1,2,2-tetra (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) -1,1'-biphenyl, 1,4'-bis (chloromethyl) Poly) condensates of benzene, 1,4'-bis (methoxymethyl) benzene and the like, and halogenated bisphenols such as tetrabromobisphenol A, condensation products of terpenes and phenols, etc. Polyphenols are not limited to these. These can be used alone or in combination of two or more.

As a preferable phenol resin, a phenol aralkyl resin (having aromatic extension A resin having an alkyl structure) is particularly preferably a resin characterized in that it has a structure selected from at least one of phenol, naphthol, and cresol, and is selected as an alkylene moiety of its linker At least one of a self-benzene structure, a biphenyl structure, and a naphthalene structure (specifically, Xylok, naphthol, phenol, phenol novolac resin, cresol-phenol novolac resin, phenol -Naphthol novolac resin, etc.).

Amine compounds, amine compounds; diaminodiphenylmethane, diethylene triamine, triethylene tetramine, diamino diphenyl hydrazone, isophorone diamine, dicyandiamine, from Nitrogen compounds such as the dimer of linolenic acid and polyamine resin synthesized by ethylenediamine.

Acid anhydride compounds, carboxylic acid compounds; phthalic anhydride, 1,2,4-phthalic anhydride, pyromite anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic acid Dicarboxylic anhydride, methyl nadic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclic [2,2,1 ] Heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4 -Anhydrides such as anhydrides; carboxylic acid resins obtained by the addition reaction of various alcohols, methanol-modified polysilanes and the above anhydrides; others; examples include imidazole, trifluoroborane-amine complexes, and guanidine derivatives. Compounds and the like are not limited thereto. These can be used alone or in combination of two or more. In the present invention, particularly in terms of reliability, it is preferable to use a phenol resin.

The use amount of the hardener in the epoxy resin composition of the present invention is preferably 0.7 to 1.2 equivalents relative to 1 equivalent of the epoxy group of the entire epoxy resin. When the amount of epoxy equivalent is less than 0.7 equivalent, or when it exceeds 1.2 equivalent, there is a possibility that hardening is incomplete and good hardened physical properties cannot be obtained.

In the epoxy resin composition of the present invention, a polymerization catalyst may be used as a curing agent, or it may be used when a curing agent is not used. Specific examples of usable polymerization catalysts include: 2 -Imidazoles such as methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo (5, 4,0) tertiary amines such as undecene-7, phosphines such as trimethylphosphine, triphenylphosphine, tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecylammonium salt, Quaternary ammonium salts such as cetyltrimethylammonium salts, quaternary phosphonium salts such as triphenylbenzylphosphonium salts, triphenylethylphosphonium salts, tetrabutylphosphonium salts, etc. (the relative ion of the quaternary salts is halogen , Organic acid ion, hydroxide ion, and the like are not particularly specified, but organic acid ion, hydroxide ion are preferred.), Metal compounds such as stannous octoate, and the like. When a hardening 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 and quaternary phosphonium salts are particularly preferred.

Furthermore, when using an amine compound such as a tertiary amine as a polymerization catalyst, it is also possible to harden it without a hardener or a hardening amount in an amount smaller than a predetermined amount, or to harden it by anionic polymerization. .

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

Specific examples of other epoxy resins include novolac epoxy resin, bisphenol A epoxy resin, biphenyl epoxy resin, triphenylmethane epoxy resin, and phenol aralkyl ring. Oxygen resin and so on. Specific examples include: bisphenol A, bisphenol S, thiobiphenol, pyrene bisphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'-tetramethyl- [1,1'-biphenyl] -4,4'-diol, hydroquinone, resorcinol, 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, two Cyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1'-biphenyl, 4,4'-bis (methoxymethyl) -1,1'-biphenyl, 1 Polycondensates of 1,4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene, etc. and their modifications, halogenated bisphenols and alcohols such as tetrabromobisphenol A Derived silsesquioxane-based epoxy resins (chain-like, epoxy-based epoxy resins, epoxy-propylamine-based epoxy resins, epoxy-propyl ester-based epoxy resins, etc.) Epoxy resins such as cyclic, ladder-shaped, or epoxy resins with epoxy group structure in these siloxane structures with at least two or more mixed structures, but not Not limited to these.

The epoxy resin composition of the present invention may contain a phosphorus-containing compound as a flame retardancy-imparting component. The phosphorus-containing compound may be a reactive type or an additive type. Specific examples of the phosphorus-containing compound include trimethyl phosphate, triethyl phosphate, tricresol phosphate, tris (xylyl) phosphate, cresyl diphenyl phosphate, and 2,6-dimethyl (xylene). ) Cresol phosphate, 1,3-phenylene bis (xylene) phosphate), 1,4-phenylene bis (xylene) phosphate), 4,4'-biphenyl ( Bis (xylene) phosphate ester) and other phosphate esters; 9,10-dihydro-9-aza-10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H- Phosphines such as 9-aza-10-phosphaphenanthrene-10-oxide; phosphorus-containing epoxides, red phosphorus, etc. obtained by reacting epoxy resin with active hydrogen of the above-mentioned phosphines, preferably phosphate esters Type, phosphine type or phosphorus-containing epoxy compound, particularly preferred are 1,3-phenylene bis (dimethyl (xylene) phosphate), 1,4-phenylene bis (dimethyl (xylene) phosphate), 4,4'-biphenyl (di (xylene) phosphate) or contains a phosphorus epoxide. The content of the phosphorus-containing compound is preferably phosphorus-containing compound / total epoxy resin = 0.1 to 0.6 (weight ratio). Below 0.1, the flame retardancy is insufficient, and above 0.6, there is a possibility that the moisture absorption and dielectric properties of the cured product may be adversely affected.

Furthermore, if necessary, an antioxidant may be added to the epoxy resin composition of the present invention. Examples of usable antioxidants include phenol-based, sulfur-based, and phosphorus-based antioxidants. The antioxidant can be used alone or in combination of two or more. The usage-amount of an antioxidant is 0.008-1 weight part normally with respect to 100 weight part of resin components in the epoxy resin composition of this invention, Preferably it is 0.01-0.5 weight part.

Examples of the antioxidant include a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant. Specific examples of the phenol-based antioxidant include 2,6-di-tertiary-butyl-p-cresol, butylated hydroxyanisole, and 2,6-di-tertiary-butyl-p-ethylphenol Β- (3,5-di-tertiary-butyl-4-hydroxyphenyl) propanoic acid stearyl, 3- (3,5-di-tertiary-butyl-4-hydroxyphenyl) propionic acid Octyl ester, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-tert-butylaniline) -1,3,5-tri , 2,4-bis [(octylthio) methyl] -o-cresol and other monophenols; 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2, 2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol), 4,4'- Butylene bis (3-methyl-6-tertiary butylphenol), triethylene glycol-bis [3- (3-tertiary butyl-5-methyl-4-hydroxyphenyl) propionate] , 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5 -Di-tertiary-butyl-4-hydroxy-phenylpropanthine), 2,2-thio-diphenylethylbis [3- (3,5-di-tertiary-butyl-4-hydroxyphenyl) Propionate], 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid-diethyl ester, 3,9-bis [1,1-dimethyl-2- {β- (3- Tertiary butyl-4-hydroxy-5-methylphenyl) propanyloxy} ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, bis (3,5 -Bisphenols such as di-tertiary butyl-4-hydroxybenzylsulfonate) calcium; 1,1,3-tris (2-methyl-4-hydroxy-5-tertiary butylphenyl) Butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tertiarybutyl-4-hydroxybenzyl) benzene, tetra- [methylene-3- ( 3 ', 5'-di-tertiary-butyl-4'-hydroxyphenyl) propionate] methane, bis [ 3,3'-bis- (4'-hydroxy-3'-tert-butylphenyl) butanoic acid] glycol ester, tri- (3,5-di-tert-butyl-4-hydroxybenzyl) Isocyanurate, 1,3,5-tris (3 ', 5'-di-tertiarybutyl-4'-hydroxybenzyl) -S-tri -2,4,6- (1H, 3H, 5H) triketone, tocopherol and other polymer phenols.

Specific examples of the sulfur-based antioxidant include: 3,3'-dithiothiopropionate dilauryl, 3,3'-thiodipropionate dimyristyl, and 3,3'-thiodipropionate Distearyl acid and the like.

Specific examples of the phosphorus-based antioxidant include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tri (nonylphenyl) phosphite, and diisodecyl N-Pentaerythritol Phosphite, Tris (2,4-di-tert-butylphenyl) Phosphite, Cycopeneopentane Di (octadecyl) Phosphite Alkyl bis (2,4-di-tertiary butylphenyl) ester, cyclonepentapentane bis (2,4-di-tertiary butyl-4-methylphenyl) ester, hydrogen phosphite Phosphites such as bis [2-tert-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] ester; 9,10-dihydro-9-oxa -10-Phenanthrene-10-oxide, 10- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phenanthroline Oxaphosphaphenanthrene oxides such as -10-oxide, 10-decyloxy-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc.

These antioxidants can be used individually or in combination of 2 or more types. Particularly, a phosphorus-based antioxidant is preferred in the present invention.

Furthermore, a light stabilizer may be added to the epoxy resin composition of the present invention as necessary.

As the light stabilizer, a hindered amine-based light stabilizer is preferred, especially HALS and the like. The HALS is not particularly limited, and examples thereof include dibutylamine, 1,3,5-tris , N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl Poly-4-piperidinyl) butylamine polycondensate, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polysuccinate Condensate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-tri -2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidinyl) imino} hexamethylene {(2,2,6,6-tetramethyl- 4-piperidinyl) imino}], bis (1,2,2,6,6-pentamethyl-4-piperidinyl) [[3,5-bis (1,1-dimethylethyl ) -4-hydroxyphenyl] methyl] butylmalonate, bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis (1,2,2 , 6,6-pentamethyl-4-piperidinyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate , 2- (3,5-di-tertiarybutyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidine ) Esters and the like. HALS can be used alone or in combination of two or more.

Further, an adhesive resin may be blended into the epoxy resin composition of the present invention as necessary. Examples of the binder resin include a butyral resin, an acetal resin, an acrylic resin, an epoxy-nylon resin, an NBR-phenol resin, an epoxy-NBR resin, a polyamide resin, and a polyurethane. Amidamine-based resin, silicone resin, and the like are not limited to these. The blending amount of the binder resin is preferably in a range that does not impair the flame retardancy and heat resistance of the hardened material. It is generally used in an amount of 0.05 to 50 parts by weight, preferably 0.05 to 20, based on 100 parts by weight of the resin component as needed. Parts by weight.

In the epoxy resin composition of the present invention, release agents such as silane coupling agents, stearic acid, palmitic acid, zinc stearate, calcium stearate, surfactants, dyes, pigments, and ultraviolet absorbers can be further added. Various admixtures and various thermosetting resins.

The epoxy resin composition of the present invention is obtained by uniformly mixing the components. The epoxy resin composition of this invention can be easily made into a hardened | cured material similarly to the conventionally well-known method. For example, the resin modified filler and hardener of the present invention and the required hardening accelerator, containing phosphorus Compounds, adhesive resins, inorganic fillers, and admixtures can be thoroughly mixed with an extruder, kneader, roller, etc. as needed to obtain an epoxy resin composition. The epoxy resin composition is encapsulated and melted. (In the case of a liquid state, there is no melting) A mold, a transfer molding machine, or the like is used for molding, and further, the hardened product of the present invention can be obtained by heating at 80 to 200 ° C for 2 to 10 hours.

The hardened | cured material hardened from the epoxy resin composition of this invention can be used for various uses. Suitable use as a semiconductor sealing material includes, for example, adhesives, coatings, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials (including printed circuit boards, wire coatings, etc.), other than sealants, and Additives for other resins. Examples of the adhesive include civil, construction, automotive, general office, medical adhesives, and other electronic material adhesives. Among these, as adhesives for electronic materials, indirect adhesives for multi-layer substrates such as build-up substrates, die attach agents, primers for semiconductors such as primers, primers for BGA reinforcement, and anisotropic conductive films ( ACF), anisotropic conductive paste (ACP), and other mounting adhesives.

As a sealant, it is suitable for packaging, dipping, transfer molding, sealing of capacitors, transistors, diodes, light-emitting diodes, ICs, LSIs, etc., ICs, LSIs such as COB, COF, TAB, etc Seals for mounting of IC packages such as flip chip, QFP, BGA, CSP, etc. (including primers for reinforcement).

Examples

Next, the present invention will be described more specifically by way of examples. The following parts are parts by weight unless otherwise specified. The present invention is not limited to these.

Various analysis methods used in the examples are described below.

Epoxy equivalent: according to JIS K 7236 (ISO 3001)

ICI melt viscosity: according to JIS K 7117-2 (ISO 3219)

Softening point: According to JIS K 7234

Hereinafter, the present invention will be specifically described with reference to examples and comparative examples.

Examples 1 to 7, Comparative Examples 1 to 4

Using methyl ethyl ketone (MEK) as a solvent, an ortho-cresol novolac type epoxy resin with a softening point of 52 ° C (EP1: EOCN-1020-52 manufactured by Nippon Kayaku Co., Ltd.), and an o-cresol novolac type with a softening point of 55 ° C Epoxy resin (EP2: EOCN-1020-55, manufactured by Nippon Kayaku), biphenol aldehyde epoxy resin (EP3: NC-3000-L, manufactured by Nippon Kayaku), and softening point 45 ° C Phenylmethane type epoxy resin (EP4: triphenylmethane (Tris PM manufactured by Honshu Chemical Industry Co., Ltd.) is epoxypropyl etherified), epoxide of bisphenol-ethylene oxide adduct of softening point of 40 ° C (EP5: manufactured by Osaka Gas Chemical Co., Ltd.) As an epoxy resin, molten silica (MSR-2122 manufactured by Hori Mori) as an inorganic filler, the following operations were performed with the composition of Table 1 below.

In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, methyl ethyl ketone (MEK) was added as a solvent while various kinds of epoxy resins and inorganic fillers described in Table 1 were charged while flushing with nitrogen, and then stirred at 25 ° C. 1 hour. Thereafter, the solvent was distilled off on a rotary evaporator, and finally, the solvent was distilled off under a reduced pressure of 120 torr at 20 torr until the solvent was completely dispersed.

The obtained modified resin filler was taken out, and the sample was embedded with platinum after sputtering. After making a cross section sample at CP 3.5 kV, the sample was observed by SEM (non-evaporation low vacuum acceleration voltage 10 kV). The particle size of any of the particles was 5.0 cm or less, and the shape in which the resin and the filler were aggregated was confirmed. The agglomeration test was performed at 25 ° C for one week. The results are shown in Table 1.

As shown in Table 1, the resin-modified filler of the present invention maintained a powdery or granular shape and the results of the agglomeration test were good both immediately after manufacturing and after the stability test. On the other hand, the mixture of the epoxy resin and the inorganic filler of the comparative example had agglomerates immediately after manufacture or stability tests, or only those with a plate-like shape and poor handling properties were obtained.

Examples 8, 9

A solution of acetone and methyl isobutyl ketone (1: 1) as a solvent, a biphenol-formaldehyde epoxy resin (EP6: Nippon Kayaku NC-3000) with a softening point of 58 ° C as the epoxy resin, and spherical silica (Admatechs 1030 DMATECHS Co., Ltd. average particle diameter 0.3 μm) As the inorganic filler, it is composed of solution 150, epoxy resin 10, and spherical silica 90 (Example 8), and solution 150, epoxy resin 20, and balls The composition of the silicic acid 80 (Example 9) was performed as follows.

A flask equipped with a stirrer, a reflux cooling tube, and a stirring device was charged with various components described above, and then stirred at 25 ° C for 30 minutes. Thereafter, the solvent was distilled off by a rotary evaporator, and finally, the solvent was distilled off under a reduced pressure of 120 to 20 torr until the solvent was completely dispersed.

The obtained modified resin filler was taken out, and the sample was embedded with platinum after sputtering. After making a cross section sample at CP 3.5 kV, the sample was observed by SEM (non-evaporation low vacuum acceleration voltage 10 kV). The particle size of any of the particles was 1 mm or less, and the shape in which the resin and the filler were aggregated was confirmed. It can be seen from Figs. 4 to 9 that the resin is mixed with the filler, and the outermost surface is covered with the filler. The agglomeration test was performed at 25 ° C for one week, and no agglomeration was found (a state in which the resins are in a large number and overlap each other).

The present invention is described in detail with reference to specific aspects, but those skilled in the art should know that various changes and modifications can be made without departing from the spirit and scope of the present invention.

Furthermore, this application is based on a Japanese patent application filed on February 19, 2014 (Japan (Japanese Patent Application No. 2014-029097), whose arrangement is incorporated by reference. In addition, all the references referred to herein are hereby incorporated as a whole.

[Industrial availability]

The resin-modified filler of the present invention is a filler that imparts fluidity to an epoxy resin composition. The hardening epoxy resin composition containing the filler is suitable for insulating materials for electrical and electronic parts and laminated boards (printed wiring boards, buildups). Substrates, etc.) or CFRP is useful for a variety of composite materials, adhesives, coatings and the like. It is particularly useful for semiconductor sealing materials for protecting semiconductor elements.

Claims (5)

A method for manufacturing a resin-modified filler, the resin-modified filler contains an inorganic filler (a), and an epoxy resin (b) having an average of 2 to 10 epoxy groups in one molecule, and the long axis is 5 cm or less, and The weight ratio of (a) and (b) was set to (a) :( b) = 70: 30 ~ 98: 2, and after kneading (a) and (b) with the solvent, the solvent was distilled off. For example, the method for manufacturing a modified resin filler according to item 1 of the application, wherein the softening point of the epoxy resin (b) is 35 to 75 ° C. For example, the method for manufacturing a resin-modified filler according to item 1 or 2 of the patent application range, wherein the average particle diameter of the inorganic filler (a) is 0.1 to 5 μm. For example, the method for manufacturing a modified resin filler according to item 1 or 2 of the patent application range, wherein the solvent is a ketone. For example, the method for manufacturing a modified resin filler according to item 3 of the patent application, wherein the solvent is a ketone.