JP2005171209A - Filler-containing resin composition and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition which has, when the level of a compounded filler is high, good fluidity, is good for handling, and can be used as a liquid sealing material that is caused to efficiently enter and fill the ten-odd μm gap between semiconductor elements and a substrate upon mounting of flip chips. <P>SOLUTION: The filler-containing resin composition (from which combinations of epoxy resins and silazanes are excluded) is provided, wherein 60% by weight or more of a filler produced by compounding a basic substance in a thermoplastic resin is compounded to the total amount and the filler is primarily dispersed in the thermoplastic resin. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a filler-containing resin composition in which a filler is primarily dispersed at a high concentration in a thermosetting resin such as a thermosetting resin, and a method for producing the same. The present invention also relates to a low-expansion filler-containing resin composition that is excellent in moisture absorption resistance and solder crack resistance.

  As a method for sealing electronic components such as semiconductor devices, a method using ceramics or a thermosetting resin has been conventionally performed. Among these, sealing with a thermosetting resin-based sealing material such as an epoxy resin is preferably performed more widely than the balance between economy and performance.

  With the recent increase in functionality and integration of semiconductor devices, the method of electrically connecting a semiconductor element and a substrate by bumps (projection electrodes) instead of the conventional method using bonding wires, which is the mainstream, so-called Surface mounting using flip chips is increasing. In this flip chip mounting type semiconductor device, a defect such as a crack may occur in a joint portion of a bump or the like in a heat cycle test. Therefore, in order to prevent this, a method (underfill) has been performed in which the gap between the semiconductor element and the substrate, the periphery of the bump, and the like are filled with a liquid epoxy resin sealing material and cured.

  A sealing material for sealing a semiconductor device such as a flip chip mounting method requires characteristics such as moisture resistance reliability, electric corrosion resistance, and heat cycle resistance. For this purpose, silica or the like is included in the sealing material. A method for improving moisture resistance reliability and heat cycle resistance by reducing the moisture absorption rate and reducing the coefficient of thermal expansion by blending the inorganic filler.

  Increasing the blending amount of inorganic fillers such as silica can reduce the moisture absorption rate and thermal expansion coefficient of the sealing material, and improve moisture resistance reliability and heat cycle resistance. As the blending amount is increased, the viscosity of the sealing material increases and the fluidity tends to be remarkably lowered, which is a problem. In particular, in flip-chip mounting, since it is necessary to fill a gap between a semiconductor element of about 10 μm and a substrate with a sealing material, the sealing material is required to have a high penetration filling property. Therefore, in order to obtain a high intrusion filling property without increasing the viscosity as much as possible even if the filling rate of the inorganic filler is increased, such a sealing material is an inorganic material having a spherical shape and a small specific surface area. Particles are required.

  From such a viewpoint, attempts have been made to use spherical silica obtained by a method of melting silica particles in a flame (for example, Patent Document 1 below) as a filler for sealing material (for example, Patent Document 2, the following Patent Document 2, 3).

  However, these spherical silicas have not been sufficiently small in terms of specific surface area. In addition, spherical silica generally obtained by the flame melting method tends to include particles having a large particle size of about several tens of μm, and there is a problem in intruding and filling a gap between a semiconductor and a substrate of about several tens of μm. Also, the surface has many irregularities and is inadequate in terms of inferior sphericity.

  In addition, attempts have been made to improve the fluidity of a liquid sealing material by using inorganic fillers having different particle size distributions (for example, Patent Documents 4 to 8 below). However, the methods disclosed in these publications are such that the specific surface area of the inorganic filler used is large, the shape is crushed, or a thermosetting resin composition comprising a thermosetting resin such as an epoxy compound and a curing agent. In view of the fact that the viscosity is too high or solid, sufficient fluidity as a liquid sealing material has not been obtained.

  In addition, attempts have been made to surface-treat silica particles and use them as a filler for sealing materials. For example, in Patent Document 9 below, the surface of silica particles dispersed in an epoxy resin for semiconductor sealing is incorporated in methyl ethyl ketone. It is disclosed that esterification treatment is performed using an acid anhydride to improve dispersibility in a resin.

  However, the above technique has a problem that the inorganic filler particles easily aggregate in the resin, are non-uniform, have a high viscosity, and as a result, have low fluidity and cannot be further improved in moldability. . Moreover, the epoxy resin and the curing agent are added together to methyl ethyl ketone in which silica is dispersed, and then the solvent is vacuum distilled. Also, acetic acid is also present in the mixture, and it is considered impossible to completely remove the solvent while maintaining the epoxy equivalent. That is, this gazette is for making a cured composition, and is different from that for preparing a silica-dispersed epoxy resin as in the present invention.

  On the other hand, in Patent Document 10 below, a chemical flame is formed by a burner in an oxygen-containing atmosphere, and an amount of metal powder that can form a dust cloud is introduced into the chemical flame and burned to produce ultrafine oxide particles. There is a disclosure of a manufacturing method for synthesis. Patent Document 11 listed below includes a first step of supplying a metal powder constituting an oxide into a reaction vessel together with a carrier gas, and forming a flame by igniting the reaction vessel to burn the metal powder. In the oxide powder manufacturing method comprising the second step of synthesizing the oxide powder, the first step supplies a mixture of the metal oxide having a small particle size and the metal powder, and the second step includes the above step. There is a disclosure of a method for producing an oxide powder, characterized in that a metal oxide is used as a nucleus to cause grain growth with an oxide synthesized by combustion of the metal powder.

JP-A-58-145613 Japanese Patent Laid-Open No. 9-235357 Japanese Patent Laid-Open No. 10-53694 JP-A-2-228354 Japanese Unexamined Patent Publication No. 3-177450 Japanese Patent Laid-Open No. 5-230341 JP-A-4-253760 Japanese Patent Laid-Open No. 5-206333 JP-A-6-283633 JP-A-60-255602 Japanese Unexamined Patent Publication No. 1-24004

  As a method of dispersing silica in a thermosetting resin such as an epoxy resin, mechanical dispersion using a roll or the like is common. However, in the case of fine particle silica such as Admafine (trade name), it is difficult to completely disperse. For this reason, the effect of reducing the viscosity of the fine particles cannot be sufficiently extracted. A method of removing the solvent by adding a resin after dispersing silica in an organic solvent is also conceivable, but heating at a high temperature is necessary to completely remove the solvent. However, when heated in the presence of silica, the epoxy reacts to change the epoxy equivalent and increase the viscosity. Moreover, since the reaction itself varies depending on the surface state of silica, it cannot be controlled.

  In the inorganic particle-containing resin composite material, it is important to connect the inorganic particles and the matrix polymer with a strong bond. Treatment with a silane coupling agent is a common method for modifying the particle surface to strengthen the bond with the matrix. However, in the case of fine particles such as Admafine (trade name), which is a metal oxide powder obtained by burning metal, it tends to agglomerate by treatment, and it becomes difficult to disperse in the resin, and the viscosity becomes high There is. For example, when epoxy silane-treated silica is blended with a thermosetting resin such as an epoxy resin, the viscosity is typically very high.

  That is, since the silica particles have a property of reacting with a thermosetting resin such as an epoxy resin, it has been a problem that high flow cannot be realized.

  The present invention was made in order to improve the above-mentioned problems, and the object is to have good fluidity and excellent handleability even when the filler content is large. An object of the present invention is to provide a resin composition serving as a liquid sealing material capable of efficiently entering and filling a gap of tens of micrometers between a semiconductor element and a substrate during flip chip mounting.

  In order to solve the above-mentioned problems, the present inventor has reached the present invention paying attention to primary dispersion of metal fine particles obtained by burning the above metal in a thermosetting resin such as an epoxy resin at a high concentration.

  First, the present invention is an invention of a filler-containing resin composition, wherein a filler containing a basic substance in a thermosetting resin (excluding an epoxy resin) is blended in an amount of 60% by weight or more based on the total amount. Is primarily dispersed in a thermosetting resin (excluding epoxy resin). Similarly, a filler in which a basic substance (excluding silazanes) is blended in a thermosetting resin is blended by 60% by weight or more based on the total amount, and the filler is primarily dispersed in the thermosetting resin. Features.

  It does not limit as a filler, A well-known thing can be used. Among these, a metal oxide powder obtained by burning metal is preferably exemplified.

Metal oxide powder obtained by burning metal is metal powder such as silicon, aluminum, magnesium, zirconium, titanium, etc., aluminum powder and silicon powder prepared in mullite composition, magnesium powder and aluminum prepared in spinel composition A chemical flame is formed in an atmosphere containing oxygen together with a carrier gas, such as a powder, aluminum powder mixed in a cordierite composition, magnesium powder, silicon powder, etc., and target silica (SiO ₂ ) in this chemical flame Metal oxides such as alumina (Al ₂ O ₃ ), titania (TiO ₂ ), zirconia (ZrO ₂ ), etc., and ultrafine particles of composite oxide are obtained. In this invention, the metal oxide powder which has a silica as a main component is preferable. The metal oxide powder obtained by burning the metal is preferably a true spherical particle having an average particle diameter of 0.05 μm to 10 μm.

  In the filler-containing resin composition of the present invention, fillers such as metal oxide fine particles obtained by burning metal are contained in an amount of 60% by weight or more based on the total amount and are primarily dispersed. The semiconductor sealing material is preferably 90% by weight or more, more preferably 95% by weight or more in order to withstand lead-free solder.

  In the filler-containing resin composition of the present invention, such ultrafine metal oxide powder is uniformly primary dispersed without condensing.

  It is preferable that the surface of the filler is treated with a basic substance in order to increase the affinity with the resin. The basic substance blended in the filler in the present invention is at least one selected from ammonia, organic amines, silazanes, silane coupling agents containing nitrogen, and cyclic compounds containing nitrogen.

  Silazanes referred to in the present invention are silicon compounds having a Si—N bond in the molecule, and are sometimes referred to as organosilazanes. For example, hexamethyldisilazane, hexaphenyldisilazane, dimethylaminotrimethylsilane, trisilazane, A compound selected from silazanes such as silazane, 1,1,3,3,5,5-hexametacyclotrisilazane, or a combination thereof. Among them, hexamethyldisilazane (HMDS) suppresses silica aggregation, tilts acidic silica to basic, improves affinity for organic substances, and improves the uniformity of adhesion of silane coupling agents, etc. In view of improving the stability to the epoxy resin, it is preferable.

The amine-based silane coupling agent, which is a basic substance, has the following general formula (R ₁ ) _n (R ₂ ) _m (R ₃ ) _l Si
N + M + 1 is 4. R ₁ is a primary, secondary and tertiary amine substituent and is bonded to the Si atom by a C—Si bond. R ₂ is a hydrocarbon group and is bonded to the Si atom by a C—Si bond. R ₃ is a hydrolyzable substituent, Si atom and Si-OR (R is a hydrocarbon group), Si-OCOR (R is a hydrocarbon group), Si-NHCOR (R is a hydrocarbon group), Si-NR _l R ₂ (R ₁ and R ₂ are hydrocarbon groups or hydrogen) and the like. Specific examples include N-phenyl-γ-aminopropyltrimethoxysilane and γ-aminopropyltriethoxysilane.

The processing amount of the basic substance relative to the filler is 0.05 to 5 μmol, preferably 0.05 to 1 μmol, per 1 m ² of the powder surface area. When the amount is less than 0.05 μmol, the treatment effect is insufficient. When the amount exceeds 5 μmol, the powder surface becomes hydrophobic and handling properties are adversely affected. Further, since the surface is hydrophobic, adhesion to an epoxy resin or the like is also deteriorated. Furthermore, since there are no hydroxyl groups on the powder surface, further treatment with a silane coupling agent or the like becomes impossible. In the case of silica or alumina, the treatment is most desirable so that the absorption peak of the hydroxyl group in the vicinity of 3700 cm ⁻¹ on the IR spectrum is not completely lost.

  The thermosetting resin used for the filler-containing resin composition of the present invention is not limited. Specifically, one or more types selected from epoxy resins, phenol resins, urethanes, polyimides and unsaturated polyesters are preferably exemplified.

  The epoxy resin is not particularly limited, and monomers, oligomers, and polymers in general having two or more epoxy groups in one molecule are used. For example, biphenyl type epoxy resin, stilbene type epoxy resin, bisphenol type epoxy resin, triphenol methane type epoxy resin, alkyl modified triphenol methane type epoxy resin, dicyclopentadiene modified phenol type epoxy resin, naphthol type epoxy resin, triazine core containing An epoxy resin etc. are illustrated. These may be used alone or in combination. Since the inorganic filler is preferably highly filled in the epoxy resin composition, a low-viscosity resin is preferable in order to maintain good fluidity of the epoxy resin composition.

The filler is preferably silica particles having the following particle size distribution.
(1) At least one or more types of silica particles selected from spherical silica particles having an average particle size of 0.01 to 30 μ and a maximum particle size of 75 μ.
(2) At least one or more types of silica particles selected from spherical silica particles having an average particle size of 0.01 to 20 μ and a maximum particle size of 45 μ.
(3) At least one or more types of silica particles selected from spherical silica particles having an average particle size of 0.01 μm to 10 μm and a maximum particle size of 20 μm.
(4) At least one or more types of silica particles selected from spherical silica particles having an average particle size of 0.01 to 5 μ and a maximum particle size of 10 μ.
(5) At least one or more types of silica particles selected from spherical silica particles having an average particle size of 0.01 to 3 μ and a maximum particle size of 5 μ.
(6) At least one kind of silica particles selected from spherical silica particles having an average particle size of 0.01 μ to 1.5 μ and a maximum particle size of 3 μ.

  The spherical silica particles are preferably spherical silica particles obtained by oxidizing fused spherical silica particles and / or metal silicon.

  As the filler in the present invention, other powders can be used in addition to the metal oxide powder obtained by burning the metal such as the spherical silica. The powder is not limited. For example, plate-like inorganic powder, fibrous inorganic powder, amorphous inorganic powder, wood powder, crushed powder of thermosetting resin, resin particles obtained by polymerization, inorganic flame retardant One or more kinds of powders selected from are preferably exemplified.

  Specifically, mica as the plate-like inorganic powder, talc, glass fiber, carbon fiber, potassium titanate whisker as the fibrous inorganic powder, calcium carbonate, crushed silica, and thermosetting resin as the amorphous inorganic powder Preferable examples include crushed powder of epoxy resin as powder, resin particles synthesized by suspension polymerization as resin particles obtained by polymerization, and aluminum hydroxide and magnesium hydroxide as inorganic flame retardants.

  The surface of the metal oxide powder obtained by burning the metal is preferably treated with a silane coupling agent in order to increase the affinity with the resin. The silane coupling agent is preferably at least one selected from epoxy silane, amino silane, acrylic silane, and thiol silane. Specifically, as a silane coupling agent, γ-glycidoxypropyltriethoxysilane, epoxy silane such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, aminopropyltriethoxysilane, ureidopropyltriethoxy Examples thereof include aminosilanes such as silane and N-phenylaminopropyltrimethoxysilane, hydrophobic silane compounds such as phenyltrimethoxysilane, methyltrimethoxysilane, and octadecyltrimethoxysilane, mercaptosilane, and the like.

  In order to fill the resin with a high amount of filler, it is effective to appropriately mix those having different particle diameters. Specifically, the idea of sequentially filling small fillers into the gaps when large fillers are closely packed is generally the Horsleld model, for example. In addition, a calculation method for blending actual powder so as to be closely packed is also known. However, it is still impossible to achieve a sufficiently low viscosity even when the above-mentioned close packing is performed on an untreated filler or a filler treated by a conventionally known method.

  The filler treated by the method of the present invention is treated more uniformly than the conventional coupling agent treatment by using a basic substance in combination, and the affinity for the resin is remarkably high. Therefore, when the filler of the present invention is blended with the resin, the viscosity becomes very low, and when the filler having a different particle size is blended so as to be close packed by the above close packing method, the low viscosity cannot be achieved by the conventional filler technology. A resin composition is obtained.

  Second, the present invention is an invention of a method for producing a filler-containing resin composition, in which a thermosetting resin (excluding epoxy resin) is added to a slurry obtained by dispersing a filler containing a basic substance in a slurry in an organic solvent. ) Or a part of the thermosetting resin (excluding the epoxy resin) is mixed, and then the solvent is removed. Similarly, after mixing a thermosetting resin or a part of the thermosetting resin with a slurry obtained by dispersing a filler containing a basic substance (excluding silazanes) in an organic solvent, the solvent is removed. It is characterized by that. Here, the basic substance and the thermosetting resin are as described above.

  By the method of the present invention, a filler such as a metal oxide can be highly filled into a thermosetting resin such as an epoxy resin. The filler surface is converted from acidic to basic with a basic substance such as hexamethyldisilazane (HMDS), and the activity of the filler on the thermosetting resin is suppressed and the increase in viscosity due to the reaction with the thermosetting resin is suppressed. Thereby, it became possible to realize low viscosity and high fluidity when filling the thermosetting resin. The order of the surface treatment step using an organic solvent and the surface treatment step using a basic substance can be interchanged.

  The organic solvent used in the present invention is a thermosetting resin such as an epoxy resin, a basic substance such as a silazane, and an aprotic one that is not reactive with a silane coupling agent, and is a metal oxide. A filler such as fine particles is well dispersed. Specific examples include methyl ethyl ketone, methyl isobutyl ketone, acetone, benzene, toluene, xylene, ethyl acetate, dimethyl ether, cyclohexane and the like.

  Silazanes are preferred as the basic substance added to the organic solvent in which fillers such as metal oxide fine particles are dispersed. For example, compounds selected from silazanes such as hexamethyldisilazane and hexaphenyldisilazane or combinations thereof are preferred. Illustrated. Among these, hexamethyldisilazane (HMDS) suppresses the aggregation of fillers such as metal oxide fine particles such as silica, tilts acidic silica to basicity, improves affinity for organic substances and improves uniformity. It is preferable in terms of improving the stability to a thermosetting resin such as an epoxy resin. The amount of the basic substance such as silazanes in the organic solvent is preferably 10 to 1000 ppm relative to the filler, and if it is less than 10 ppm, the effect of addition is poor. Living organisms remain in a thermosetting resin such as an epoxy resin, resulting in inconveniences such as a decrease in strength of the resin, a decrease in adhesion, and coloring.

  In order to remove the organic solvent from the thermosetting resin compound such as epoxy resin, it may be distilled by heating under reduced pressure. The volatile content remaining in the composition is preferably 0.5% or less.

  The method for producing a thermosetting resin composition such as an epoxy resin of the present invention preferably further includes a step of removing coarse particles in a filler such as metal oxide fine particles obtained by burning metal. This step may be added to any part in the method for producing a thermosetting resin composition such as the epoxy resin.

  Third, the present invention is a thermosetting resin composition containing a curing agent component and a curing catalyst component in the above-described epoxy resin or other thermosetting resin composition, and is particularly suitable for semiconductor encapsulation. It is an adhesive resin composition.

  The curing agent component is not particularly limited, such as an amine-based, acid anhydride-based, or phenol-based curing agent.

  Examples of amine curing agents include aliphatic polyamines, polyamide polyamines, alicyclic polyamines, aromatic polyamines, and others. Examples of the aliphatic polyamine include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and diethylaminopropylamine. Examples of the polyamide polyamine include polyamide polyamine. Examples of alicyclic polyamines include mensendiamine, isophoronediamine, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane adduct Bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) methane and the like. Examples of aromatic polyamines include metaxylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, and m-phenylenediamine. Others include dicyandiamide and adipic acid dihiraside. The mixing ratio of the amine curing agent is, in the case of an epoxy resin, the equivalent ratio of active hydrogen of amino group to epoxy group (epoxy group / active hydrogen) is usually 1 / 0.8 to 1 / 1.2, preferably 1 / 0.9 to A range of 1 / 1.1 is good.

  As the acid anhydride curing agent, those having a molecular weight of about 140 to 200 are preferably used. Examples thereof include colorless to light yellow acid anhydrides such as hexahydrophthalic anhydride, tetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride. In the case of an epoxy resin, the mixing ratio of the acid anhydride curing agent is preferably such that the equivalent ratio of the acid anhydride group to the epoxy group (epoxy group / acid anhydride group) is in the range of 1 / 0.5 to 1 / 1.3.

  The phenolic curing agent has two or more, preferably three or more phenolic hydroxyl groups in the molecule. Specific examples include phenols and substituted phenols such as o-cresol, p-cresol, t-butylphenol, tamilphenol, phenylphenol and formaldehyde reacted with acid or alkali. Instead of formaldehyde, other aldehydes such as benzaldehyde, crotonaldehyde, salicylaldehyde, hydroxybenzaldehyde, glyoxal and terephthalaldehyde can be used. A reaction product of resorcin and aldehyde or polyvinylphenol can also be used as the curing agent of the present invention. In addition, in the case of an epoxy resin, the proportion of the phenolic curing agent is such that the equivalent ratio of the phenolic hydroxyl group of the curing agent to the epoxy group (epoxy group / phenolic hydroxyl group) is usually 1 / 0.8 to 1 / 1.2, preferably 1. The range of /0.9 to 1 / 1.1 is selected from the viewpoints of heat resistance and moisture resistance.

  Examples of the curing catalyst component include tertiary amines, quaternary ammonium salts, imidazole compounds, boron compounds and organometallic complex salts.

  Tertiary amines include triethanolamine, tetramethylhexanediamine, triethylenediamine, dimethylaniline, dimethylaminoethanol, diethylaminoethanol, 2,4,6-tris (dimethylaminomethyl) phenol, N, N′-dimethylpiperazine, Examples include pyridine, picoline, 1,8-diazabicyclo (5,4,0) undecene-7, benzyldimethylamine and 2- (dimethylamino) methylphenol. Quaternary ammonium salts include dodecyltrimethylammonium chloride, cetyltrimethylammonium chloride, benzyldimethyltetradecylammonium chloride and stearyltrimethylammonium chloride. Examples of imidazoles include 2-methylimidazole, 2-undecylimidazole, 2-ethylimidazole, 1-benzyl-2-methylimidazole, and 1-cyanoethyl-2-undecylimidazole. Examples of the boron compound include tetraphenyl boron salts such as triethyleneamine tetraphenyl borate and N-methylmorpholine tetraphenyl borate. Examples of the organic metal complex salts include phosphates, and the phosphates include, for example, triphenylphosphine, tris-2,6-dimethoxyphenylphosphine, tri-p-tolylphosphine, and triphenyl phosphite. Tetra-n-butylphosphonium-o, o-diethyl phosphorodithioate and tetra-n-butylphosphonium bromide.

  The thermosetting resin composition such as an epoxy resin of the present invention includes a coupling agent, a colorant such as carbon black and bengara, a mold release agent such as natural wax and synthetic wax, as necessary, in addition to the above components. Various additives such as a silicone oil, an ion scavenger, a flame retardant, and a low stress additive such as rubber may be appropriately blended.

The thermosetting resin composition such as an epoxy resin of the present invention is useful as a sealing material for semiconductor devices and liquid crystal display devices.

  A thermosetting resin composition such as an epoxy resin in which a filler such as a metal oxide of the present invention is uniformly dispersed cannot be obtained by a conventional kneading method (1) high filler concentration, (2) dispersed as primary particles. , High dispersibility without coarse particles and pseudo-collection, (3) low viscosity, (4) low coarse particle filler-containing resin composition is obtained, semiconductor, display liquid sealing, sera substitute material, precision resin parts, etc. Can be preferably applied.

  Hereinafter, the present invention will be described using examples and comparative examples.

[Example 1]
70 parts by weight of spherical silica having an average particle size of 25 μ, a specific surface area of 1.8 m ² / g and a maximum particle size of 75 μ, an average particle size of 7 μ, a specific surface area of 4.6 m ² / g and a maximum particle size of 75 μ 30 parts by weight of spherical silica, 10 parts by weight of spherical silica having an average particle diameter of 0.5 μ, a specific surface area of 7 m ² / g, and a maximum particle diameter of 75 μ, 25 parts by weight of epoxy resin (828 EL), and 0 by KBM403 .4 parts by weight, 0.01 parts by weight of butylamine, 100 parts by weight of methyl ethyl ketone, and after mixing in a mixer, disperse the powder with a disperser and heat at 120 ° C. for 3 hours under reduced pressure to remove the solvent. Removal of a viscous column liquid was obtained. When the epoxy equivalent of the resin composition was measured, a value of 224 was obtained in terms of resin. The epoxy equivalent of 825EL itself was 225. When the ash content was measured by heating the resin composition to 800 ° C., a value of 81.5% was obtained.

[Example 2]
70 parts by weight of spherical silica having an average particle size of 25 μ, a specific surface area of 1.8 m ² / g and a maximum particle size of 45 μ, an average particle size of 7 μ, a specific surface area of 4.6 m ² / g and a maximum particle size of 45 μ 30 parts by weight of spherical silica, 10 parts by weight of spherical silica having an average particle diameter of 0.5 μm, a specific surface area of 7 m ² / g, and a maximum particle diameter of 45 μ, 25 parts by weight of epoxy resin (828EL), and 0 of KBM403 .4 parts by weight, 0.01 parts by weight of KBM903, 100 parts by weight of methyl ethyl ketone, and after mixing in a mixer, disperse the powder with a disperser and heat at 120 ° C. for 3 hours under reduced pressure to remove the solvent. Removal of a viscous column liquid was obtained. When the epoxy equivalent of the resin composition was measured, a value of 225 was obtained in terms of resin. The epoxy equivalent of 828EL itself was 225. When the ash content was measured by heating the resin composition to 800 ° C., a value of 81.5% was obtained.

[Comparative Example 1]
70 parts by weight of spherical silica having an average particle size of 25 μ, a specific surface area of 1.8 m ² / g, and a maximum particle size of 75 μ, an average particle size of 7 μ, a specific surface area of 4.6 m ² / g, and a maximum particle size of 75 μ 30 parts by weight of spherical silica, 10 parts by weight of spherical silica having an average particle diameter of 0.5 μ, a specific surface area of 7 m ² / g, and a maximum particle diameter of 75 μ, 25 parts by weight of epoxy resin (828 EL), and 0 of KBM403 After mixing 4 parts by weight and 100 parts by weight of methyl ethyl ketone in a mixer, the powder was dispersed with a disperser, and the solvent was removed by heating at 120 ° C. for 3 hours under reduced pressure. The epoxy resin was cured. And I couldn't get it out of the container.

[Example 3]
70 parts by weight of spherical silica having an average particle size of 7 μ, a specific surface area of 4.6 m ² / g and a maximum particle size of 20 μ, an average particle size of 0.5 μ, a specific surface area of 7 m ² / g and a maximum particle size of 20 μ 30 parts by weight of spherical silica, 25 parts by weight of epoxy resin (828EL), 0.4 parts by weight of KBM403, 0.01 parts by weight of aniline, 100 parts by weight of methyl ethyl ketone, mixed in a mixer, The powder was dispersed by heating at 120 ° C. for 3 hours under reduced pressure to remove the solvent, and a viscous liquid was obtained. When the epoxy equivalent of the resin composition was measured, a value of 224 was obtained in terms of resin. The epoxy equivalent of 828EL itself was 225. When the ash content was measured by heating the resin composition to 800 ° C., a value of 80.0% was obtained.

[Comparative Example 2]
70 parts by weight of spherical silica having an average particle diameter of 7 μ, a specific surface area of 4.6 m ² / g and a maximum particle diameter of 20 μ, an average particle diameter of 0.5 μ, a specific surface area of 7 m ² / g and a maximum particle diameter of 20 μ 30 parts by weight of spherical silica, 25 parts by weight of epoxy resin (828EL), 0.4 parts by weight of KBM403, 100 parts by weight of methyl ethyl ketone, and after mixing in a mixer, the powder is dispersed with a disperser, When the solvent was removed by heating at 120 ° C. for 3 hours under reduced pressure, the epoxy resin was cured and could not be removed from the container.

[Example 4]
Average particle size 2.mu., specific surface area of 2m ² / g, a maximum particle size of 10 [mu] 70 parts by weight of spherical silica of an average particle size of 0.5 [mu], a specific surface area of 7m ² / g, a maximum particle size of 10 [mu] of the spherical 30 parts by weight of silica, 25 parts by weight of epoxy resin (828EL), 0.4 parts by weight of KBM403, 0.01 parts by weight of butylamine and 100 parts by weight of methyl ethyl ketone are mixed in a mixer, and then mixed with a disperser. The body was dispersed and heated at 120 ° C. for 3 hours under reduced pressure to remove the solvent to obtain a viscous liquid. When the epoxy equivalent of the resin composition was measured, a value of 224 was obtained in terms of resin. The epoxy equivalent of 828EL itself was 225. When the ash content was measured by heating the resin composition to 800 ° C., a value of 80.0% was obtained.

[Example 5]
70 parts by weight of spherical silica having an average particle size of 2 μ, a specific surface area of 2 m ² / g, and a maximum particle size of 5 μ, a spherical particle having an average particle size of 0.5 μ, a specific surface area of 7 m ² / g, and a maximum particle size of 5 μ 30 parts by weight of silica, 25 parts by weight of epoxy resin (828EL), 0.4 parts by weight of KBM403, 0.01 parts by weight of 2PHZ (manufactured by Shikoku Kasei), 100 parts by weight of methyl ethyl ketone, and after mixing in a mixer The powder was dispersed with a disperser, and the solvent was removed by heating at 120 ° C. for 3 hours under reduced pressure to obtain a viscous liquid. When the epoxy equivalent of the resin composition was measured, a value of 224 was obtained in terms of resin. The epoxy equivalent of 828EL itself was 225. When the ash content was measured by heating the resin composition to 800 ° C., a value of 80.0% was obtained.

[Example 6]
Average particle size 2.mu., specific surface area of 2m ² / g, a maximum particle size of 70 parts by weight of spherical silica of 5 [mu], an average particle diameter of 0.5 [mu], a specific surface area of 7m ² / g, spherical maximum particle diameter of 5 [mu] 30 parts by weight of silica, 25 parts by weight of epoxy resin (828EL), 0.4 parts by weight of KBM403, 0.01 parts by weight of ammonia and 100 parts by weight of methyl ethyl ketone are mixed in a mixer, and then mixed with a disperser. The body was dispersed and heated at 120 ° C. for 3 hours under reduced pressure to remove the solvent to obtain a viscous liquid. When the epoxy equivalent of the resin composition was measured, a value of 224 was obtained in terms of resin. The epoxy equivalent of 828EL itself was 225. When the ash content was measured by heating the resin composition to 800 ° C., a value of 80.0% was obtained.

[Example 7]
Average particle size 2.mu., specific surface area of 2m ² / g, a maximum particle size of 70 parts by weight of spherical silica of 5 [mu], an average particle diameter of 0.5 [mu], a specific surface area of 7m ² / g, spherical maximum particle diameter of 5 [mu] 30 parts by weight of silica, 25 parts by weight of epoxy resin (828EL), 0.4 parts by weight of KBM403, 0.01 parts by weight of ethylenediamine and 100 parts by weight of methyl ethyl ketone are mixed in a mixer, and then mixed with a disperser. The body was dispersed, and the solvent was removed by heating at 120 ° C. for 3 hours while reducing the pressure to obtain a viscous liquid. When the epoxy equivalent of the resin composition was measured, a value of 224 was obtained in terms of resin. The epoxy equivalent of 828EL itself was 225. When the resin composition was heated to 800 degrees and ash content was measured, a value of 80.0% was obtained.

[Example 8]
70 parts by weight of spherical silica having an average particle diameter of 2 μ, a specific surface area of 2 m ² / g and a maximum particle diameter of 105 μ, an average particle diameter of 0.5 μ, a specific surface area of 7 m ² / g and a spherical particle having a maximum particle diameter of 105 μ 30 parts by weight of silica, 25 parts by weight of epoxy resin (828EL), 0.4 parts by weight of KBM403, 0.01 parts by weight of butylamine and 100 parts by weight of methyl ethyl ketone are mixed in a mixer, and then mixed with a disperser. The body was dispersed to a maximum particle size of 10μ through a 10μ filter. The solvent was removed by heating at 120 ° C. for 3 hours under reduced pressure to obtain a viscous liquid. When the epoxy equivalent of the resin composition was measured, a value of 224 was obtained in terms of resin. The epoxy equivalent of 828EL itself was 225. When the ash content was measured by heating the resin composition to 800 ° C., a value of 79.9% was obtained.

[Example 9]
70 parts by weight of spherical silica having an average particle diameter of 2 μ, a specific surface area of 2 m ² / g and a maximum particle diameter of 105 μ, an average particle diameter of 0.5 μ, a specific surface area of 7 m ² / g and a spherical particle having a maximum particle diameter of 105 μ 30 parts by weight of silica, 25 parts by weight of epoxy resin (828EL), 0.4 parts by weight of KBM403, 0.01 parts by weight of butylamine and 100 parts by weight of methyl ethyl ketone are mixed in a mixer, and then mixed with a disperser. The body was dispersed and passed through a 5μ filter to a maximum particle size of 5μ. The solvent was removed by heating at 120 ° C. for 3 hours under reduced pressure to obtain a viscous liquid. When the epoxy equivalent of the resin composition was measured, a value of 224 was obtained in terms of resin. The epoxy equivalent of 828EL itself was 225. When the resin composition was heated to 800 ° C. and the ash content was measured, a value of 79.8% was obtained.

[Comparative Example 3]
70 parts by weight of spherical silica having an average particle size of 2 μ, a specific surface area of 2 m ² / g, and a maximum particle size of 5 μ, a spherical particle having an average particle size of 0.5 μ, a specific surface area of 7 m ² / g, and a maximum particle size of 5 μ 30 parts by weight of silica, 25 parts by weight of epoxy resin (828EL), 0.4 parts by weight of KBM403 and 100 parts by weight of methyl ethyl ketone are mixed in a mixer, and then the powder is dispersed with a disperser and decompressed. However, when the solvent was removed by heating at 120 ° C. for 3 hours, the epoxy resin was cured and could not be removed from the container.

[Example 10]
95 parts by weight of spherical silica having an average particle size of 0.5 μ, a specific surface area of 7 m ² / g and a maximum particle size of 105 μ, an average particle size of 0.2 μ, a specific surface area of 16 m ² / g and a maximum particle size of 105 μ 5 parts by weight of spherical silica, 25 parts by weight of epoxy resin (828EL), 0.4 parts by weight of KBM403, 0.01 parts by weight of butylamine and 100 parts by weight of methyl ethyl ketone were mixed in a mixer, and then dispersed. Then, the powder was dispersed and the maximum particle size was adjusted to 3μ through a 3μ filter. The solvent was removed by heating at 120 ° C. for 3 hours under reduced pressure to obtain a viscous liquid. When the epoxy equivalent of the resin composition was measured, a value of 224 was obtained in terms of resin. The epoxy equivalent of 828EL itself was 225. When the ash content was measured by heating the resin composition to 800 ° C., a value of 79.9% was obtained.

[Comparative Example 4]
95 parts by weight of spherical silica having an average particle size of 0.5 μ, a specific surface area of 7 m ² / g and a maximum particle size of 105 μ, an average particle size of 0.2 μ, a specific surface area of 16 m ² / g and a maximum particle size of 105 μ 5 parts by weight of spherical silica, 25 parts by weight of epoxy resin (828EL), 0.4 parts by weight of KBM403, 100 parts by weight of methyl ethyl ketone, and mixed in a mixer, the powder was dispersed with a disperser, The maximum particle size was adjusted to 3μ through a 3μ filter. When the solvent was removed by heating at 120 ° C. for 3 hours under reduced pressure, the epoxy resin was cured and could not be removed from the container.

[Example 11]
70 parts by weight of spherical silica having an average particle diameter of 0.5 μ, a specific surface area of 7 m ² / g, and a maximum particle diameter of 45 μ, 30 parts by weight of kaolin having an average particle diameter of 6 μ, and 25 parts by weight of epoxy resin (828EL) Then, 0.4 parts by weight of KBM403, 0.01 parts by weight of butylamine and 100 parts by weight of methyl ethyl ketone were mixed in a mixer, and then the powder was dispersed with a disperser and heated at 120 ° C. for 3 hours while reducing the pressure. The solvent was removed to obtain a viscous liquid. When the epoxy equivalent of the resin composition was measured, a value of 224 was obtained in terms of resin. The epoxy equivalent of 828EL itself was 225. When the ash content was measured by heating the resin composition to 800 ° C., a value of 80.0% was obtained.

[Comparative Example 5]
70 parts by weight of spherical silica having an average particle diameter of 0.5 μ, a specific surface area of 7 m ² / g, and a maximum particle diameter of 45 μ, 30 parts by weight of kaolin having an average particle diameter of 6 μ, and 25 parts by weight of epoxy resin (828EL) Then, 0.4 parts by weight of KBM403 and 100 parts by weight of methyl ethyl ketone were mixed in a mixer, and then the powder was dispersed with a disperser and heated at 120 ° C. for 3 hours under reduced pressure to cure the epoxy resin. I couldn't get it out of the container.

[Example 12]
70 parts by weight of spherical silica having an average particle diameter of 0.5 μ, a specific surface area of 7 m ² / g, and a maximum particle diameter of 45 μ, 30 parts by weight of glass fiber fiber having a diameter of 7 μ, and 25 parts by weight of epoxy resin (828 EL) Then, 0.4 parts by weight of KBM403, 0.01 parts by weight of butylamine and 100 parts by weight of methyl ethyl ketone were mixed in a mixer, and then the powder was dispersed with a disperser and heated at 120 ° C. for 3 hours while reducing the pressure. The solvent was removed to obtain a viscous liquid. When the epoxy equivalent of the resin composition was measured, a value of 224 was obtained in terms of resin. The epoxy equivalent of 828EL itself was 225. When the ash content was measured by heating the resin composition to 800 ° C., a value of 80.0% was obtained.

[Comparative Example 6]
70 parts by weight of spherical silica having an average particle diameter of 0.5 μ, a specific surface area of 7 m ² / g, and a maximum particle diameter of 45 μ, 30 parts by weight of glass fiber fiber having a diameter of 7 μ, and 25 parts by weight of epoxy resin (828 EL) Then, 0.4 parts by weight of KBM403 and 100 parts by weight of methyl ethyl ketone were mixed in a mixer, and then the powder was dispersed with a disperser and heated at 120 ° C. for 3 hours under reduced pressure to cure the epoxy resin. I couldn't get it out of the container.

[Physical properties of Examples]
The physical properties and the like of the resin compositions obtained in the above examples and comparative examples were examined as follows. The results are shown in Tables 1 to 3 together with Comparative Examples.
<Measurement of Viscosity> Using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.), the viscosity (Pa · S) at 25 ° C. was measured.
<Physical properties of cured product>
1 part by weight of the epoxy curing agent 2PHZ was added to the resin compositions obtained in Examples 1 to 12 and heated at 190 ° C. for 5 hours to obtain a cured product. The physical properties of the cured product were examined as follows.
<Bending strength> The bending strength was measured based on JISK6911.
<Water Absorption> A disk having a diameter of 50 × 3 mm was left in a constant temperature and humidity chamber of 85 ° C./85% RH for 168 hours, and the water absorption was measured.
<SEM Observation> When the fracture surface fractured by measuring the bending strength was observed with SEM, the interface between the particles and the resin was good, the particles were not aggregated, and the particles were not detached.

<< Measurement of physical properties of comparative examples >>
The solidified product was taken out by cutting the container and heated at 190 ° C. for 5 hours to obtain a cured product. Furthermore, the cured product was cut with a cutter, the sample was adjusted, bending strength and water absorption were measured, and SEM observation was performed.

  From the result of Tables 1-3, compared with Comparative Examples 1-6, Examples 1-12 of this invention have a viscosity below a fixed value, are excellent in bending strength, have a low water absorption, and resin and particle | grains are integral. You can see that

[Example 13]
80 parts by weight of spherical silica having an average particle diameter of 0.5 μ, a specific surface area of 7 m ² / g, and a maximum particle diameter of 45 μ, 20 parts by weight of IST polyimide varnish, Skybond 703, and hexamethyldisilazane of 0. After mixing 01 parts by weight and 100 parts by weight of methyl ethyl ketone in a mixer, disperse the powder with a disperser and remove the methyl ethyl ketone by heating at 90 ° C. for 3 hours under reduced pressure to obtain a viscous liquid. Obtained. When the obtained liquid was sandwiched between slide glasses and observed with a microscope, it was found that the silica particles were not agglomerated but were dispersed to the primary particles. A tough film was obtained by applying the liquid, drying and baking. Silica in the film was uniformly dispersed without aggregation.

[Comparative Example 7]
After 80 parts by weight of spherical silica having an average particle diameter of 0.5 μ, a specific surface area of 7 m ² / g, and a maximum particle diameter of 45 μ, IST polyimide varnish, and Skybond 703 are mixed in a mixer by 20 parts by weight, When dispersion was attempted with three rolls, the mixture did not liquefy and did not get on the roll.

[Example 14]
80 parts by weight of spherical silica having an average particle diameter of 0.5 μ, a specific surface area of 7 m ² / g, and a maximum particle diameter of 45 μ, Sanyo Chemical Co., Ltd. polyol excel flow 20 parts by weight, and hexamethyldisilazane 0.01 parts by weight Part, 100 parts by weight of methyl ethyl ketone was mixed in a mixer, and then the powder was dispersed with a disperser and heated at 90 ° C. for 3 hours under reduced pressure to remove methyl ethyl ketone to obtain a viscous liquid. . When the obtained liquid was sandwiched between slide glasses and observed with a microscope, it was found that the silica particles were not agglomerated but were dispersed to the primary particles. When a urethane resin main component (isocyanate) and a tin catalyst were blended into the obtained liquid, a urethane cured body in which silica particles were uniformly dispersed was obtained.

[Comparative Example 8]
80 parts by weight of spherical silica having an average particle diameter of 0.5 μ, a specific surface area of 7 m ² / g, and a maximum particle diameter of 45 μ, and a polyol excel flow manufactured by Sanyo Chemical Co., Ltd. in a 20 parts by weight mixer are mixed. When dispersion was attempted with a roll, the mixture did not liquefy and did not get on the roll.

[Example 15]
80 parts by weight of spherical silica having an average particle diameter of 0.5 μ, a specific surface area of 7 m ² / g, and a maximum particle diameter of 45 μ, 20 parts by weight of Dainippon Ink Chemical Co., Ltd. phenol resin TD2131, and 0 of hexamethyldisilazane .01 parts by weight, 100 parts by weight of methyl ethyl ketone, mixed in a mixer, then the powder is dispersed with a disperser and heated at 120 ° C. for 3 hours under reduced pressure to remove the methyl ethyl ketone to obtain a viscous liquid Got. When the obtained liquid was sandwiched between slide glasses and observed with a microscope, it was found that the silica particles were not agglomerated but were dispersed to the primary particles. When the obtained liquid was cooled to room temperature, a solid material in which silica was uniformly dispersed was obtained. The solid was pulverized, mixed with hexamine, mixed, pressurized and heated to obtain a cured phenol resin in which silica particles were uniformly dispersed.

[Comparative Example 9]
After 80 parts by weight of spherical silica having an average particle diameter of 0.5 μ, a specific surface area of 7 m ² / g, and a maximum particle diameter of 45 μ, 20 parts by weight of Dainippon Ink Chemical Co., Ltd. phenol resin TD2131 were mixed, When dispersion was attempted with three rolls, the mixture was in the form of solid powder and did not get on the roll.

  From the results of Examples 13 to 15, it can be seen that the effects of the present invention are exhibited even in combinations of various thermosetting resins and basic substances.

  The thermosetting resin composition of the present invention comprises (1) high filler concentration, (2) dispersed as primary particles, high dispersion without coarse particles and false collection, (3) low viscosity, (4) low roughness By making use of the filler-containing resin composition having a particle amount, it can be widely applied to the fields of semiconductors, liquid display sealing, ceramic substitute materials, precision resin parts and the like.

Claims (22)

  A filler containing a basic substance in a thermosetting resin (excluding an epoxy resin) is mixed in an amount of 60% by weight or more based on the total amount, and the filler is primarily dispersed in the thermosetting resin (excluding an epoxy resin). A filler-containing resin composition characterized by comprising:   The filler-containing resin composition, wherein the basic substance is at least one selected from ammonia, organic amines, silazanes, a silane coupling agent containing nitrogen, and a cyclic compound containing nitrogen.   A filler in which a basic substance (excluding silazanes) is blended in a thermosetting resin is blended in an amount of 60% by weight or more based on the total amount, and the filler is primarily dispersed in the thermosetting resin. Filler-containing resin composition.   The filler-containing resin composition according to claim 3, wherein the thermosetting resin is at least one selected from an epoxy resin, a phenol resin, urethane, polyimide, and an unsaturated polyester.   5. The filler-containing material according to claim 1, wherein the filler contains at least one kind of silica particles selected from spherical silica particles having an average particle size of 0.01 μm to 30 μm and a maximum particle size of 75 μm. Resin composition.   The filler-containing material according to any one of claims 1 to 4, wherein the filler contains at least one kind of silica particles selected from spherical silica particles having an average particle size of 0.01 to 20 µ and a maximum particle size of 45 µ. Resin composition.   The filler-containing material according to any one of claims 1 to 4, wherein the filler contains at least one kind of silica particles selected from spherical silica particles having an average particle size of 0.01 µm to 10 µm and a maximum particle size of 20 µm. Resin composition.   The filler-containing composition according to any one of claims 1 to 4, wherein the filler contains at least one kind of silica particles selected from spherical silica particles having an average particle size of 0.01 to 5 µ and a maximum particle size of 10 µ. Resin composition.   The filler-containing material according to any one of claims 1 to 4, wherein the filler contains at least one kind of silica particles selected from spherical silica particles having an average particle size of 0.01 to 3 µ and a maximum particle size of 5 µ. Resin composition.   5. The filler according to claim 1, wherein the filler contains at least one kind of silica particles selected from spherical silica particles having an average particle diameter of 0.01 μm to 1.5 μm and a maximum particle diameter of 3 μm. Filler-containing resin composition.   The filler-containing resin composition according to any one of claims 5 to 10, wherein the spherical silica particles are spherical silica particles obtained by oxidizing fused spherical silica particles and / or metal silicon.   One or more kinds of powders selected from plate-like inorganic powder, fibrous inorganic powder, amorphous inorganic powder, wood powder, crushed powder of thermosetting resin, resin particles obtained by polymerization, and inorganic flame retardant The filler-containing resin composition according to any one of claims 1 to 11, wherein a body is blended.   The plate-like inorganic powder is mica, the fibrous inorganic powder is talc, glass fiber, carbon fiber, potassium titanate whisker, the amorphous inorganic powder is calcium carbonate, crushed silica, and crushed powder of the thermosetting resin. The body is a crushed powder of epoxy resin, the resin particles obtained by the polymerization are resin particles synthesized by suspension polymerization, and the inorganic flame retardant is selected from aluminum hydroxide and magnesium hydroxide. 12. The filler-containing resin composition according to 12.   The filler-containing resin composition according to any one of claims 1 to 13, wherein the filler is treated with a silane coupling agent.   The filler-containing resin composition according to claim 14, wherein the silane coupling agent is at least one selected from epoxy silane, amino silane, acrylic silane, and thiol silane.   After mixing a part of the thermosetting resin (excluding the epoxy resin) or a part of the thermosetting resin (excluding the epoxy resin) into the slurry obtained by dispersing the filler containing the basic substance in the slurry in the organic solvent, the solvent A method for producing a filler-containing resin composition, wherein the filler is removed.   The resin composition according to claim 16, wherein the basic substance is at least one selected from ammonia, organic amines, silazanes, a silane coupling agent containing nitrogen, and a cyclic compound containing nitrogen. Manufacturing method.   A feature is that a thermosetting resin or a part of the thermosetting resin is mixed with a slurry obtained by dispersing a filler containing a basic substance (excluding silazanes) in a slurry in an organic solvent, and then the solvent is removed. A method for producing a filler-containing resin composition.   The method for producing a resin composition according to claim 18, wherein the thermosetting resin is at least one selected from an epoxy resin, a phenol resin, urethane, polyimide, and an unsaturated polyester.   The method for producing a filler-containing resin composition according to any one of claims 16 to 19, wherein the abundance of the basic substance when mixed is 1 ppm to 1000 ppm with respect to the filler.   The method for producing a filler-containing resin composition according to any one of claims 16 to 20, wherein a volatile content remaining in the composition is 0.5% or less.   The thermosetting composition characterized by mix | blending the hardening | curing agent or the catalyst with the filler containing resin composition of Claims 1-15.