JP2013077784A - Method of preparing resin composition, resin composition, and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of preparing a resin composition, a resin composition, and a semiconductor device, capable of obtaining a resin composition excellent in fluidity and curing characteristics when sealing a semiconductor element.SOLUTION: A method of the present invention is a method for preparing a resin composition that seals a semiconductor chip 120 installed on a circuit board 110 and fills a gap between the circuit board 110 and the semiconductor chip 120 as well at the time of sealing. The method includes a crushing step for crushing a row material containing a powder material of a curing resin and a powder material of a first inorganic filler material, a surface treatment step for performing surface treatment on a powder material of a second inorganic filler material, a mixing step for mixing the row material after crushing with the second inorganic filler material whose surface has been treated, and a kneading step for kneading a mixture having been mixed in the mixing step.

Description

  The present invention relates to a resin composition manufacturing method, a resin composition, and a semiconductor device.

  With recent demands for higher functionality and lighter, thinner and smaller electronic devices, semiconductor packages used in these electronic devices are becoming smaller and multi-pin than ever.

  As a semiconductor package that meets such requirements, a circuit board having a circuit board and a semiconductor chip (semiconductor element) electrically connected to the circuit board via metal bumps, and joined by metal bumps; A semiconductor device including a so-called flip chip type package in which an underfill material is formed in a gap (gap) with a semiconductor chip (semiconductor element) and is further sealed (covered) with a molding material made of a resin composition. Widely used. Further, when the semiconductor chip (semiconductor element) is sealed (covered) with the molding material without using the underfill material and the molding material as separate members, the resin composition is used for the circuit board and the semiconductor chip (semiconductor element). A semiconductor device including a flip chip package that is filled in a gap between the two and is reinforced by collective sealing has been studied (for example, see Patent Document 1). In the present invention, when the semiconductor chip (semiconductor element) is sealed (covered) with the molding material without using the underfill material and the molding material as separate members as described above, the resin composition is used for the circuit board and the semiconductor chip. Filling a gap (gap) between (semiconductor element) is called “batch sealing”. By applying such a collective sealing material (mold underfill material), a semiconductor device including an economically reliable flip chip package can be obtained.

  The resin composition has a curable resin, an inorganic filler, and the like, and the collective sealing material (mold underfill material) is obtained by molding the resin composition by, for example, transfer molding. It is done. When the resin composition contains an inorganic filler, the difference in thermal expansion coefficient between the resin composition and the semiconductor chip can be reduced, and a more reliable semiconductor package can be obtained.

  By the way, in the manufacturing process of the resin composition, there is a kneading step of kneading the raw material including the powder material of the curable resin and the powder material of the inorganic filler. It is carried out by a kneader such as an extrusion kneader such as a mold kneading extruder or a roll kneader such as a mixing roll.

  Further, the downsizing of the semiconductor package and the increase in the number of pins reduce the pitch of the metal bumps connecting the circuit board side and the semiconductor chip side, thereby reducing the gap distance between the substrate and the semiconductor chip. For this reason, it is necessary to use a fine inorganic filler so that the resin composition can be filled between the substrate and the semiconductor chip.

  However, in the conventional method for producing a resin composition, if the raw material contains a fine inorganic filler obtained by cutting coarse particles, it cannot be sufficiently kneaded in the kneading step. The fluidity and curability of the resin composition when sealing the chip are deteriorated. As a result, the moldability of the resin composition when sealing the semiconductor chip with the resin composition is reduced, and there is a portion where the resin composition is not filled between the semiconductor chip and the circuit board, resulting in insufficient strength. As a result, the reliability decreases.

JP 2004-307645 A

  The objective of this invention is providing the manufacturing method of a resin composition, the resin composition, and a semiconductor device which can obtain the resin composition excellent in the fluidity | liquidity at the time of sealing a semiconductor element, and sclerosis | hardenability.

Such an object is achieved by the present inventions (1) to (9) below.
(1) A resin composition for sealing a semiconductor element placed on a substrate, which is filled in a gap between the substrate and the semiconductor element during the sealing. A manufacturing method for
A pulverizing step of pulverizing a raw material containing a powder material of a curable resin and a powder material of a first inorganic filler;
A surface treatment step of performing a surface treatment on the powder material of the second inorganic filler;
A mixing step of mixing the raw material after pulverization and the surface-treated second inorganic filler;
And a kneading step of kneading the mixture mixed in the mixing step.

  (2) In the said surface treatment process, the manufacturing method of the resin composition as described in said (1) which attaches a coupling agent to the surface of the powder material of a said 2nd inorganic filler.

  (3) The manufacturing method of the resin composition as described in said (1) or (2) whose average particle diameter of the said mixture is 1-100 micrometers.

  (4) The particle size distribution of the mixture is that the particle size of 250 μm or more is 2% by mass or less, the particle size of 150 μm or more, less than 250 μm is 15% by mass or less, and the particle size of less than 150 μm is 80% by mass or more. 3) The manufacturing method of the resin composition in any one of.

(5) The raw material includes a curing accelerator,
The said curable resin is a manufacturing method of the resin composition in any one of said (1) thru | or (4) containing an epoxy resin and a phenol resin type hardening | curing agent.

  (6) The method for producing a resin composition according to any one of (1) to (5), wherein an airflow type pulverizer is used in the pulverization step.

  (7) The method for producing a resin composition according to any one of (1) to (6), wherein a biaxial kneading extruder is used in the kneading step.

  (8) A resin composition produced by the method for producing a resin composition according to any one of (1) to (7).

(9) a substrate;
A semiconductor element installed on a substrate;
A semiconductor comprising: sealing the semiconductor element, and having the resin composition according to (8) filled in a gap between the substrate and the semiconductor element when the semiconductor element is sealed. apparatus.

  ADVANTAGE OF THE INVENTION According to this invention, even when it contains the fine inorganic filler which cut the coarse grain, the resin composition excellent in the fluidity | liquidity at the time of sealing a semiconductor element and sclerosis | hardenability can be provided. Thereby, the moldability of the resin composition when the semiconductor element is sealed with the resin composition is improved, and the resin composition can be reliably filled between the semiconductor element and the substrate. Can be improved.

  In addition, by including the powder material of the first inorganic filler in the raw material in the pulverization step, it is possible to suppress the raw material from adhering to the wall surface of the pulverizer, and to easily and reliably finely pulverize the raw material. can do.

  In addition, by performing surface treatment on the second inorganic filler, the fluidity of the resin composition is improved by improving the wettability between the second inorganic filler and the curable resin. The moldability such as the property is improved.

It is a figure which shows an example of the manufacturing process of the resin composition in embodiment of the manufacturing method of the resin composition of this invention. It is a side view which shows typically the structural example of the grinding | pulverization apparatus used in embodiment of the manufacturing method of the resin composition of this invention. It is a top view which shows typically the inside of the grinding | pulverization part of the grinding | pulverization apparatus shown in FIG. It is sectional drawing which shows the chamber of the grinding | pulverization part of the grinding | pulverization apparatus shown in FIG. It is sectional drawing which shows typically embodiment of the semiconductor device of this invention.

  Hereinafter, a method for producing a resin composition, a resin composition, and a semiconductor device of the present invention will be described in detail based on preferred embodiments shown in the accompanying drawings.

  FIG. 1 is a diagram illustrating an example of a production process of a resin composition in an embodiment of a method for producing a resin composition of the present invention, and FIG. 2 is a diagram of a grinding apparatus used in an embodiment of a method of producing a resin composition of the present invention. FIG. 3 is a side view schematically showing a configuration example, FIG. 3 is a plan view schematically showing the inside of the pulverizing section of the pulverizing apparatus shown in FIG. 2, and FIG. 4 is a chamber of the pulverizing section of the pulverizing apparatus shown in FIG. FIG. 5 is a sectional view schematically showing an embodiment of the semiconductor device of the present invention.

  In the following description, the upper side in FIGS. 2 and 4 is “upper”, the lower side is “lower”, the left side is “left”, and the right side is “right”. 2, the description of the nozzle 71 and the like is omitted, the description of the supply unit 73 and the like is omitted in FIG. 3, and the description of the nozzles 71 and 72, the supply unit 73 and the like is omitted in FIG. Has been.

  First, the whole manufacturing process until it manufactures the resin composition for sealing (covering) of a semiconductor chip (semiconductor element) from a raw material is demonstrated.

First, each material which is a raw material of a resin composition is prepared.
The raw material has a curable resin, a first inorganic filler (first inorganic particles), and a second inorganic filler (second inorganic particles), and further, if necessary, a curing accelerator. And a coupling agent or the like. As curable resin, an epoxy resin etc. are mentioned, for example, It is preferable to use the epoxy resin which used the phenol resin type hardening | curing agent as a hardening | curing agent.

Examples of epoxy resins include biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol type epoxy resins such as tetramethylbisphenol A type epoxy resins, and crystalline epoxy resins such as stilbene type epoxy resins; phenol Novolac epoxy resin, novolac epoxy resin such as cresol novolac epoxy resin, polyfunctional epoxy resin such as triphenolmethane epoxy resin, alkyl-modified triphenolmethane epoxy resin, phenol aralkyl epoxy resin having phenylene skeleton, biphenylene Aralkyl type epoxy resins such as phenol aralkyl type epoxy resins having a skeleton, epoxy resins having a dihydroanthraquinone structure, and dihydroxynaphthalene Type epoxy resins, naphthol type epoxy resins such as epoxy resins obtained by glycidyl etherification of dihydroxynaphthalene dimers, triazine nucleus-containing epoxy resins such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate, dicyclopentadiene-modified phenol Bridged cyclic hydrocarbon compound-modified phenol type epoxy resins such as epoxy type epoxy resins are exemplified, but not limited thereto. These epoxy resins preferably do not contain Na ⁺ ions or Cl ⁻ ions, which are ionic impurities, as much as possible from the viewpoint of the moisture resistance reliability of the obtained resin composition. From the viewpoint of curability of the resin composition, the epoxy equivalent of the epoxy resin (B) is preferably 100 g / eq or more and 500 g / eq or less.

  The lower limit of the blending ratio of the epoxy resin in the resin composition of the present invention is preferably 3% by mass or more, more preferably 5% by mass or more, and still more preferably with respect to the total mass of the resin composition. 7% by mass or more. When the lower limit is within the above range, the resulting resin composition has good fluidity. Moreover, the upper limit of the epoxy resin (B) in the resin composition is preferably 30% by mass or less, more preferably 20% by mass or less, with respect to the total mass of the resin composition. When the upper limit is within the above range, the obtained resin composition can have good reliability such as solder resistance.

  Examples of the phenol resin-based curing agent include monomers, oligomers, and polymers in general having two or more phenolic hydroxyl groups in one molecule, and the molecular weight and molecular structure thereof are not particularly limited. For example, phenol novolak resin, cresol Novolak resins such as novolac resins; modified phenol resins such as terpene-modified phenol resins and dicyclopentadiene-modified phenol resins; phenol aralkyl resins having a phenylene skeleton or a biphenylene skeleton; bisphenol compounds such as bisphenol A and bisphenol F; Examples include compounds obtained by novolacizing compounds, and these may be used alone or in combination of two or more. Among these, the hydroxyl equivalent is preferably 90 g / eq or more and 250 g / eq or less from the viewpoint of curability.

  Although it does not specifically limit about the lower limit of the compounding ratio of the phenol resin in the resin composition of this invention, It is preferable that it is 2 mass% or more with respect to the total mass of a resin composition, and it is 3 mass% or more. It is more preferable that the content is 5% by mass or more. When the lower limit value of the blending ratio is within the above range, sufficient fluidity can be obtained. Further, the upper limit of the blending ratio of the entire phenol resin (A) is not particularly limited, but is preferably 25% by mass or less, more preferably 15% by mass or less in the total resin composition, More preferably, it is 6 mass% or less. When the upper limit of the blending ratio is within the above range, good reliability such as solder resistance can be obtained.

  In addition, phenol resin (A) and epoxy resin (B) are equivalent ratio (EP) of the number of epoxy groups (EP) of all the epoxy resins (B), and the number of phenolic hydroxyl groups (OH) of all the phenol resins (A). ) / (OH) is preferably blended so as to be 0.8 or more and 1.3 or less. When the equivalent ratio is within the above range, sufficient curing characteristics can be obtained when the resulting resin composition is molded.

  As the first inorganic filler and the second inorganic filler, for example, inorganic fillers known to those skilled in the art related to semiconductor sealing materials can be used, specifically, fused silica, spherical Examples thereof include silica, crystalline silica, alumina, silicon nitride, and aluminum nitride.

  As a curing accelerator, when using an epoxy resin as a curable resin and a phenol resin-based curing agent as a curing agent, the reaction between the epoxy group of the epoxy resin and the phenolic hydroxyl group of a compound containing two or more phenolic hydroxyl groups is promoted. What is necessary is just to be used, and what is used for the epoxy resin composition for general semiconductor sealing can be utilized. Specific examples include phosphorus atom-containing curing accelerators such as organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, adducts of phosphonium compounds and silane compounds; Amidines such as tertiary amines, 1,8-diazabicyclo (5,4,0) undecene-7, 2-methylimidazole, and further nitrogen atom-containing curing accelerators such as quaternary salts of the tertiary amines and amidines. Among these, a phosphorus atom-containing curing accelerator can obtain preferable curability. From the viewpoint of the balance between fluidity and curability, at least one kind selected from the group consisting of tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds. Compounds are more preferred. Tetra-substituted phosphonium compounds are particularly preferred when emphasizing fluidity, and addition of phosphobetaine compounds, phosphine compounds and quinone compounds when emphasizing the low modulus of heat of cured resin compositions. In particular, an adduct of a phosphonium compound and a silane compound is particularly preferable when importance is attached to the latent curing property.

  Examples of the organic phosphine that can be used in the resin composition of the present invention include primary phosphine such as ethylphosphine and phenylphosphine, secondary phosphine such as dimethylphosphine and diphenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, and triphenyl. Tertiary phosphine such as phosphine.

  Examples of the tetra-substituted phosphonium compound that can be used in the resin composition of the present invention include compounds represented by the following general formula (1).

  However, in the said General formula (1), P represents a phosphorus atom. R3, R4, R5 and R6 each represents an aromatic group or an alkyl group. A represents an anion of an aromatic organic acid having at least one functional group selected from a hydroxyl group, a carboxyl group, and a thiol group in the aromatic ring. AH represents an aromatic organic acid having at least one functional group selected from a hydroxyl group, a carboxyl group, and a thiol group in an aromatic ring. x and y are integers of 1 to 3, z is an integer of 0 to 3, and x = y.

  Although the compound represented by General formula (1) is obtained as follows, for example, it is not limited to this. First, a tetra-substituted phosphonium halide, an aromatic organic acid and a base are mixed in an organic solvent and mixed uniformly to generate an aromatic organic acid anion in the solution system. Then, when water is added, the compound represented by the general formula (1) can be precipitated. In the compound represented by the general formula (1), R3, R4, R5 and R6 bonded to the phosphorus atom are phenyl groups, and AH is a compound having a hydroxyl group in an aromatic ring, that is, phenols, and A Is preferably an anion of the phenol. Examples of the phenols in the present invention include monocyclic phenols such as phenol, cresol, resorcin, and catechol, condensed polycyclic phenols such as naphthol, dihydroxynaphthalene, and anthraquinol, bisphenol A, bisphenol F, and bisphenol S. Examples include polycyclic phenols such as bisphenols, phenylphenol, and biphenol.

  Examples of the phosphobetaine compound that can be used in the resin composition of the present invention include compounds represented by the following general formula (2).

  However, in the said General formula (2), X1 represents a C1-C3 alkyl group and Y1 represents a hydroxyl group. i is an integer of 0 to 5, and j is an integer of 0 to 4.

  The compound represented by the general formula (2) is obtained, for example, as follows. First, it is obtained through a step of bringing a triaromatic substituted phosphine that is a tertiary phosphine into contact with a diazonium salt and replacing the triaromatic substituted phosphine and the diazonium group of the diazonium salt. However, the present invention is not limited to this.

  Examples of the adduct of a phosphine compound and a quinone compound that can be used in the resin composition of the present invention include a compound represented by the following general formula (3).

  However, in the said General formula (3), P represents a phosphorus atom. R7, R8 and R9 each represent an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, and may be the same or different from each other. R10, R11 and R12 each represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and may be the same or different from each other, and R10 and R11 may be bonded to form a cyclic structure.

  Examples of the phosphine compound used for the adduct of the phosphine compound and the quinone compound include aromatic compounds such as triphenylphosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, trinaphthylphosphine, and tris (benzyl) phosphine. Those having a substituent such as a substituent or an alkyl group and an alkoxyl group are preferred, and examples of the substituent such as an alkyl group and an alkoxyl group include those having 1 to 6 carbon atoms. From the viewpoint of availability, triphenylphosphine is preferable.

  In addition, examples of the quinone compound used for the adduct of the phosphine compound and the quinone compound include o-benzoquinone, p-benzoquinone, and anthraquinones. Among them, p-benzoquinone is preferable from the viewpoint of storage stability.

  As a method for producing an adduct of a phosphine compound and a quinone compound, the adduct can be obtained by contacting and mixing in a solvent in which both organic tertiary phosphine and benzoquinone can be dissolved. As the solvent, ketones such as acetone and methyl ethyl ketone which have low solubility in the adduct are preferable. However, the present invention is not limited to this.

  In the compound represented by the general formula (3), R7, R8 and R9 bonded to the phosphorus atom are phenyl groups, and R10, R11 and R12 are hydrogen atoms, that is, 1,4-benzoquinone and triphenyl A compound to which phosphine is added is preferable in that the elastic modulus during heating of the cured product of the resin composition can be kept low.

  Examples of the adduct of a phosphonium compound and a silane compound that can be used in the resin composition of the present invention include compounds represented by the following general formula (4).

  However, in the said General formula (4), P represents a phosphorus atom and Si represents a silicon atom. R13, R14, R15 and R16 each represents an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group, and may be the same or different from each other. In formula, X2 is an organic group couple | bonded with group Y2 and Y3. In formula, X3 is an organic group couple | bonded with group Y4 and Y5. Y2 and Y3 represent a group formed by releasing a proton from a proton donating group, and groups Y2 and Y3 in the same molecule are bonded to a silicon atom to form a chelate structure. Y4 and Y5 represent a group formed by releasing a proton from a proton donating group, and groups Y4 and Y5 in the same molecule are bonded to a silicon atom to form a chelate structure. X2 and X3 may be the same or different from each other, and Y2, Y3, Y4, and Y5 may be the same or different from each other. Z1 is an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group.

  In the general formula (4), as R13, R14, R15 and R16, for example, phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, naphthyl group, hydroxynaphthyl group, benzyl group, methyl group, ethyl group, Examples thereof include n-butyl group, n-octyl group and cyclohexyl group. Among these, aromatic group having a substituent such as phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, hydroxynaphthyl group or the like. A substituted aromatic group is more preferred.

  Moreover, in General formula (4), X2 is an organic group couple | bonded with Y2 and Y3. Similarly, X3 is an organic group bonded to the groups Y4 and Y5. Y2 and Y3 are groups formed by proton-donating groups releasing protons, and groups Y2 and Y3 in the same molecule are combined with a silicon atom to form a chelate structure. Similarly, Y4 and Y5 are groups formed by proton-donating groups releasing protons, and groups Y4 and Y5 in the same molecule are combined with a silicon atom to form a chelate structure. The groups X2 and X3 may be the same or different from each other, and the groups Y2, Y3, Y4, and Y5 may be the same or different from each other. The groups represented by -Y2-X2-Y3- and -Y4-X3-Y5- in general formula (4) are composed of groups in which a proton donor releases two protons. The proton donor is preferably an organic acid having two or more carboxysyl groups and / or hydroxyl groups, more preferably two or more carbons constituting an aromatic ring each having a carboxyl group. Alternatively, an aromatic compound having a hydroxyl group, more preferably an aromatic compound having a hydroxyl group on at least two adjacent carbons constituting the aromatic ring is exemplified.

  Specific examples of the proton donor include, for example, catechol, pyrogallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,2′-biphenol, 1,1′-bi-2-naphthol, salicylic acid, 1 -Hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chloranilic acid, tannic acid, 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-propanediol and glycerin, Among these, catechol, 1,2-dihydroxynaphthalene, and 2,3-dihydroxynaphthalene are more preferable.

  Z1 in the general formula (4) represents an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, Aliphatic hydrocarbon groups such as hexyl group and octyl group, aromatic hydrocarbon groups such as phenyl group, benzyl group, naphthyl group and biphenyl group, glycidyloxypropyl group, mercaptopropyl group, aminopropyl group and vinyl group Although a reactive substituent etc. are mentioned, Among these, a methyl group, an ethyl group, a phenyl group, a naphthyl group, and a biphenyl group are more preferable at the point that the thermal stability of General formula (4) improves.

  As a method for producing an adduct of a phosphonium compound and a silane compound, a silane compound such as phenyltrimethoxysilane and a proton donor such as 2,3-dihydroxynaphthalene are added to a flask containing methanol, and then dissolved. Sodium methoxide-methanol solution is added dropwise with stirring. Furthermore, when a solution prepared by dissolving a tetra-substituted phosphonium halide such as tetraphenylphosphonium bromide prepared in methanol in methanol is added dropwise with stirring at room temperature, crystals are precipitated. The precipitated crystals are filtered, washed with water, and vacuum dried to obtain an adduct of a phosphonium compound and a silane compound. However, it is not limited to this.

  It is preferable that the mixture ratio of the hardening accelerator (D) which can be used for the resin composition of this invention is 0.1 to 1 mass% in all the resin compositions. When the blending amount of the curing accelerator (D) is within the above range, sufficient curability and fluidity can be obtained.

  Examples of the coupling agent include silane compounds such as epoxy silane, amino silane, ureido silane, mercapto silane, etc., and react or act between the epoxy resin and the inorganic filler, and the epoxy resin and the inorganic filler. Those which improve the wettability of the interface and the strength of the interface are preferred.

  Examples of the epoxy silane include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane. Etc.

  Examples of the aminosilane include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, and N-β (aminoethyl) γ-aminopropyl. Methyldimethoxysilane, N-phenylγ-aminopropyltriethoxysilane, N-phenylγ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-6- (aminohexyl) 3 -Aminopropyltrimethoxysilane, N- (3- (trimethoxysilylpropyl) -1,3-benzenedimethanane, etc. Potential of protecting the primary amino moiety of aminosilane by reacting with ketone or aldehyde It may be used as an aminosilane coupling agent. Examples of the ureidosilane include γ-ureidopropyltriethoxysilane, hexamethyldisilazane, etc. Examples of the mercaptosilane include γ-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane. A silane coupling agent that exhibits the same function as a mercaptosilane coupling agent by thermal decomposition such as bis (3-triethoxysilylpropyl) tetrasulfide and bis (3-triethoxysilylpropyl) disulfide, These silane coupling agents may be pre-hydrolyzed, and these silane coupling agents may be used alone or in combination of two or more.

  The lower limit of the proportion of the coupling agent that can be used in the resin composition of the present invention is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0% in the resin composition. .1% by mass or more. If the lower limit value of the coupling agent blending ratio is within the above range, the wettability between the inorganic filler and the curable resin is improved, and the fluidity of the resin composition is improved, thereby improving the moldability such as fillability. To do. Moreover, as an upper limit of a coupling agent, 1.0 mass% or less is preferable in all the resin compositions, More preferably, it is 0.8 mass% or less, Most preferably, it is 0.6 mass% or less. If the upper limit of the mixing ratio of the coupling agent is within the above range, it is preferable that the moldability such as burrs is not lowered.

  In addition, as for the raw material, the predetermined material may be abbreviate | omitted among the said materials, and the material other than the above may be included. Examples of other materials include a colorant, a release agent, a low stress agent, and a flame retardant.

  Examples of the flame retardant include brominated epoxy resin, antimony oxide, and non-halo / non-antimony type. Examples of the non-halo / non-antimony flame retardant include organic phosphorus, metal hydrate, nitrogen-containing resin, and the like.

(Crushing (first crushing))
As shown in FIG. 1, the raw material containing the curable resin and the powder material of the other components used in the present invention and the powder material of the first inorganic filler, if necessary, has a predetermined particle size distribution. Grind (finely pulverize) as follows. In this crushing step, raw materials other than the first inorganic filler are mainly pulverized. In addition, by including the first inorganic filler in the raw material, it is possible to suppress the raw material from adhering to the wall surface of the pulverizer, and the inorganic filler having a relatively large specific gravity collides with other organic components. By doing so, the raw material can be finely pulverized easily and reliably. Thus, the 1st composition containing multiple types of powder materials, such as curable resin, a 1st inorganic filler, and also a hardening accelerator, is obtained.

  As the pulverizer, for example, a continuous rotary ball mill, an airflow pulverizer (airflow pulverizer) or the like can be used, but an airflow pulverizer is preferably used. In the present embodiment, an airflow type pulverizing apparatus 1 described later is used as an example of a preferable aspect. The pulverization step and the pulverizer 1 will be described in detail later.

  The first inorganic filler used in this step is surface-treated with a coupling agent in advance, or the first inorganic filler, a powder material such as a curable resin, and a surface treatment agent such as a coupling agent are used. It can also coexist and be pulverized.

(surface treatment)
A surface treatment is performed on the powder material of the second inorganic filler. As this surface treatment, for example, a coupling agent or the like is attached to the surface of the powder material of the second inorganic filler. By attaching a coupling agent to the surface of the second inorganic filler, the components other than the second indefinite filler containing the curable resin and the second inorganic filler can be easily combined, and the second inorganic filler The moldability such as filling property is improved by improving the fluidity and uniformity of the resin composition starting from the improvement of the wettability between the material and the curable resin. Thus, the 2nd composition containing the powder material of the 2nd inorganic filler is obtained. This surface treatment process will be described in detail later.

(mixture)
Next, the first composition obtained in the pulverization step and the second composition obtained in the surface treatment step are mixed with a mixing device. As this mixing device, for example, a high-speed mixing device having rotating blades can be used.

(Kneading)
Next, the mixed mixture is kneaded with a kneader. As this kneading apparatus, for example, an extrusion kneader such as a uniaxial kneading extruder, a biaxial kneading extruder, or a roll kneader such as a mixing roll can be used. It is preferable to use it. In this embodiment, an example of using a single-screw kneading extruder and a twin-screw kneading extruder will be described as an example of a preferred mode. This kneading step will be described in detail later.

(Degassing)
Next, the kneaded resin composition is deaerated by a deaeration device as necessary.

(Sheet)
Next, the degassed bulk resin composition is formed into a sheet shape by a sheet forming apparatus to obtain a sheet-shaped resin composition. For example, a sheeting roll or the like can be used as the sheet forming apparatus.

(cooling)
Next, the sheet-shaped resin composition is cooled by a cooling device. Thereby, grinding | pulverization of a resin composition can be performed easily and reliably.

(Crushing (second crushing))
Next, the sheet-shaped resin composition is pulverized with a pulverizer so as to have a predetermined particle size distribution to obtain a powdered resin composition. As this pulverizer, for example, a hammer mill, a stone mill, a roll crusher or the like can be used.

  As a method for obtaining a granular or powdery resin composition, for example, a die having a small diameter is installed at the outlet of the kneader without passing through the sheet forming step, the cooling step, and the pulverizing step. It is also possible to use a granulation method typified by a hot cut method for obtaining a granular or powdery resin composition by cutting a molten resin composition discharged from a predetermined length with a cutter or the like . In this case, after obtaining a granular or powdery resin composition by a granulation method such as a hot cut method, it is preferable to perform deaeration before the temperature of the resin composition is lowered so much.

(Tablet)
Next, when manufacturing a tablet-shaped molded body, the powdered resin composition is compression-molded by a molded body manufacturing apparatus (tablet apparatus), and a resin composition that is a molded body (compressed body) is obtained. Can be obtained.

  In addition, in the manufacturing method of a resin composition, the said tableting process is abbreviate | omitted and it is good also considering a powdery resin composition as a completed body.

  As shown in FIG. 5, this resin composition is used, for example, for sealing a semiconductor chip (IC chip) (semiconductor element) 120 in a semiconductor package (IC package) (semiconductor device) 100. In order to seal the semiconductor chip 120 with the resin composition, there is a method in which the resin composition is molded by, for example, transfer molding or the like, and the semiconductor chip 120 is sealed as the sealing material (sealing portion) 140.

  That is, the semiconductor package 100 includes a circuit board (substrate) 110 (in FIG. 5, the dimensions are the same as those of a sealing material 140 described later, but the dimensions can be adjusted as appropriate) and metal bumps on the circuit board 110. The semiconductor chip 120 is sealed with a sealing material 140 made of a resin composition. The semiconductor chip 120 is electrically connected via a (connecting portion) 130. Further, when the semiconductor chip 120 is sealed, the resin composition is also filled in a gap (gap) between the circuit board 110 and the semiconductor chip 120, and the sealing material 140 made of the resin composition is used. Reinforcement is made.

  Here, when the semiconductor chip 120 is sealed by molding the resin composition by transfer molding, it is preferable to use a method called a mold array package (MAP) in which a plurality of semiconductor chips 120 are sealed together. In this case, the semiconductor chips 120 are arranged in a matrix, for example, and sealed with a resin composition, and then individually cut. When encapsulating a plurality of semiconductor chips 120 by such a method, the fluidity of the resin composition needs to be better than when encapsulating the semiconductor chips 120 one by one. Needless to say, the semiconductor chips 120 may be sealed one by one.

  Further, the mold temperature during transfer molding is preferably about 160 to 190 ° C., and the injection pressure of the resin composition is preferably about 3 to 12 MPa. In addition, it is preferable to reduce the pressure in the mold during transfer molding.

The resin composition can be suitably used when the gap distance (gap length) G between the semiconductor chip 120 and the circuit board 110 is about 15 to 100 μm.
It can be preferably used in the case of about μm.

Next, the pulverizing apparatus 1 will be described.
In addition, the said grinding | pulverization apparatus 1 is an example, It is not limited to this. For example, each dimension is an example, and other dimensions may be used.

  A pulverization apparatus 1 shown in FIG. 2 is a pulverization apparatus used in a pulverization step when producing a resin composition. As shown in FIGS. 2 to 4, the pulverizing apparatus 1 is an airflow type pulverizing apparatus that pulverizes raw materials including a plurality of types of powder materials by an air current, and includes a pulverizing unit 2 that pulverizes the raw materials, a cooling device 3, The high-pressure air generator 4 and the storage part 5 for storing the pulverized raw material are provided.

  The pulverizing unit 2 includes a chamber 6 having a cylindrical (tubular) portion, and the raw material is pulverized in the chamber 6. Note that air (gas) swirling flow is generated in the chamber 6 during pulverization.

  Although the dimension of the chamber 6 is not specifically limited, It is preferable that the average value of the internal diameter of the chamber 6 is about 10-50 cm, and it is more preferable that it is about 15-30 cm. The inner diameter of the chamber 6 is constant along the vertical direction in the configuration shown in the drawing, but is not limited to this, and may vary along the vertical direction.

  An outlet 62 for discharging the pulverized raw material is formed at the bottom 61 of the chamber 6. The outlet 62 is located at the center of the bottom 61. Further, the shape of the outlet 62 is not particularly limited, but is circular in the illustrated configuration. Moreover, the dimension of the outlet 62 is not particularly limited, but the diameter is preferably about 3 to 30 cm, and more preferably about 7 to 15 cm.

  The bottom portion 61 of the chamber 6 is provided with a pipe line (tube body) 64 having one end communicating with the outlet 62 and the other end communicating with the storage portion 5.

  Further, a wall portion 63 surrounding the periphery of the outlet 62 is formed in the vicinity of the outlet 62 of the bottom portion 61. The wall portion 63 can prevent the raw material from being unintentionally discharged from the outlet 62 during pulverization.

  The wall portion 63 has a cylindrical shape. In the configuration shown in the drawing, the inner diameter of the wall portion 63 is constant along the vertical direction, and the outer diameter gradually increases from the upper side to the lower side. That is, the height (length in the vertical direction) of the wall portion 63 gradually increases from the outer peripheral side toward the inner peripheral side. Moreover, the wall part 63 is curving in concave shape by side view. Thereby, the pulverized raw material can move smoothly toward the outlet 62.

  Further, a protrusion 65 is formed at a position corresponding to the outlet 62 (pipe 64) at the top of the chamber 6. The tip (lower end) of the projection 65 is located above the upper end (exit 62) of the wall 63 in the configuration shown in the drawing. The upper end of the protrusion 65 and the upper end of the wall 63 may coincide with each other in the vertical direction.

  In addition, although the dimension of the wall part 63 and the projection part 65 is not specifically limited, respectively, The length L from the upper end (exit 62) of the wall part 63 to the front-end | tip (lower end) of the projection part 65 is about -10-10 mm. It is preferable that it is about -5 to 1 mm.

  The sign “−” of the length L means that the tip of the protrusion 65 is located below the upper end of the wall 63, and “+” means that the tip of the protrusion 65 is on the wall 63. It means to be located above the upper end.

  In addition, a plurality of nozzles (first nozzles) 71 for ejecting air (gas) sent from a high-pressure air generator 4 (described later) into the chamber 6 are installed on the side (side) of the chamber 6. Yes. Each nozzle 71 is arranged along the circumferential direction of the chamber 6. The interval (angular interval) between two adjacent nozzles 71 may be equal or different, but is preferably set equal. Further, the nozzle 71 is installed so as to be inclined with respect to the direction of the radius of the chamber 6 (radius passing through the tip of the nozzle 71) in plan view. The number of nozzles 71 is not particularly limited, but is preferably about 5 to 8.

  The nozzles 71 and the high-pressure air generator 4 constitute the main part of the swirling flow generating means for generating a swirling flow of air (gas) in the chamber 6.

  In addition, a nozzle (second nozzle) 72 that ejects (introduces) the raw material into the chamber 6 by air sent from the high-pressure air generator 4 is installed on the side of the chamber 6. Since the nozzle 72 is installed on the side of the chamber 6, the raw material ejected from the nozzle 72 into the chamber 6 can instantaneously get on the swirling flow of air and start swirling.

  The position of the nozzle 72 on the side of the chamber 6 is not particularly limited, but in the illustrated configuration, it is disposed between two adjacent nozzles 71. The position of the nozzle 72 in the vertical direction may be the same as or different from the nozzle 71, but is preferably the same. Further, the nozzle 72 is installed so as to be inclined with respect to the direction of the radius of the chamber 6 (radius passing through the tip of the nozzle 72) in plan view.

  For example, all nozzles including each nozzle 71 and nozzle 72 can be configured to be arranged at equal intervals (equal angular intervals). In this case, the interval between the two nozzles 71 located next to the nozzle 72 is twice the interval between the other two adjacent nozzles 71. Moreover, it can also be set as the structure by which each nozzle 71 is installed at equal intervals (equal angular interval), and the nozzle 72 is arrange | positioned in the intermediate position of the two adjacent nozzles 71. FIG. From the viewpoint of crushing efficiency, it is preferable that the nozzles 71 are installed at equal intervals (equal angular intervals), and the nozzles 72 are arranged at an intermediate position between two adjacent nozzles 71.

  In addition, a cylindrical supply section (supply means) 73 that communicates with the nozzle 72 and supplies raw materials is installed on the upper portion of the nozzle 72. The upper end portion (upper end portion) of the supply unit 73 has a tapered shape in which the inner diameter gradually increases from the lower side toward the upper side. Further, the opening (upper end opening) at the upper end of the supply unit 73 constitutes a supply port, and is disposed at a position shifted from the center of the swirling flow of air in the chamber 6. The raw material supplied from the supply unit 73 is supplied from the nozzle 72 into the chamber 6.

  The reservoir 5 has an air vent 51 that discharges air (gas) in the reservoir 5. The air vent 51 is provided in the upper portion of the reservoir 5 in the illustrated configuration. The air vent 51 is provided with a filter that allows air (gas) to pass therethrough and does not allow the raw materials to pass. For example, a filter cloth or the like can be used as the filter.

  The high-pressure air generator 4 is connected to the cooling device 3 via a pipe 81, and the cooling device 3 is connected to each nozzle 71 and nozzle 72 of the pulverizing unit 2 via a pipe 82 that branches into a plurality on the way. Has been.

  The high-pressure air generator 4 is a device that compresses air (gas) and delivers high-pressure air (compressed air), and is configured to adjust the flow rate and pressure of the air to be sent. The high-pressure air generator 4 has a function of drying the air to be sent out and reducing its humidity, and is configured to adjust the humidity of the air to be sent out. The high-pressure air generator 4 dries the air before being ejected from the nozzles 71 and 72 (before being supplied into the chamber 6). Therefore, the high-pressure air generator 4 has functions of pressure adjusting means and humidity adjusting means.

  The cooling device 3 is a device that cools the air sent from the high-pressure air generating device 4 before it is ejected from the nozzles 71 and 72 (before being supplied into the chamber 6), and the temperature of the air can be adjusted. It is configured as follows. Therefore, the cooling device 3 has a function of temperature adjusting means. As the cooling device 3, for example, a water-cooled liquid refrigerant type device, a gas refrigerant type device, or the like can be used.

Next, the grinding process will be described.
(Crushing step (first crushing step))
In this pulverization step, the pulverizing apparatus 1 is used to supply a raw material containing a powder material of a curable resin (which may include components used in the present invention such as a curing agent and a coupling agent) and a powder material of the first inorganic filler. Grind (pulverize) to obtain a predetermined particle size distribution. That is, the pulverizing apparatus 1 further finely pulverizes the raw material containing a plurality of types of powder materials such as the curable resin and the first inorganic filler, thereby obtaining a raw material (first composition) having a predetermined particle size distribution. As a result, in the kneading process of the raw material of the present invention including the fine inorganic filler from which coarse particles are cut, the curable resin is easily dissolved, and the raw material can be kneaded easily and reliably, and the semiconductor chip is sealed. The resin composition excellent in the fluidity | liquidity and sclerosis | hardenability at the time of doing can be manufactured.

  Here, the first inorganic filler does not need to be pulverized in this step, but when the raw material includes the first inorganic filler, the pulverizing apparatus 1 pulverizes the raw material on the inner surface of the chamber 6. Adhesion of the raw material can be suppressed, and the raw material can be finely pulverized easily and reliably by collision of an inorganic filler which has a high specific gravity and does not easily melt and other components.

  The content of the first inorganic filler in the raw material in the first pulverization step is preferably about 5 to 70% by mass, more preferably about 20 to 60% by mass in consideration of the pulverization efficiency. .

  In addition, the content of the inorganic filler in the final product can reduce the difference in thermal expansion coefficient between the resin composition and the semiconductor chip, and 50 to 90 mass to obtain a more reliable semiconductor package. % Is preferable, and about 75 to 88% by mass is more preferable.

  The pressure of the air supplied into the chamber 6 is preferably set to 0.3 MPa or more, and more preferably set to about 0.5 to 0.8 MPa.

  If the pressure is less than the lower limit, although depending on other conditions, the pulverization ability becomes insufficient, the raw material cannot be finely pulverized, and the target particle size distribution may not be obtained. On the other hand, if the pressure is too large, depending on the structure of the air vent 51, problems such as an increase in the internal pressure in the reservoir 5 and a decrease in the pulverizing ability occur.

The amount of air supplied into the chamber 6 is preferably set to 1 Nm ³ / min or more (0 ° C., 1 atm), and more preferably about ^{3 to 5} Nm ³ / min.

  When the amount of air is less than the lower limit, depending on various conditions such as the average value of the inner diameter of the chamber 6, the pulverization ability becomes insufficient, the raw material cannot be finely pulverized, and the target particle size distribution is obtained. There is a possibility that it cannot be done. On the other hand, if the flow rate is too large, depending on the structure of the air vent 51, problems such as an increase in the internal pressure of the reservoir 5 and a decrease in the pulverization ability occur.

  The temperature of the air supplied into the chamber 6 is preferably set to 20 ° C. or less, more preferably set to 15 ° C. or less, and further preferably set to about 0 to 5 ° C.

  When the temperature exceeds the upper limit, although depending on other conditions, the raw material adheres to the inner surface of the chamber 6 during pulverization, thereby reducing the yield. On the other hand, if the temperature is too low, characteristic deterioration due to condensation or moisture absorption occurs.

  Further, the humidity of the air supplied into the chamber 6 is preferably set to 40% RH or less, and more preferably set to about 0 to 15% RH.

  When the temperature exceeds the upper limit, although depending on other conditions, the raw material absorbs moisture during pulverization, and the properties such as curability of the resin composition are lowered, and the moldability is deteriorated.

  The flow rate and humidity of the swirling flow of air can be adjusted (set) to the target values in the high-pressure air generator 4, respectively, and the temperature of the air can be adjusted to the target value in the cooling device 3. It can be adjusted (set).

  When the raw material is pulverized, the high pressure air generator 4 and the cooling device 3 are operated to supply the raw material from the supply unit 73.

  Compressed high-pressure air (compressed air) is sent from the high-pressure air generator 4, and the air is cooled by the cooling device 3 and ejected from the nozzles 71 and 72 into the chamber 6. As a result, a swirling flow of air is generated in the chamber 6.

  The supplied raw material is ejected (introduced) from the nozzle 72 into the chamber 6 by the air sent from the high-pressure air generator 4, and swirls in the chamber 6 by the swirling flow, and particles collide with each other. It is crushed by. Then, as the mass (particle diameter) decreases, each particle gathers toward the center of the chamber 6, gets over the wall 63, is discharged from the outlet 62, passes through the pipe 64, and is stored in the reservoir 5. Transferred to and stored.

  On the other hand, the air that has flowed into the reservoir 5 is discharged from the air vent 51 to the outside. For this reason, in this pulverization apparatus 1, it is not necessary to provide a cyclone type separation device, and the yield can be improved by not providing the cyclone type separation device.

  By performing this pulverization step, the raw material is finely pulverized and classified. In this case, the particle size distribution of the raw material is preferably such that the particle size is 250 μm or more, 3% by mass or less, the particle size is 150 μm or more, less than 250 μm is 15% by mass or less, and the particle size less than 150 μm is 80% by mass or more. More preferably, the above is 2% by mass or less, the particle size is 150 μm or more, less than 250 μm is 10% by mass or less, and the particle size less than 150 μm is 90% by mass or more. Thereby, in the kneading step, the curable resin is easily melted, the raw materials can be easily and reliably kneaded, and a resin composition excellent in fluidity and curability when sealing a semiconductor chip is manufactured. be able to.

  The average particle size of the raw material after pulverization is preferably about 1 to 100 μm, more preferably about 5 to 50 μm. Thereby, in the kneading step, the curable resin is easily melted, and the raw materials can be kneaded easily and reliably.

  Here, the average particle diameter of the first inorganic filler before pulverization used in the present invention is preferably about 0.1 to 30 μm, and more preferably about 1 to 10 μm. The first inorganic filler preferably has a particle content of more than 24 μm of 1% by mass or less, more preferably 0.1% by mass or less. In the first inorganic filler, the content ratio of particles exceeding 24 μm may be zero. As a result, even when the gap distance between the circuit board and the semiconductor chip is small, the first resin composition is filled between the circuit board and the semiconductor chip. It is possible to prevent one inorganic filler from being caught.

  Moreover, the magnitude relationship between the average particle diameter of the first inorganic filler and the average particle diameter of the second inorganic filler is not limited, and is appropriately selected depending on the material design.

  The particle size distribution, average particle size, maximum particle size, and the like of the first inorganic filler and the raw material after pulverization are measured using, for example, a laser diffraction particle size distribution measuring apparatus (manufactured by Shimadzu Corporation, SALD-7000, etc.). be able to.

  In addition, it is preferable to mix a raw material with a mixing apparatus prior to this grinding | pulverization process. As this mixing apparatus, for example, a high-speed mixing apparatus having a rotating blade, a drum mixer, or the like can be used.

  In addition, in this invention, it does not prevent performing surface treatment using surface treatment agents, such as a coupling agent, for the 1st inorganic filler, but after carrying out surface treatment of the 1st inorganic filler beforehand, this process is carried out. It may be carried out, or it is possible to appropriately select a treatment method such as bringing a surface treatment agent into contact with the first inorganic filler and components such as a curable resin.

Next, the surface treatment process will be described.
(Surface treatment process)
In this surface treatment step, a treatment liquid such as a coupling agent is attached to the surface of the powder material of the second inorganic filler by a predetermined surface treatment apparatus, that is, the second inorganic filler to which the treatment liquid is attached, that is, A powder material (second composition) containing the second inorganic filler to which the treatment liquid is attached is obtained. By attaching a coupling agent to the surface of the second inorganic filler, the components other than the second indefinite filler containing the curable resin and the second inorganic filler can be easily combined, and the second inorganic filler The moldability such as filling property is improved by improving the fluidity and uniformity of the resin composition starting from the improvement of the wettability between the material and the curable resin.

  Moreover, it is preferable that the average particle diameter of a 2nd inorganic filler is about 0.1-30 micrometers, and it is more preferable that it is about 1-10 micrometers. Moreover, it is preferable that the content rate of the particle | grains exceeding 24 micrometers is 1 mass% or less, and, as for a 2nd inorganic filler, it is more preferable that it is 0.1 mass% or less. In the second inorganic filler, the content ratio of particles exceeding 24 μm may be zero. Thus, even when the gap distance between the circuit board and the semiconductor chip is small, when the resin composition is filled between the circuit board and the semiconductor chip, the second inorganic material is interposed between the circuit board and the semiconductor chip. It is possible to prevent the filler from being caught.

  The mass ratio of the first inorganic filler to the second inorganic filler in the resin composition is such that the first inorganic filler: second inorganic filler is 10:90 to 90:10. Preferably, it is 20:80 to 80:20, more preferably 30:70 to 70:30.

Next, the mixing process will be described.
(Mixing process)
In this mixing step, the first composition obtained in the pulverization step and the second composition obtained in the surface treatment step are mixed by a mixing device. As this mixing device, for example, a high-speed mixing device having rotating blades can be used.

  The particle size distribution of the mixture mixed in this mixing step is preferably such that a particle size of 250 μm or more is 2% by mass or less, a particle size of 150 μm or more, less than 250 μm is 15% by mass or less, and a particle size of less than 150 μm is 80% by mass or more. More preferably, the particle size is 250 μm or more, 1% by mass or less, the particle size is 150 μm or more, less than 250 μm is 10% by mass or less, and the particle size is less than 150 μm is 90% by mass or more. Moreover, it is preferable that the average particle diameter of a mixture is about 1-100 micrometers, and it is more preferable that it is about 5-50 micrometers. Thereby, in the kneading step, the curable resin is easily melted, the raw materials can be easily and reliably kneaded, and a resin composition excellent in fluidity and curability when sealing a semiconductor chip is manufactured. be able to.

Next, the kneading process will be described.
(Kneading process)
In this kneading step, the mixture (raw material) mixed in the mixing step is kneaded by a kneading device. As the kneading apparatus, a mixing roll known to those skilled in the art, a single screw kneading extruder, a twin screw kneading extruder, and the like can be used, but a single screw kneading extruder, a twin screw kneading extruder are preferable, A twin-screw kneading extruder is more preferable.

  In addition, the kneading energy given per kg of the mixture using a kneading apparatus is preferably about 0.01 to 0.5 kWh / kg, more preferably about 0.05 to 0.4 kWh / kg. . The kneading energy in the present invention is a value obtained by dividing the power value when the kneading apparatus is constantly kneading the material by the processing amount of the material per time.

  In the present invention, by employing the first pulverization step and the surface treatment step, sufficient kneading can be performed with low kneading energy even in the kneading of the resin composition using the fine inorganic filler from which coarse particles have been cut.

  If the kneading energy is smaller than the lower limit value, the mixture cannot be sufficiently kneaded, improving the wettability of organic components such as resin and inorganic filler in the mixture, or sufficiently uniform the components. You may not get it. On the other hand, when the kneading energy is larger than the upper limit, the reaction of the mixture proceeds rapidly, so that there is a possibility that moldability and the like such as a decrease in fluidity of the resin composition may be deteriorated.

  Moreover, it is preferable that heating temperature is about 70-140 degreeC, and it is more preferable that it is about 90-130 degreeC. Thereby, a mixture can be knead | mixed reliably.

  The kneading time is preferably about 2 to 20 minutes, more preferably about 5 to 15 minutes. Thereby, a mixture can be knead | mixed reliably.

  As described above, according to the method for producing the resin composition, a resin excellent in fluidity and curability when sealing a semiconductor chip, even if it contains a fine inorganic filler obtained by cutting coarse particles. A composition can be provided. As a result, the moldability of the resin composition when the semiconductor chip is sealed with the resin composition is improved, and the so-called narrow gap for reliably filling the resin composition between the semiconductor chip and the circuit board is achieved. The wraparound property can be ensured, and the reliability of the semiconductor package can be improved.

  In particular, the raw material is pulverized using the pulverizing apparatus 1 and the mixture mixed in the mixing step is preferably kneaded with the specific kneading energy, preferably using a uniaxial or biaxial kneading extruder. Thus, a resin composition containing a fine inorganic filler and excellent in fluidity and curability can be easily and reliably produced.

  As mentioned above, although the manufacturing method of the resin composition of this invention, the resin composition, and the semiconductor device were demonstrated based on embodiment of illustration, this invention is not limited to this. Moreover, the other arbitrary processes may be added to this invention.

  Next, specific examples of the present invention will be described. Table 1 shows the composition of the composition when all were finally mixed.

Example 1
<Raw materials>
<Raw material of the first composition>
[First inorganic filler]
-SO-25H manufactured by Admatechs Co., Ltd. (average particle size 0.5 μm, particles exceeding 24 μm 0.1% or less): 22.50 parts by mass

[Curable resin]
-Nippon Kayaku Co., Ltd. NC-3000 (phenol aralkyl type epoxy resin having a biphenylene skeleton, epoxy equivalent 276 g / eq, softening point 57 ° C.): 8.33 parts by mass

[Curing agent]
-Nippon Kayaku Co., Ltd. GPH-65 (phenol aralkyl resin having a biphenylene skeleton, hydroxyl group equivalent 196 g / eq, softening point 65 ° C.): 5.52 parts by mass

[Curing accelerator]
Curing accelerator 1 (curing accelerator represented by the following formula (5)): 0.30 parts by mass

[Ion scavenger]
-DHT-4H (hydrotalcite) manufactured by Kyowa Chemical Industry Co., Ltd .: 0.15 parts by mass

[Release agent]
-WE-4M (Montanate ester wax) manufactured by Clariant Japan Co., Ltd .: 0.30 parts by mass

[Flame retardants]
-CL-303 (aluminum hydroxide) manufactured by Sumitomo Chemical Co., Ltd .: 2.50 parts by mass

[Colorant]
-MA-600 (carbon black) manufactured by Mitsubishi Chemical Corporation: 0.30 parts by mass

<Raw material of the second composition>
[Second inorganic filler]
-Denki Kagaku Kogyo Co., Ltd. fused spherical silica FB-5LDX (average particle size 4.2 μm, particles greater than 24 μm 0.1 mass% or less): 59.70 parts by mass

[Coupling agent]
• GPS-M (γ-glycidoxypropyltrimethoxysilane) manufactured by Chisso Corporation: 0.20 parts by mass • S810 (γ-mercaptotripropylmethoxysilane) manufactured by Chisso Corporation: 0.20 parts by mass

<Manufacture of resin composition>
The raw material of the first composition was pulverized under the following conditions using the pulverizer 1 shown in FIG. 2 to obtain a first composition. The particle size distribution and average particle size of the first composition after pulverization are as shown in Table 1 below.

Pressure of air supplied into the chamber: 0.7 MPa
Temperature of air supplied into the chamber: 3 ° C
Humidity of the air supplied into the chamber: 9% RH

  Moreover, the coupling agent was made to adhere to the surface of the 2nd inorganic filler using the ribbon blender, and the 2nd composition was obtained.

  Next, after the first composition and the second composition were mixed with a Henschel mixer, the mixed mixture was kneaded under the following conditions using a twin-screw kneading extruder.

Kneading energy given per kg of mixture: 0.11 kWh / kg
Heating temperature: 110 ° C
Kneading time: 7 minutes

  Next, the kneaded mixture was degassed, cooled, and then pulverized with a pulverizer to obtain a powdery resin composition. And the said powdery resin composition was compression-molded with the molded object manufacturing apparatus, and the resin composition was obtained.

(Example 2)
A resin composition was obtained in the same manner as in Example 1 except that the raw materials were changed as follows and the mixture was melt-kneaded under the following conditions.

<Raw materials>
<Raw material of the first composition>
[First inorganic filler]
-Tatsumori fused spherical silica MUF-6: 20 parts by mass

[Coupling agent]
-Chisso Co., Ltd. GPS-M: 0.10 parts by mass

[Curable resin]
-Nippon Kayaku Co., Ltd. NC-3000: 7.13 parts by mass-Mitsubishi Chemical Co., Ltd. YL-6810 (bisphenol A type epoxy resin, epoxy equivalent 170 g / eq, melting point 47 ° C): 1.81 parts by mass

[Curing agent]
• Nippon Kayaku Co., Ltd. GPH-65: 1.21 parts by mass • Mitsui Chemicals Co., Ltd. XLC-4L (phenylene skeleton-containing phenol aralkyl resin, hydroxyl group equivalent 165 g / eq, softening point 65 ° C.): 3.77 Parts by mass

[Curing accelerator]
Curing accelerator 1 (curing accelerator represented by the above formula (5)): 0.33 parts by mass

[Ion scavenger]
-DHT-4H manufactured by Kyowa Chemical Industry Co., Ltd .: 0.15 parts by mass

[Release agent]
-WE-4M manufactured by Clariant Japan Co., Ltd .: 0.30 parts by mass

[Flame retardants]
・ Sumitomo Chemical Co., Ltd. CL-303: 2.50 parts by mass

[Colorant]
-MA-600 manufactured by Mitsubishi Chemical Corporation: 0.30 parts by mass

<Raw material of the second composition>
[Second inorganic filler]
-Tatsumori fused spherical silica MUF-6 (average particle size 10.6 [mu] m, particles 0.1 mass% or less exceeding 24 [mu] m): 39.70 parts by mass-Admatechs Co., Ltd. SO-25H: 22.50 mass Part

[Coupling agent]
-Chisso Co., Ltd. S810: 0.20 mass part Compared with Example 1, the power value was reduced, the processing amount of the raw material was increased, and the kneading energy given per kg of the mixture was 0.05 kWh / kg.

(Example 3)
A resin composition was obtained in the same manner as in Example 1 except that the raw materials were changed as follows and the mixture was melt-kneaded under the following conditions.

<Raw materials>
<Raw material of the first composition>
[First inorganic filler]
・ Fused spherical silica FB-5LDX manufactured by Denki Kagaku Kogyo Co., Ltd .: 10.00 parts by mass ・ SO-25H manufactured by Admatechs Co., Ltd .: 10.00 parts by mass

[Curable resin]
YL-6810 manufactured by Mitsubishi Chemical Corporation (bisphenol A type epoxy resin, epoxy equivalent 170 g / eq, melting point 47 ° C.): 3.08 parts by mass YX-8800 manufactured by Mitsubishi Chemical Corporation (dihydroanthraquinone type crystalline epoxy) Resin, epoxy equivalent 181 g / eq, softening point 109 ° C.): 3.08 parts by mass

[Curing agent]
SN-485 manufactured by Nippon Steel Chemical Co., Ltd. (phenylene skeleton-containing naphthol aralkyl resin, hydroxyl position of naphthol is α-position, hydroxyl group equivalent 210 g / eq, softening point 87 ° C.): 2.77 parts by mass Sumitomo Bakelite ( PR-HF-3 (phenol novolak resin, hydroxyl group equivalent 105 g / eq, softening point 80 ° C.): 1.85 parts by mass

[Curing accelerator]
Curing accelerator 2 (curing accelerator represented by the following formula (6)): 0.42 parts by mass

[Ion scavenger]
-DHT-4H manufactured by Kyowa Chemical Industry Co., Ltd .: 0.15 parts by mass

[Release agent]
-WE-4M manufactured by Clariant Japan Co., Ltd .: 0.15 parts by mass

[Low stress agent]
-Toray Dow Corning Co., Ltd. FZ-3730 (silicone oil): 0.15 mass part

[Flame retardants]
・ Sumitomo Chemical Co., Ltd. CL-303: 2.50 parts by mass

[Colorant]
-MA-600 manufactured by Mitsubishi Chemical Corporation: 0.30 parts by mass

<Raw material of the second composition>
[Second inorganic filler]
-Electrochemical Industry Co., Ltd. fused spherical silica FB-5LDX: 60.35 parts by mass-Admatechs Co., Ltd. SO-25H: 5.00 parts by mass

[Coupling agent]
-Toray Dow Corning CF4083 (N-phenyl-γ-aminopropyltrimethoxysilane): 0.20 parts by mass

  Kneading was performed under substantially the same conditions as in Example 1, and the kneading energy given per kg of the mixture was 0.32 kWh / kg. The kneading energy increased compared to Example 1 because the raw material composition was different from Example 1.

Example 4
A resin composition was obtained in the same manner as in Example 1 except that the mixture was melt-kneaded under the following conditions using a single screw extruder.

  Compared to Example 1, the power value was increased, the raw material throughput was reduced, and the kneading energy applied per kg of the mixture was 0.39 kWh / kg.

(Comparative Example 1)
A resin composition was obtained in the same manner as in Example 1 except that the steps up to the kneading step in the production method were changed as described below.

<Manufacture of resin composition>
Using a Henschel mixer, the raw materials of the first composition and the second composition used in Example 1 were pulverized under the following conditions. The particle size distribution and average particle size of the raw materials after pulverization are as shown in Table 1 below.
Henschel mixer speed: 150 rpm

Next, the pulverized raw materials were kneaded under the following conditions using a single-screw kneading extruder.
Kneading energy given per 1 kg of raw material: 0.63 kWh / kg
Heating temperature: 100 ° C
Kneading time: 9 minutes The subsequent manufacturing method is the same as in Example 1.

(Comparative Example 2)
A resin composition was obtained in the same manner as in Example 1 except that the fused spherical silica FB-5LDX of the raw materials of the second composition and the kneading conditions were changed as follows.

[Inorganic filler]
-Spherical fused silica FB-950 manufactured by Denki Kagaku Kogyo Co., Ltd. (average particle size 38 μm, particles 37% by mass exceeding 24 μm): 59.70 parts by mass Kneading energy given per 1 kg of raw material: 0.17 kWh / kg
Heating temperature: 100 ° C
Kneading time: 7 minutes

[Evaluation]
For each of Examples 1 to 4 and Comparative Examples 1 and 2, each evaluation of the resin composition was performed as follows. The results are as shown in Table 1 below.

(Spiral flow)
Using a low-pressure transfer molding machine (KTS-15 manufactured by Kotaki Seiki Co., Ltd.), a mold for spiral flow measurement according to ANSI / ASTM D 3123-72, a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, The resin composition was injected under a pressure time of 120 seconds, and the flow length was measured. The spiral flow is a fluidity parameter, and the larger the value, the better the fluidity. If the spiral flow value is 70 cm or more, there is no problem, and if it is 80 cm or more, good moldability can be obtained.

(Gel time (curability))
The resin composition is placed on a hot plate controlled at 175 ° C. and kneaded with a spatula at a stroke of about 1 time / second. The time from when the resin composition was melted by heat until it was cured was measured and used as the gel time. The gel time indicates that the smaller the value, the faster the curing.

(Elevated flow viscosity)
Using a flow tester CFT-500C manufactured by Shimadzu Corporation, a resin composition dissolved under test conditions of a temperature of 175 ° C., a load of 40 kgf (piston area 1 cm ² ), a die hole diameter of 0.50 mm, and a die length of 1.00 mm. The apparent viscosity η was measured. This apparent viscosity η was calculated from the following formula. Q is the flow rate of the resin composition flowing per unit time. Further, the higher flow viscosity indicates that the smaller the numerical value, the lower the viscosity.

η = (4πDP / 128LQ) × 10 ⁻³ (Pa · second)
η: Apparent viscosity D: Die hole diameter (mm)
P: Test pressure (Pa)
L: Die length (mm)
Q: Flow rate (cm ³ / sec)

(Fillability)
Flip chip BGA (substrate is bismaleimide / triazine resin / glass cloth substrate with a thickness of 0.36mm, package size is 16x16mm, chip size is 10x10mm, gap between substrate and chip is 70μm), low pressure transfer molding Using a machine (manufactured by TOWA, Y series), the resin composition was sealed and molded under the conditions of a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a curing time of 120 seconds. The filling property of the resin composition in the gap between the substrate and the chip is observed with an ultrasonic flaw detector (Hitachi Construction Machinery My Scorpe). “○” indicates that there is no unfilling, and “×” indicates that there is no filling. It was judged.

(Rectangular pressure (viscosity))
Using a low-pressure transfer molding machine (40t manual press manufactured by NEC), a rectangular flow having a width of 13 mm, a thickness of 1 mm, and a length of 175 mm under the conditions of a mold temperature of 175 ° C. and an injection speed of 177 cm ³ / sec. The resin composition was injected into the channel, the change with time of pressure was measured with a pressure sensor embedded at a position 25 mm from the upstream tip of the channel, and the minimum pressure during the flow of the resin composition was measured. The rectangular pressure is a parameter of melt viscosity, and the smaller the value, the lower the melt viscosity and the better. If the value of the rectangular pressure is 6 MPa or less, there is no problem, and if it is 5 MPa or less, a good viscosity can be obtained.

(Curing torque ratio)
Using a curast meter (Orientec Co., Ltd., JSR Curast Meter IVPS type), the curing torque of the resin composition was measured over time at a mold temperature of 175 ° C., and the curing torque value 120 seconds after the start of measurement. The maximum curing torque value up to 300 seconds later was determined, and the curing torque ratio: (curing torque value after 120 seconds) / (maximum curing torque value after 300 seconds) × 100 (%) was calculated. Curing torque in the curast meter is a parameter of thermal stiffness, and the larger the curing torque ratio, the better the thermal stiffness immediately after molding.

  As apparent from Table 1 above, in Examples 1 to 4, good results were obtained in all of spiral flow, gel time, elevated flow viscosity, fillability, rectangular pressure and curing torque ratio.

  On the other hand, in Comparative Example 1, which is an example in which the pulverization step and the surface treatment step of the present invention are not performed, kneading cannot be performed with low kneading energy, and thus high kneading energy was applied. However, kneading becomes excessive and the reaction proceeds too much. Almost all evaluations were impossible. Comparative Example 2 is an example of using general-purpose silica containing large particles, which was good except for the filling property, but a large number of coarse silica particles, that is, unfilled frequently occurred in the vicinity of the gap between the substrate and the chip. .

DESCRIPTION OF SYMBOLS 1 Crusher 2 Crusher 3 Cooling device 4 High pressure air generator 5 Reservoir 51 Air vent 6 Chamber 61 Bottom 62 Exit 63 Wall 64 Pipe 65 Projection 71, 72 Nozzle 73 Supply part 81, 82 Pipe 100 Semiconductor package 110 Circuit board 120 Semiconductor chip 130 Metal bump 140 Sealing material

Claims (9)

A manufacturing method for manufacturing a resin composition for sealing a semiconductor element placed on a substrate, which is also filled in a gap between the substrate and the semiconductor element during the sealing Because
A pulverizing step of pulverizing a raw material containing a powder material of a curable resin and a powder material of a first inorganic filler;
A surface treatment step of performing a surface treatment on the powder material of the second inorganic filler;
A mixing step of mixing the raw material after pulverization and the surface-treated second inorganic filler;
And a kneading step of kneading the mixture mixed in the mixing step.   The method for producing a resin composition according to claim 1, wherein in the surface treatment step, a coupling agent is attached to the surface of the powder material of the second inorganic filler.   The method for producing a resin composition according to claim 1 or 2, wherein the mixture has an average particle size of 1 to 100 µm.   4. The particle size distribution of the mixture is as follows: a particle size of 250 μm or more is 2% by mass or less, a particle size of 150 μm or more, less than 250 μm is 15% by mass or less, and a particle size of less than 150 μm is 80% by mass or more. The manufacturing method of the resin composition of description. The raw material includes a curing accelerator;
The method for producing a resin composition according to claim 1, wherein the curable resin contains an epoxy resin and a phenol resin-based curing agent.   The method for producing a resin composition according to any one of claims 1 to 5, wherein an airflow type pulverizer is used in the pulverization step.   The method for producing a resin composition according to any one of claims 1 to 6, wherein a twin-screw kneading extruder is used in the kneading step.   A resin composition produced by the method for producing a resin composition according to claim 1. A substrate,
A semiconductor element installed on a substrate;
9. A semiconductor device comprising: the resin element according to claim 8, wherein the semiconductor element is sealed, and the gap between the substrate and the semiconductor element is filled when the semiconductor element is sealed. .

Images