TW201136977A - Epoxy resin composition - Google Patents

Abstract

The present invention provides an epoxy resin composition having low viscosity, high fluidity and excellent storage stability. The epoxy resin composition contains epoxy compound (A), curing agent (B), curing accelerator (C), inorganic filler (D) and silane coupling agent (E). The epoxy compound(A) comprises 80-20wt% of an alicyclic diepoxy compound(a1) represented by formula(I) or formula(II) and 80-20% of an epoxy compound(a2) other than the alicyclic diepoxy compound (a1).

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition, and more particularly to a bottom charge suitable as a semiconductor resin sealing material, particularly a flip chip assembly. The epoxy resin composition of the material. [Prior Art] In recent years, with the spread of small electronic devices such as digital cameras and mobile phones, there has been a continuing demand for miniaturization of LSI devices. Therefore, in place of the conventional wire bonding assembly, an assembly method called flip chip assembly has been gradually spread by directly assembling the semiconductor wafer to the circuit board and minimizing the assembly area. In flip-chip assembly, the surface of the pad for forming the wafer connection is oriented toward the lower side. Electrically and mechanically, the pad for the connection is opposed to the opposite package or printed circuit board (PCB) by solder bumps. The electrode of the surface is connected. At this time, a gap is formed between the assembled substrate and the wafer due to the solder bumps. A resin composition called a bottom entangled material between the sealed assembly substrate and the wafer is injected into the gap. The bottom ram filler usually contains epoxy resin and ruthenium dioxide. The bottom 塡 filling material not only buryes the above-mentioned voids, but also seals the electrical contacts using the solder bumps and protects them from the surrounding (preventing the intrusion of moisture in the atmosphere), and also prevents excessive force from acting on the machinery. The purpose of the solder bump joint of the joint (to increase the joint strength). Recently, the thickness of the underfill of the underfill has been strongly pursued by the narrow gap and narrow pitch of the solder bumps assembled by flip chip bonding. Pay attention to

S -4- 201136977 In order to solve the cerium oxide filling material which is one of the constituent components of the underlying ceramium material of the above-mentioned problems, a ceramium filling material of different particle diameters is mixed (JP-A-2007-204511) The surface treatment is disclosed in Japanese Unexamined Patent Application Publication No. Publication No. Publication No. No. Publication No. Publication No. No. Publication No. Publication No. Publication No. Publication No. Publication No. Publication No. No. Publication No. Publication No. JP-A Etc., continue to try to improve the fluidity of the bottom enamel. Further, one of the physical properties relating to the fluidity of the above-described underfill material is the viscosity. If the viscosity of the bottom and crucible is lowered, the fluidity can be expected to rise. However, when the content of the cerium oxide particles, which is a large factor depending on the viscosity, is reduced, the content of the resin component increases, and the linear expansion in the state after the hardening of the bottom enamel is increased, and the reliability is lowered. problem. It is also conceivable to use a method of lowering the viscosity of the resin itself constituting the bottom enamel as another method of lowering the viscosity of the underfill. However, as the epoxy resin which can be generally obtained, a epoxy propylene type epoxy compound having a high viscosity can be cited. As the epoxy compound which is low in viscosity and can be easily obtained, an alicyclic epoxy group can be cited. For example, Patent Publication No. 43 22〇47 discloses an epoxy resin composition containing an alicyclic diepoxide compound having a specific structure. [PRIOR ART DOCUMENT] [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A-2007-204233 (Patent Document No. JP-A-2002-146233) [Patent Document 5] Japanese Patent Laid-Open Publication No. Hei. No. 2008-297373 (Patent Document 7) Japanese Patent No. 4322047 [The problem to be solved by the invention] However, the reactivity of the alicyclic epoxy group is extremely high, and if it is mixed with cerium oxide, it will increase in viscosity. An epoxy resin composition containing an alicyclic epoxy group and ruthenium dioxide has a problem in storage stability. Therefore, the object of the present invention is to provide an epoxy resin composition which has low viscosity, high fluidity and excellent storage stability. In particular, it is an object of the present invention to provide an epoxy resin composition suitable as a bottom entanglement material in a flip chip assembly which is low in viscosity, high in fluidity, and excellent in storage stability. Further, it is an object of the present invention to provide a semiconductor package using the above epoxy resin composition as a bottom charge material. [Means for Solving the Problems] The present invention includes the following inventions. (1) An epoxy resin composition comprising an epoxy compound (A), a hardener (B), a hardening accelerator (C), an inorganic filler (D), and a ring of a government coupling agent (E) Oxygen resin composition 'The aforementioned epoxy compound (A) is based on the following formula. 201136977

(Here, the ^^^^ can be the same or different from each other', and may not contain a hydrogen atom, a halogen atom, an oxygen atom or a hydrocarbon atom of a halogen atom or an alkoxy group which may have a substituent.) Take the following general formula (II):

(herein, R21 to R38 may be the same 'may be different' each other means a hydrocarbon group which may further contain a hydrogen atom, a halogen atom, an oxygen atom or a halogen atom or an alkoxy group which may have a substituent.) 20 to 80% by weight of the cyclopentadiene compound (a1) and 80 to 20% by weight of the epoxy compound (a2) other than the alicyclic diepoxide (al), and the inorganic cerium (D) Inorganic fine particles surface-treated with a decane coupling agent. (2) The epoxy resin composition according to the above (1), wherein the ratio of the curing agent (B) is 0.6 to 1.05 equivalent to 1 equivalent of the component (A); 1 part by weight, the formulation of the hardening accelerator (C) is 1 糸 0'1 to 10 parts by weight of the 201136977 example; based on the total amount of the components (A), (B), (c) and (D) 'Mi's inorganic enamel filling material (D) is formulated in a proportion of 3 〇 to 8 〇 by weight; and the proportion of the arkane coupling agent (E) is 0.1 to 5 by weight in parts (A). Share. (3) The epoxy resin composition according to the above (1) or (2), wherein the alicyclic diepoxide (al) is a compound in which Ri~Ri8 in the above formula (1) is a hydrogen atom And/or a compound of the above formula (II) wherein r2i to r3i are a hydrogen atom. (4) The epoxy resin composition according to any one of the above (1) to (3) wherein the inorganic fine particle type cerium oxide fine particles, alumina fine particles or titanium oxide fine particles. (5) The epoxy resin composition according to any one of the above (1) to (4), wherein the sulfonate coupling agent which is surface-treated with the inorganic fine particles is an epoxy group-containing decane coupling agent or an amine group-containing group Decane coupling agent. (6) The epoxy resin composition according to any one of (1) to (5) wherein the inorganic fine particles have an average particle diameter of 0.1 to 50/m. The epoxy resin composition according to any one of the above-mentioned items, wherein at least a part of the arsenal coupling agent of the inorganic fine particles is bonded by a chemical bond to the fine particles. The total surface area is based on the area ratio of the surface of the fine particles coated with the decane coupling agent bonded by a chemical bond of 1% or more. (8) The epoxy resin composition according to any one of the above items (1) to (7), which is for use as a bottom charge material.

S201136977 (9) A semiconductor package comprising a semiconductor package having an assembled substrate and a semiconductor wafer that is disposed on the assembled substrate, wherein a gap between the assembled substrate and the semiconductor wafer is as described above The epoxy resin composition material according to any one of (1) to (8) is sealed. [Effects of the Invention] The epoxy resin composition of the present invention contains the above-mentioned specific died epoxy compound as a resin component, and contains inorganic fine particles having a surface of a decane coupling agent as an inorganic cerium material, and is near room temperature (for example, f °C) has low viscosity and high fluidity, and is excellent in storage safety (lifetime) after a long period of time. Further, the epoxy resin composition of the present invention is excellent in stability over time. The epoxy resin composition of the present invention is very suitable as an assembly semiconductor for flip chip assembly because of its low and high fluidity at room temperature and long-term storage stability (good use period p) The bottom of the gap between the wafers is filled with the material. That is, the epoxy resin composition of the present invention has a low viscosity and a high fluidity near the room temperature at the bottom implantation operation, even when the substrate and the semiconductor wafer are narrowly spaced. When the narrow pitch is formed, the homogeneous bottom enthalpy injection can be performed on all the injection surfaces in a short time. The epoxy resin composition of the present invention has a good service life and can maintain a low viscosity near room temperature for a long time. And high fluidity. Therefore, there is a great advantage of the workability of the bottom sputum filling. When the hard ring family is sealed as a bottom bump, the 丨~30 qualitative hardening viscosity 艮) 〇历经,有部塡

S 201136977 When the viscosity of the epoxy resin composition of the filler is high, a method of increasing the temperature of the resin composition and lowering the viscosity at the time of injection is generally employed. However, if the temperature of the resin composition is raised, the curing reaction of the epoxy resin composition is promoted, and as a result, the viscosity is further increased. Depending on the situation, there is a tendency to harden the resin composition before it is completely injected. When the epoxy resin composition of the present invention is used, since it has a good service life and can maintain a low viscosity and a high fluidity near room temperature over a long period of time, it is not necessary to utilize the viscosity of the heating during the bottom filling operation. Adjusted to provide a stable and homogeneous bottom charge injection. Further, the semiconductor package (semiconductor device) sealed by the epoxy resin composition of the present invention has high reliability because a homogeneous bottom susceptor is injected. [Formation for Carrying Out the Invention] The epoxy resin composition of the present invention contains an epoxy compound (A), a curing agent (B), a curing accelerator (C), an inorganic cerium filling material (D), and a decane coupling agent ( E). The aforementioned epoxy compound (A) is derived from the following general formula (I):

(here, Ri~Ris may be the same or different), and a hydrocarbon group which may further contain a hydrogen atom, a halogen atom, an oxygen atom or a halogen atom may be used.

S -10- .201136977 Alkoxy having a substituent) or by the following formula (Π):

R38 R37 (II) (here, R21 to R38 may be the same or different, and each represents a hydrocarbon group which may also contain a hydrogen atom, a halogen atom 'oxygen atom or a halogen atom or an alkoxy group which may have a substituent) The alicyclic diepoxide (ai) and the epoxy compound (a2) other than the alicyclic diepoxide (a1) are represented. In the above alicyclic diepoxide compound U1), an alicyclic diepoxy compound represented by the above formula (I) and an alicyclic diepoxide compound represented by the above formula (11) can be used. Either of them can be used. The alicyclic diepoxide (a1) has a low viscosity in the vicinity of room temperature (e.g., 5 to 30 °C), so that the epoxy resin composition can be imparted with high fluidity. In the above formula (I), examples of the halogen atom represented by Ri to R18 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the hydrocarbon group represented by 1 to 1118 include a lower alkyl group having 1 to 10 carbon atoms, and specific examples thereof include a linear alkyl group such as a methyl group, an ethyl group or a hexyl group, an isopropyl group, and a new one. a branched alkyl group such as a pentyl group or a 2-ethylhexyl group. The hydrocarbon group may also contain an oxygen atom or a halogen atom. The halogen atom is the same as the above. The case of containing an oxygen atom means a case where an OH group has a substituent or has a carboxyl group. The alkoxy group represented by the above may, for example, be a lower alkoxy group having 1 to 10 -11 to 201136977, and specific examples thereof include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Wait. The alkoxy group may have a substituent, and examples of the substituent include a lower alkoxy group and a halogen atom. In the present invention, a compound (3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate) wherein R1 to Rl8 in the above formula (1) are a hydrogen atom is preferred. As the 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, for example, CELLOXIDE CEL-2021P manufactured by DAICEL Chemical Industry Co., Ltd. and ERL422 1 manufactured by Union Carbide can be obtained. In the above formula (II), examples of the halogen atom represented by R21 to R38 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The hydrocarbon group represented by the above is a lower alkyl group having 1 to 10 carbon atoms. Specific examples thereof include a linear alkyl group such as a methyl group, an ethyl group or a hexyl group, an isopropyl group, a neopentyl group, and the like. a branched alkyl group such as 2-ethylhexyl or the like. The hydrocarbon group may also contain an oxygen atom or a halogen atom. The halogen atom is exemplified by the above. The case of containing an oxygen atom means a case where the oxime H group is a substituent or has a carboxyl group. Examples of the alkoxy group represented by Rn to R38 include a lower alkoxy group having 1 to 1 carbon atom. Specific examples thereof include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Wait. The alkoxy group may have a substituent, and the substituent may, for example, be a lower alkoxy group or a halogen atom. In the present invention, it is preferred that the compound of the above formula (11) wherein r21 to R38 are a hydrogen atom (bicyclohexyl-3,3'-diethylene oxide). The compound of the above formula (II), for example, having a cyclohexyl group

S -12- 201136977 -3,3 The unsaturated compound of the diene skeleton reacts with an oxidizing agent, especially with an organic peracid (percarboxylic acid, peracetic acid, perbenzoic acid, perisobutyric acid, trifluoroperacetic acid, etc.) Manufacturing. From the point of view of reactivity 'degree of stability, peracetic acid is a preferred epoxidizing agent among organic peracids. For the production of the compound of the above formula (II), reference is made to Japanese Patent No. 43 22047. In the case of the epoxy compound (a2) other than the alicyclic diepoxy compound (al), if it has two or more epoxy groups in one molecule, any one may be used, and in particular, bisphenol A may be mentioned. And F-type epoxy resin, phenol novolac type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, cyclopentadiene type epoxy resin, etc. are demonstrated. Among these, in order to achieve low viscosity, bisphenol A and F type epoxy resins are preferred. In the present invention, 20 to 80% by weight of the alicyclic diepoxide (al) and SO to 20% by weight of the epoxy compound (a2) other than the alicyclic diepoxide (al) are blended as the ring. Oxygen compound (A). The total amount of the compound (al) and the compound (a2) was 100% by weight. When the compound (al) is blended in an amount of less than 2% by weight, the effect of imparting fluidity to the epoxy resin composition is weak. On the other hand, when the compounding amount of the compound (al) exceeds 80% by weight, the cured product of the epoxy resin composition becomes brittle and the impact resistance is lowered. A preferred blending amount is 25 to <75 wt% of compound (ai), 75 to 25 wt% of compound U2) 'better blending amount is 3 〇 to 70 wt% of compound (al) '70 to 30 wt% of compound (a2). By forming the epoxy compound (A) as described above, an epoxy resin composition having a low viscosity at room temperature and having high fluidity can be obtained. In addition,

S -13- 201136977 Epoxy compound (A), which is often referred to as epoxy resin. A phenol resin or an acid anhydride 'amine compound can be used for the curing agent (B) which hardens the epoxy compound (A). From the viewpoint of low viscosity of the composition, among these, an acid anhydride is preferred. Examples of the acid anhydride as the curing agent (B) include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, alkylated methyltetrahydrophthalic anhydride, and hexahydroortho Phthalic anhydride, methyl himic anhydride, dodecenyl succinic anhydride, and the like are described. The blending ratio of the acid anhydride (B) is preferably from 0.05 to 1.05, more preferably from 0.80 to 1.00 equivalent, per 1 equivalent of the epoxy group in the epoxy compound (A). When the amount of the acid anhydride (B) is less than 0.60 equivalent, the curing property may be insufficient. On the other hand, if it exceeds 1.05 equivalent, the unreacted acid anhydride may be present in a large amount, and the cured product may be obtained. The glass transition temperature is reduced. Further, the equivalent relationship between the epoxy compound (A) and the acid anhydride (B) is relative to that in the compound (A)! The epoxy group 'is one equivalent of the acid anhydride group in the acid anhydride. By using the above-mentioned curing agent (B) in a compounding amount within the above range, the balance between hardenability and fluidity is excellent. These hardeners may be used alone or in combination of two or more. The phenol resin as the curing agent (B) is a compound containing two or more phenolic hydroxyl groups, and examples thereof include a phenol novolak resin, a novolak type phenol resin such as a cresol novolak resin, a trisphenol methane type phenol resin, and a trisphenol propane. Type phenol resin, hydrazine modified phenol resin 'dicyclopentadiene modification

S -14- 201136977 Modified phenol resin such as phenol resin, benzoquinone-based resin with phenylene and/or extended benzene skeleton, aralkyl naphthoate with phenyl and/or extended benzene skeleton An aralkyl type phenol resin such as a resin, a bisphenol compound or the like. The amine compound as the curing agent (B) is a compound containing two or more primary amines or secondary amines, and examples thereof include diethylenetriamine, triethylenetetramine, tetraethyleneamine, and m-xylylene. Aliphatic polyamines such as diamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, isophoronediamine, 1,3-diaminomethylcyclohexane, double An alicyclic polyamine such as 4-aminocyclohexylmethane, norbornene diamine, hydrazine or diaminocyclohexane; or an aromatic polyamine such as an exophenylene diamine. When the amount of the benzoquinone resin or the amine compound is used, the OH group equivalent (active hydrogen equivalent) of the phenol resin and the amine group equivalent (active hydrogen equivalent) of the amine compound can be made per equivalent of the epoxy group. 0.60~1 .〇5. A hardening accelerator (C) is formulated in the composition of the present invention. The hardening accelerator (C) is not particularly limited as long as it is a curing accelerator for an epoxy resin such as an imidazole, a tertiary amine or a phosphorus compound. Examples thereof include imidazoles such as 2-methylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole; benzyldimethylamine and dimethylamine; a tertiary amine system such as methyl phenol, triethylene diamine, etc.; a 4-grade salt of a tetrabutyl saddle such as bromide; an organic acid salt of a diterpene double-cycloid (DBU) or DBU; A phosphorus compound such as a phosphate ester or the like. Such a potential use can be achieved by microcapsule coating and formation of a wrong salt or the like. In combination with hardening conditions, inferior can be used alone or in combination with 2

S -15- 201136977 or more. The compounding amount of the hardener (C) is preferably 〇1 to 1 〇 by weight, more preferably 5% to 5 parts by weight based on 100 parts by weight of the epoxy compound (A). When the amount of the curing accelerator (C) is less than 0 to 1 part by weight, the hardening promoting effect is hardly obtained. On the other hand, if the amount is more than 10 parts by weight, the reaction may become too fast. By using the hardening accelerator (C) in the amount of the above range, the hardening can be performed rapidly, and the increase in the sealing step can be expected. The inorganic cerium (D) is formulated in the composition of the present invention. The above-mentioned non-filled material (D) is an inorganic fine particle surface-treated with a decane coupling agent. The precursor microparticles are selected from the group consisting of cerium oxide microparticles, alumina microparticles, and oxygen microparticles. Among these, it is better to cut by the low coefficient of linear expansion. By containing cerium oxide in the composition, the coefficient of linear expansion of the epoxy resin can be made small. Therefore, when an epoxy resin is used as the underfill of the semiconductor package, the linear expansion coefficient of the cured ruthenium can be made close to the linear expansion of the semiconductor wafer or the substrate, and as a result, the solder bump can be avoided. The stress concentration at the joint of the joint improves the connection reliability during the heat cycle treatment. The inorganic fine particles as the inorganic cerium filler (D) are surface-treated with a coupling agent. The decane coupling agent herein is preferably an epoxy decane coupling agent or an amine group decane coupling agent. Examples of the epoxy group-containing coupling agent include 2-(3,4-epoxycyclohexyl)ethyloxydecane, 3-glycidoxypropyltrimethoxynonane, and 3-ring promotion. The weight is obtained, the hard-boiled production machine describes the composition of the titanium-free dioxane composition, the bottom-swelling system and the decyl-alkyl-containing decane-trimethoxypropane-16-201136977 oxypropylmethyldiethoxy decane, 3-ring Oxypropoxypropyltriethoxydecane, and the like. Examples of the amine group-containing decane coupling agent include N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane and N-2-(aminoethyl)- 3-Aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropyltriethoxy chopping, 3-aminopropyldimethoxy sand, 3 - Aminopropyltriethoxysilane, 3-triethoxydecyl-N-(l,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethyl The hydrochloride salt of oxydecane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxydecane, and the like. In the case where SU describes the shape of the inorganic fine particles, g is preferably spherical, and particularly from the viewpoint of fluidity, it is preferred to melt the cerium oxide and approximate the true sphere. Further, among the aluminas, it is preferred to melt the alumina and approximate the true sphere. The average particle diameter of the inorganic fine particles is preferably 11 to 1 0 y m, more preferably 5 5 to 5 ym. By using particles such as cerium oxide having an average particle diameter in such a range, intrusion into a narrow gap can be ensured. The average particle diameter referred to herein means the median diameter d5〇. The surface treatment method of the inorganic fine particles may be a dry method in which a decane coupling agent is sprayed or a vapor state is sprayed while uniformly stirring the inorganic fine particles, and if necessary, heat treatment is performed; and the inorganic fine particles are dispersed in a solvent. On the other hand, a wet method in which a decane coupling agent is diluted in water or an organic solvent in a slurry state while being stirred and mixed, and then the solvent is removed. It is preferred that the sand chamber coupling agent is bonded to the -17- 1 201136977 by a chemical bond, and the enthalpy of the argon-containing argon-like alkane is used to form a surface. The opposite is true. Face-to-face, the same as the oxygen is also covered by the child. The grain 3⁄4 is shown in Table I, and the amount is added to the front. Theoretical addition amount of physicochemical decane coupling agent (g) = [weight of cerium oxide (g) x specific surface area of cerium oxide (m2 / g)] / minimum coated area of decane coupling agent (m2 / g) The minimum coverage area of the mixture is calculated as follows. When the functional group is a trialkoxy decane, Si(0)3 obtained by hydrolysis is assumed to be one Si atom formed by a sphere having a radius of 2.1 〇A and three 0 atoms formed by a sphere having a radius of 1.52A. The bond length of Si-Ο is 1.51A' tetrahedral angle 109.5°, and further assume that all three 0 atoms in the model react with the stanol group on the surface of cerium oxide, and calculate the smallest of the three yttrium atoms that can be coated. Round area. As a result, the coated area per molecule was 13.3 Χ1 0·2βιη2/molecule. For example, in the case of 3-glycidoxypropyltrimethoxydecane (molecular weight: 2 3 6.3 ), the minimum coated area is 3 3 0 m 2 /g. If the calculated minimum coated area is applied to the above formula, the theoretical addition amount of the decane coupling agent can be obtained. The minimum coated area of the decane coupling agent is represented by the following formula. The minimum coated area of the decane coupling agent (m2/g) = [6.02χ10 23 χ13·3χ l〇-2Q]/the molecular weight of the decane coupling agent is chemically bonded to the theoretical addition amount of the decane coupling agent in the present invention. The proportion of the decoupling coupling dose on the surface of the cerium oxide is the sand that is chemically bonded to the surface of the sand dioxide relative to the total surface area of the oxidized chopping

S -18 - 201136977 The surface area of the surface area of the cerium oxide coated with the alkane coupling agent is referred to as "chemical bond surface treatment rate" in the specification. Preferably, the surface treatment rate of the chemical bond can be analyzed by differential thermal analysis. When subjected to a dioxometric gravimetric/differential thermal analysis (TG/DTA) surface treatment with a decane coupling agent, it is from room 800. .附近 Near the boiling point of the decane coupling used, the weight of the particles is reduced. This weight reduction is caused by scattering at a temperature near the decane point which is physically or chemically bonded on the two sides without chemical bonding. If the temperature near the boiling point is exceeded and the temperature is further raised until the weight of the cerium oxide particles is observed to be further reduced. This is because the Si-O-Si decane coupling agent is thermally decomposed on the surface of the cerium oxide particles due to high temperature, and the decane coupling agent is lost. Therefore, depending on the boiling point of the decane coupling agent to be used, the boiling point of the alkane coupling agent + the temperature of 30 ° C), the weight of the cerium oxide particles in the temperature of ~800 °C is decreased, and the above-mentioned chemical conversion rate (%) is calculated by the following formula. Chemical bond surface treatment rate (%) = [weight loss per ig silica sand in the boiling point of the decane coupling agent (g) / theoretical addition amount (g) per 1 g of the coupling agent] xl00 hoarding ratio (in The system is more than 10%. (DTA) is carried out to differentiate the cerium particles to warm up near the temperature until the cerium oxide cerium oxide particle surface coupling agent is in boiling at 800 ° C, and the shell II can be reduced in weight and the bonding bond is bonded. The organic fraction is eliminated by measuring (the temperature of the two-key surface treatment bow + 30. ~800 yttrium oxide decane-19-.201136977 The boiling point of the decane coupling agent exemplified in the above, for example due to Is 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (molecular weight: 246.4, boiling point: 31 (TC), 3-glycidoxypropyltrimethoxydecane (molecular weight: 236.3, boiling point) : 2 90 ° C), in this case, the weight loss of cerium oxide substantially in the range of 350 ° C to 800 ° C can be measured. In the present invention, it is preferred. The inorganic fine particles such as cerium oxide having a surface treatment ratio of 10% or more are used, and more preferably 30% or more of the inorganic fine particles are used. Further, 60% or more of the inorganic fine particles are used in the fine particles, and 80% or more of the inorganic fine particles are preferably used. By using the inorganic fine particles such as cerium oxide having a surface treatment ratio of the chemical bond, the resin component can be improved. In addition, since the acidity (for example, stanol group) on the surface of the inorganic fine particles such as cerium oxide is reduced, the storage stability of the epoxy resin composition can be improved and the viscosity can be suppressed from increasing (A) and (B). The ratio of the total amount of the components (C) and (D) is preferably from 30 to 80% by weight, more preferably from 35 to 80% by weight, further preferably from 35 to 80% by weight. More preferably, it is 45 to 75% by weight. If the proportion of the inorganic filler (D) is less than 30% by weight, the resin component is relatively increased, and the linear expansion coefficient of the obtained cured product tends to become large. On the other hand, when the blending ratio of the inorganic ceramium filler (D) exceeds 80% by weight, the viscosity of the composition tends to increase and the fluidity tends to decrease. The decane coupling agent (E) is formulated in the composition of the present invention. In the case of a decane coupling agent (E), By using well known, the preferred system using, for example 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Silane, 3-glycidoxy propyl

S -20- .201136977 based on trimethoxy decane, 3-glycidoxy propyl methyl diethoxy decane, 3-glycidoxy propyl triethoxy decane, etc. a decane coupling agent; for example, N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxy Decane, N-2-(aminoethyl)-3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3- Triethoxydecyl-N-(l,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxydecane 'N-(vinylbenzyl)- An amine group-containing decane coupling agent such as a hydrochloride of 2-aminoethyl-3-aminopropyltrimethoxydecane or the like can be used as a surface treatment agent for the above-mentioned inorganic cerium filling material (D). The same species can also use different people. The blending ratio of the above decane coupling agent (E) is preferably from 1 to 5 parts by weight, more preferably from 0.5 to 3 parts by weight, based on 100 parts by weight of the epoxy compound (A). By making it within such a range, the tightness of the wafer or the surface of the substrate becomes high and the reliability can be improved. In addition to the components (A) to (E) described above, pigments, dyes, modifiers, thixotropic agents may be formulated in the epoxy resin composition of the present invention, without departing from the object of the present invention. Additives such as an imparting agent, an anti-coloring agent, an antioxidant, a releasing agent, a surfactant, a diluent, and the like. Each of the components (A) to (E) may be formulated in a predetermined ratio to prepare an epoxy resin composition of the present invention. Use a self-rotating public-transition mixer, dry mixer, belt mixer, Henschel mixer (^^11"1^1111&6〇, etc., at room temperature (furnace 1 such as 5~3〇°C) Just fine.

S -21- • 201136977 The prepared epoxy resin composition can be used for the first use of the adhesive. When used as a bottom cladding of a semiconductor package, the dispenser injects an epoxy resin composition into a gap between the assembly substrate and the semiconductor wafer through which the bumps are placed on the assembly substrate. The injection was carried out at room temperature (5 to 30 ° C). Then, in the desired curing condition, for example, the temperature is 100 to 200 ° C, preferably 100 to 190 ° C, more preferably 100 to 180 ° C, and the curing time is 30 to 600 minutes, preferably 45. Minutes, more preferably 60 to 480 minutes to make it harden. The hardening temperature can rise or fall. Since the epoxy resin composition of the present invention has low viscosity and high fluidity in the vicinity of the room temperature of the bottom crucible filling industry, the epoxy resin composition is not heated and the viscosity is adjusted before the injection, even when the assembly base is to be used. When the semiconductor wafer has a narrow gap and a narrow pitch, the bottom portion of the injection surface can be uniformly filled (without remaining between the members or bubbles) in a very short time. Further, the epoxy resin composition of the present invention is not only used as a bottom material but also suitable for use in connection between objects (members) to be placed in a narrow gap. For example, it can be applied to a follower between a lens holder and a lens used in a photographing lens such as a photographing device, a photo sensor, or a module camera for carrying. The material of the lens holder used in the photographic lens unit is not specific. For example, a liquid crystal polymer: LCP (liquid crystal polymer (black PPS (polyphenylene sulfide)) PEEK (polyether ether ketone) or the like thermoplastic resin, benzene For each use, it can be used as a thermosetting resin such as phenolic tree 22-201136977 grease, which can be used as a small unit filled with a gap between the board and the inner side. Further, examples of the material of the optical lens include enamel; glass; and a resin composition obtained by polymerizing and crosslinking a reactive organic monomer such as an epoxy group, a vinyl group or a (meth) acryl fluorenyl group. Things and so on. In the manufacture of the photographic lens unit, a narrow gap exists between the lens holder and the lens. The epoxy resin composition of the present invention is injected into this gap. Since the epoxy resin composition of the present invention has low viscosity and high fluidity, it will homogeneously penetrate into the aforementioned gap in a short time. Then, if it is hardened under the above-described hardening conditions, the lens frame and the lens are firmly attached. [Examples] The present invention will be specifically described by the following examples, but the present invention is not limited to the examples. First, each measurement method will be described. [Example 1] 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate as an alicyclic diepoxide at room temperature using a self-rotating conversion mixer (DAICEL) Manufactured by Chemical Industry Co., Ltd., CELLOXIDE 2021P, R, R1S = H) in the formula (I), 10.0 parts by weight, bisphenol F-type epoxy resin ("Re- 3 03 L, manufactured by Nippon Kayaku Co., Ltd.", 10.0 parts by weight, Methylhexahydrophthalic anhydride as a curing agent (manufactured by Nippon Chemical Co., Ltd., MH700, acid anhydride equivalent: about 168) 233 parts by weight, epoxy resin adduct of imidazole as a hardening accelerator Hardening agent (Novacure HX-3088, manufactured by Asahi Kasei E Materials Co., Ltd.), 1.2 parts by weight of r-glycidoxypropyltrimethoxydecane (manufactured by Tokyo Chemical Industry Co., Ltd.) as a decane coupling agent, 4 parts by weight and As a cerium oxide -23-201136977 cerium oxide SC4500-SQ (Admatechs Co., Ltd., average particle size l.Oym, specific surface area 4_0m2 / g, treated with aminopropyl triethoxy decane surface 67.4 parts by weight of spherical molten cerium oxide was stirred and mixed to prepare an adhesive composition. [Example 2] In place of the cerium oxide SC4500-SQ as a cerium material, cerium oxide SC4 5 00-SEJ (manufactured by Admatech Co., Ltd., average particle diameter: 1.0/zm, specific surface area: 4.0 m 2 /g, An adhesive composition was prepared in the same manner as in Example 1 except that 67.4 parts by weight of a true spherical molten cerium oxide surface-treated with r-glycidoxypropyltrimethoxydecane was used. [Example 3] In addition to the substitution of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate as an alicyclic diepoxide (manufactured by DAICEL Chemical Industry Co., Ltd., CELLOXIDE 202 1 P , in the general formula (I), Ri to R18 = h) 10.0 parts by weight 'using bicyclohexyl-3,3'-dioxirane (r2| to R38 = Η in the formula (II)) An adhesive composition was prepared in the same manner as in Example 2 except for 10.0 parts by volume. [Comparative Example 1] In place of the cerium oxide SC4500-SQ as a cerium material, silica sand SC-C3 (manufactured by Admatech S. Co., Ltd., average particle diameter io from m, specific surface area: 4.0 m 2 /g, without surface) was used. An adhesive composition was prepared in the same manner as in Example 1 except that 67.4 parts by weight of the treated true spherical molten silica sand was treated. -24 - .201136977 [Comparative Example 2] Two parts by weight of bisphenol F-type epoxy resin was used, except that one part by weight of an alicyclic diepoxide CELLOXIDE 2021P (manufactured by DAICEL Chemical Industry Co., Ltd.) was used. An adhesive composition was obtained in the same manner as in Example 2 except for (manufactured by Nippon Kasei Co., Ltd., re-303L). The composition of the compositions of the respective examples and comparative examples is shown in Table 1. In Table 1, each compounding amount represents a part by weight. [Table 1] Formulation Formulation Formulation Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Cycloaliphatic dioxane compound 2021P (R1 to R18 = H of the formula (1)) 10.0 10.0 - 10.0 One formula (丨丨) R21~R38=H-10.0 I—Epoxy Resin RE-303L 10.0 10.0 10.0 10.0 20.0 Hardener MH7O0 23.3 23.3 27.3 23.3 23.3 Hardening accelerator HX-3088 1.2 1.2 1.2 1.2 1.2 Decane coupling agent r-ring gas Propyl propyl trimethyl decyl oxime 0.4 0.4 0.4 0.4 0.4 Filler SC4S00-SQ 67.4 — — I— SC4500-SEJ A 67.4 67.4 A 67.4 SC-C3 I—*67.4 — The raw materials used are as follows. <Cycloaliphatic diepoxide>. 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by DAICEL Chemical Industry Co., Ltd., CELLOXIDE 202 1 Ρ' Ri~Ris=Η) in I). Bicyclohexyl-3,3'-dioxirane (R2i~R38=H in the formula (II)) -25- 201136977 <Epoxy resin> . Bisphenol F type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., RE-3 03 L) <hardener> • Methyl hexahydrophthalic anhydride (manufactured by Nippon Chemical and Chemical Co., Ltd., MH700, anhydride equivalent: About 168) <hardening accelerator>. Epoxy resin adduct hardener of imidazole (Novacure HX- 3 08 8 manufactured by Asahi Kasei E Materials Co., Ltd.) <塡 塡 filling material> • SC4500-SQ (Admatechs limited stock) Made by the company, the average particle size is 1.0/zm, the specific surface area is 4.0m2/g, and the true spherical molten cerium oxide is treated with r-aminopropyltriethoxydecane. According to TG/DTA at 350 °C The weight reduction rate at ~800 °C was 0.40%. . Cerium oxide SC4500-SEJ (Admatechs Co., Ltd., average particle size 1.0 " m, specific surface area 4. 〇 m2 / g, true spherical shape treated with glycidoxypropyl trimethoxy decane The weight reduction rate of the molten cerium oxide at 350 ° C to 800 ° C according to TG/DTA was 1.01%. • Ceria SC-C3 (Admatechs Co., Ltd., average particle size 1.0 / zm, specific surface area 4.0 m2 / g, true spherical spheroidal cerium dioxide without surface treatment) according to TG / DTA at 35 ° ° The weight reduction rate at C to 800 ° C was 0.17%. <decane coupling agent>. Glycidoxypropyltrimethoxydecane (manufactured by Tokyo Chemical Industry Co., Ltd.)

S -26- .201136977 [Evaluation method] (Chemical bond surface treatment rate of cerium oxide) For various types of cerium oxide SC4500-SQ' SC4500-SEJ' SC-C3 ' TG/DTA (EXSTAR6300' Seiko Instruments) The sample was heated from room temperature to 8 ° C (temperature rising rate: 20 ° C / min). The weight loss at 350 ° C to 800 ° C was measured, and the weight reduction rate was calculated as described above. Then, the chemical bond surface treatment ratio was calculated from the following formula for SC4500-SQ and SC4500-SEJ which were surface-treated by a decane coupling agent. Chemical bond surface treatment rate (%) = [weight loss per lg of cerium oxide at 350 ° C to 800 ° C (g) / theoretical addition amount of decane coupling agent per lg of cerium oxide (g)] X 1 0 0 For each of the compositions obtained in the examples and the comparative examples, the evaluation of the viscosity and the permeability was carried out as follows. The evaluation was carried out for the immediately-prepared composition (initial) and a composition which was left to stand for 24 hours from the start of the preparation in an environment of a temperature of 25 ° C and a humidity of 50% (after 24 hours). The results are shown in Table 2. (Viscosity) The rheometer (PHYSICA, UDS200/Paar, manufactured by Physica) was used to obtain the average of the viscosity at the cutting speed of 15-25S·1 at 25 °C (unit P a · S). (Permeability) The composition (room temperature) was injected to one side while the MATSUNAMI sediment board (18x18 mm, gap 70 μηι, manufactured by Matsunaga Glass Industry Co., Ltd.) was maintained at 50 t, and the time until the gap was measured was measured ( second).

S -27- 201136977 (Filling property) In the above permeability test, the glass plate after the composition was injected was visually observed, and the bubble-free person was regarded as 〇, and the bubbled person was regarded as X. [Table 2]

Measurement item unit Example 1 Example 2 Comparative Example 1 Comparative Example 2 Chemical bond kneading treatment rate of 矽% 35 83 0 83 Viscosity 25 ° C (initial) Pa.s 2.0 1.6 6.1 21.1 Viscosity 25 弋 (2 after you) Pa -s 4.5 2.6 45.0 27.4 Permeability 50 °C (initial) seconds 152 137 270 338 Permeability 50eC (24h after > seconds 167 152 640 364 Fillability (initial > 〇〇 XX fillability (after 24h) 〇〇 XX by table 2, the epoxy resin composition of Example 2 has a very low viscosity, excellent permeability and susceptibility, and shows good results even after 24 hours and is excellent in storage stability. The initial viscosity of the epoxy resin composition of 3 is very low. 8 P a · S. These epoxy resin compositions are applicable as the bottom enthalpy of the semiconductor package. [Example 4] Dimensions: 1 mm X 1 mm, bump pitch: 2 0 0 // m, gap: 43 to 45/zm device test article 'Inject the adhesive composition of Example 1 at 60 ° C to Gap and make it infiltrate' then, by performing at 1 0 0 t: 1 hour, then at 1 2 hours of heating at 50 °C to harden it

S •28- 201136977 is a semiconductor device model (3cmx4Cm). After the hardening, it was observed that the penetration state of the adhesive composition of the device test article was good, and no defects such as an unpermeated portion of the adhesive composition, residual bubbles, and the like were observed on the device test article. Moreover, after the hardened test piece of the device is supplied to a thermal cycle test at -50 ° C for 30 minutes and at 125 ° C for 30 minutes, even after 200 cycles, there is no peeling of the adhesive surface, and even if the flipping is stopped, it is practical. The extent to which no fault has occurred. Further, the adhesive composition of Example 1 was itself cured under the same conditions as above to obtain a cured sample. The glass transition temperature (Tg) of the obtained cured product sample was 171 ° C, and it was confirmed that the cured product sample had good heat resistance. [Example 5] Injecting, hardening, and heat cycle test using a semiconductor device model (3 cm x 4 cm) in the same manner as in Example 4 except that the adhesive composition of Example 1 was used instead of the adhesive composition of Example 2. . After the hardening, it was observed that the penetration state of the adhesive composition of the device and the test article was good, and no defects such as an unpermeated portion of the adhesive composition, residual bubbles, and the like were observed on the test piece of the device. In addition, even after the cycle of 200 cycles, there is no peeling of the next face, and even if it is turned over, it stops. It remains practically free from failure. Further, the adhesive composition of Example 2 was itself cured under the same conditions as above to obtain a cured sample. The glass transition temperature (Tg) of the obtained cured product sample was 165 ° C, and it was confirmed that the cured product sample had good heat resistance. [Example 6] Using a black LCP (liquid crystal polymer) as a representative lens structure

S • 29- ‘201136977, using a lenticular lens as a lens, and the combination of the two is a model for a photographic lens unit used in small-sized imaging devices, optical sensors, and portable module cameras. The lens was attached to a lens holding portion (a cylindrical rib protruding from the inner surface of the holder in the cylinder) in a cylindrical lens holder made of black LCP, and the center of the lens was adjusted to the center of the holder. At this time, there is a gap of about 1 〇 〇 // m between the inner circumferential surface of the bracket and the outer circumferential end surface of the lens. Next, the adhesive composition of Example 1 was injected from the gap described above, and the adhesive composition was applied to the inner peripheral surface of the stent and the gap between the rib arch and the outer peripheral portion of the lens, and then at 100 ° C for 1 hour, followed by It was hardened by heating at 150 ° C for 2 hours to obtain a holder having a lens. By visually observing the lens-attached stent after hardening, after evaluating the permeability and the entanglement of the adhesive composition, the adhesive composition was uniformly spread to the inner peripheral surface of the stent and the gap between the rib arch and the outer peripheral portion of the lens. 'No residue of non-permeate or bubbles, etc. was observed. This shows good permeability and susceptibility. Further, the bracket having the lens prepared here is supplied to -50. (: 30 minutes of thermal cycle test at 30 ° C, 125 ° C, even after 10 〇 cycle, the lens is firmly attached to the bracket and shows good adhesion. [Simplified illustration] Μ .

JWS [Main component symbol description] int Pick.

S -30·

Claims (1)

.201136977 VII. Patent application scope: 1. An epoxy resin composition containing epoxy compound (A), hardener (B), hardening accelerator (C), inorganic cerium filling material (D) and decane An epoxy resin composition of the coupling agent (E) which is obtained by the following general formula (I): 0 (Here, '{^~feet^ can be the same' or different from each other, and means a hydrocarbon group which may also contain a hydrogen atom, a 'atom atom or a halogen atom or a alkoxy group which may have a substituent) or the following Formula (II): (here, Rn to R38 may be the same or different from each other, and may represent an alicyclic ring which may also contain an argon atom, a hydrogen atom of a hydroxy atom or a dentate atom, or an alkoxy group which may have a substituent). 20 to 80% by weight of the group bis epoxy compound (al) and 80 to 20% by weight of the epoxy compound (a2) other than the alicyclic diepoxide (al) (the inorganic filler (D) is The inorganic fine particles surface-treated with a decane coupling agent. S-31-201136977 2 - The epoxy resin composition of the ninth aspect of the patent application, wherein the ratio of the hardener (B) is 〇6 to 1.05 equivalents relative to 1 equivalent of the component (A); The compounding ratio of the hardening accelerator (C) is 0·1 to 10 parts by weight based on 1 part by weight of the component (A); and the total of the components (A), (B), (C) and (D) The blending ratio of the inorganic cerium filler (D) is 30 to 80% by weight based on the amount; the blending ratio of the decane coupling agent (E) is 〇·1 to 5 with respect to 1 part by weight of the component (A). Parts by weight. 3. The epoxy resin composition according to claim 1, wherein the alicyclic diepoxide (al) is a compound of the formula (1) which is a hydrogen atom and/or the formula (II) Among them, R21 to R31 are compounds of a hydrogen atom. 4. The epoxy resin composition according to claim 1, wherein the inorganic microparticles are cerium oxide microparticles, alumina microparticles or titanium oxide microparticles. The epoxy resin composition according to claim 1, wherein the decane coupling agent which is surface-treated with the inorganic fine particles is an epoxy group-containing decane coupling agent or an amine group-containing decane coupling agent. 6. The epoxy resin composition of claim 1, wherein the inorganic microparticles have an average particle diameter of from 1 to 50/zm. 7. The epoxy resin composition of claim 1, wherein at least a portion of the decane coupling agent of the inorganic microparticles is bonded by a chemical bond S-32-201136977, based on the total surface area of the microparticles, The ratio of the area of the surface of the microparticles coated with a quinone coupling agent bonded by a chemical bond is 1 〇% ». 8 _ For example, the epoxy resin composition of the scope of the patent application is for the bottom sputum material. a semiconductor package comprising a semiconductor package in which an assembly substrate and a bump are disposed on the assembly substrate, and a gap between the assembly substrate and the semiconductor wafer is as claimed in the patent application. The cured product of the epoxy resin composition of item 1 is sealed. S -33- 201136977 IV. Designation of Representative Representatives: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ . 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: