TW200813152A - Epoxy resin composite and die bonding agent containing the same - Google Patents

Abstract

An epoxy resin composite and a die bonding agent for semiconductor containing the epoxy resin composite are provided in the present invention. The epoxy resin composite can form a stable B stage and provide a cured product without void. The epoxy resin composite includes: (A) epoxy resin; (B) epoxy resin curing agent, wherein the ratio of a reactive group equivalent of the epoxy resin curing agent and the epoxy group equivalent of the epoxy resin is 0.8-1.25; (C) thermoplastic resin particle which is solid at 25 DEG C;, wherein the content of the thermoplastic resin particle is 3 mass part-60 mass part when the sum of (A) epoxy resin and (B) epoxy resin curing agent is 100 mass part; and (D) epoxy resin curing accelerator, wherein the content of the epoxy resin curing accelerator is 0.1 mass part~10 mass part when the sum of (A) epoxy resin and (B) epoxy resin curing agent is 100 mass part.

Description

200813152 IX. Description of the invention: [Technical field of invention] The epoxy resin of the (four) state is stabilized, and the epoxy tree is used for the use of the adhesive for semiconductors. 】 It is excellent in _=ability and moisture resistance, so it is used in the field of high-speed semiconductors. In recent years, its application field is microscopically designed as a meta-resin, its viscosity or flow material, square® 'liquid nucleus oxygen Careful attention should be paid to handling. ;:= Sexual factors are subject to change, the most important thing to note. In recent years, the die-bonding materials that have been fixed on the substrate have been accompanied by high-capacity and high-capacity materials, and a way to make large-scale accumulations of Japanese and Japanese films has been studied. Therefore, for the accumulation of a wafer on the viscosity %t σ, the improvement of the collection can be carried out with accurate and high performance, and the addition of a second oxidant to the inorganic resin such as alumina can be applied to the adhesive. Printing the die-bonding of the conductive filler This method makes it difficult to mount the wafer accurately and efficiently: however: there is a space-type, six φ + 层 layered Japanese-day film. Problems such as die shift (20081152) In order to solve the above problems, it is proposed to heat the resin at a lower temperature after the grease is applied to the substrate:): Even if the liquid epoxy tree becomes a so-called B-stage state, On the top, it loses fluidity and the fat is completely hardened. The B-stage method has a method of 're-synthesis reaction after the wafer, and (7) a method of solidifying the hardening temperature such as forcibly stopping the hardening of the reaction system, and the reaction system is a common method (1), although it is adaptable彳 Literature]). Among them, there are many types of Taitu w., and it is a method of Yiyi, but the stability of the third-order state is not the same as the method (7), the type of reaction system is limited; the qualitative is not necessarily sufficient. And "the sorrow of stability is B F all can be; ^ 罟: ± The stability indicated is that even after placing a white sin for a predetermined period of time, it is also a state. If the stability is poor, it cannot be a big beta. The yield is reduced. (4) W-dwelling products, after loading and loading W' (4) Since the B-order is completely Wei, if the process time is insufficient, the hardening is not charged, the system is fixed, the line is combined (_ b〇nding) or In the resin sealing (resin sea, the unhardened component may volatilize, etc., resulting in a productivity gap, and the reliability of the production port is lowered. It is expected that even if the wire bonding system is cured at the same rate, it does not occur. The present invention provides a stable B-order L and k. An epoxy resin composition containing a hardened material such as a void, and the like The present invention is a composition for a semiconductor. 200813152 That is, the present invention is a composition comprising: (A) an epoxy resin; (B) an epoxy resin hardener, and (B) an epoxy resin hardener The equivalent of the basic group is 0.8 to L25 relative to the epoxy group of the epoxy resin of (A); the thermoplastic resin particle of the solid (C) at 25 ° C in the field, phase (A) epoxy resin and (B) epoxy resin hardener, a total of 1 〇〇 馨 馨 ,, thermoplastic resin particles are 3 parts by mass to 60 parts by mass; and Berry (D) epoxy resin hardening promotion The amount of the agent is 0.1 parts by mass to 1 part by mass based on the total mass parts of the (A) epoxy resin and the (B) epoxy resin hardener. Preferably, (C) The thermoplastic resin particles which are solid at 2 51 are supplied from Methacrylic resin, phenoxyresin, and butadienesinH (having a predetermined molecular weight and particle diameter. The composition invented by Shishi has excellent storage stability in the B-order state. The yield of the body product. Further, by adjusting to a predetermined volatile component and viscosity, it is possible to provide almost no sclerosing even when the resin sealing process is performed while hardening. [Embodiment] In the present invention, 'as the (A) epoxy resin, a well-known j-ring or a resin can be used. For example, a novolac type, a bisphenol type, a biphenyl type, a phenol aralkyl type, and the like can be used. A cyclopentadiene type, a naphthalene type, 8 200813152 an amine group, a (sil) Qne modified epoxy resin described later, a mixture thereof, and the like. Among them, the best ones are the double type A, the double type F type and the Shixi steel epoxy resin. Also, at 25tT, preferably a liquid resin, more preferably a viscosity of less than or equal to 1 () Pa.s, more preferably a viscosity of less than or equal to 1 ^ · S ° Wei) n The sun-hardening agent (B) can use a well-known hardening agent, for example, a benzoquinone resin (paste-modified benzene surface fat of a shirt (4)), a coffee, and an amine. In view of the balance between the hardenability and the stability of the B-stage state, it is preferred to use a clumpy m and a modified benzoquinone resin. The styrene resin can be exemplified by a varnish type, a double bismuth type, a trihydroxy phenyl ketone type, a naphthalene type, a cyclopentanthene sulfonium group, or the like, and can be used singly or in combination. ^Two = or more than two of these resins. Among them, the secret varnish p and the type are better. Moreover, the viscosity is less than or equal to 10 a. The viscosity is less than or equal to 1 Pa·s. The above (A) epoxy resin and (8) a curing agent, at least a part or all of the special fat, have a sulphuric acid resin in the molecule. The paste-modified tree is an example of a copolymer which can be reacted with a compound of _(iv). Fang Zhizhi polymer can be exemplified by the following formula (3) or (4) OR11 OR11

R12 OR1»

R12 (3)

X

X 200813152

Wherein R11 is a hydrogen atom in the case of a phenol resin, an oxiranyl group represented by the following formula in the case of an epoxy resin, · R12 is a hydrogen atom or a fluorenyl group; and X is a hydrogen atom or a bromine group. The atom; η is an integer greater than or equal to 0, preferably an integer of 0 to 50, particularly preferably an integer of 1 to 20. Examples of the other aromatic polymer include an alkenyl group-containing compound of the following formulas (5) to (8).

10 200813152

In the case of R1, r, 2, X and n, as described above; 111 is an integer equal to 〇, preferably an integer of 0 to 5, particularly preferably or 1 with the above aromatic polymer The reacted organic polyfluorenone is a compound of the formula (9): (9) (R13WR14)bSicva.b)/2 wherein R13 is a hydrogen atom or an organic group containing an amine group, an epoxy group, a hydroxyl group or a carboxyl group, or Alkoxy; R]4 is a substituted or unsubstituted monovalent hydrocarbon group, a trans group, an alkoxy group, or an alkenyl group (alkenyl〇xy); a, b is satisfied with O.OOlSa^l, 1 The number of ^b^3, 1 <a+b^4. The number of germanium atoms in the molecule is from 1 to 1000, and R13 in a molecule directly bonded to the Shi Xi atom is greater than or equal to 1. Here, the organic group containing an amine group of R13 may, for example, be a group wherein c is 1, 2 or 3. 200813152

The epoxy group-containing organic group may, for example, be a group wherein C is 1, 2 or 3.

The organic group having a hydroxyl group may, for example, be a group wherein d is 0, 1, 2 or 3, and e is 1, 2 or 3. 200813152 WA ^ ^ Λ.Λ

HO - (CH2)d - (c2)-oh As the organic group having a carboxyl group, hydrazine is exemplified by the following group, and f is an integer of 1 10 here.

-CH2i-COOH Further, examples of the alkoxy group include alkoxy groups having a carbon number of 1 to 4 such as a methoxy group, an ethoxy group or a n-propoxy group. Further, the substituted or unsubstituted anthracene of Ri4 is preferably a group having an inverse number of 1 to 1 Q, and examples thereof include a deuterium, a tert-propyl group, an isopropyl group, an n-butyl group, and the like. An isobutyl group, a tert-butyl group, an ethyl group, a pentyl group, a hexyl group, a cyclohexyl group, an octyl group, a decyl group, etc.; an ethyl group such as a pentyl group, a novel group, an acryl group, a butenyl group; The aryl group such as a base, a toluene group, an aryl group such as a benzyl group or a aryl group of a hydrogen atom of the above hydrocarbon group, and a ruthenium group which are all substituted by a * atom or the like. ‘,... part or 1 i a, b is the above value, preferably 〇.〇k 働^理?5如兑!, more ideal heart^

In the 4 is the number of 矽 atoms is 5~2〇〇. An angling number is 2~ '"Organic polyfluorene 13 200813152 I--- Oxane may be a compound of the formula (10) or (11). [Chem. 14]

H

o 15115 R-siIR

151 151 R-Si-H

Η 15-15 RIs'— R \iy ο [Chem. 15]

〇 15115 R—s'丨 R I ,6 ,R

ο 15-15 RIS1— R

R 15115 R - si - R \^/ T- too 11 /\ wherein R16 corresponds to R13 of the above formula (9) and is a monovalent hydrocarbon group containing an amine group, an epoxy group, a hydroxyl group or a carboxyl group. R15 corresponds to R14 of the formula (9), which is a substituted or unsubstituted monovalent hydrocarbon group, preferably a mercapto group or a phenyl group; p is an integer of 0 to 1000, preferably an integer of from 3 to 400; q is an integer of 0 to 20, preferably an integer of 0 to 5. Examples of such an organic polyoxane include the following examples. [化16] 14 200813152

〇 3 - 3 H L H c-si-c I H 〇 3 ^ 3 H L H c-silc H 3 1 3 H L H clsl-c 120

393HL H c-si-c I H

〇 3 - 3 H L H c-si-c i H 〇 3 - 3 H L H c-sl-c 丨 50 il-o c-si-

H;-o c-si—H c—si—c Η Η - Η clsllc 50 0· 3 - 3 H L H clsi—c Η Hi-H clsloolc

The molecular weight of the organopolyoxane of the formula (9) is preferably from 100 to 100,000. When the molecular weight of the organopolyoxane is within the above range, the uniformity of uniform dispersion of the organopolyoxane in the matrix occurs by the structure or molecular weight of the aromatic polymer reacted with the organopolysiloxane. Structure, or organic polyoxyalkylene to form a fine layer of separated sea in the matrix 15 200813152 ... - plant - island structure. In the case of organic poly-stone oxy-energy, the molecular weight of the molecule is 1GG~1GGGG. In the case of the second day, the molecular weight of the organic poly-Wei-burn is higher than that of the structure; the other aspect is in 1 〇〇〇~ In the case of 100,000, the formation of the sea moon island, especially the molecular weight of the island structure, can be selected according to the use of the 3 uniform structure or

If eight; gentleman :: hardened material is hard and brittle; on the other hand, if the right knife is set to more than 100,000, then the island has a total surface, force, so it is not good.曰 Produce a bureau. The above-mentioned scented aromatic polymer should be used in the presence of uranium-based catalysts, such as uranium-based catalysts, which are known to be used in the presence of uranium-based catalysts. Let Fang Fang " & In the case of the addition of the (8) hardener in the composition of the square ,, the ratio of the addition of the νλ, ί sheep to the Β hardener is the equivalent of the epoxy group and the hardener. The reactive group in the reactive ratio (epoxy resin) / (hardener) 9.25, special ^ xiang = $ (epoxy) / (hardener) ^ 1.1. When the equivalent ratio is not ^#', the section, * is unreacted in the - part, resulting in the properties of the hardened material; seeing the fact that the semiconductor device using the hardened material may fail. % Plastic Resin Particles The composition of the present invention is characterized in that it contains particulate (C) hot pasteable resin particles. The thermoplastic resin was solid at 25 ° C. That is, ^ during storage and at the temperature applied to the substrate ' does not form with epoxy resin 16 200813152

(A) a compatible resin phase. The thermoplastic resin may be a well-known resin, and examples thereof include AAS resin, AES resin, AS resin, ABS resin, MBS resin, vinyl chloride resin, vinyl acetate resin, and mercaptopropene baking. Acid function Eucalyptus sinensis, this milk base tree sorghum, polybutadiene resin, various fluororesins, various fluorenone resins, polycondensation acids, various polyamines, polyamide-imide, Polyimide, polyetherimide, polyether ether ketone, polyethylene, polyethylene oxide, polyethylene terephthalate, Polycarbonate polystyrene, polysulfone, polyether oxime, polyvinyl alcohol, polyvinyl ether, polyvinyl butyral, polyvinylpyrene (p〇iyVinyi formal), polystyrene (p〇iyphenylene oxide) ), polyphenylene sulfide, polybutylene dimercaptoate, polypropylene, polymethylpentene (P〇lymethylpentene) and the like. Among the above resins, what are the methacrylic resins, phenoxy resins, butadiene resins, and polymers? Their copolymers. Or ' can also be the core of the particle (core): structure. The above various thermoplastics of mole=c^' =, the shape of the can-plastic plastic resin particles may be inflamed A, mouth or prismatic shape, indefinite shape, crumb shape/near spherical shape, cylindrical shape, preferably The near-spherical shape and the age of the crystal are preferably adjusted according to the use, (= indefinite shape of the corner portion. 1C) thermoplastic resin particles 17 200813152 .-i , average particle diameter. Generally, the maximum particle #, that is, 9δ% cumulative particle diameter, the reason 4 is smaller than the temple at 10, particularly preferably less than or equal to 5; the average particle size, that is, the median diameter, is ideally 〇1 _ ~5 (four), special S wants μιη~2 μπι. When the maximum particle # is larger than the upper limit value or the upper limit of the average particle size, the β-staged stage or the f-hardening stage is present, and the part of the particle heat-hardenable resin is not sufficiently swollen and dissolved and remains. It also impairs the properties of the composition after hardening. On the other hand, when the average particle diameter is less than the above lower limit value, the composition_viscosity becomes large, and the workability is remarkably deteriorated. Further, the measurement of the particle diameter can be performed by an electron microscope observation or a diffraction diffraction method (ι·diffraction scattering me1:hod). In particular, when the composition of the present invention is used in a die bond, the maximum particle size is preferably the following on the substrate, and particularly preferably the average particle diameter of the thickness or It is preferable that the thickness is 1 G% or less, and particularly preferably 5% or less of the thickness. In the case where the maximum particle diameter is larger than the above-mentioned enthalpy limit value or the average particle diameter is larger than the above-mentioned upper limit value, there is a B-staged stage or a hardening stage, and a part of the particulate thermoplastic resin is not sufficiently swollen or dissolved and remains, causing hardening. The subsequent appearance of the adhesive is poor, or the wafer surface is damaged or exposed. (C) The thermoplastic resin particles may have a crosslinked structure. Demon, since it is preferred to form a structure in which the thermoplastic resin (6) is uniformly dispersed in the ring-reduced network structure, it is preferred that the degree of crosslinking is low, and more preferably, there is no crosslinked linear molecular chain. 18 200813152 (c) The molecular weight of the heat recordable tree can be adapted according to the type of resin. The standard system is that the average number of styrene converted by styrene is 1〇, 〇〇〇~1〇, 〇〇〇, 000, preferably 1〇, 〇〇〇~1 重量 weight average The molecular weight is from 100,000 to 100,000,000, preferably '1 〇〇, 〇〇〇~10, _, _. When the number average molecular weight is less than the above lower limit = or the weight average molecular weight is less than the above lower limit value, the Β1 becomes too low and the Β order is formed at an early stage, so that the Α step shape can become unstable. And there is a hardness that cannot obtain a sufficient degree of gradation, especially in the case of voids or outflows or grain displacement in the use of the viscous material, the possibility that the number average molecular weight is greater than the above upper limit, or the weight average molecular weight A is In the case of the above upper limit value, the = sub-members become higher, and the difference from T2 is less than 8 (rc, which is close to the c-order appearance temperature and makes the B-order state unstable) and exists in the B-stage. After the post or C-stage, the particle thermoplastic resin partially blocks the formation of the epoxy resin network structure. In order to obtain a stable B-stage state, (c) the amount of the thermoplastic resin particles, relative to the (4) ring The oxygen resin and the (8) epoxy resin hardener are replaced by 1 part by mass '(four) parts by weight to 60 parts by mass (including the examples 1 and 11)', preferably 5 parts by mass to 5 parts by mass, more preferably It is 1 part by mass to 30 parts by mass. When the content is less than the above lower limit value, there is a sufficient method to obtain sufficient B-stage (four) hardness, especially in the use of the die-bonding material, gap or outflow or grain. Possible problems such as displacement. On the other hand, in the case of the upper limit of the upper limit, there is a possibility that the B-stage state becomes too hard, especially in the use of the adhesive crystal material, which may cause insufficient adhesion. 19 200813152, good is the heat of (c) It is difficult to carry out surface treatment of the resin particles. The material can be made at the surface of the county (4). It is a well-known surface treatment. It is a decane coupling agent, for example, ue-based trimethoxy-stone, B. Dilute triethoxylate 6, vinyl: cut oxime ethoxy) oxalate, β_(3,4-epoxycyclohexyl)ethyltrimethoxy::di: glycidoxypropyl three曱oxydecane, γ-glycidol = earth di二 ethoxy Wei, γ·glycidoxypropyl triethoxy di 222 propyl propyl oxomethyldimethoxy (tetra), γ- Methyl-trimethoxy-Wei, m-propenyloxypropyl-methyl hydrazine, γ-?-propyl-propoxy-triethoxy zeoxime, :ethyl)γ-aminopropylmethyldimethoxy Kewei, guanyl ethane=yltrimethoxy, sigmaethyl) γ-aminopropyl ternary, γ-aminopropyltrimethoxy decane, γ-aminopropyltriethyl hydrazine Aminopropyltrimethoxydecane, mercaptopropyl group...methylpropanol =5 with: ethylenetrimethoxy oxypropyltrimethoxypropenyl phenylaminopropyl Trimethoxydiyl, trimethoxygen, Ν_俨.矣 考 考 考 十 十 十 十 十 十 十 十 十 十 十 十 十 n 疏 疏 疏 疏 疏 疏 疏 疏 疏 疏 疏 疏 疏 疏 疏 疏 疏 疏 疏 疏 疏 疏The surface area of the lipid particles may depend on the thermoplastic tree 10 . The weight part is 5 parts by weight of the total weight of the (4) coupling agent. (D) As the hardening promotion, a well-known hardening promotion can be used. 200813152 ^ For example, organic stone mites and imidazole can be cited. An organic compound such as a tertiary amine. Examples of the organic dish include triphenylsulfonium, tributylsulfonium, diphenylmethylphosphonium, tris(p-methoxyphenyl)phosphine, and tris (pair B). Oxygen, earth) phosphine, triphenylphosphine-triphenyl borate derivative, tetraphenylphosphine-tetraphenylboronic acid. Examples of Mi Nu can be exemplified by: 2-methyl-sit, 2-ethyl-sodium, ethyl-methyl-methyl saliva, 2-phenyl-sodium, 2-phenyl-4-methylimidazole, hydrazine Examples of the ancestors: basal addition, phenyl-- and the examples thereof include triethylamine, benzylamine, α-methyldiazabicyclo (5AG), dec-7. Among them, it is used in combination with tetraphenylphosphine-tetraphenylborate derivative or hydroxymethylimidazole and benzoate as a hardener. ^ The amount of the accelerator added is preferably 100 parts by weight relative to (4) the epoxy resin and the total of 100 parts by weight of the ruthenium-reducing agent, and it is preferable that the weight is 1 part, and the weight is 1 part, particularly preferably G· 2 parts by weight to 5 parts by weight. In the case of the above lower limit value, there is a case where the resin composition is in a possible state, and in the case where it is more than the above upper limit value, it may be: 曰, and (10) or 6th-order state. When the stability of the J month b 〇佶, the benzene о knife resin is (8) hardener, it is better that: φ 7 represents the tetraphenylphosphine tetraphenyl borate derivative 1 = The hydroxymethyl imidazole derivative represented by the following formula (2) is (D) a hardening accelerator. [Chemical 1] 21 200813152

Wherein R1 to R8 are each a group or a 13⁄4 atom. a hydrocarbon that is independently a hydrogen atom or has a carbon number of 1 to 1 [ [Chemical 2]

Hydrocarbyl group. Soil, R is carbon number 1, ΜΜΑίΜ siJicate), talc r magnesium telluride, tannic acid refers to r: combined materials, the charge can be alone =

Used above. When the composition of the combination of them is used in the case of a spotting agent, the upper thickness of the upper portion of the upper portion of the upper portion of the height of the car is 2 〇〇/. Or 2〇% below 1一/ρ; πγ τ know 'don't be ideal 10% of the thickness Γο〇 Γ-T J ; ""f J 10〇/〇,^ . The temple is ideally 5% or less of the thickness. In the case of the most = diameter 2: the upper limit value or the average particle diameter is larger than the above-mentioned upper limit value, there is damage to the wafer, the substrate, the gold wire (_ wire), and the like.

The local reservoir force is generated at the boundary between the inorganic filler and the outer portion, which impairs the function of the semiconductor device. ~ - ^ 述 夕 烧 偶 ' ' 例如 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' Triethoxy, p-vinylethylene trimethoxy oxalate, γ-mercapto propylene methoxy propyl methyl decyloxy decane, γ-methacryloxypropyltrimethoxy decane, γ_ Methyl propylene methoxy propyl decyl dioxo decane, γ-mercapto propylene methoxy propyl triethoxy decane, γ propylene methoxy propyl tri methoxy oxane, Ν _ β ( Aminoethyl) hydrazine-aminopropyl I-monomethoxy decane, Ν_β(aminoethyl)γ-aminopropyltrimethoxy 矽^Ν_β(aminoethyl)γ-aminopropyl Triethoxy oxime, γ-aminopropyltrimethoxy decane, γ-aminopropyltriethoxydecane, Ν_phenyl_γ-aminopropyltrimethoxydecane, γ- Mercaptopropyl decyl decyloxy decane, γ-巯 乂 7 ζ ζ ζ 机 机 机 机 机 机 机 机 机 机 机 机 机 机 机 机 机 机 机 机 机 机 机 机 机 机 机 机 机More preferably, it is preferred to carry out the kneading treatment under the reduced pressure on the pre-wetting of the (4) component and the filler treated by the coupling ship surface. Thereby, the interface between the filling surface and the epoxy resin can be brought into a state, and the moisture resistance reliability is particularly improved. 23 200813152 'r-propyl propyl dimethoxy milk, bis(triethoxypropyl) tetrasulfide, hydrazine-isoxanoic acid _propyl^ 3 7# bis-lacyl decane. These simmering couplers may be used singly or in combination of two or more. Of these, it is preferred to use γ-glycidoxypropyltrimethoxy decane. As! The filler is preferably a sulphur dioxide, and is added in an amount of 1 part by mass to 4 parts by mass based on 1 part by mass of the total amount of (Α) (D), preferably 10 parts by mass to 200 parts by mass. Share.

ά ά Α — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — 。 。 。 Additives include: Shi Xi Xuan couple & flame retardant, ion trapping agent (i〇n snoring), sacrifice, coloring agent, adhesion promoter and so on. One of the above decane coupling agents may, for example, be γ-glycidoxypropyl dimethoxy decane, γ-glycidoxypropyl decyl diethoxy decane, γ _ glyceroloxy propyl triethyl ethane. Oxydecane, p-styryl tridecyloxydecane, γ-mercapto propylene methoxypropyl decyl decyloxy decane, mercapto propylene methoxy propyl trimethoxy decane, γ-methyl propylene醯-methoxypropyl methyldiethoxy decane, γ-methyl propylene methoxy propyl triethoxy decane, γ propylene methoxy propyl trimethoxy oxalate, oxime amino ethyl phenamine Propyl decyl decyloxydecane, Ν-β(aminoethyl)aminopropyltrimethoxy decane, N-β(aminoethyl)γ-aminopropyltriethoxydecane , 丫-aminopropyl dimethoxy decane, γ-aminopropyl triethyl decyl decane, Ν phenyl 1 - aminopropyl dimethoxy decane, γ 毓 propyl propyl methyl a decyloxydecane, a fluorenyl-mercaptopropyltrimethoxy decane, a bis(triethoxypropyl)tetrasulfide, and an isocyanide 24 200813152 1 acid propyl diethoxy decane. These decane coupling agents may be used singly or in combination of two or more. Of these, it is preferred to use γ-glycidoxypropyltrimethoxyxanthene. In the case of using the above coupling agent, the amount thereof is usually 〇"quality" to 孓〇 part by mass, preferably 0.3 parts by mass, based on 100 parts by mass of the above (Α) to (D). ~3·〇 parts by mass. Preparation of the inner knife

The composition of the present invention can be obtained by a known method, for example, using a mixer, a roll, or the like, mixing the components (a), (c), and (D), and mixing (8) and the above-mentioned silky component in the case of use. The mixing sequence, time, temperature, pressure and other conditions can be controlled as needed. It is preferred to remove volatile components from the respective components under reduced pressure, typically less than about 1 mmHg, preferably less than or equal to 5 mmHg, prior to the above mixing. Under the repeated force, for (A), (B ° at temperature 12 (TC~17 (TC, preferably just under the condition of c~16()t: 4], when ~8 hours left ^, (C) The particulate thermoplastic resin is allowed to stand at 80 C 120 C for 20 hours to 3 hours, whereby the amount of reduction can be made less than or equal to a predetermined amount in the TGA measurement described later. The material is loaded into the aiuminiumcen, and the empty aluminum crucible is used as the reference sample. The temperature is increased from 25C to 3〇0°C in the air by 1〇 at $/min. At least one heat peak value is observed on the lower temperature side of the (A)% oxygen resin hardening peak. The far heat peak, for example, as shown in Fig. 1, is compared with the total heat of the (A) epoxy resin. Small. During the fever reaction, pass the 25 200813152 -----factory. V. ...v.. :. ... .. - ..- ' . Microscopic observation 5 see (thermal plasticity) The resin particles are plasticized and swollen, = semi-mixed phase such as adult (A) epoxy resin, and the composition becomes a B-stage state. Preferably, the peak temperature of the heat generation peak on the low temperature side (T1) ) Generous, equal to 8 〇 C ' is preferably greater than or equal to 9 〇. 〇, and harder heat -, the temperature (T2) is 70 ° C ~ 1 HTC or above 1HTC, preferably 8 〇 ° ° ° ° ° 100°c or loot: or more. In this way, (C) thermoplastic resin particles are mixed with epoxy resin (A) from room temperature (25. 〇 until the initiation of the exothermic reaction), so the composition The a-stage stability is improved. The 'low-temperature side exothermic reaction is a phase change-based reaction, and is not based on a chemical reaction such as a hardening reaction, and is independent of the hardening reaction of the epoxy resin, so that the B-stage stability can be obtained. Preferably, the composition of the present invention is placed in an aluminum crucible, and the empty sample is used as a reference sample, and the temperature is n1 in the air (the speed of rc/min is raised from 25° ί to 3〇〇t: one side In the TGA measurement, the Berry to 20 ° C is reduced to 1%. The best is less than or equal to 〇. The mass loss is mainly due to the volatilization of the volatile components of the silk scarf. As the volatile component, for example, List: epoxy resin, epoxy resin hardener, hot fat particles The low molecular weight component, the solvent used in the synthesis of the other components of the reduced object, etc. The mass reduction amount described above can be used to decompress the components of the epoxy lion group as described above. ==Divided by this. Thereby, the process of sealing the V-junction resin after wafer loading (4) accounts for the high temperature of the crystallizing agent, and 歹"50C~2GGC^When the temperature can reduce the volatile component in the bonding agent 26 200813152 f = = the possibility of voids, can be a certain degree of hardening in the line bonding process or the month of the seal of the tree, can shorten the process time Γ, in the air - face 1 (rc / The speed of minutes is from 25.匸 进行 进行 进行 四 四 四 rc rc rc rc rc rc rc rc Pa Pa Pa Pa Pa Pa Pa Pa Pa Pa Pa Pa Pa Pa Pa Pa Pa Pa Pa Pa Pa Pa Pa Pa Pa Pa Pa Pa Pa Pa Pa Pa Pa Pa Pa Pa Pa Pa Pa Pa Pa Pa 〇. The viscosity of the underarm is less than the above lower limit. 'The trick is the process after wafer loading, that is, wire bonding or resin sealing.

The possibility of moving from the clothing position in the month. Further, in the case of 15 (TC 〜 2 〇 (TP Γ = degree ΐ: the above upper limit value, there is a possibility that the composition is insufficient during wafer loading, and the bonding is insufficient. By adjusting the viscosity to upper == The consumption _ ' can provide a hardened material which is hardened even in the wire connection system, and has no voids. The condition of the composition of the present invention can be determined according to the composition of the composition. Or the use is suitable for adjustment, and it is desirable that the temperature is in the dry circumference of 丁, Τ2, especially considering the stability Β in the Β-stage state: (Τ2-20°c). The time can be corresponding to the temperature. Selecting. That is, in the range of T!~T2, when the temperature of the lower temperature side is selected, it is set to a longer time, and the temperature of the high temperature side is selected to be shorter. Here, at a low temperature and for a short time In the case of the situation, there is a possibility that 6 = cannot be fully carried out, especially in the case of the crystal grain displacement in the use of the viscous material. Moreover, at the high temperature and the long time two; when: the presence of the red phase of the red phase, the stellite material

The possibility of problems such as insufficient adhesion. I 200813152 Wafer loading conditions' can also be adjusted appropriately. The main conditions are composition or use for temperature, time, and wafer loading: preheating force with::. The purpose of preheating is removed;: the temperature, time, dust g, . , , ', soil and the moisture of the adhesive, 敕 斑 : : : : : : : : : 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Threat: Pre-"Cai" is 50C~l50t, time is 1〇~, clock::;; 25°C^250t C degree is 25C~200., time is ~1〇 is 〇.〇1 MPa~10 MPa The composition of the knife guide is particularly applicable to the adhesive for semiconductors. The semi-master is not particularly limited to the application of large wafers or wafers and layers for accurate and efficient installation. EXAMPLES Hereinafter, the present invention will be further described by way of examples and comparative examples, but the present invention is not limited by these examples. One embodiment 1 II. η^examples 4 '曰 Tables and Table 2 The amount of each component, using the pit planetary Μ "" 0 mixing, through the pit three-roller ^ ' at 25 c with a lamp mixer to prepare each example, to test, compare In addition, in Tables i and 2, (4) indicates the following components, and the numbers indicate the parts by mass. (A) Ozone resin % oxygen tree month a (double I type _ oxy resin) , epoxy equivalent 18Q, RE3 (10) (trade name) 'Japan Chemical Music Co., Ltd. Dream Diesel' 200813152 Resin m (Synthesis Example 1) Anthrone-modified epoxy resin oxime (Synthesis Example 3) (B) Hardener curing agent b (phenol novolac, epoxy equivalent 110, LD92 (trade name), manufactured by Minghe Chemical Co., Ltd. >5-ketone-modified hardener η (Synthesis Example 2) ' (C) particulate thermoplastic resin particulate thermoplastic resin e (Processing Example 1) β-particle-shaped thermoplastic resin (Processing Example 2) Particle form Thermoplastic resin g (Processing Example 3) Particulate thermoplastic resin h (Processing Example 4) Particulate thermoplastic resin i (Processing Example 5) Particulate thermoplastic resin j (Processing Example 6) Particulate thermoplastic resin k (Treatment) Example 7) Particulate thermoplastic resin 1 (polyacrylic acid vinegar vinegar, number average molecular weight 500,000, weight average molecular weight 1,500,000, average particle size 10 diameter 1 μηι, maximum particle size 3 μιη) (D) hardening accelerator' Hardening accelerator c (tetraphenylphosphine-tetraphenyl borate, ΤΡΡ-Κ (commercial-name), manufactured by Beixing Chemical Co., Ltd.), hardening accelerator d (triphenylphosphine, ruthenium, Beixing Chemical Co., Ltd. Made by the company), inorganic filler cerium oxide (Spherical molten cerium oxide, average particle size 〇·8 μηι, most 29 200813152 large particle size 3 μπι, SE2030 (trade name), manufactured by Adomatex Co., Ltd.), carbon black (Denka Black (trade name), electrical chemistry Industrial Co., Ltd.), decane coupling agent (KBM-403 (trade name), manufactured by Shin-Etsu Chemical Co., Ltd.).

Synthesis of an anthrone-modified resin (Synthesis Example 1) 42.0 g (42.0 g) was added to a flask equipped with a stirring blade, a dropping funnel, a thermometer, an ester adapter, and a reflux tube. The epoxy resin of the formula (12) and the benzene of 168.G g were subjected to azeotropic dehydration under conditions of 13 () ΐ / 2 hours. It is then cooled to (10). c, drip 〇 5 g of the catalyst (made as CAT hole _5QT made by chemistry), immediately drip about 3 () minutes into the organic poly 11 thief of formula (15) and (4) A mixture of toluene, further in (10). Γ / 士 , ^ , 〇 C / 6 small ~ under the conditions to make it mature. After removing the A, the yellow translucent epoxy equivalent of 400, organic, η Dra S/Z:) L, and the yoke yoke contained 46 4, the price of the face is marked as an oxime modified ring Gas resin 111.)) (Recombination Example 2) In the reflux tube white (four),: Γ funnel, thermometer, ester should be azeotropically dehydrated. Then; == main 100 c, drip 0.5 g of touch 200813152 Yue Chemical Manufactured CAT-PL-5〇T), immediately with a mixture of 3 gg (0.05 mol) of the organopolyfluorenone fish 3 benzene of formula (15), stepped into 1 〇 (rc/6 The hour ##A removes the f-benzene from it and obtains 4% of the brown. The benzene is equivalent to 340, and the organic polylith is produced by human: η~20 Pa · s/25t:, is an anthrone modified hardener η兀, 41·1 parts by weight). Record it (Synthesis Example 3) in a flask equipped with a stirring leaf and a drop-return tube, and add (iv) u, an ester adapter and epoxy resin to 275.2 g of A| , ············································································· (letter g (0.014 m)), immediately A mixture of 31·2 toluene was added dropwise in about 30 minutes, and the organic polyfluorenone was introduced into a mixture of 124.8 g. The occluded product was subjected to 290, and the organic polyoxane contained white opaque. Solid (epoxy equivalent ring gas resin 〇. 3 丨 · 2 parts by weight). Record it as low oxime ketone [Chemistry 17]

31 200813152

3 [Chem. 19]

Q 〇 H2VC_

Bar 1 ——( , 0* (14) where n/m= 1/19, the average value of n + m is 5 [20] CH3 I H-Si-0 I CH3 ch3 I 3 Si-0 I CH3 H Hl H c—si丨c 5 [Chem. 21] ch3 I H-Si-0 CH, 6 3 I 3 H1-H c—s'—c 8 5 Η 3 » 3 h.lh c—*s—c 6) Treatment of particulate thermoplastic resin (Processing Example 1) 100 g of a particulate thermoplastic resin (polydecyl acrylate) was added to a flask equipped with a stirring blade, a dropping funnel, a thermometer, and a reflux tube. The number average molecular weight of 500,000, the weight average molecular weight of 32 200813152 1,500,000, the average particle diameter of 丨μηι, the maximum particle diameter of 3 μηη) and 9 〇〇g of water were sufficiently stirred at 25 ° C until the whole became a uniform slurry. Add 1 μg of water to a flask equipped with a stirring blade, a dropping funnel, a thermometer, and a reflux tube, and add 2 g of a decane coupling agent (γ-mercaptopropene) to the surface while stirring for 1 minute. Methoxypropyltrimethoxydecane) was further matured at 25 ° C for 2 hours. The aqueous solution of the decane coupling agent was dropped into the slurry of the particulate thermoplastic resin/water in about 3 minutes, and the step was carried out at 25. (:/12 hours under conditions to make it mature. From which water is removed, k is a white powder. It is referred to as a particulate thermoplastic resin 2. (Processing Example 2) Installing a money mixing blade, a dropping funnel, a thermometer, The reflux tube is burnt; "Taijia § particulate thermoplastic resin (polyacrylic acid-day coat, number average molecular weight 500,0 (8), weight average of seven 5::: two 1 ', maximum particle size 3 μη 〇 with 900 g of water, there are mixing blades, dropping funnel, clever" = water. Table also women's (four) water, - surface mixing - surface with the addition of _ agent (γ-glycidoxypropyl three Oxygen was added dropwise to 2 g of the scorpion scorpion for a few hours, and the mixture was cooked to a fineness of Γ/2 π(10) hours. The material of the material was progressed to the end of the color. It was recorded as particulate thermoplasticity. Resin f. (Processing Example 3) Adding 100 g of particulate thermoplastic resin (polymercaptopropionic acid, number average molecular weight) in a 200813152 bottle of Anshang's winning blade, dropping funnel, thermometer, and return tube 500, _, weight average molecular weight 1,500:000 'average grain after i array, maximum grain size 3 A) and 9 〇〇 g of water,

In the pit I fully search until the whole becomes a uniform slurry. Add 1 〇〇g of water to the flask equipped with the mixing blade >1: a dropping funnel, a thermometer, and a reflux tube, and add 2 g of decane coupling agent N-stupyl in about 1 minute. Aminopropyltridecyldecane), further. It is made into 2 small 2 conditions. In about 3G minutes (4) the hetero-coupled agent is dissolved in water to a slurry of particulate thermoplastic resin/water, and it is further matured under the conditions of two hours. Remove water from it and get the end of the white seven. This is referred to as particle-shaped thermoplastic (Processing Example 4). The sputum funnel, thermometer, and reflux tube of the bottle are used to make a number of micro-butter pastes (the surface of acrylic acid is filled under the pit). 〇π〇 and _ g of water, H see the positive moon bean becomes a uniform slurry. In addition to the ampoule, let the two points of the right = right to obtain a white powder. Record it as a particle: ί:: remove water ' 34 200813152 (Processing example 5) Add 1 〇〇g of particulate thermoplastic resin to the welding bottle with stirring blade, dropping funnel, thermometer and return tube in the women's clothing (including the core part of the butyl ginseng gel, partially crosslinked poly for armor) The core/shell structure of the outer skin of the decyl decenoate § is the average particle size i net, the maximum (four) 3 _) and the water of _ g are fully stirred until the whole becomes a uniform slurry. Add _ g of water to the flask of the mixing leaf >, the dropping funnel, the thermometer, and the reflux tube, and add 2 g of the diarrhea to the person 2 (the 曱, _ _ oxygen) Propyl trimethoxy-Wei), further matured under the conditions of two. The decane-three-dollar drop to the grain in about 30 minutes In the New Lion/Water (4), it is matured under the conditions of J/J. From which water is removed, and again; Ά ° It is recorded as a thermoplastic resin i. (Processing Example 6) A particulate thermoplastic resin with a stirring blade, a dropping funnel, a thermometer, and a reflux tube (polystyrene, particle size 1 _ knife, / large! ^f0 'weight average molecular weight 3 〇〇, _ , the average gossip mix jade stone * take 杈 3 μηι) with 90 〇 g of water, fill and stir at 25 ° C -: two? flow tube of the flask to add 100 § water, ethylene trimethoxy Add 2 § of the Wei coupler to the left and right of the clock (for benzene to 30.), and further into the slurry of water at 25 ° for 2 hours, proceed to 25. (10) hours of strip 35 200813152 The water was removed from f' to obtain a white powder. It was recorded as a piece to make it into a pellet-like thermoplastic (Process Example 7). In the case where a stirring blade and a bottle were installed, a 1 〇〇 # dropping funnel, a thermometer, and a reflux tube were added. burn

Made of vinegar, the average number of octagonal heat can be turned over (poly methacrylic acid average particle size 1 jum, 2 ^ 3, coffee 'weight average molecular weight 9,000, full lion until 敕 Mm) and 9GG g water, at 25t: Blade, drip funnel Γ 3, evenly slurry. In addition, the lion water '-face-face is additionally installed: dimethyl acetonyloxy two base gas: = 2g of decane coupling agent (in the case of γ-, 虱 、, 虱 虱 矽 )), further The droplets were poured into a pellet at 25 ° C / 2; the Wei coupling agent was dissolved in water, and the slurry of the resin/water was further mixed to a color powder. It is referred to as a particulate thermoplastic tree = #4: For example, the method is used to test each composition. The results are shown in Table 3 and ^广= some of the towels, "ND" means not detected, "NA" means that the reaction is carried out, the wafer cannot be attached, and the test method (a) - using DSC (not bad scanning pyrostat / mettler) Manufacture), take the epoxy resin group. About U)mg into the original _ towel, the heart of the _ ^ according to the sample, in the air towel at 1 (rt / minute heating rate from the pit to Meng ° 300 ° C, 200813152 For the composition of the milk resin, measure the viscosity after placing the predetermined hiring in the last 2 times. Degree and square, 匕 (C) Qualitative pair is 2Gt higher than T1 (Taste Example 丨~4 Bribe), epoxy resin composition 1Q minutes to make it B-stage, and b

The epoxy resin after a predetermined time shown in the table is placed under the second 25 Λ, and the same method as in (a) is used for DSC measurement, and the peak value of the C-stage (four) measured after the β-stage is used as the pre-existing value. The ratio of the peak area of the subsequent C-stage to the initial difficulty (d) is as shown in Fig. 2 as a test piece, and observation of each test piece is performed to calculate the number of test pieces containing voids/total test The number of pieces (20). The test piece was produced as follows. Applying an epoxy resin composition (50 μηι thick, 12 rrmixio, ^) on a BT substrate (200 μm thick, 35 πίττας xu, Dmmx35 mm) coated with a solder resist (3 〇 _ thick) on the surface / m l2mm). It is heated to a temperature of 20 ° C higher than T1, and is heated to a B-stage by heating for 1 〇 minutes, and the stone formed with a nitride film is loaded at 150 C/1 MPa/Ι second. A wafer (called μηι thick, 12.5 mm x 12.5 mm) was prepared into a test piece. (e) After the B-th order | = clothing as the test piece of the Figure 2, after the B-stage, the product before the wafer loading 'after 25 ° placed the table for the predetermined time, The wafer was loaded in the same manner as in (4), and SAT observation was performed to calculate the number of test pieces including the voids 37 200813152 1 / the total number of test pieces (20 pieces). (f) is the overflow after 1 loading. Observation 2 (M is the maximum of the overflow width of the test piece produced by the (4) towel. The so-called fillet refers to the tree oozing out from the wafer due to the flow. If the overflow width is large, the distance to the wire connection terminal on the substrate is such that the width is required to be less than or equal to 10 〇 μιη. If the number is more than 10 〇, the number of test pieces is unqualified, and the number of test pieces (20 pieces) is unqualified. • (g) overflows in 2 = when the test piece of Fig. 2 is produced, after the B-stage, before the wafer is loaded, the method LC places the predetermined time shown in each table, and then calculates the same wearer day as (1). In the Japanese film, the overflow width of the film was measured in the same manner as (f), and the number of test pieces per unacceptable test piece/the total number of test pieces (20 pieces).

38 200813152

j!clk613 〔! <] Example 11 a 34.6 η 65.4 Ο ' -s 163.5 a mr-4 Example 10 a 34.6 η 65.4 Ο ο) m 106.5 r 1 < wo Example 9 a 34,6 η 65.4 ◦ a S 123.5 r —Η in Example 8 a/o 50.3/13.7 b 36.0 Ο < 123.5 ι 1 f IT) * Example 7 m 78.4 b 21.6 Ο -S 123.5 - to Example 6 a 34.6 η 65.4 ο a 123.5 Example 5 a 34.6 η 65.4 Ο •- S 123.5 1—ί in Example 4 a 34.6 I η ! 65.4 ο — ^ S 123.5 赘1· I f ^T) Example 3 a 34.6 η 65.4 Ο ^ S 123.5 r—* Implementation Example 2 a 34.6 η 65.4 ο ^ -S 123.5 r—H tn Example 1 a 34.6 η 65.4 ο — -S 123.5 vn (A) Epoxy Resin (Β) Hardener (D) Hardening Accelerator (c) Thermoplasticity Resin particle cerium oxide carbon black KBM-403 200813152 [Table 2]

Reference Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 (A) Epoxy resin aamam 34.6 34.6 78.4 34.6 78.4 (B) Hardener η 65.4 η bnb 65.4 21.6 65.4 21.6 (D) Hardening accelerator c 1 c 1 c 1 d 1 d 1 (C) Thermoplastic resin particles k 20 0 0 0 0 Ceria 123.5 123.5 123.5 123.5 123.5 Carbon black 1 1 1 1 1 KBM-403 1.5 1.5 1.5 1.5 1.5 40 200813152

[e<] Embodiment 11 rn On sr * gr··, 00 T—ir—< : <N m Os On Μη 00 On oo σί rn Os 20/20 20/20 20/20 20/20 丨20 /20 ο δ Ο ο (Ν δ ο CN δ ο Γ <| δ Example 10 S ES r-< 1 -< 〇! * ^"' * 1—< SS 00 vd G\ rn ON \ o 〇δ oo ο Ci δ ο CJ ο ο CN Ο 19/20 17/20 15/20 14/20 14/20 Example 9 inch*f τ—η 〇\ oo 5 r—sss S y—> &lt N m vd Os ^T) On OO home o CN δ o CN o Ο CN ο S ο (Ν ΓΠ ο CN Ο ο ο Qj ο ο CN Ο ο CN δ Example 8 ss CN| >< r &lt ;ssgr—< Os s; αί rn αί ON 〇\ o (N 〇oo ο δ ο ο Ο (Ν δ ο (Ν Ο ο ο ο δ ο CN Ο ο δ Example 7 ss < N r * s 1—« s 1 to Ϊ—* τ-H 00 a\ 00 卜: ON wo ON (N o CN δ o Q o ο CN δ ο § ο CN ο ο CN Ο ο CJ ο ο (Ν δ ο Ci ο ο ο Example 6 st—i ON OO t—I 〇r—H sti , <1 gr—H 卜vd ON \〇Os ir> ON Os o CN oo CN o ο 04 Ο ο (Ν ο Ci ο ο <Ν Ο ο rg ο δ ο CN Ο ο δ Example 5 Os (N On ί· < 〇sg l> y « r-< (N 〇i (N v〇Os VO On 00 Os δ o (N o Ο ο Ο CN Ο ο Ci ο ο CN Ο ο CS ο CJ δ ο (Ν Ο ο δ Example 4 oo r—HS r_H sr—^ g OO T—< O) ON ... ON OO vd 0's Bu\D ON ooo CN o ο ο ο (Ν Ο ο (Ν δ ο CN Ο Ο CN Ο ο 04 Ο ο ο ο δ Example 3 ON G\ 2 sy—* ST 4 0 i—H 1 tr—^ τ—H Bu\D On inch in On m ON CN On o cs δ oo ο <Ν Ο Ο ο CJ ο ο CN Ο ο C! Ο (Ν Ο ο ο ο CN δ Example 2 o rH r—« sr—1 s 〇1 < r—* CN Os ON ON 卜 0's in ... ON o CN oo CN ο δ Ο ο ο ο ο (Ν Ο ο (Ν Ο ο 04 ο ο CN Ο ο (Ν δ Example 1 oo ON I· < r-' » sr—· g (N r - < r - I1 inch s; Os v〇On τ - H VD Os o CN ooo Ο i (Ν Ο ο ο ο § ο (Ν Ο 04 ο ο Q ο ο (Ν δ δ 1 Tire ] i T2[°C] cn r—^ m (N tn ΓΠ m r- 4 weeks [%] 8 weeks [%] 16 weeks [%] 24 weeks [%] (d) Void 4 weeks [%] ι 8 Week [%] 16 weeks [%]J 24 weeks [%] (f) Overflow | 4 weeks [%] I 8 weeks [%] 16 weeks [%] 24 weeks [%] -1 (b) A-order stability (c) B-order stability (e) B-order gap (g) After-level overflow i inch 200813152 [Table 4]

Reference Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 (a) T1 [°C] 75 ND ND ND ND Reactivity T2 [°C] 192 185 198 132 125 】Day 103 100 100 104 110 (b) A-order stability 2 days 105 101 100 〗 08 132 3 days 112 102 101 126 175 7 days 128 102 101 182 258 4 weeks [%] 98.1 96.9 97.8 79.4 72.1 (c) B-order stability 8 weeks [%] 97.4 95.9 96.9 74.2 63.5 16 weeks [%] 97.1 95.0 96.2 70.2 53.8 24 weeks [%] 96.8 94.3 95.1 65.2 45.3 (d) Void 0/20 0/20 0/20 0/20 0/20 4 weeks [%] 0/20 0/20 0/20 NA NA (e) Clearance after B-stage 8 weeks [%] 0/20 0/20 0/20 NA NA 16 weeks [%] 0/20 0/20 0/20 NA NA 24 weeks [%] 0/20 0/20 0/20 NA NA (f) Overflow 0/20 20/20 20/20 0/20 0/20 4 weeks [%] 15/20 20/20 20/20 NA NA ( g) Overflow after B-stage 8 weeks [%] 12/20 . 20/20 20/20 NA NA 16 weeks [%] 5/20 20/20 20/20 NA NA 24 weeks [%] 3/20 20/ 20 20/20 NA NA

As shown in Table 3 and Table 4, the composition of the present invention has an increase in viscosity at the A-stage of less than 30%, and is excellent in storage stability at the A-stage. Further, the composition of the present invention exhibits an initial 95% or 95% or more of hardening heat generation even after a predetermined period of time in the B-stage state, and is excellent in storage stability at the B-stage. In Comparative Example 1 and Comparative Example 2, the storage stability at the B-stage was approximately 95%, but if the wafer was loaded after the B-stage, voids or overflow occurred. On the other hand, even after the B-stage, the composition of the present invention has no voids and overflow. Examples 12 to 17 42 200813152 Each component of the mass parts shown in Table 5 was used, and a planetary mixed β port of 25 ° C was used. Perform this combination and pass it through a 25-inch three-roller at μ. The composition is prepared by mixing the ☆ and mixing the ☆. In addition, in the preparation of the composition: 刖'. The epoxies, hardeners, and hardening accelerators were placed in a 150+C: 5 mmHg thermostat for 6 hours, and the particulate thermoplastics were placed in the crucible (8). C: % small 犄 in a thermostatic bath of 5 mmHg or less is subjected to a treatment for removing volatile components. When this treatment is performed, "-" is used to indicate the table 5, and for example, "epoxy resin a_" indicates that the above-mentioned epoxy resin a is subjected to the above treatment. [4 5] ----- Example 12 Example 13 Example] 4 Example 15 Example 16 _——-- f Example 17 (A) Epoxy resin a- 3.· cl- 3.- S- a- --------- 34.6 34.6 34.6 34.6 34 6 34.6 (B) Hardener n- n- 1> n- n- ---·---- n- —:--- --- 65.4 65.4 65.4 65.4 65.4 _65.4 (D) Hardening accelerator ο- Ι ο- Ι ο- Ι c- 1 Ο Ι c~ 1 (C) Thermoplasticity e- e- e- f- --- --* h- Resin particles 20 5 50 20 g_ 20 20 Ceria 123.5 108.5 153.5 123.5 123.5 123.5 Carbon black 1 1 1 1 1 J__ KBM-403 1.5 1.5 1.5 1.5 1.5 1.5

For each of the obtained compositions, the above tests (a) to (g) and the following tests (h) to (k) were carried out. Further, tests for (h) to (k) were also carried out for the above examples in the above examples ι to 丨丨. The results are shown in Tables 6 and 7 in 0 43 200813152

(h) TGA Take 10 mg of each composition into an aluminum crucible, use an empty aluminum crucible as a scallop, and use a TGA (thermogravimetric analyzer, thermogravimetric analyzer/MEITLER) in the air. Take 1〇. The temperature increase rate of 〇/min was raised from 300 ° C to 300 ° C, and the mass loss (%) was measured up to 200 ° C. (i) Viscosity from 150 ° C to 200 ° C

280 μΐ of each composition was placed in a parallel disk with a diameter of 18 mm and a gap of i”2 mm, and a rheometer (rhe_eter) (manufactured by UBM Co., Ltd.) was used to raise the temperature by 1 (TC/min). The speed was raised from 25t: 3 〇 (TC, 150 ° C to 20 (the viscosity of TC was measured, and the average value was obtained. (j) The void after resin sealing was tested as shown in FIG. 4 for the resin-sealed semiconductor device. For the SAT, the SAT observation was performed on each test piece, and the number of test pieces containing voids/the total number of test pieces (20 pieces) was calculated. The test piece was produced as follows. The surface was coated with a solder resist (3〇μηι thick). The BT substrate (200 μπι thick '35 mm x 35 mm) was coated with an epoxy resin composition (5 〇 thick, 12 mm x 12 mm). It was heated at a temperature 20 ° C higher than Τ 1 for 1 使 to refine it to 15 ( Rc (wafer) interesting. c (substrate) A Mpa / 1 second loading formed with nitrided (four) wafer (_ thick, ΐ 2·5 mm 5 mm), KMC-2520 (Xinyue Chemical Industry's epoxy, in the mold The temperature is 17宂' injection time is 1 〇 second, the injection pressure is 7〇KPa' molding time is 9G seconds, and the post-hardening condition is (10). The size of the test piece after molding was a curry thickness, 35 mm x 35 44 200813152 1 (k) Grain displacement after resin sealing The crystal grains of 20 test pieces of FIG. 4 were measured using a soft X-ray transmission device. Displacement value: Here, the grain displacement value is the total value of the linear movement distance of the four corners of the wafer, and the total value is greater than 50 μηι is unqualified, and the number of unacceptable test pieces/the total number of test pieces (20 pieces) is calculated. 6]

Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 (a) Reactivity T1 [°C] 99 104 96 101 100 87 T2 [°C] 192 191 193 193 190 194 (b) Stage A Stability 1 day 101 100 103 101 102 102 2 days 102 101 107 102 104 103 3 days 105 102 111 104 108 108 7 days 110 104 119 108 114 115 (C) B-order stability 4 weeks [%] 97.4 97.0 98.1 97.0 96.4 97.6 8 weeks [%] 96.4 96.3 97.9 95.7 95.7 97.0 16 weeks [%] 96.1 96.0 97.2 95.4 95.4 96.4 24 weeks [%] 95.8 95.1 96.8 95,4 95.1 95.9 (d) Void 0/20 0/20 0/20 0/20 0/20 0/20 (e) Clearance after B-stage 4 weeks [%] 0/20 0/20 0/20 0/20 0/20 0/20 8 weeks [%] 0/20 0/ 20 0/20 0/20 0/20 0/20 16 weeks [%] 0/20 0/20 0/20 0/20 0/20 0/20 24 weeks [%] 0/20 0/20 0/20 0/20 0/20 0/20 (f) Overflow 0/20 0/20 0/20 0/20 0/20 0/20 (g) Overflow after B-stage 4 weeks [%] 0/20 0/20 0/20 0/20 0/20 0/20 8 weeks [%] 0/20 0/20 0/20 0/20 0/20 0/20 16 weeks [%] 0/20 0/20 0/20 0 /20 0/20 0/20 24 weeks [%] 0/20 0/20 0/20 0/20 0/20 0/20 45 200813152 [Table 7] Example 1 Example 2 Example 3 Example 7 Implementation example 8 EXAMPLES] Example 1 Reference Example 1 (h) TGA [%] 1.5 2.1 1.2 2.6 1.9 0.6 0.9 0.8 (i) Viscosity at 150 ° C to 200 ° C [Pa · s] 210 220 280 350 420 8.2 1020 9.4 (j) Sealed gap 6/20 13/20 2/20 18/20 7/20 0/20 20/20 0/20 (k) Grain displacement after sealing 0/20 0/20 0/ 20 0/20 0/20 20/20 0/20 20/20

[Table 8] Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 (h) TGA [%] 0.6 0.8 0.4 0.7 0.5 0.8 (i) Viscosity at 150 ° C to 200 ° C [Pa- s] 230 12 950 240 320 38 (j) Sealed gap 0/20 0/20 0/20 0/20 0/20 0/20 (k) Grain displacement after sealing 0/20 0/20 0 /20 0/20 0/20 0/20 The compositions of Examples 12 to 17 have a reduction of less than 1% by (h) TGA, and (i) B-order viscosity is 10 Pa · s to 1000 Pa · s, so even if it is hardened in the resin sealing process, no voids are generated and there is no grain displacement. The composition of the present invention can form a stable B-stage state and can be suitably used as a binder for semiconductor products requiring high yield. Further, the composition having a predetermined wave composition and viscosity can enter the wire bonding process and the resin sealing process even if the curing process is not performed after the wafer is loaded, and the productivity of the semiconductor device can be improved. BRIEF DESCRIPTION OF THE DRAWINGS 46 200813152 FIG. 1 is a DSC chart of the composition of Example 1. Fig. 2 is a cross-sectional view showing the structure of a test piece loaded with a ruthenium wafer produced in the examples. Fig. 3 is a conceptual diagram showing voids and overflow. Fig. 4 is a cross-sectional view showing the structure of a resin-sealed semiconductor device test piece produced in the examples. [Main component symbol description] 47

Claims (1)

200813152 X. Patent Application Scope 1. A composition comprising: (A) an epoxy resin; a hardened (4), (B) an epoxy tree 1 and a hardening agent, although The amount of the epoxy group of the (A) epoxy resin is 0.8 to 1.25. The field (C) is a solid thermoplastic resin particle at 25 ° C, relative to (A) The total amount of the epoxy resin and (B) epoxy resin hardener (10) is the mass damage, the thermoplastic resin particles are 3 parts by mass to 6 parts by mass; and, (D) the epoxy resin hardening accelerator, relative to (A) The epoxy resin and the (B) epoxy resin hardener are a total of 1 part by mass, and the epoxy resin hardening accelerator is 0.1 part by mass to 1 part by mass. 2. The composition according to claim 1, wherein the total mass of the (A) epoxy resin and the (B) epoxy resin hardener is 5 parts by mass to 50 parts by mass. (C) Thermoplastic resin particles. 3. The composition according to claim 1, wherein (c) the thermoplastic resin particles are selected from the group consisting of methacrylic resin, phenoxy resin, butadiene resin. ), particles of a thermoplastic resin of polystyrene or a copolymer thereof. 4. The composition according to claim 1, wherein (c) the thermoplastic resin particles have a polystyrene-converted number average molecular weight of 1 〇, 〇〇〇~1000,000, and a weight average molecular weight of 1 〇〇, 〇 〇〇~10, 〇〇〇, 〇〇〇. 5. The composition according to claim 1, wherein (C) heat 48 200813152 _ _ ---I--- the plastic resin particles have a median size of 〇·1 to 5 μηη And a 98% cumulative particle diameter of 1 μm or less. 6. The composition of claim 1, wherein the surface of the thermoplastic resin particles is treated with a silane coupling agent. 7. The composition of claim 1, further comprising an inorganic filler. 8. The composition of claim 1, wherein at least a portion of the (A) epoxy resin and/or (B) epoxy resin hardener has a singular S residue in the molecule. 9. The composition according to any one of claims 1 to 8, wherein in the aluminum crucible, an empty aluminum crucible is used as a reference sample, and one side of the air is 1 ( The speed of rc/min rises from the pit to 〇C δ into the 仃Dsc, and at least a heat-generating peak appears on the lower temperature side of the (A) epoxy resin hardening value=, the low-temperature side is produced, The peak temperature (T1) of half = 1^ is rib art or 8 (rc or more, and compared with (A), the peak temperature of the hardening peak of the oxygen resin (D2) is less redundant or 70 C or more. For the composition described in item 9 of the patent application, the speed of the knife is increased from 25t: to 3 (Krc, _ to · C. The mass reduction is less than or equal to 1%, and: Ship Narrative: 49 200813152 I The temperature is raised from 25 ° C to 300 ° C in the air at a rate of 10 ° C / min. When the viscosity is measured by a rheometer, the viscosity at 150 ° C ~ 200 ° 为 is 1 〇? 3.3 to 1000 ? & 4. 11. A crystallizing agent comprising the composition according to any one of claims 1 to 10. & 12.- A method of manufacturing a semiconductor device, comprising: ^1) applying a die attaching agent as described in claim 11 to a substrate; W2) a temperature in a range of temperatures T1 to (T2 - 201) The above-mentioned coated adhesive is B-staged; 3) a semiconductor element is placed on the B-stage paste; and 4) the adhesive is hardened. 50