TW526233B - Liquid epoxy resin composition for semiconductor sealing, sealed semiconductor device, and production process of sealed semiconductor device - Google Patents

Abstract

Disclosed is a liquid epoxy resin composition for sealing a semiconductor device which comprises (A) a cyanic acid ester, (B) an epoxy resin, (C) an inorganic filler, (D) a metal chelate and/or a metal salt, and at least one of (E1) an acid anhydride, (E2) a dihydrazide compound and (F) a silicone resin gel, wherein at least one of components A and B is liquid at room temperature, component E1 is liquid at room temperature, and the weight ratio of component C to the total weight of the composition, the weight ratio of component A to component B, and the weight ratio of component E1, E2 or F to the total weight of the composition except component C each ranges a specific ratio.

Description

526233 Description of the invention (1) Field of i The present invention relates to a semiconductor device sealed with a resin composition and used for sealing a liquid substance for sealing semiconductor devices and the like, and a method for manufacturing the same. Free background Epoxy resin composition has excellent electrical properties and is strongly used in various electrical and electronic fields. In particular, it is a conductor device for high sealing reliability. Methods for sealing a semiconductor device with a resin composition have been widely performed, including die-casting using a powder 'or casting using a liquid composition and a dispenser. As electronic devices have become more flexible and versatile in recent times, the demands for higher integrity, higher density, smaller thickness, and smaller package sizes have increased. In order to meet these needs, the type of semiconductor package, such as ball grid array (BGA) (high density can be achieved by its column connection), chip size package (c s p) chip module (MCM) as examples. These novel types of semiconductor packages are sealed with a conventional poor molding die and a powdery sealing material, which can achieve the limit of whiteness and deformed wiring (bending of the wiring). Therefore,,, sealing material. The use of a liquid sealing compound is more advantageous than the following method: the powder sealing compound is first compacted into a bond ingot and plasticized in a trough. However, liquid sealing: ^ Its sealing processability and reliability are superior to powder sealing compounds. The advantages of liquid sealing compounds over liquid sealing compounds = the degree of semiconductor sealing of epoxy resin, and it is widely used in sealing half The trend of epoxy-like composition, a new type of semiconductor for the weight appears through the use of area arrays, and multiple crystal sealing technology. The thickness is reduced by the two-step pressing step of using liquids today, and the problem of materials is poor. Powder due to bag

89110252.ptd 526233

The curing agent contained therein and its high adhesive strength to the wafer are not hydrolyzable in the humidity resistance reliability test. In addition, the sealing compound used in die casting is solid (powder) at room temperature, so that the amount of filler can be increased and the resin has an increased glass transition temperature (Tg), thus exhibiting excellent solder resistance and heat resistance Sudden degeneration. On the other hand, the curing accelerator body 'is a compounding limit. Generally, the agent, but its specificity and epoxy based on dicyanide need too high and poor electrical properties due to cross-linked structure and due to chemical use at room temperature as a sealing compound lipid viscosity. In addition, the void energy can hardly be caused in addition. In addition, any period of use and high, for the curing agent and choice of liquid sealing compounds can be used because the resulting compound should be one-pack type and The limitation of long pot life and the use of amine compounds and anhydrides as curing agents or curing acceleration have the following disadvantages. Among the amine compounds, the liquid aromatic amine compound 1 is reactive and produces only a short pot life. Although solid amines such as canonical diammonium have a long pot life, their reaction initiation temperature and the resulting compounds are hygroscopic. The cured epoxy resin cured by the acid anhydride curing agent has not only the S-linked chain is easily hydrolyzed, so the reliability of moisture resistance is poor, and the adhesion is not enough, so the reliability of heat resistance is poor. The phenolic curing agent of the powdery sealing compound is hardly applicable to a liquid-filled liquid state. If it is used, Jiang Keda ’s Secret Girl A ~ /, will greatly reduce the viscosity of the liquid epoxy tree and add a bath agent as a solvent. It also deteriorates the reliability and needs fast curing at 1 ° C. Therefore, it is necessary to form a powdery sealing compound: ratio. Known curing system cannot be full

526233 V. Description of the invention (3) Yu Keli here has a processability powder in the printing grease which has the ability to change the elastic mold technology. Even though the powder and rubber are evenly distributed with the cycloepoxy resin, The density can reduce the use of die-casting and other aspects of the invention, and the tightness of the semiconducting wiring substrate is extremely high in the test. Generally, due to the separation of the double siloxane, the dispersion of the oxygen resin grease sealant and Adhesive, low-level overview of the present state of epoxy-induced wetness of a resin composition and this type of large-scale sealing. Under the circumstances, there is an urgent need to develop a liquid sealing compound having sealing reliability and curability not inferior to that of the molding compound. When the moon bean wafer is sealed such as B G A or C S P, the printed wiring board will be used markedly on the board, and then sealed with a super-radial wide module. For this reason, sealing compounds are usually packaged (hereinafter referred to as low-elasticity components). Known low elasticity ingredients include polybutadiene silicone oil. However, it has the following thermal degradation (oxidation) that lacks bonds and has a low long-term thermal stability, but the powdery polysiloxane fluid moves upwards and the viscosity of the liquid has only a small effect on reducing elasticity. Due to the poor phase valley property and its small specific gravity, the upper separated phase is formed in the compound. In addition, the interface between the packaging substrates oozes out, which can cause interface separation. Therefore, it is also necessary to improve the elastic component. The object is to provide a semiconductor for sealing, which is fast-cured to provide semi-heat reliability while maintaining the conventionally satisfactory mold-in-mold mounting. For example, the seal tree is warped, and it is used to reduce the olefin rubber and the polymerization point. Polybutadiene heat resistance. Grease tends to increase, and cannot be in a liquid state. Polyoxygenated oil is easy to be in a liquid state. Polyoxygenated oil is like a mold release agent. It is necessary to seal the liquid used in dense devices. Conductor devices are liquid-sealed. 89110252.ptd 526233

V. Description of the invention (4) The cured resin with advantages of the compound, that is, it has a low degree of operation and a long pot life. It is liquid under the dish, and it is easy to use.-The purpose is to provide-a kind of sealed semiconductor device. == ¼monthly purpose composition, which has the aforementioned characteristics. In addition to reading, it can be a cured product with low elasticity without the problems of phase separation such as agglomeration and upward movement. / It is another object of the invention to provide a semiconductor device sealed by using a liquid epoxy resin composition. 'Another purpose of this description is to provide a method for manufacturing a semiconductor device. The present invention provides a liquid epoxy resin composition for sealing a semiconductor device.' The liquid epoxy resin composition includes (A) a cyanate ester, (B) an epoxy resin, (C) Inorganic filler / (D) metal chelate and / or metal salt, and (E1) anhydride, wherein at least one of components (8) and (B) is liquid at room temperature, and component E1 is at room temperature The following is a liquid, the weight ratio of component C to the total weight of the composition is 0.6 to 0.5, the weight ratio of component A to component B is 0.776 to 1.43, and component E1 is in addition to component c. The weight ratio of the total weight of the external composition is from 0.01 to 0.3. The present invention also provides a liquid epoxy resin composition for sealing a semiconductor device, which includes (A) a cyanate ester, (B) an epoxy resin, (c) an inorganic filler, (D) a metal chelate, and / or Metal salt and (E2) dihydrazine compound, in which at least one of the components A and B is liquid at room temperature, and the weight ratio of the component C to the total weight of the composition is 0. 6 0 to 0. 95, The weight ratio of component A to component B is from 0.50 to 1.82, and the weight ratio of component E2 to the total weight of the composition other than component C is from 0.001 to 0.15.

526233 V. Description of the invention (5) The present invention also provides a liquid epoxy resin composition for sealing semiconductor devices, which includes (A) cyanate ester, (B) epoxy resin, (c) inorganic filler, and (D) ) Metal chelate and / or metal salt, and (F) polysiloxane resin gel 'wherein at least one of components A and B is liquid at room temperature, and the weight ratio of component a to f B is 0 · 76 to 丨 · 43, the reset ratio of component c to the total weight of the composition is 0.6 to 0.95, and the weight ratio of component F to the total weight of the composition other than component c is higher than 〇 〇1 and below 0.3. The present invention further provides a semiconductor device sealed with each of the aforementioned liquid epoxy resin compositions. The invention further provides a method for sealing a semiconductor device, which comprises injecting each of the aforementioned liquid epoxy resin compositions using a molding die. Detailed Description of the Sheep In order to make the epoxy resin composition of the present invention liquid, the mixture of ingredients A and B must be liquid at room temperature. In order for the mixture of ingredients A and 8 to be liquid at room temperature, at least one of them must be liquid at room temperature. As the component A, the cyanoacetate is a compound having a cyanate group (_〇CN), including 4,4-ethylenediphenyl dicyanate (hereinafter referred to as the compound AJO, 2, 2-bis (4 -Cyanoxybenzyl) propane, bis (4-cyanooxy-3, 5-dioxine = period) A: k and bis (4-cyanooxyphenyl) sulfide. Compound A1 2 liquids at room temperature ' The latter two are crystalline solids at room temperature. These cyanate ester compounds: prepolymers are also useful as component A. The component A to be used is selected from these compounds and used as the component B When epoxy resins are mixed, a mixture liquid is produced at room temperature. Component A preferably contains 4, 4'-ethylenediphenylene cyanate (Aΐ). Compound

526233 V. Description of the invention (6) — A 1 has cyanate groups at both ends of the bisphenol E skeleton, which is represented by the formula:

NCO

OCN (A1) and it is a liquid with a viscosity of about 100 centipoise (cP) at room temperature. Among them, Bu Neng, such as the aforementioned 2,2-bis (4 ~ cyanuric acid with a bisphenol A skeleton and his bis (4-cyanoxy-3,5 ~ di; The "yuan" system is highly crystalline and solid at room temperature. Even if this ester is used, it can crystallize cyanide by dissolving it in a liquid epoxy tree when hot. It tends to crystallize when cooled. Curing. The inventors found that the cyanide ester and the compound a 1 with a bisphenol E skeleton were combined with your compound to cure this kind of solidification. In use, it can prevent the semiconductor sealed electricity due to ionic impurities. Especially the ionic impurities in the cyanate ester as the component A (, clothing, bromine ions, gas impurities; r, ^. (For example, ammonium ions, lice ions, 4 acid ions and nitrate ions) The lunar land is much smaller. The content of the service person Λ, 卞) is satisfactory. The pregnant compound A1 has a composition A1 / A compared to w1, which is 0. ϊ to work, especially 苴. The weight ratio of vermiculite, the chemical compound Ai will be called L especially eight series 0.5 to 1, especially Π 7 stone 1 l mouth weight A 1 is lower than 0 ~ system U · 7 to 1. Ruhua. ^ It is difficult to prevent crystalline cyanate from curing as a component B. The epoxy resin is a compound of each molecular base. This epoxy resin is, has-or more propylene oxide, single: Liquid epoxy resin and liquid epoxy resin are preferred. Mixture of oxygen-resin resin and solid epoxy resin: ingredients and liquid

_〇252.Ptd Useful epoxy package Page 11 526233 V. Description of the invention (7) Including 'but not limited to' double g-point A epoxy melt (n_i coffee oxygen resin, tooth "oxygen epoxy resin, may Soluble fat, acyclic epoxy resin, biphenyl ring \ day, propylene oxide epoxy resin. Among these epoxy resins ::: lipid Hope A or double-F epoxy ::: Ze is prepared by molecular distillation as shown below. It is better because = ,, where η is 0 or 1, and the amount of impure impurities is better. Low viscosity and very small distance from 0Η-CH.-CH-CH, •.-O-2r0-〇- ch2-CA :, ch2 are the physical properties and sealing of the cured resin; ^ depend on ~ degree), proportional It should be from 0.50 to 1.82, preferably from 0 to 76 to 1 Zn Π η π, preferably from 0.91 to 1 M, and from 0.91 to h 43 is more reasonable. P know "^ soil. The limitation of the injury A / B ratio is based on the following 4: The cyanogen ester of tritium is trimerized in the presence of a metal catalyst, and is split into two parts. This reaction is mainly above 180, t t at high temperatures. Composite resin systems containing cyanate esters and epoxy resins also involve reactions between cyanoacetate groups and epoxy groups, so this system appears to accompany; = competing reactions. If the ratio is greater than " 2, then the reaction system: The lice tree is known, leaving the cyanate groups uncured in the curing of less than 16 G t. The unreacted cyanate groups in the humidity resistance reliability test such as In a pressure cooker test (PCT), it will hydrolyze to urethane groups, which will further undergo decarboxylation, resulting in the failure of humidity resistance reliability. On the other hand, if A / B ratio /, at 0.50, the excess epoxy resin remains unreacted and causes a decrease in the crosslinking density of the cured resin, which will cause a reduction in glass transition temperature

ϋΐΗΙ 89110252.ptd Page 12 526233

5. Description of the invention (8) or increase in hygroscopicity. As a result, the cured resin has an increased coefficient of thermal expansion 'and may have deteriorated thermal cycling and reflow (refl ow) reliability. Inorganic fillers that can be used as ingredient 0 include crystalline silica, molten oxygen, f, alumina, calcium carbonate, and oxides. Although there are no restrictions, it is preferred that the fused oxide stone be spherical or have no corners, and have a size of 100 micrometers such as 丄 丨 丨, take the size of human particles' so as not to scratch the semiconductor wafer. The weight ratio of the component C to the total weight of the composition is 0.6 to 0.95, more preferably 70 to 0.90, and still more preferably 75 to 085. If the ratio of component 0 is less than •, a resin composition with a large resin content will experience an increased shrinkage when sealed. In addition, the cured resin has an increased coefficient of thermal expansion that tends to cause increased warpage or flaws in the wiring substrate, such as cracks in the wafer during the application of rubbing stress. In addition, the cured resin has an increased moisture absorption which causes it to crack when flowing. ^ The ratio of component c is greater than 0 ·%, then the composition is said to be too viscous in the absence of liquid components, which is difficult to handle as a liquid and cannot be densely used as a curing catalyst for metal chelate and / cyanate component D . Metals More non-ionic or ion-free metals of the chelate ring include iron, origin, compound, tin, positions including acetamone, salicylic acid, including naphthenate and octene salt. In one very specific embodiment of the present invention, it is referred to as compound D1) or cobalt (I 11) for chelation as component D to produce the following chelate as j / or metal salt system as component A, which has 1 to 6 Or even daughter metal chelates. Metal chelates Aluminum, and manganese. The composition of the metal chelate compound is the same as that of the present invention. Metal salt coating ′ Iron (I I I) chelate (hereinafter abbreviated as compound D2) is used. Metal chelates are known for cyanate esters.

Page 13 526233 V. Description of the invention (9) ::: is 2 :: approx., The above trimerizes to form a tri-skeleton. Into. Because: chelates can independently catalyze the cyanate esters depending on the metal, and the absorption of cyanate groups by the solidification catalyst of the ′ compound differs from the main species. different. -Generally speaking: Zinc? : Department: According to the metal chelate used. "In reaction systems such as copper: manganese, titanium, aluminum, and aluminum, it also contains epoxy resin and so on. In addition to cyanate esters: :: coffee, it does not. And; reaction mechanism changes 2 The oxazoline bone II between the acid group and the epoxy group is involved in the concrete example described below, gas wood, and the reaction. In the polysilicone resin with low elasticity, the composition contains The tendency of the liquid to change is large; the surface tension: the system has a thixotropic surface, which is disadvantageous in applications where the sealing surface must be flat, such as a BGA package with a heart shape, convex surface, ty d_). ^ "Force :: , Compound D of ingredient D is remarkable in heart and sweetness. "_ 的 同 配 同 并 ^ Example 〇 1 ethylene propylene show one, salicylaldehyde, and benzene hydrazone to u05 'is particularly from. ⑽u ...: 1,2,?: Curing catalyst M can be obtained Satisfactory curing characteristics and length = relatively, when there is no dam around the wafer like a board package.

89110252.ptd Page 14 526233 V. Description of Invention (ίο) It is almost non-flowing to effectively seal a small area. Sheets or wiring will be exposed and cause defects. In this case, the main crystal D2-cobalt (III) chelate is used as A month, and high thixotropy can be achieved by using chemical Mτη into L as component 0. Cobalt Π Ι) There are no particular restrictions on the ligands of the chelate. The same roots, water-sparging, and benzyl alcohol. The curing catalyst ^ includes ethylene and propyl, depending on the amount of the cyanate ester of the component A. In the better D2 /, it is regarded as 0 to Γ ::, 01, which is from 0 to 0 · 0 3 〇 It is used in the same soil of Tonger 乂 山 n 丄 上 平 乂, which is passed on by the driver ’s best amount. The curing characteristics and long pot life of the curing agent D2. The 7-man full-threatening fat composition may contain (E) a curing accelerator selected from (E1) anhydride and (E2) dihydrazine compound.

The acid anhydride E1 is a curing accelerator for the reaction between a cyanate ester (component A) and an epoxy resin (component β). The ingredient £ 1 reduces the epoxy composition 'and has a significant effect on the fluidity of a good sealing compound. Since the epoxy resin composition of the present invention is liquid at room temperature, it should also be liquid at room temperature. The weight ratio of W wounding E1 to the total weight of the composition other than component c is from 0.00 to 0.3, more preferably from 0.05 to 0.2, and still more preferably from 0.1 to 0.15. If the weight-to-weight ratio is less than 0 · 0 1, the aforementioned effects are hardly obtained. If it exceeds 0.3, the reactivity of the system decreases, and the resulting cured resin has a reduced reliability in moisture resistance. Although the curing reaction hardly occurs in a system consisting solely of ingredients, the inventors have discovered that a system containing ingredients A and ^, an unknown mechanism, exhibits satisfactory reactivity. It is speculated that the hydroxyl group and the active hydrogen species generated in the reaction between

89110252.ptd Page 15 526233 V. Description of the invention (11) Form a 1 sialin skeleton 'to accelerate the reaction with anhydride. The dihydrazine compound E2 is a compound of each molecule, in which the active gas of the nh2 terminal group is reacted with a π-group (-NHNH2) group and the like. Dihydrazide human group, hydrazine hydrochloride, hexamethylene dihydrazine ... Dihydrazine, 2: E =: The price is not limited to, hydrazino-6-methylamino-symmetric-tri; The total amount of hydrazine and 2,4-component E2 to the composition other than component C is preferably from 0.2 to 0.2 °. ,. 2 to " ... crossing; Γ Cheng: That is, if the reset ratio is lower than 0.01, the aforementioned effect can hardly be obtained. If the weight 1 ratio exceeds 0.15 ', the reactivity is so high that the pot life is short. : However, the component E2 is a solid at room temperature, so it has a low J stress at 15 °. ° Above exhibits high with epoxy resin

Hr! Dagger. In addition, the active hydrogen of the dihydrazine compound is also highly reactive with the hydrogen acid ester group (—0CN) of the hydrogen acid ester at or above. In other words, 'representing ingredients A — B, ingredients B — E2, and ingredients A — E2j, the conventional resin composition exhibits potential curing properties (ie, long ~ is expected to have high adhesion. Π 1 is one of the dihydrazine compounds U's 2,4-dihydrazino-6-methylamine-symmetric monotriphine (hereinafter abbreviated as 2. 4) Τ) has a heat-resistant dimorphine nucleus having a hydrazino group attached thereto. JP_B —6 3 — 1 952 6Professor 2 · 4ητ exhibits excellent potential curing properties and heat resistance in the reaction of toilet epoxy resins / When heated, it is composed of component A, component B, component 2 · 4ΗΤ, and component D When the resin composition is cured, thermal analysis shows that the exothermic peaks are near 120 C and 150 °. Although the correct reaction mechanism is unknown,

526233 V. Description of the invention (12) '" However, it is speculated that the temperature rise first causes a reaction between cyanate ester (component A) and 2.4HT (component E2)' as a competition between components A and E2. The reaction between the reaction product and the wound B, the reaction between the unreacted component a and the component b, and the reaction between the reaction E2 and the component B. In other words, it is believed that the reaction between components A and B should occur at about 150 ° C in the presence of component D alone, and at 120 ° in the coexistence of 2.4HT. 〇 Initiated at lower temperatures. In the composition disclosed in the previous Jp — B — 63 — 1 9 526, since it is expected that 2 · 4ΗT can provide the main curing agent for epoxy resin, it is used in a large amount of 10 i30 PHR. However, in the present invention, if the component E2 is added in a trace amount having a weight ratio of 0.001 to 0.15 to the total amount of the composition other than the component ^, the curing reaction of the component A is about 1 20 The fact that the temperature is lowered at ° C confirms that the component E2 can be used as a reaction accelerator for the reaction between the components A and B. The addition of ingredient E2 triggers the reaction of the three ingredients A, B, and E2 at a low temperature of about 120 C. It always shows that the formula specified above has a very effective balance. Because the curing of the liquid sealing compound takes into account the heat resistance of the packaging substrate, it is generally completed at 150 ° C or below 150 t, so the aforementioned effects are significant. The gelation time of the three-component systems A, B, and D at 150 ° C was about 10 minutes, and the addition of 2.4HT as the component E2 shortened the gelation time to 2 "to 3 minutes. '' Since component E2 is a low-reactivity solid (particle) at room temperature, it exists in the composition in an insoluble and dispersed state and hardly causes a reaction. Therefore, the viscosity of the composition changes at room temperature Suppressed Y and ^: Reckless

526233 V. Description of the invention (13) The extended service life is manifested at high temperature, which has a greater effect than the semi-conductor wetness and electrical characteristics on the road, which can damage the fine effect of E 2 and extend the sealing component E 2 with no more than etiquette, sealed in fine E2 is particularly good at 30 microns. . The granular component E2 should be finely ground in advance to make it optimally reactive. Particles that improve the surface area for reaction with other ingredients are preferred. In order to produce a uniformly cured resin sealed in a fine electric device to obtain satisfactory resistance, it is also necessary to make the solid component E2 into fine particles. In addition, the particles can prevent sedimentation in the liquid composition, and it can also have the pot life of the compound. Based on all these considerations, an average particle size of 1000 microns is better. In order to obtain a uniform curing resin for semiconductor devices on the circuit, the average particle size below the composition is better, below 5 microns is S containing nitrogen atoms forming a solid cross-linked structure with the epoxy resin, 1 2 嶋 curing accelerator such as The strong adhesion of the anhydride is due to the full resistance and heat resistance of the product. As a component F, a polysilicone resin gel, a polyether grease, is a mixture of oil between powder and oil (the main production of polysiloxane resin gel :: evening milk :: poly "The oil is added to the heated epoxy resin, and it is stirred at: = # 社: strong courage to finely disperse the gel ingredients, and the finely dispersed state prepared by ':: at:' shows low flexibility = will There are things like agglomeration and moving up 2 = the total weight of component F to the composition other than component C should be 'not island':

526233 V. Description of the invention (14) --- 0.01 and less than 0.3, more preferably 0.01 and less than 0.2. Adding the component F at a weight ratio of 0.3 or more can increase the viscosity and reduce the processability of the epoxy resin composition. Adding component F at a weight ratio of not higher than 0.001 is not effective in the elastic modulus. '— As the component F, the silicone resin gel preferably contains a polysilicone polymer represented by the following chemical formula and a self-curing silicone rubber or gel.

Where R represents an alkyl group (for example, fluorenyl or ethyl) or phenyl; χ represents a polyoxyalkylene-containing group (for example, polyoxyethyl, polyoxypropyl, or poly (oxyethyl) / Oxypropyl)); and 1, m, and η each represent an integer of 丨 or more. In the above chemical formula, 1 / (l + m + n) is preferably from 0.05 to 0.99; m / (l + m + n) is preferably from 0.001 to 0.5; & n / (1+ m + n) is preferably from 0.0001 to 08. The silicone polymer may be a block copolymer or a random copolymer. The self-curing silicone rubber or gel is not particularly limited as long as it has a vinyl group or the like to which an S 1 fluorene group can be added. The addition reaction type is preferred. They can be used individually or in mixtures. Silicone polymers can help self-curing silicone rubbers or gels disperse to form fine sea-island structures. It is expected that some silicone polymers will react with self-curing silicone rubbers or gels. The epoxy resin composition may further include (G) a coupling agent selected from (G1) a titanate coupling agent and (G2) an epoxy silane coupling agent. Although it is generally known to use a silane coupling agent containing silicon as a metal nucleus (for example, bad oxygen silane and amine silane) in an epoxy compound 526233 V. Description of the invention (15) Sealing compounds, the inventors have found that titanium The nuclear titanate coupling agent G1 can produce improved flow and low-temperature rapid curing in solid systems containing cyanate esters and epoxy resins. Coupling agents commonly used in epoxy sealing compounds have hydrolyzable groups (eg, methoxy groups) that can react with inorganic components (eg, silica) and functional groups (eg, epoxy resins) that can react with organic components Base or vinyl). The inventors knew that adding the epoxy silane coupling agent G2 to a system containing cyanoacetate would produce: a significant adhesive strength 'which seems to be attributable to High reactivity between epoxy groups of mixture G2. It is preferably added in a weight ratio of 0.001 to 0.01 to the total weight of the composition other than the component c, especially from 0.05 to 0.05, and particularly from 0.001 to •. In a weight ratio of less than 0.001, almost no component 〇 is added in a weight ratio of greater than ° · 1, which will cause cross ρ; f reduction in sealing reliability and service life. The ring and resin composition may further include an amine compound as a component, and provide a curing accelerator for the reaction of components A, B, and rhenium. In the case where the metal or metal salt is used as a catalyst containing a cyanate ester and an epoxy resin library, high temperature is required, but the curing is due to the metal compound and the metal salt hardly i resin. Reaction, and improve curing reactivity. There are no particular restrictions on the amine compounds that are used as parts of pupae, and they include ′, ° ’Λ, dicyandiamide, and hydrazine compounds. Amine compounds with active hydrogen such as

89110252.ptd Page 20 526233 V. Description of the invention (〖6) __ In order to accelerate the opening of the epoxy ring, and thus improve the reactivity, the compound is used in combination with acidic liver to accelerate curing. == 于 = 其 :: 解 产品 的Effective in the agent system. Bu Ma curing acceleration = component β, the component Η is from 0.0001 to 〇, especially from .005 to U, especially ^ weight: ^ plus better period. It is shown that the curing properties and long applicable strength of the product are as follows: of :: The epoxy resin composition of the present invention can also include defoamers, surfactants, ionomers, ketones, funnels, and ions. Molds, mixtures, and so on. Agents, diluents, and other epoxy-based epoxy resin compositions invented by the above-mentioned ingredients are mixed in the process, in: ~ in the machine, #mixer, etc. 'and finally defoam in vacuum: There are special restrictions on kneading yam among $$ T and so on. Clothing service. The preparation sequence of the ingredients is using a dispenser and a printing device = a product in a sealed semiconductor device ', and a liquid epoxy resin coat is produced. In accordance with the semiconductor of the present invention, the use of a liquid epoxy resin composition " Π :, printing device, etc. is carried out: for the use of the osmium under atmospheric pressure as explained, the denseness in the mold is sealed with the :: mold. Same as above; __, using melting in a die-casting material tank 89110252.ptd 1 page 21 526233 V. Description of the invention (17) The ingot (solid sealing compound) melted and liquefied is carried out through die-casting. If liquid sealing compounds can be molded in the mold, this will simplify the process and reduce costs. To achieve this in large-scale manufacturing, liquid sealing compounds must be cured within minutes at the molding temperature to obtain sufficient strength that can be removed from the mold. From this point of view, the liquid composition of the present invention is cured in-plane at a number of 500 ° C and sufficient strength is obtained in 15 minutes, so it can be applied to sealing in a molding die. Since the epoxy resin composition of the present invention has mold adhesion, it is recommended to coat the mold cavity with a fluorine type or a polysiloxane type agent. The sealing with the epoxy resin composition in the molding die can be performed, for example, as follows. , The semiconductor wafer is placed in a mold, and the mold is tightly closed. The liquid-epoxy resin composition was injected into the cavity through the flow, and maintained at 1 ^ ^ at 500 ° c. The sealed semiconductor wafer is removed from the mold and placed at 150. After curing for 3 hours, a resin-sealed semiconductor device was obtained. In this way, a semiconductor device can be easily manufactured by injection. The invention will now be described in more detail with reference to examples, but it should be understood that the invention is not to be construed as being limited thereto. Compounds used in the examples ... In-position _A — (— mannate) ·· 〇〇1 ^ gAsahiChibaK.K.2AroCyL-10 (4,4,-^ c-based dibenzyl cyanate, a compound having a bisphenol E skeleton, is present Warm liquid) is 〆B ^ IO ^ · ArOCy Β_ι〇 (2, 2-bis (in cyanophenyl) propane), a compound with a bisphenol A skeleton, purchased from Asahi Chiba κ · κ ·, at room temperature Down, magu

89110252.ptd Page 22 526233 V. Description of the invention (body 18) M30: AroCy M-30 (compound with bisphenol F skeleton, solid at room temperature) purchased from Asahi Chiba KK _B (ring Gas resin: YD8125: purchased from Toto Kasei K · K · (double test A type epoxy resin prepared by molecular distillation; epoxy equivalent · 1 75; viscosity: 40 poise (P) at 25)

Epikote 828: purchased from Yuka Shell KK · (bisphenol A epoxy resin) Component C (inorganic material): Commercially available spherical fused oxidized stone. Part D (metal chelate or metal salt): iron triacetate (in) [(CH3C0CHC0CH3) 3Fe] (abbreviated as Fe (III) (acac) 3) triethyl-cobalt acetone (in) [(CH3COCHCOCH3 ) 3C〇] (abbreviated as Co (III) (acac) 3) Manganese naphthenate salt component E1 (anhydride): B650 · Purchased from Dainippon Ink and Chemicals, Inc.

Epichlon B650 (methyl hexahydrophthalic anhydride; molecular weight: ι68) B570 · purchased from Dainippon Ink and Chemicals, Inc.

Epichlon B570 (fluorenyltetrahydrophthalic anhydride) component E2 (dihydrazine compound) ······························································ ·· （· 平均 · （· ··

89110252.ptd Page 23 526233

Small · See footnotes in Tables 3 and 4) ADH: · Ethyl Dihydrazine (average particle size: 15 microns) SDH. Amber monohydrazine (average particle size: 15 microns) VDH. Valeric acid dihydrazine (average Particle size · 15 micron) Siloxane is obtained by dispersing a specified amount of RTV polysilicone resin (purchased from Toshiba Silicone Co., Ltd., at 80 ° C) in a dispenser.

Ltd.) XE5818) was dispersed in epoxy resin (YD8125 or Epikote 828) for 3 hours to prepare. Ingredient G (Coupling ZII: KR-TTS: PlenAct KR-TTS (a titanate coupling agent represented by the following chemical formula: commercially available from Ajinomoto Fine Techno K · K ·)

CH3 / 〇X CH3-CH-O-Ti-hO-C-G ^ Has) 3 Specific gravity: 0 · 9 5; red-brown liquid) A187: purchased from Nippon Unicar Co., Ltd. (represented by the following chemical formula Epoxy Silane Coupling Agent: (CH3〇) 3SiC3H6〇CH2CH-CH9 V) Component Η (amine compound) · 2ΜΑ-0Κ · Cure Sol 2ΜΑ-0Κ, purchased from Shikoku Chemicals Corp. (2,4-diamine -6- [2'-methyl-sigma syl- (1 ')]-ethyl-s-Misaraisoisocyanuric acid adduct) PN-23: purchased from Ajinomoto Co., Ltd.

89110252.ptd Page 24 526233 V. Description of the invention (20) Examples 1-1 to 1-23 and comparative implementations _ Examples 1 to 1-6 The ingredients shown in Tables 1 and 2 below were evenly mixed in a mixer. The mixture was mixed in place and defoamed in a vacuum to prepare a liquid epoxy resin composition. The physical properties and curing properties of the resulting liquid epoxy resin composition were measured as follows. In addition, each resin composition was used to seal the silicon wafer mounted on the printed circuit board and bonded to the printed wiring board through wiring, and then heated at 120 ° C for 1 hour, and then at 150 ° C for 3 hours. The resin composition is cured. The silicon wafer thus sealed was subjected to the following reliability test. The results obtained are shown in Tables i and 2. Measurement and test methods: 1) Viscosity The viscosity (initial viscosity) of the liquid epoxy resin composition at 25 ° C was measured using a Brookfield viscometer. 2) Thixotropic index Measure the viscosity of the liquid epoxy resin composition at the speed of 丨 / 丨 〇 used in the above measurement (1). Divide the measured value by the viscosity measured in (1) above to get the thixotropic index. 3) Application period The composition is at 5. Mouth storage for 1 month, and the use of Locke (ΊΛΓΛ // 彳 viscosity at 25 ° c. The ratio of the measured value to the initial viscosity measured in (1) above is considered as applicable 4) Gelation time 4 In degrees. Up =======

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Think of gel time. 5) Warp around a flat epoxy glass-breaking laminate (35mm x 35mm) to form a 1mm high dam made of silicone rubber, and apply an oxygen resin composition of 20 · Yoshizumi ^ to the dam. The area surrounded, and the surface of a liquid ring to measure the warpage of the laminate with a surface roughness meter. ,, curing. Le 6) Flow height Place a flat ceramic plate on a pressure table maintained at 701 grams of liquid An epoxy resin composition was dropped thereon and 0.65 was cured. Measure the height of the cured resin. U set for 5 minutes ’and Ό PCT reliability. Sealed with epoxy resin and mounted on epoxy glass laminate. Shixi chip (9mm X 9mm) with a width of A1 pattern circuit, and borrow! 3: Honestly. The test plate was tested in a pressure cooker at 121 ° C, 2 atmospheres. The r η required to measure a circuit failure is 2 m. ^ Time 8) TCT (Temperature Cycle Test) reliability enables the same test plate as used in (7) to undergo a temperature cycle in the gas phase, each cycle is from -55 ° Cx 30 minutes, room temperature χ 5 minutes and 125 ° Cx 30 minutes. At the end of 100,000 cycles, a 7-way fault occurrence rate was measured (n = 10). 9) Reflow reliability The same test plate as used in (7) was set at 30 in a thermostat. 〇 and 60% RH stand for 192 hours, and then reflow oven (highest temperature

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89110252.ptd Page 28 526233 V. Description of the invention (24) Table 1 (continued) 1-16 8 rH ο ο S r «H ο < Ν ο rH ooo O 1 § cn rH 1 2Ό0” 250 CO oo M5 8 丨 Η ο 1900 ο ο CN 0.01 oooo 1 R (N, _ < 〇ψ ^ Ι 35Ό0 ”8 inch ν—Η rH 8 inch o 144 Ο 2 ο ο 8 τ» Η ο ο CN S oo 1 28.0 o 1003 〇ir-H 230 ”ο ο ro 〇o 143 8 ▼ • Η ο ο 8 ο ο» η (Ν ooi 026 o 1 so 1 '丨 丨, __ < 7Ό0 ”8 f—f BU 400 oo | 142 8 r—1 ο ο S ο ο O 3 oooi 1 〇 \ · 1—! 〇1-Ή 35 Ό0 ”ο (Μ (N ioo | 141 8 τ—1 ο ο 8 1-Η ο ο (N 〇oooo 1010 • / Ί rsj rH rH 10Ό0 ”沄 rH ioo 〇〇 2 ο ο 8 ο ο in < N < doooo 8 Os R 〇ί * · Η 110Ό0” 〇 They (N rH oo 2 ο ο 8 ο ο Ο CN oooo 〇00 O < N (N p 1Γ10 ”vq 1 oo Yemeng im L10 1 1 ΒΙΟ Μ30 YD8125 1 Epikote828 B650 Β570 ρ m Fe (inXacac) 3 Co (fflXacac), 1 fog Noodle bucket (c): Oxidation viscosity (P) Thixotropic index曲 (μπι) Flow rate (mm) PCT (hr) TCT (%) 甏 ft 1 赃 _ 翮 考 3) / \ ω LiM mi 1 I mmm \ (D) i ^ m Reliability M ΐ | Β ·

89110252.ptd Page 29 526233 V. Description of the invention (25) Table 1 (continued) 1-23 8 1— 丨 &quot; &lt; ο ο S &quot; Η ο O (N (N 〇oo! 0.13 O 1 CO &lt; N tH Ο Γ · Η 9,30 ”&lt; N 8 inch oo 1-22 8 ο ο 8 ο oooo S o 1130 Also» —ί Ο rH \ 〇r—H Γ30 ”〇CO o 'iR o | 1 -21 8 ο ο Ο 1-— »ο R o (N (noo O oo ο c &lt; t 0,15” 8 VO rn t-ι &lt; N oo 1-20 8 Yan Yi ο ο Ο Ο ο R o un (N 0.005 ooooo on tH Q tH 45, <2900 rH o wear | 149 8 ο ο 8 ο R o Os GN ooooo ί 1166 3100 12,00 ”o (N oo 148 8 — ο ο ο R ooooo &lt; N s CTs ο 1—ί or—H 11Ό0 ”〇r—ί soo | M7 ο ο 8 OO oo ΓΝ | do 〇8 ON r— &lt; or— &lt; 8,00” inch \ 〇 &lt; 5 § oo mmmm LIO ΒΙΟ Μ30 YD8125 Epikote 828 B650 B570 1 m 鸦 Fe (IIIXacac) 3 Co (III) (acac) 3 1 1 KR-TTS | | A187 j: mmsm (q: Viscosity (P) Jiao Lin Jian Qiao ίΚμίϋ) Strength _ Degree (dirty) PCT (hr) TCT (%) 1 Re-fiber 0 / 〇) 1 1 Hemp fiber lifting day (B) Acid 酣 El) Dew If fm (D) ί 1 i rn ^ KG) 丨 Reliability Department Hall (face fiber) 89110252.ptd Page 30 526233 Description of invention (26) Table 2 ο γ «Ή ο ο ο τ—Η ο m cn rH oo &lt; N 〇oooo 1180 ο rH v〇t * —! 16Ό0 ”1700 o rH or—Η ο ο 8 ο ο oooooooo 450 cn r—H 〇1-H 8,30” o CO ro vn rH o in oo可 r—Η 8 rH ο ο ο ο en ooooooo 00 (2 sr— ^ p__l p 8Ό0 ”〇, n cn ogo CO 8? &Gt; -Η ο ο 8 &lt; Ν ο Wu ooooooo 1170 s &lt; N 1— 1 p 2ΓΟΟ ”1600 cn ^ —1 8 CO oo 8 r—1 ο ο Ο 1 1—4 ο ο ro oo cs c5 oooo | 11270 99,00” 8 &gt; k 8 cn ot 8 ο ο 8 ο R ooooooo CO QQ 9,00 ”3700 o 8 ot 11 o Than the soft surface fiber L10 ΒΙΟ Μ30 YD8125 Epikote 828 B650 j B570 im FeCinXacacX Co (in) (acac) 3 1 1 KR-TTS A187 Na Weidou (c): Oxidation cleavage viscosity (P) Thixotropic shock pot life Glue-like warpage (fcum) Beach thickness (mm) PCT (lir) TCT (%) Resurface%) Cyan surface A) mmmm Acid head El) Lead S 1 paleo Catalyst (D) Even Brocade (G) 1 Reliability 1 1 1 Thief (weight i 働89110252.ptd Page 31 526233 V. Description of the invention (27) # = = Ϊ St, B, ◦, D, AE1 The epoxy resin composition of the present invention III, edition, which has the advantages of the conventional liquid sealing compound- "Production: I operation, long application, and provide cured resin with excellent humidity resistance and heat resistance. Under the conditions of 4, 4'-ethylene glycol, one ethylene glycol, one acid, and two soils, each ratite was used at a specific ratio to the total component A, the people can eclipse them, It is a solid cyanate at room temperature, while still preventing the resin composition from curing. A resin composition containing polyoxymethylene resin gel as a low-elastic component reduces the modulus of elasticity without accompanying the upward movement of particles, particles, or phase separation in the liquid phase. The resin composition containing iron (III) chelate, i μ, f ^ ^ as a curing catalyst has a &gt; IL mobility and non- ¥ small thixotropy ^ ^ Ί ^ Γ, so it is beneficial Applications where the sealing surface must be flat, such as BGA. X. The resin composition containing the intact (I I I) integrators is used as the curing catalyst for W1 and Boma. The composition of the resin is highly thixotropic, so it is beneficial to see COB encapsulation in crystal kappa. Around the daily film> There are cases where, for example, a resin composition containing a titanate coupling agent exhibits improved fluidity and low-temperature rapid curing. The two requirements of high integrity, high yield, I p M + + η in the small thickness and weight reduction of the semiconductor I sealed conductive semiconductor package sealed with the aforementioned liquid ring &lt; oxygen resin composition, and Excellent moisture and heat resistance reliability. -Li Li Xie Er seat "2-1 to 2: _3 (H Example 2 — 1 The ingredients shown in Tables 3 to 5 below are mixed in a mixer to defoam in a vacuum, to prepare a liquid ring Oxygen resin composition ...

526233 V. Description of the invention (28) Based on the physical properties and curing properties of the same square composition as in the previous examples, the liquid epoxy resin composition produced in the process is subject to the shear force, according to the following test method The measurement method uses the degree of each resin composition. The reliability of the silicon wafer on the same substrate as in the previous example and the sealed Shixi wafer with two parameters = I and the wire bonded to the printed wiring board were evaluated; the test results produced by the test method were evaluated in the same manner as in the examples. Not in Tables 3 to 5. 1 〇) Adhesive strength under shear force Using an antiquities coated on 10 X 10 square meters to-100 mm I, 10 :: area of the epoxy resin composition is drawn in the lengthwise direction to measure: broken = … The combination of the nameplate and the ΐ Ϊ Ϊ: Ϊ oxygen, lipid composition is injected into the cavity with a previously coated air mold release agent for sealing semiconductor wafer mold, maintained at 15 ° C After 15 minutes, it was removed from the mold and post-cured at 15 ° C for 3 hours.

89110252.ptd Page 33 526233 Description of the invention (29) Table 3 2-10 ο ο 8 r * -H o CNI ο O ο ο τ—Η 'τ-Η r—f R &lt; N Ο Γ45 ”230 Ον Ο r—f 8 (ο oo (N 8 τ * —i ο ο 8? -Ή o ο d ο ο οα Η 00 ι &gt; r 'Γη r- ο; F—Η Ο &lt; Ν 8 cn oo 00 (N ο ο ο ο 8 τ «—4 o ο &lt; Ί o ο ο · ~! δ 00 ΓΟ, __ 丨 _ 丨-&lt; 0,45” 8 η o CN 8 oo &lt; Ν 8 τ »Η ο ο Ο ι «Η o Ό ο &lt; N 〇ο ο R bu &lt; N _ &quot; _ _Ι 〇5,30” ο * / Ί Γ〇 卜 ο in Pl 8 tn oo 8 ο ο 8 o ο o ο ο &lt; Nf * η 卜 ί〇CN Ο r—lo rH 8,00 ”ο inch * π ο * n O oo CS 8 ο ο * door o ο (N 〇ο ο Os Μ MD rr-Ή ο r— Η; 0,20 ”ο rH BU ο 8 inch oo &lt; N ο ο ο ο Ο ra o CN ο (N 〇ο ο 2 Ον r- σ \ 8 * r &gt; ι—Η 〇: 3W, 〇 mm S Inch difference o Μ ο ο ο ο Ο o ο o ο ο ψ ^ Μ r ~ 4 4241 | 3900 Yu Guangying cn r &gt; H Γ30 ”ο: \ ο ri inch oo &lt; Ν 8 ο ο 8 f» * 4 o ο o ο ο ι—Ι r &quot; H ο · _ __ m rH r— &lt; 〇 r —J Γ30 ”((Ν 00 ο On 8 in oor—f (Ν 8 ο ο 8 y— &quot; 4 o cs ο o ο ΓΟ CO ο rH p ί- · Η Γ30” Ο ο ο »n § o 1 1 m L10 ΒΙΟ Μ30 YD8125 Epikote 828 2 ♦ 4ΗΊΓ j Polysiloxane; 臓 F)! I Fe (ni) (acac) 3!! Co (ffl) (acac) 3 1 Α187 \ mmm (Q: mm Viscosity (P) Thixotropic purpose period Application function (P · Π1) Drooping degree (mm) Viscous ship (kg / cm2) under shear force 1 PCT (hr) TCT (%) I Fiber%) 1 Μ i Dihedral Curing Catalyst (D) 1 talP: Five reliability ll $ $, 1 i

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89110252.ptd Page 36 526233 Description of the invention (32) Table 5 (N 8 O o 8 fH O o &lt; N oooo rM r— (t—-1 § 〇〇τ-1 CO rH heterogeneous sentence O bu rH oi gr * H 〇cn (N 8 y—4 oo 8 ooooo cs om F * ·· A oc properly in ON: o (N ΓΛ ....... j 0Ό5 ”oo (T) 8 CN | s ( No os appeal 8 1 ~ 1 oo 8 ........._ 1 oooo &lt; N 〇ot—H yn op 1—1 9Ό0 ”inch r- o guide τ- ·· Η g O ooi—ioooo ci ooo Ch δ VO R 〇tH τ · —Ί r—i 0,15 ”R \ 〇d 〇 8 o R &lt; N 8 rH oo 8 cn o JN o (N 〇oo CN 1536 8 rrH o τ-Ή 5,00 ”〇cn MD a &gt; ο rH 8 cn R &lt; N 8 r—4 oo 8 o CS o &lt; N 〇oo rH rH 10952 δ p 1 $ cn · rH Γ40” «ο Ch rsrsi O tn O rH &lt; N o 2 oo 8 ooooo tH so 1 · —H p Γ30 ”1200 ο 〇 8 CN 8 8 y-1 1 Comparative Example 雠 L10 BIO M30 YD8125 00 M a PJ 2 · 4ΗΤ M atatn m JBV! Su I Aldehyde A187 ″ 1 (q: mm viscosity (P) 1W surface contact adhesive? Warp (μηι) height of flow toilet (mm) 3 woven plating under shear force W2) TCT (%) again 'Dirty〇 / ) M 1 lit mmmuB) Dihedral _ shovel E2), S Curing agent (D) Even down (G) Reliability composition m &amp; mo i ^ l Load Φ Gangde q® t ί φ φ si ^ &gt; &lt; Nils 璧 璧: M / KJiif r · 锟 89110252.ptd Page 37 526233

526233 V. Description of the invention (34) It is required to be excellent in humidity resistance and heat resistance reliability. The sealing device for manufacturing a semiconductor device according to the present invention can use the liquid epoxy resin assembly of the invention. There is no need to make powdered molding materials into ingots as known to the art, nor is it necessary to melt the ingots, which greatly increases. The method of the present invention can meet the requirements of the degree of semiconductor packaging, small thickness, and weight reduction, and provide a semiconductor device with excellent reliability. It is advisable to cover Examples 3-1 to 3-2 6 and Comparative Example 3-defoaming the components shown in Tables 6 and 7 below in a mixer in a vacuum to prepare a liquid epoxy resin set to be consistent with the previous The physical properties and curing properties of the produced composition were measured in the same manner as in the examples. In addition, the reliability of the silicon wafer on the mounting and distribution substrates is hermetically sealed with each resin composition, and the silicon wafer is sealed with the previous embodiment. The obtained results show a method in which the die-casting technology of the semiconductor wafer product through injection is required to facilitate the process simplicity, high integrity, high-density moisture resistance and financial and thermal properties can be uniformly mixed into the product. Raw liquid epoxy resin. The same wires as in the previous examples were bonded to the printed wiring. They were evaluated in the same way as produced in Tables 6 and 7.

89110252.ptd Page 39 526233 V. Description of the invention (35) Table 6 ro oo 8 mmti ooo &lt; N CM 〇ο ο ο ο ο ο 00 QN bu CT) rH Ο rH 9,00 ”1 8 oo CC cn 8 rH 〇o 8 r—fo home o \ 〇cn o ο ο ο ο ο ο 1177 &lt; N Ο 13,30 ”8 * n ο ο 8 CO oo Π I 8 rH oo 8 iH o &lt; N o (N οο ο ο ο ο \ 〇1 ΓΝ) Ο r- ^ H 9Ό0 ”cs Ο r—f 8» noo CO R o oo 8 〇o (N 〇ο ο ο ο ο 00 1500 I fH ρ iH 9,30 ”Γ ~ (8 · 〇oo &lt; n CO O oooooo CN o ο ο ο ο ο ο F: o — 6,30” ι—Η 8 cn oo inch ΓΛ 8 oo; ooo 矜 d ο ο ο ο ο ο γ1 _Η Ον o rn o 15Ό0 ”〇 inch F—Η ooo rn 〇ooof—4 ooo in (N 3 ο ο ο ο ο ο ο 4275! 4000 (N TH 8,30” 8 R 8 oom 8 oo 8 tH ooo (N 〇ο ο ο ο ο ο 00 8 CTi &quot; F &quot; H or «H 8,30" § cn 8 in oo I1 · (1 ro 8 rH oo 8 rH ooo ο ο ο ο ο ο 00 m CO O rH rH rH ot—H 8,30 ”§ ο ο 1 o Shi Su Liao L10 BIO M30 YD8125 oc S 3 1 U3 B650 B570 MI atn S | 1 A 1 Μ Η 1 1 m 2 ΜΑ-ΟΚ 」1 PN-23 1 KR-TTS 1 Α187« Wf (c): Oxygen transfer viscosity (p) Thixotropic index period rubber Warping time (μιη) Evening fiber height (mm) a S 'ΰ H wmm 1 I 1 ίϋ 雠 雠 i (B); 面 El) 1 i Curing boot agent (D) G) Reliability! I Composition (SSi score)

89110252.ptd Page 40 526233 V. Description of the invention (36) Table e (continued) 348 8 ο ο 8 ο ο ο 1 o.oi 1 ο ο ο ο ο 00 8 »〇cn r— &lt; ο τ- &gt; Η 33,00 ,, | 丨 s CO r— ^ 1 o 347 〇ο ο 8 Ϊ—1 ο ο ο rn ο ο ο ο ο (η &lt; N ο 1 8 &lt; T) pH CNj 2 ΌΟ ”O r- oo CO po 3-16 8 rH ο ο 8 rH ο ο ο f— &lt; ο ο ο ο 026 ο 450 (N rH r—H τ—Η 6Ό0” 8 — 〇 \ o 8 〇o 345 8 ο ο 8 ο ο ο ο ο ο ο ο ο On rH Ο r * &quot; H 1Γ15 ”CO 00 o inch oo 3-14 8? Ο ο S r—1 ο Mouth ο ο ο CN ο ο ο ο ο I r—J r—1 〇 γ-Η 9,15 ”&lt; N p tH S oo 343 S ο ο ο rH ο ο ο g ο ο ο: ο ο ο ο CN rH 8,00” iR O rn 8 moo 342 o ο ο 8 1-Η ο: 〇ο: 〇CO ο ο ο ο ο ο 00 g rH Ο τ—Η 830 ”1 O Csj o inch oo | 341 8 ρ · Η ο ο ο ο ο ο ο ο ο ο ο ο ο ο 747, Ο ι? -Η 9,00 ”O cn Os d 8 in oo 340 2 8 ο 8 ο ο ο S ο ο ο ο ο ο 00 ON, fH ο 930” s rH r— &lt; 8 * oo Implementation number L10 ΒΙΟ Μ30 YD8125 Epikote 828 Β650 Β570 ίΙΓ Β I am ρ! X !! X: &amp; 1 Aldehyde 2ΜΑ-ΟΚ Ν-23 KR-TTS; Α187! Viscosity index (p) Thixotropic index pot life g CIXZ Warpage (μπι) Force Height (mm) &amp; Ph £ 2 Re 臓%) | Cyan Baking A) Epoxy Blessing Purpose (B) Acid 酣 Ε1) t Curing Catalyst (D) 丨 Amination 働! (Η) Qi ! KQi 1! Reliability composition (ΜΜΜΪ)

89110252.ptd Page 41 526233 V. Description of the invention (37) Table 6 (continued) 3-26 8 〇ο ο ο ο &lt; Ν ο ο ο ο CA ο 〇〇〇 (N 1-Η τ-f 1 —J t—H 3,00 ”O» door oo o I: oo 3-25 8 — 〇ο 8 r—4 ο ο «η &lt; Ν ο ο ο ο ν〇ο CO 8 (N ι—Η rH rH 4,30 ”CO ooo 3-24 8 〇ο s ο ο &lt; Ν ο ο ο ο ο Ο (Μ rH 947 210 τ-Η 〇11Ό0” 1 fH 1 oo 3-23 ο — 〇ο ΓΟ s ο ο ο ο S ο Ο ο Ο 00 8 ir &gt; cn r—f tN | 5,30 ”o tn tH 1 oo 3-22 8 〇ο 8 I ο ο ο CN Ο ο ο ο ο ο Ο oo inch§ r. t—H 8 1 oo 3-21 8 p—4 〇ο 8 ι—4 ο ο ο &lt; Ν Ο ο ο ο ο ο ο 00 8 ro r · ^ 6,30 ”rn 1 oo 3-20 8 τ—Η 〇ο 8 1 11 \ ο ο ο Ο 0.05 ο ο ο ο ο CO Ο 卜 o (N o 35,00 ”8 &lt; N bl csi I o Another 3-19 8 〇ο 〇 F—Η ο ο ο Μ ο rH ο ο ο ο ο &quot; i (N 1— &lt; Γ30 ”s τ—4 § oo nmrnm \ L10 B10 Μ30 YD8125 00 1 a Β650 Β570! Polysilicon Wish F) 1 ΐ .X 11 酹 2ΜΑ- ΟΚ ΡΝ-23 KR-TTS! Α187 Very few materials (C): Oxidation viscosity (P) Contact purpose period a S 适用 Ε ^ (μηι) ifif] Concentration (mm) I a TCT (%) Liic Cyanide A) Cyclic_Gu) Acid anhydride (E1) Cured side (D) Aminated griffon) Couple τβ agent (G) ί Reliability composition (Liping)

89110252.ptd Page 42 526233 V. Description of the invention (38) Table 7 9 cn ο ο 〇ο 8 »—ι ο ο ο ο 85.8 ο ο ο ο ο ο 1014 3500 BU r—f rH 9,00” iR 8 〇o rn 8 〇ο ο f—Η ο ο ο ο &lt; Ν Ο ο ο ο ο ο ο 1 8 inch &lt; N 〇rH 8,30 ”O rH rH S oom 8 τ ~ Η 〇ο η ο ο ο 00 Η &lt; Ν Ο ο ο ο ο ο ο ο cs t—4 pr—H 5Ό0 ”8 ooo ro cA 8 rH 〇ο 8 &lt; Ν ο ο ο &lt; Ν ο ο ο ο ο ο 1ο 8 t—H or—t 2Γ00 ”1000 in 400 | R PAN (Τ) Ο 〇ο 8 rH ο ο ο ο ο ο ο ο ο ο 11025 Hitomi r—i 8,30” S o CO oo τ-Η cf ) 8 Strictly 〇ο 8 rH ο ο ο Ο ο ο ο ο ο ο! S rH rH o rH 8,30 ”2000 \ D 〇8 &lt; N o yn 8 Dirty L10 B10 Μ30 YD8125 00 α ω Β650 Β570 i ί X Mo V with ο 9 υ 1 1 Pain 2ΜΑ-ΟΚ PN-23 KR-TTS Α187 (c): Viscosity made of oxygen (P) Number of difficulties during application period Warpage of gelation time (μπι) a. fi S shock S 'g Oh TCT (%) reflow (%) cyanogen A) mmmwB) § 1 Xin if Jian 1 coupling agent (G). Reliability composition ( Note: 89110252.ptd Page 43 526233 Description of the invention (39) The epoxy resin of the present invention containing ingredients A, B, C, D, and F is a liquid at room temperature, and it has a conventional liquid sealing compound. It has low viscosity, easy operation, and long pot life, and provides a resin that has no elasticity-without accompanying coacervation or upward movement of particles or in the liquid. In the case of using 4, 4'-ethylenediphenylcyanate for the total component A, it can be used in combination with other solids at room temperature while still preventing the resin composition. Curing. &lt; Θ said &apos; &gt; A resin composition containing an iron (III) chelate as a curing catalyst exhibits high fluidity and very little thixotropy ', and thus it is advantageous for dense, frank applications such as BGA. The resin group containing cobalt (III) chelate as a curing catalyst has high thixotropy, so it is favorable for no COB encapsulation around the wafer. 1 豕 疋 The composition exhibits reduced and low temperature appearance. When the resin composition contains a liquid acid needle, the thixotropy exhibits improved fluidity in sealing and rapid curing. The composition exhibits the inverse of epoxy resin. In the case where the resin composition contains a titanate coupling agent, improved fluidity and fast curing properties at low temperatures. In the case where the resin composition contains an amine-based compound, it should be accelerated and have improved curing reactivity. The semiconductor device can meet the requirements of thickness and weight reduction. It must be sealed with the aforementioned liquid epoxy resin composition. High integrity, high density, and small requirements of the conductor package, and excellent reliability in humidity resistance and heat resistance.

526233

89110252.ptd page 45 526233 Schematic description 89110252.ptd page 46

Claims (1)

526233 ε. 2 9 Correction Dragon_Case No. 89110252 χ2 Month_Six, Shen ¥¥ Li ~ Qianwei 1 · A liquid epoxy resin composition for sealing semiconductor devices, which includes (A) chaotic acid ester (B) epoxy resin, (c) inorganic filler, (D) metal chelate and / or metal salt, and (E1) acid anhydride, wherein at least one of the component and 6 is liquid at temperature, the component is E 丨 is liquid at room temperature. The weight ratio of component C to the total weight of the component is 0 6 0 to 0 9 5. The weight ratio of component A to component B is 0 · 7 6 to 1 · 4 3. And the weight ratio of the component E to the total weight of the composition other than the component c is from 0.01 to 0.3. 2. The liquid epoxy resin composition according to item 1 of the patent application scope, wherein the component A includes (Al) 4, 4, -ethylenediphenylcyanate, and the weight ratio of A1 / A is 0.1. To 1. 3. The liquid epoxy resin composition according to claim 1 of the patent scope, which further includes (F) a polysiloxane resin gel, wherein the weight ratio of the component ρ to the total weight of the composition other than the component is less than 0. . 3. 4. If the liquid epoxy resin composition according to item 3 of the patent application scope, wherein the component D includes (D1) iron (I II) chelate or (D2) cobalt (ΙΠ) integration, please, the component D1 or D2 pairs The weight ratio of the component A is from 0.001 to 0.001. 5. If the liquid epoxy resin composition according to item 1 of the patent application scope further includes (G1) a titanate coupling agent, wherein the weight ratio of the component G1 to the total weight of the composition other than the component c is 0.0 0 1 to 0.1. 6. The liquid epoxy resin composition according to item 1 of the application, wherein the liquid bad emulsion resin composition can be used for sealing semiconductor devices. 7. A liquid epoxy resin composition for sealing semiconductor devices, which includes (A) cyanoacetate, (B) epoxy resin, (C) inorganic filler, (D) metal complex and / or metal salt , And (E2) a dihydrazine compound, of which A and 6 mi II 89110252.ptc Page 47 526233 At least one of them is liquid at room temperature, the weight ratio of component c to the total weight of the composition is 0.60 to 0.95, the weight ratio of component a to component B is 0.50 to 1.8, and component E2 is divided by The weight ratio of the total weight of the composition other than the component c is 0.01 to 0.15. 8. The liquid epoxy resin composition according to item 7 of the patent application scope, wherein the component A includes (A1) 4,4'-ethylenediphenylcyanate, and the weight ratio of m / a is 0. 1 to 1. 9. The liquid epoxy resin composition according to item 7 of the application, wherein the average particle size of the dihydrazine compound is less than or equal to 1000 microns. ) 1. The liquid epoxy resin composition according to item 7 of the scope of the patent application, in which the mysterious E2 includes 2,4-dihydrazino-6-fluorenylamino-symmetric-tri-11. 1 1 · The liquid epoxy resin composition according to item 7 of the patent claim, which further includes (F) a polysiloxane resin gel, wherein the weight ratio of component F to the total weight of the composition other than component c is Less than 0.3. 1 2 · The liquid epoxy resin composition according to item 丨 丨 in the application scope, wherein the component D includes (D1) iron (in) chelate or (D2) lead (hi) chelate 'component D1 or D2 The weight ratio to component a is ooooi to q. 〇1. 1 3. If the liquid epoxy resin composition of item 7 of the scope of the patent application, further includes (G2) epoxy silane coupling agent, wherein the weight ratio of component G2 to the total weight of the composition other than component c is 0. 〇〇 丨 至 0.1. 14 · The liquid epoxy resin composition according to item 7 of the patent application, wherein the liquid epoxy resin composition can be used for sealing semiconductor devices. 15. A method for sealing a semiconductor device, which comprises injecting a liquid epoxy resin composition such as the item 7 in the scope of the patent application using a molding die. 89H0252.ptc Page 48 526233 ___ 89110252-_ Month and month _ Amendment _ 6. Scope of patent application 16 · A liquid epoxy resin composition for sealing semiconductor devices, which includes (A) cyanate ester, (β) epoxy resin, (C ) Inorganic filler, (0) gold eyebrow chelate and / or metal salt, and (F) polysiloxane resin gel, wherein at least one of components A and B is liquid at room temperature, and component A versus component β The weight ratio is 0 · 76 to 1. 4 3, the weight ratio of wound C to the total weight of the composition is 0 06 to 0 · 95, and the total weight of component F to the composition other than component C The weight ratio is higher than 0.01 and lower than 0.3. 1 · 7. The liquid epoxy resin composition according to item 16 of the application, wherein the component A includes (Al) 4,4-ethylenediphenylcyanate, and the weight ratio of αι / α is 0. 1 to 1. 1 8 · The liquid epoxy resin composition according to item 16 of the patent application scope, wherein the component D includes (D1) iron (III) chelate or (1) 2) cobalt (1 丨 丨) meal compound The weight ratio of the component D1 or D2 to the component A is from 0.00001 to 0.0001. 1 9 · If the liquid epoxy resin composition according to item 16 of the patent claim, including (E1) liquid acid anhydride, the weight ratio of the ingredients to the total weight of the composition other than the component c is 0.01. To 0.3. 20. If the liquid epoxy resin composition according to item 16 of the patent application scope, the basin further includes (G1) a titanate coupling agent, wherein the weight ratio of the component G1 to the total weight of the component c = 0 is 0. 0 0 1 to 0 · 1. '、, 乂 1.2 The liquid epoxy resin composition in the 16th scope of the patent application, basin = 2 amine compounds, in which the weight ratio of component Η to component B is 0.001. For example, the 16th in the claim range The liquid epoxy resin composition of the item, the liquid resin composition can be used for sealing semiconductor devices. Eight