TWI323275B - Adhesive composition and adhesive sheet for semiconductor device - Google Patents

Description

• Nine, invention description: , [Technical field of invention belongs to j · , Pack = 7:: Guide: Adhesive composition and semi-conductor for the device are applicable to various semi-conductive semiconductors used in semiconductors. For n-pieces of a laminated IC wafer suitable for a busy substrate having a s IC ^ circuit, a substrate, a surface mount fixed semiconductor device, a build-up substrate, etc. On the 1c day, the film is adhered to or higher than the heat-dissipating 3 〃, ic substrate, in particular, the ic chip and the circuit substrate, the circuit board, the higher density layer of the insulating layer, the circuit forming FPC (flexible Adhesive composition and adhesive sheet for adhesion between printed circuit and board, FPC and circuit board, circuit board and protective film, π wafer and board, board, heat sink and circuit board. [Prior Art] · At present, electronic devices such as mobile phones and notebook PCs are becoming smaller, lighter, faster, and more highly functional. Their IC chips tend to be high-density and high-speed. The assembly technology is also based on QFp. (Quad nat buckles, in order to set the wire on the side of the seal 4), and developed into a new assembly form such as BGA (BaU (10) eight), CSP (Chip Scale package), McP (Multi CMp package). Even in the case of a substrate on which a semiconductor such as an IC chip is mounted, the lead frame must be adjusted to form a tape circuit substrate or a printed circuit board having a finer and more dense structure. This function is particularly applicable to the wiring layer 317818 5 1323275 . It is more important to add layers to the substrate. - These substrates are generally provided with wiring on the support and an insulating layer that is electrically connected to the wiring. The insulation layer is important to be electrically insulated, but Various other characteristics are required. In the manufacturing method for manufacturing a substrate, the method is a support for forming a wiring circuit on the surface of the surface, and an adhesive sheet having an adhesive layer having a main component of an uncured adhesive. Bonding to the wiring and the adhesive layer, the adhesive layer is buried between the wirings, and the adhesive layer is hardened by heating, etc. The adhesive layer of the hardened layer has the function of an insulating layer. In the case of medium foaming or voids remaining in the wiring, the insulation property is deteriorated. Therefore, when the wiring layer is buried in the wiring, it is required to have no foaming or no production in the wiring, and the voids are buried in the wiring compartment. The characteristics of the 疋 wiring, which is important in the embedding characteristics, are micronized and high in density. It can be used as an adhesive in the above adhesive layer, such as polyimide resin, epoxy resin, resin, benzene. A thermosetting resin such as a diene-containing copolymer such as a butadiene resin or a styrene-containing copolymer, which has a heat resistance and a heat-resistant temperature cycle, and which corresponds to For example, in the ic package, the temperature of the IC is higher than 100C due to the heat generated by the IC during the ic package. The 1C package is exposed to room temperature to high temperature (1〇〇t&gt ; c or more) temperature change Accordingly in the IC package, which is required to be of high-temperature heat resistance, heat corresponding to the temperature cycle of temperature changes. On the other hand, the metal or the like wiring, the wiring formed building body of the support, must 317818

A 6 1 f edge layer 荨 thermal expansion rate or nMt will be due to phase bonding. When the above-mentioned high temperature is chained, the stress caused by the difference of /sa ... expansion leather is different. Stress (four). In recent years, the proportion of density due to (4) has increased greatly, and its stress: In addition, when stacking substrates with laminated wiring,

The insulating layer of the layer, the light (4) (four) heating reading system depends on the number of (4) sheets, and the heat resistance is required at this time. Therefore, the conventional adhesives as described above do not sufficiently satisfy these characteristics. Specifically, when the adhesive layer is poor in fluidity, for example, when the adhesive layer is buried in the high-density wiring, significant air bubbles are mixed. Therefore, it is necessary to increase the fluidity and lower the viscosity of the adhesive layer. However, when the above-mentioned bonding, the adhesive layer is excessively bleed out, and the workability is deteriorated. On the other hand, after the semiconductor device of the 1C wafer or the like is fabricated, the stress generated under the gradual change of the temperature from Φ to room temperature to a high temperature (above 10 ° C) is applied to the insulating layer and the 1C wafer. Inter-layer peeling or substrate warpage originating from the insulating layer may occur in the inside of the substrate. Such problems are particularly remarkable in a laminated substrate such as a build-up substrate in which a plurality of sound lines and an insulating layer are laminated. Interlayer peeling and substrate Warpage will reduce the electrical stability of the semiconductor device, so it needs to be improved. At the same time, 'in the above-mentioned multi-layer high-density assembly method, the substrate is thin to achieve the purpose of using a layer of adhesive on the insulating film through the adhesive layer. TAB (Tape Automated Bonding; with automatic 7 317818 1323275 ' _ ), such as a metal foil substrate (FPC), etc., in which the insulating film is usually a resin film such as poly-imine resin. Until now, these adhesives have problems such as insufficient adhesion between the insulating film and the metal layer, and subsequent changes in temperature, etc., which tend to cause a decrease in adhesion, and the like. The imide film is extremely difficult to bond. - In the bonding force, the state of the interface of the support has a great influence, and the moisture absorption of the adhesive also has an influence, for example, the lower the hygroscopicity, the more inclined In order to suppress the change of adhesion, it is necessary to have a low hygroscopic adhesive. In recent years, the use of lead has been avoided, thereby increasing the temperature of the IR return rod (secret (4) (4) (10) (10). Therefore, the moisture contained in the adhesive layer is Gas during reflow

Therefore, it is easy to form the expansion due to the adhesive agent of the house (void phenomenon. / / I Therefore, in order to eliminate the moisture-iZp of the factor of the granulation phenomenon, 卜 ^. The semi-product control tube before reflow is in the moisture proof Under the condition: The management under the moisture-proof state requires a large amount of work and cost, and it is necessary to suppress the granulation phenomenon occurring during reflow, and it is excellent in the reflow-resistant squeezing of the adhesive composition. In the material of the material, the electrical stability of the edge can be important, but it is directly under the temperature, or the sensation of the sensation is reduced for a long time, and the gamma is easy to produce. Fanny is # (Galvanic effect) and so on. Therefore, 'in response to these needs, from the xt丄 彳 彳 申 申 申 申 申 申 申 申 使用 使用 使用 使用 使用 使用 使用 使用 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 - Adhesive agent of a stupid (four)-stage copolymer, NZ 317818 8 丄JZJZ/:). [Patent Document 1] Japanese Patent Laid-Open Publication No. 2002-241728 (Summary of the Invention) Since the adhesive composition of the past has various excellent properties Characteristics, but an insulating film such as the above-mentioned polyimine film or a metal layer such as a copper junction Insufficient adhesion. Further, in the case where the temperature is changed repeatedly or heated for a long period of time, the deterioration of characteristics such as adhesion and the like, and the insufficient thermal deterioration property occur. If the heat deterioration resistance is insufficient, the insulation properties are also lowered. The present invention has been made in view of the above circumstances, and an object thereof is to provide an adhesive composition for a semiconductor device and an adhesive sheet for a semiconductor device which are excellent in various adhesive properties and heat deterioration resistance. • Another object of the present invention is to use a new assembled form such as BGA (ball grid _y, ball grid array), CSP (chip scale package), CM (multi chip module), and the like. In the semiconductor device, the conventional adhesive has a problem of peeling between the edge layer and the adhesive layer and between the IC wafer and the adhesive layer due to repeated changes in temperature. Therefore, the disadvantages of (4) and poor embedding can be solved. In other words, an adhesive composition for a semiconductor device and an adhesive for a semiconductor having excellent electrical stress stability and excellent thermal cycle resistance, and excellent adhesion between copper and a polyimide film are provided. sheet. Further, the present invention provides an adhesive composition for a semiconductor device and an adhesive sheet for a semiconductor device, which can improve the problem existing in the conventional adhesive, that is, gasification occurs at the time of reflow by the moisture content of the adhesive, and Excellent humidity resistance. 317818 9 1323275, in order to solve the above problems, the present invention provides a first-semiconductor device. The adhesive composition is characterized in that it contains an epoxy resin (4), a resin (8), and contains ethylene and has an The epoxy resin (4) reacts with the official base and (4) or the biological material of the material, the silk material (〇, and the hardened value of the measured dynamic point elasticity φ ρ ping Γ T of the lowest melt viscosity of 400 to 50000 In the range of s, the above-mentioned adhesive composition for a semiconductor device is preferable. The above-mentioned adhesive composition for a semiconductor device preferably has an elongation ratio after curing of 30% or more. With the adhesive composition, the moisture absorption rate after hardening is preferably 1% or less. The above-mentioned adhesive composition for a semiconductor device is hardened and left in an environment of 15 Torr for 24 hours, at: (8) to 28 The dynamic viscoelasticity of the underarm is preferably in the range of 5 〇〇pa to 5 MPa. The above-mentioned adhesive composition for a semiconductor device, the content of the aforementioned ethylene-based copolymer (C) 20 to 8 〇 mass% of the total solid amount In the above-mentioned adhesive composition for a semiconductor device, the functional group equivalent of the ethylene-based copolymer (C) is preferably from 100 to 2,500. In order to solve the above problems, the present invention further provides a second semiconductor device for adhesion. a composition comprising an epoxy resin (A), a phenol resin (B), and an unsaturated group containing ethylene and having a functional group reactive with the epoxy resin (a) or an epoxy hardener The ethylene-based phalloids 10 317818 V ^ J323275 (c') and the siloxane compound (D) of the acid-lowering derivative. The above-mentioned adhesive composition for a semiconductor device, the content of the polymer (C,) is the total solid form The amount of 2G to 8. The mass ^, '[A total of the above-mentioned adhesive composition for a semiconductor device, the complex: the content of the unsaturated carboxylic acid derivative in the good polymer (C) is described as a total of ethylene In the above-mentioned adhesive composition for a semiconductor device, the functional group equivalent weight of the polymer (c,) is preferably from 100 to 2,5 Å, and the above-mentioned semiconductor device adhesive is used. In the composition, the ratio of (4) to the former (four) resin (B) It is preferred that the company is in the range of epoxy resin 。. "Ribi 1:6 to 1: The above-mentioned adhesive composition for a semiconductor device, the above-mentioned gas igniting::=. As in the formula (1) or The end of the formula (7) contains an amine group

ψ CHs Μ-ft丨-Si--0CHa ck CHe03⁄4 (1)

(2)

Cf3 M 〒 H2N-R4) i—0 visit Ning—.巧—βϊ~ΝΗβ Q) CH3 to the appearance base, m and η represent 0 (wherein R represents an integer number of carbon atoms to 10) 317818 11 The composition of the composition is used to form a carrier composition Oxygen is burned, 3 is set to ~, and the solid amount is preferably 0.05 to 10% by mass. In order to solve the above problems, the present invention provides a first half 2 sheet: it is characterized in that at least on the surface of the support body, the adhesive layer is formed by the adhesive composition of the GU-semiconductor device. Further, the second semiconductor package " /, is characterized in that, on at least one side of the metal layer, the layer is sequentially applied to the layer by the first 戎坌_main sequence product + body device with the viscous (four) composition. - the J layer, and the insulating film or peeling film. In the present invention, in order to solve the above problems, a first type of adhesive sheet is provided, and the two sides of the first film of the above-mentioned first edge are laminated on the two sides of the film, and the two layers are formed by the composition of the (four) agent. Layer and insulating film or peeling film. The adhesive composition and the adhesive sheet which can be provided by the present invention have various excellent properties such as fT, heat resistance, heat-resistant temperature cycle property, stress relaxation property, electrical=sexuality, resistance to repellency, and the like, and low hygroscopicity. It has excellent adhesion and heat deterioration resistance. The present invention also provides an excellent adhesive relaxation property, a good economy, a cyclical property, an electrical stability, and an excellent adhesion between copper and a polyimide film. Therefore, the adhesive composition and the adhesive sheet according to the present invention can be exemplified by the fact that the layer and the interlayer peeling and the π defect are caused by the change in temperature. Therefore, as in the adhesive composition according to the invention 317818 12

IJ, the object and the adhesive sheet can improve the stability of the semiconductor farm. In addition, due to its moisture resistance, the moisture contained therein is vaporized during reflow, thereby improving the reflow resistance as in the adhesive. Therefore, it is possible to reduce the management and the cost of doing it. U +1. Moisture-proof state of the mouth:: The present invention provides an adhesive sheet which can be used industrially, and which has electrical characteristics and adhesive strength and is excellent in resistance to PCT 16, resistance to back, and workability.干鲁_[Embodiment] The present invention will be described in detail below. <Adhesive Composition for First Semiconductor Device> •, Ben? The first adhesive composition for a semiconductor device (hereinafter also referred to as a "adhesive composition") is a thermosetting adhesive composition which contains as an essential component: an epoxy resin (4) (hereinafter referred to as (4) Component), a phenol resin (B) (hereinafter referred to as component (B)), and an ethylene-based copolymer (c) containing at least two specific monomer components (hereinafter referred to as component (c)). In the adhesive composition of the first semiconductor device of the present invention, the movement of the crucible before hardening is performed, and the lowest melt viscosity in the viscoelasticity must be

When the lowest melt viscosity of the dynamic viscoelasticity measured before the hardening of Pa · s is above 4 〇〇pa · s, the resin flow during processing is small, and when it is below 5 〇, 〇〇〇Pa · s, the wiring Easy to bury, so it is not easily affected by the unevenness of the bonding surface. That is, when the minimum melt viscosity is in the range of 400 to 50,000 Pa·s, the wiring of the adhesive composition of the invention of the present invention, especially the high-density wiring, is excellent in embedding. And extremely easy to process. The minimum melt viscosity can be adjusted by adjusting the types (A), (B), and (C) components and the blending amount. For example, the minimum melt viscosity can be adjusted by, for example, adjusting the amount of the component (C) in the conditioning composition as described later in the range of 20 to 80% by mass of the total solid content. In the present invention, the lowest melt viscosity measured by the dynamic viscoelasticity before hardening can be determined by the following conditions to determine the lowest viscosity of the viscosity change. ··[Conditions for measuring the lowest melt viscosity] • Device: Shear modulus measuring device (Rheo Stress RS75 (product name) manufactured by HAAKE)

• Measurement temperature range: -10 ° C - 300 ° C • Temperature increase rate: 3 ° C / min • Measurement frequency: 1 Hz • Load: 15 N Distortion: 0.01% ± 0.0025% Adhesive composition of the present invention The dynamic viscoelasticity at 200 ° C to 280 ° C after hardening is preferably in the range of 500 Pa to 200 MPa, more preferably in the range of IMPa to 100 MPa. That is, the adhesive sheet of the adhesive layer can be formed on the support by using the first adhesive composition of the present invention, and after being bonded (temporarily bonded) to the adhered body, heating is performed to harden the adhesive composition. Adhered to the adherent body. Therefore, when the hardened first adhesive composition is placed on the main substrate such as a BGA or a laminated substrate via a solder ball (step of soldering) 14 317818 1323275, 'heating 2 Ο 0 to 2 0 0 °C. Therefore, if the dynamic viscoelasticity at 2 Ο 0 to 280 °C after hardening is in the range of 500 Pa to 200 MPa, voids are suppressed at the reflow step, and the reflow resistance is improved. Its stress relaxation is also improved. The dynamic viscoelasticity is an adhesive sheet on the release film which is made of the first adhesive composition and has a thickness of ΙΟΟμπι after curing, and the peeling film is removed after the adhesive composition is hardened. Rheovibron DDV-II manufactured by 〇rientech Co., measured at a frequency ΐΗζ, a heating rate of °3 ° C / min. The first adhesive composition of the present invention generates voids in the reflow step or the like, and since the main cause of the granulation phenomenon is moisture, the moisture absorption rate after hardening is 1 in order to improve the reflow resistance. % below is better. The lower limit of the moisture absorption rate is not particularly limited, and the smaller the moisture absorption rate, the more excellent the above effect is. The moisture absorption rate described above can be adjusted by adjusting the types of components (A), (B), (C), and the amount of 5 weeks. For example, as will be described later, the (C) sizing amount of the knives in the composition is adjusted to 2 〇 to the mass of the total solid content. In the range of 乂, the ratio of (4) component to (8) component is adjusted to be in the range of 1:0.6 to 1: M, and the moisture absorption rate can be adjusted. The first adhesive composition of the present invention preferably has a stretching ratio of 3% by weight after hardening: when the iMt ratio is 3 (%) or more, the stress relaxation property is increased, # Μ Μ, occupies: different materials In this case, it is possible to alleviate the difference in the expansion between the high temperature and the temperature change, and to suppress the surface curvature and the interlayer peeling caused by the difference in thermal expansion.

317818 15 1323275 • The above-mentioned elongation ratio can be adjusted by adjusting the components (A), (B), (C), and the amount of blending. For example, as described later, by adjusting the amount of the component (C) in the composition to be within the range of 20 to 80% by mass of the total solid content, the ratio of the component (A) to the component (B) is adjusted to be the functional group equivalent ratio. In the range of 1:0.6 to 1:1.4, the ratio of the unsaturated carboxylic acid or its derivative in the cerium component is in the range of 0.1 to 40% by mass, and the functional group equivalent in the adjusting component is 1 Torr to The elongation ratio can be adjusted within the range of 2,5, etc. The first adhesive composition of the invention of Lulu is placed in an environment of 150 ° C for 24 hours after hardening, 200. (: The dynamic viscoelasticity to 28CTC is preferably in the range of 500pa to 5〇〇MPa, and more preferably in the range of 3MPa to 2〇〇MPa. For example, when the substrate is formed by the build-up method, because In this case, a plurality of layers of the adhesive layer are provided, and in order to harden the adhesive, it is necessary to apply the same number of layers as the number of layers of the number of layers to be exposed to the hardening temperature. Therefore, the heat deterioration resistance of the repeated exposure to the hardening temperature becomes extremely important. Therefore, even after hardening, it is placed after 24 hours of accelerated test, and it is 2 〇〇. (:: to 28〇. When the viscoelasticity of the 〇 is still in the range of 5〇〇pa to 5〇〇MPa, the heat deterioration resistance is excellent. The measurement of the turbulent viscoelasticity here is adhesive. After the composition of the agent is hardened, the dynamic viscoelasticity can be measured at 200 C to 280 ° C as described above, except that it is left in an environment of 150 ° for 24 hours. The rate can be adjusted by adjusting the type of the component (A), the component (B), the component (c), and the amount of the compound. For example, as described later, the component (c) of the composition 16 317818 ^ ^ 1323275 is adjusted. The functional group equivalent weight can be adjusted within the range of 100 to 2,5 。, and the dynamic viscoelasticity can be adjusted. ' 纟Inventive sputum group secret' and hardened with polyimide film (trade name: UPilex5〇S, The adhesion between Japan's Ube Industries Co., Ltd. is 1叩. It is preferably 45N/ema when it is peeled off, and after it is hardened, it is placed in an environment of 121. 〇 and humidity 100% for 3 hours. The adhesion between the above and the polyimide film is 18 〇. When the direction is peeled off, it is better to use the shoulder (10) or more. This can improve the stress relaxation. , heat-resistant temperature cycle, adhesion force, etc., can also reduce its hygroscopicity. Therefore, it can improve its physical impact, especially the physical impact of the reflow step, and can also improve the manufacturing Resistance to voids generated by moisture or the like during production of a substrate such as a BGA or a laminated substrate. The composition of the first adhesive composition of the present invention is further described in detail. νIn the adhesive composition of the present invention, When the component is heated, it reacts with (φ) into #φ分 and/or (C) component to form a 3: undone network structure. The effect of the present invention can be obtained by combining the above components with the lowest melt viscosity. (4) The composition and the W component are particularly useful for heat-resistant temperature cycling, electrical stability, adhesion between copper and a polyimide film, and reflow resistance. Further, the component (C) is particularly effective for stress relaxation, heat cycle resistance, electrical stability, adhesion between steel and a polyimide film, and durability.

[(A) Component J% oxygen resin is a resin containing two or more epoxy groups in its molecule. 317818 17 (VIII) Ingredients such as glycidol, glycosylamine, linear aliphatic epoxide, triglyceride, can be used. These can be used alone... Two oxyacids can be used alone or in combination of two or more. Specifically, for example, bisphenol A type epoxy furnace, de bisphenol 8 punishment ^ (10) tree bismuth bisphenol F type epoxy resin, discriminating S type soil oxygen resin, naphthalene type ring shrinking sweet taste - thinking ^ functional epoxy Resin, triglycerin diiso-sodium acrylate type epoxy resin, three-ring type ringing fl匕, 'from base-amino-r-fluorene, oleyl-diaminodiphenyl-r-type epoxy tree

Luna, tetraglycidyl-m-xylylenediamine-type eucalyptus, its jasper, milkwood, quaternary glutinous, quaternary glycoside, aminomethylcyclohexene-fired epoxy tree, etc. Oxygen resin 'tetraphenyl glycidol test ethyl bromide type epoxy resin = 2 glycerin 趟 趟 型 type epoxy resin and other polyglycoglycan bond type epoxy 1 曰 'age type lytic resin, burning base ring Multifunctional soluble phenolic epoxy resin such as oxygen resin, cyclopentene type linoleum 孓 孓%, latex resin, bisphenol epoxy resin, epoxy resin, and epoxy resin The secret epoxy resin is used for the paint. Lulu/, medium-aged epoxy resins are suitable for use in the present invention because of their low cost. The oxime oxime oxygen resin is excellent in both insulation and heat resistance and is also suitable for use in the present invention. Specific examples of the component (A) which is suitable for use in the present invention include bisphenol type which is commercially available under the trade name of eU ΕροχΥ co.: epik〇te 806, 828 834, 1001, and the like. , trade name: γχ_4000, γχ_4000ϋ, etc. Bi-phenol type epoxy resin, etc., manufactured by Petrochemical Shell Ep0Xy Co. Trade name: Epicot 152, 154, 180S65, 1032 H60, 157S70, etc. Phenolic type, trade name: 6〇4, etc. Four shrinkage..·3178^8^ 18 1323275 Glyceryl diphenyl decane type, trade name: HP-7200, HP-7200H, etc. Functional epoxy resin, manufactured by Nippon Chemical Co., Ltd. • Product name: phenolic type of o-nonphenol paint for EOCN102S, 103S, 104S, 1020, etc., trade name: triphenyl decane type such as EPPN501H, 502H, etc. Epoxy resin, etc. The halogenated epoxy resin in the component (A), particularly when a brominated epoxy resin is used, is effective in making the adhesive composition flame retardant, and therefore is preferable. Specific examples of the brominated epoxy resin include those manufactured by Petrochemical Shell Epoxy Co., Ltd., and the product name: BREN, which is manufactured by Sakamoto Chemical Co., Ltd., and is sold under the trade name: EPIKOTE (trademark) 5045, 5046, 5050. -S, BREN-105, BREN-301, etc. Even if a halogenated epoxy resin is substituted for a halogenated epoxy resin, etc., there will be no problem. The component (A) is preferably an epoxy equivalent (equivalent to a molecular weight per one epoxy group) of from 100 to 4,000, more preferably from 100 to 2,000, particularly preferably from 100 to 1,000. If the epoxy equivalent is 100 or more, if it is hardened, it is difficult to leave the component (A) which is not changed, so that bubbles are less likely to be generated. When the epoxy equivalent is 4,000 or less, it is easily dissolved in a solvent and has good compatibility with other resins. The content of the component (A) in the first adhesive composition of the present invention is preferably from 3 to 45% by mass based on the total solid content of the adhesive composition, more preferably from 5 to 25% by mass. [Component (B)] The phenol resin is a resin obtained by addition and condensation of a phenol and an aldehyde. (B) Specific examples of the component include a novolak type phenol resin, a phenolic resin phenol resin, a phenol resin for phenol paint, a phenol resin such as a bisphenol resin, and a xylene resin, etc. 19 317818, &gt; Among them, the phenol resin for phenol paint has good reactivity, and it is excellent in moisture resistance and heat resistance in the use of a semiconductor device. The component (B) preferably has a hydroxyl group equivalent (molecular weight per one hydroxyl group) of from 5 Å to 4,000, preferably from 1 Å to 2, more preferably 〇 00, and particularly preferably from 1 〇〇〇 to 1 。. If the basis weight is 50 or more, the adhesive is less likely to become brittle after curing, and if it is 4 or less, it is easily dissolved in an organic solvent and is therefore suitable for production. In the first adhesive composition of the present invention, the content of the component (B) is preferably from 2 to 30% by mass based on the total solid content of the adhesive composition, and more preferably from 5 to 25 % by mass. In the first adhesive composition of the present invention, the ratio of the component (A) to the component is preferably in the range of the functional group equivalent ratio of from 1:0.6 to 1:1.4, and ι: ' 〇 [7 to 1. I.1 Better in the range. That is, when the component (A) is 1 and the content of the component (B) is 〇.6 or more, the adhesive composition after curing is less likely to become brittle, so that it has better strength and better stress relaxation property. (4) When the content of the component (1) is 1 or less and the content of the component (B) is 1 or less, deterioration of the adhesive strength can be suppressed, and the adhesion of the adhesive force can be suppressed after exposure to a high temperature. When the ratio of the component (A) to the component (B) is within the above range, the elongation of the adhesive composition after curing can be improved. After hardening and then placed in the environment of i5 (rc) for 24 hours, the dynamic rate of 200 to 28 亦 is also suitable for use on a semiconductor device. Medium, (A) component and (B) component The functional group equivalent ratio is a ratio of the number of the mercapto group (the functional group of the component (A)) in the component (A) to the number of the functional group of the hydroxyl component in the component (B). [(C) component] 20 317818, ', for example, 275 - (c) component contains an unsaturated carboxylic acid containing at least a functional group of a compound which can react with the component (A) as a monomer component or A vinyl-based copolymer of a derivative (hereinafter also referred to simply as an unsaturated carboxylic acid or a derivative thereof). By containing the component (C), the first adhesive composition of the present invention can be made flexible, thereby improving the stress relaxation property. At the same time, it can also improve its moisture resistance. Further, as described above, the combination of the component (A) and the component (B) improves the cycle resistance, electrical stability, and adhesion between copper and a polyimide film. The "monomer component" herein refers to a compound which forms a repeating unit of the polymer when it is polymerized by polymerization to form a polymer. For example, a polymerization system in which the monomer component is ethylene contains a repeating unit represented by the formula [CH2_ _] by a double bond break. - The total amount of ethylene and unsaturated carboxylic acid or a derivative thereof in the component (C) is preferably 40 to 98% by mass based on the total monomer component. The proportion of ethylene in the component (c) is preferably 4% by mass or more based on the total monomer component, more preferably 50 to 98% by mass. • An example of a functional group contained in the above-mentioned (4) component which is contained in the saturated (d) or its derivative may be an amine group, an iso- 1 vine group, a glycidyl group, a thiol group (including an acid anhydride group thereof), and a stone. An alcoholic group, a thiol group, a methyl group, a methyl group, a thiol group, a brewing group, and the like. Among them, an amine group, a carboxyl group, a glycidyl group, and a diyl group have high reactivity, and therefore are preferred. Specific examples of the functional group, such as glycidyl group and ": such unsaturated group (tetra) acid or a material thereof, may be exemplified by acrylic acid, methyl acrylic acid, cis-butyl sulphate, and sulphuric acid. Examples of acrylonitrile-containing cigarettes. Examples of glycidyl-containing groups 317818 21 1323275 dilute acid glycidol vinegar, methyl acrylate cold glycidol, etc., containing a base such as acrylic acid, methyl acetonate, methyl propyl acid Acrylic acid, ethyl acetoacetate, hydroxyethyl methacrylate, etc. (c) The proportion of unsaturated acid or its derivative in the knives is from 0.1 to 40% by mass of the total monomer component is preferably '0.8 to 2 〇 mass% Better.

When the ratio of unsaturated (d) or its derivative in the component (c) is qi mass% or more, the reactivity with the component (4) can be improved, and the elongation after hardening and the adhesion to the substrate after hardening can be improved. force. The solubility in organic solvents can also be improved and is therefore suitable as a coating. When the ratio is 4 (% by mass or less), the stability in the coating state is good. The component (C) may contain, in addition to the monomer components of ethylene and an unsaturated carboxylic acid or a derivative thereof, under the conditions of non-destructiveness and the scope of the present invention. Other monomers may be copolymerized with the above-mentioned ethyl hydrazine and an unsaturated acid or a derivative thereof, for example, methyl acetoacetate, ethyl acetoacetate, methyl i-propyl acrylate, A mercapto or aryl ester of (meth)acrylic acid such as ethyl acetoacetate or a vinyl acetate. The content of the monomer (C) is preferably 40% by mass or less based on the total monomer component, more preferably 3% by mass or less. In the component (C) of the present invention, the monomer component is particularly preferably an ethylene-containing copolymer of ethylene and (meth)acrylic acid vinegar. Since the main chain of the ethylene-based copolymer has no diene bond, it almost loses its elasticity when placed at a high temperature, and can maintain its stress relaxation for a long period of time (4). And because it contains vinegar (the side chain of the bond, the solubility in the organic solvent is high, and it is not easy to hydrolyze, because 22 317818 1323275 • This can inhibit the adhesive composition in the high temperature and high humidity environment, The gas stability is improved. Specific examples of the ethylene-based copolymer of the monomer component of ethylene and (meth) acrylate are ethylene-(T-based) acrylate-maleic anhydride copolymerization, and Acrylic acid based vinegar _(f-based) propylene glycol glycan vinegar copolymer, ethylene-(mercapto)acrylic acid glycidyl ester copolymer, ethylene _(mercapto) propylene-wolf I copolymer, 乙妇_ (Methyl) propyl benzoic acid glycidyl vinegar - ethyl acetate = water. Among them, ethylene-(meth)acrylic acid alkyl ester-cis-succinic anhydride copolymer, 'Women's-(meth)acrylic acid-based vinegar (methyl) propylene glycol glycan ester copolymer, ethylene A glycidyl (meth)acrylate copolymer is preferred. These ethylene-based copolymers may be used singly or in combination of two or more kinds thereof. In the first adhesive composition of the present invention, it is preferred to use two or more of the above ethylene-based copolymers. In the copolymer of the monomer component containing ethylene and (meth) acrylate, the ratio of the acrylate is preferably 5 to 4 mol% of the total monomer component. When it is 5 #^耳% or more, since it has a good solubility in an organic solvent, it is suitable as a coating solution (coating). When it is 40 mol% or less, the effect of suppressing electrical characteristics by hydrolysis is high. The mass average molecular weight of the component (C) is preferably in the range of M 〇〇 to 2, 〇〇〇, 〇〇〇, more preferably 100,000 to 1,000,000. The mass average molecular weight is determined by colloidal permeation chromatography (GPC) using styrene as a standard value. In particular, the functional group equivalent of the component (C) (i.e., the amount per unit functional group: the amount (mass average molecular weight divided by the number of functional groups)) is in the range of 100 to 2,5^, and the stretching after hardening Rate and adhesion between the substrate and the substrate 317818 / 23 1323275. The functional group of the component (c) is a functional group which is contained in the unsaturated carboxylic acid or a derivative thereof and which is reactive with the above component (A). The content of the component (C) in the present invention is preferably from 20 to 80% by mass based on the total solid content of the adhesive composition, more preferably from 30 to 70% by mass. (When the content of the bismuth component is within the above range', it has excellent effects of the present invention, in particular, it is excellent in stress relaxation, heat-resistant temperature cycle property, adhesion between copper and a polyimide film, and moisture resistance. The content of the component (C) is preferably in the range of 2 to 200 parts by mass, more preferably 50 to 150 parts by mass, per 100 parts by mass of the component (A), and when the content is 2 parts by mass or less, The adhesive layer has a good film forming property of 20 parts by mass or more. The strength of the adhesive layer is high. [矽 oxane compound (D)] The viscous (four) composition of the present invention (4) Μ 含 石 1 1 compound (D (hereinafter also referred to as component (D)). Therefore, when the component (A)-(c) is dissolved in an organic solvent to form a coating material, the compatibility of each component is improved. It also has the advantage of reducing the moisture absorption rate after hardening, etc. (9) The component is preferably a reactive group having reactivity with an epoxy group. It can be exemplified by a minus 1 oxy group, an amine group, a methyl propyl group, and a lobe. I, etc. The composition, the alkane-containing oxane compound on the net and the sputum is not the following formula (1) or ten _ a 杈仫 杈仫, deduction At least one of the compounds of formula (2) is preferably selected from the group. 31781^^ 24 CHe CHs CHg 丨一 Si-〇七1卜〇七+一记一 NH2 (1) CHa CHa CH3

HgN&quot;-- 03⁄4

CHa 〇#S/-0(2) CHa 〇 CHs R are each independently, and represent a stretching group having a carbon number of 1 to 10, and m and n are each independently, representing an integer of 0 to 10. The alkylene group as R1 in the formula (1) may be a straight chain or a branched chain, and particularly preferably a linear alkyl group having 2 to 5 carbon atoms. • m is preferably an integer from 3 to 8. n is preferably an integer from 〇 to 8. Examples of the oxirane compound containing an amine group at both terminals of the formula (1) and the formula (2) are exemplified by Toshiba Ketone Co., Ltd., trade name: tsl93〇6 (diamine-oxymethane) ) 'Trade name: TSL9886 (diaminopolyoxyalkylene), trade name: TSF4706 (diaminobisoxane), trade name: XF42_a2645 (diamine polyoxyalkylene), and the like. The content of the (1) component in the first adhesive composition A of the present invention is preferably 0.05 〇 mass 〇/〇, more preferably 5% by mass, based on the total solid content of the lining agent composition. In the case of 5% by mass or more, the (A)-(C) component of the coating composition of the adhesive composition of the present invention is excellent in compatibility, and the moisture absorption rate after stone formation is also low. When the mass is below ϊ〇%, it can be suppressed by the persuasion | 25 317818 1323275. &lt;Other optional components. In the adhesive composition of the present invention, it is preferable to further add a coupling agent in order to improve the adhesion to the adherend. _

The coupling agent is preferably used, for example, an organic stone coupling agent, a titanium coupling agent or an inductive coupling agent. D In the first adhesive composition of the present invention, it is more preferable to further contain an epoxy hardener in the above-mentioned (in) component. This promotes the hardening reaction of the first adhesive of the present invention and the heat resistance of the composition. As the sheet epoxy curing agent, a generally used one can be used, and specific examples thereof include a phosphorus-based catalyst such as imidazole or 1,8-diazabicyclo(5,4,fluorene)undecene. In the first-adhesive composition of the present invention, the content of the epoxy hardener is preferably from 〇1 to 1% by mass to 3% by mass to 3% by mass. In the adhesive composition, it is preferable to use a filler such as a substance or an organic filler for the purpose of adjusting the coefficient of thermal expansion, transmitting zero, or controlling the workability. Machine charging: examples of machine fillings can be exemplified by dioxide dioxide, oxidation, titanium oxide, = yttrium, magnesium reduction, carbon _, titanium nitride, nitrogen cutting, tungsten nitride, carbon cutting, titanium carbide , carbonization error, carbon (tetra) mesh, mica, trioxide: =: 箄 carbon black, hydrazine, hydroxide feed, magnesium hydroxide, organic surface treated with trimethyl decyloxy and the like. Examples of the organic succinimide include polyethylenimine, polystyrene 317818f: &gt; 26 1323275. Ether ether ketone, polyether quinone imine, polyester quinone imine, nylon, fluorenone and the like. The content of the filler in the first adhesive composition of the present invention is 100 parts by mass of the above-mentioned (A) component, (B) component, and (c) component, and the component (D) which is an optional component. It is preferably in the range of 2 to 95 parts by mass, more preferably 5 to 50 parts by mass. The first adhesive composition of the present invention can be prepared by dissolving the essential components, i.e., the above components (A) to (C), in an organic solvent, and then adding the component (1)) of any component to form a coating layer. · The organic solvent used therein can be derived from N-mercapto-2-indanthrone, N,N-di-p-acetamide, hydrazine, hydrazine, dimethyl carbamide, pyridine, mercaptoethyl ketone, Methyl isobutyl ketone, terpene benzene, xylene, bismuth acetonide, tetrachloro π pentane, -ethanol, methanol, methyl cellosolve, and the like are selected and used in appropriate amounts and amounts. • It is preferable that the coating is adjusted to have a solid content of 5% by mass or more, preferably 1 to 5 Å by mass. When the solid content concentration is 5% by mass or more, the adhesive sheet having a uniform thickness of the adhesive layer can be easily produced. _Lu <Adhesive Composition for Second Semiconductor Device> The adhesive composition for the second semiconductor device of the present invention contains an essential component: epoxy resin (A) (hereinafter referred to as (A) component), and Resin (,) (hereinafter referred to as component (8)), and an unsaturated host acid or derivative thereof having a functional group reactive with an epoxy resin (4) or an epoxy hardener, and an ethylene copolymer of ethylene (C) () (hereinafter referred to as (Ci) component), and a hardening type adhesive composition of the compound (D) (hereinafter referred to as (D) component). 'The 317818 Ί 27 1323275 used in the second adhesive composition of the present invention will be described below.

f(A) component J. The epoxy resin of the same epoxy ray wax (4) in the second adhesive composition: in combination with the above-mentioned first-adhesive agent, especially the insulating property of the above-mentioned epoxy resin with a bifunctional epoxy resin Resistance: Rolling: The fat is cheaper and more used. Ding...they are all good, so it is suitable for the invention. The ring of the 4 epoxy resin is promoted to 200 Γ), the clothing is preferably 10〇 to 4,000, 100 to 10,000, 100 to M〇 should be B main, Gan r* J is more than 100 in the difficult field. • • 卞 ', hard to leave unhardened 8%, oxygen equivalent is 4, _ or less, it is easy to produce bubbles. The compatibility of the ring is good. The amount of f is preferably in the bath, and the content of the other resin - % oxygen resin (A) is preferably from 3 to 40% by mass of the total solid content of the resin of from 5 to 25% by mass. In order to promote the hardening reaction of the second adhesive composition of the present invention, an amine-based catalyst such as saliva, 1,8-diazabicyclo(5,4,anthracene)-carbene, j-phenylphosphine is preferably used. An epoxy curing agent such as a phosphorus catalyst.罾Tb) Component] The component (B) can react with the epoxy resin (A) to form a three-dimensional network structure. The same resin as the desired resin (B) in the above first adhesive composition can also be used in the second adhesive composition. Among them, the lacquer-like resin has good reactivity, and is excellent in tooth wettability and heat-preservation in semiconductor devices. The ratio of the above epoxy resin (A) to the phenol resin (B) is preferably from 1:0.6 to 1:1, and more preferably from 1:7 to 1:1.1. When the ratio of the epoxy 28 317818 V, v: fat (eight) to the resin (B) is small at a functional group equivalent ratio of 1: ο, the hardened material is liable to become brittle. When the ratio of the above is a large proportion of riding fat (Β), the adhesion (four) is low. - [(C1) component] The (B) copolymer (e) constituting the present invention is an unsaturated carboxylic acid containing a B group capable of reacting mainly with at least an ethylene resin or an epoxy hardener. Or its derivatives. The functional group reactive with the above epoxy resin or epoxy hardener may be as described in the component (c) of the first-adhesive composition and the anti-accumulation of the component (A) The same functional group. Specifically, for example, an amine group, a different acid, a vinegar group, a glycidyl group, a slow group (including an acid group thereof), a sulphur group, a thiol group, a vinyl group, a methyl group, a thiol group, and a vinegar group. Base. Among them, an amine group, a buffer group, a glycidyl group, and a hydroxyl group have high reactivity, and therefore are preferred. The functional group is particularly preferably a glycidyl group or an ester group. Specific examples of the unsaturated citric acid or a derivative thereof containing such a group are as follows. An olefin such as acrylic acid/methyl ruthenium acrylate, maleic acid (anhydride) or carboxyl group-containing propylene, containing a glycidyl group such as glycidyl acrylate, glycidyl methacrylate, etc., The hydroxy group is hydroxy hydroxy acrylate, hydroxymethyl methacrylate, ethyl acrylate, methacrylic acid by ethyl ester or the like. (C) In addition to the above-mentioned main monomer component, it may further contain a small amount of a third monomer. The third monomer copolymerizable with the above ethylene and the functional group-containing unsaturated carboxylic acid or a derivative thereof may, for example, be decyl acrylate, ethyl acrylate, decyl methacrylate or ethyl methacrylate. An alkyl or aryl ester of acrylic acid, vinyl acetate or the like. 317818 29 1323275 It is preferred that the above-mentioned ethyl ketone copolymer is derived from unsaturated acid to TM. ...% by mass is better. When the content of the derivative component in the copolymer is 〇.丨% by mass or more, the reactivity with the component (A) or the component (B) can be improved, and the solubility in the organic solvent can also be improved. . When the content is 40% by mass or less, the stability of the coating is maintained. When the third monomer component is present, the content is preferably 〇/〇 or less, more preferably 3% by mass or less.

Preferred examples of the above ethylene-based copolymer in the present invention include ethylene (mercapto) acrylate-maleic anhydride copolymer, and ethyl bromide (alkyl) acrylate-(mercapto)acrylic acid glycidol. Ester copolymer, ethylene methyl acrylate glycidic vinegar copolymer, ethylene _ (meth) acrylate copolymer, terephthalic acid - (mercapto) styrene glycidyl ester - vinyl acetate copolymer. Among them, ethylene-(meth)acrylate-maleic anhydride copolymer, vinyl methyl)acrylic acid acetonitrile-(mercapto)propyl-glycidyl hydrazine copolymer, and ethylene _(meth) acrylate A glycidyl S-based copolymer is preferred. In the second adhesive (f) f of the present invention, it is also preferred to use two or more kinds of the above ethylene-based copolymers (c,;: the ethylene-based copolymer (C,) is added for the purpose of making the adhesive composition flexible, preferably Add the above vinyl methyl) propylene vinegar. The copolymer containing 乙-(meth)acrylic acid has no thermal degradation (becoming inelastic) when it is placed at an ancient temperature because it has no diene bond in the main chain, and can be protected after a long period of time: : Stress is pure. In addition, because the side chain contains a misbonded bond, the organic solvent has a high degree of 'the valley', and because it is not easily hydrolyzed, it can suppress the sticking electrode of the adhesive composition in a high-temperature and high-humidity environment, Gao Qi Electric stability. The ratio of the bupropion S monomer to the monomer is preferably 5 to 4 (mol%). At 5 m. /. 317818 30 1323275 -., can improve its solubility in organic solvents, so it is suitable as a coating. When it is less than or equal to 4% by mole, it is not easy to reduce its electrophoresis due to hydrolysis, and it is better to use the summer average molecular weight of 2, _, _ of 1,000 to 2 _ 〇〇〇 糸 ’! 〇〇, 〇〇0 S !, _, _ better. Heart I: points: The amount is determined by colloidal permeation chromatography (GPC) with benzophenone as 2:. for:. The elongation ratio of the above-mentioned ethylene-based copolymer (c,) of the comon-based copolymer (C,) is preferably 5% or more by more than 5%. The elongation in the present invention is a value determined by the thickness of ns K676. When the stretching ratio is 5% or more, the film formability is good, and the viscosity of the adhesive composition layer after curing of the resin can be increased. The solubility of the above-mentioned acetylated copolymer (CI) in an organic solvent is more than or equal to that. Better' 6〇% or better. The solubility is 5% or more - the film does not know how to make the thickness extremely thin. The solubility is 100 g of the sample added to the solution of 1 〇〇g of the solution f. Then 8 (dissolved for 12 hours under rc to dissolve &lt; again = to room temperature, the solution is then made of nylon. The amount of the insoluble component (8) g after the 'leaf residue' was calculated by the following formula. Solubility (%) = [( l〇〇g - (x) g) / l〇〇g] xl 〇〇曰 in the first month The above ethylene copolymer (C') is in the range of 2 to 2 (9) parts by weight of the epoxy resin (A) and the epoxy hardener for 1 〇〇, and 50 to 15 parts by weight. More preferably, when the content is 2 parts by weight, it is easier to maintain good film formability. If it is 2 parts by weight or more, the film is not easily brittle. [(D) component] 317818 31 Second adhesive composition The component (9) which can be contained in the medium-sized product is the same component. (I. The first adhesive agent group is preferably a medicinal base, and the reactive group is preferably a hydroxy group, a base group, a methyl group C. a dilute group, an epoxy group, etc., wherein the two substances are further reduced by a formula (1) or a formula (2) or a formula (2) ) shown on both ends of the amine-containing compound Oxygen compound. 〒CHa (1) I〗 卜 nh2 CH3 CHa CHa 〒 Ύ CHa H,N-RHSH〇^^〇VsL^Nfla (2)

Cfls

CH3 Q • The R1 in the formula is independent, indicating the number of carbon atoms i to i〇, and 11 are independent, representing the integer from 〇 to ι〇. An example of the oxoalkylating compound having an amine group at both terminals represented by the above formula (1) or (2) is exemplified by Toshiba Ketone Co., Ltd., trade name: (diaminodioxane) , trade name: TSL9886 (diaminopolyoxyalkylene), sigma name. TSF4706 (diaminodioxane), trade name: XF42 A2645 (diamine polyoxyalkylene) and so on. The ratio of the above-mentioned component of the cerium oxide compound (D) in the second adhesive composition is 〇 5 to 10 by mass of the total solid content. /. 〇.3 to 5 mass 32 317818 ^ ^ sheet of the first semiconductor device with an adhesive sheet (hereinafter referred to as the tenth knot and then (four) to ^ one side 'layered the foregoing invention or the second adhesive composition Adhesive layer formed. Metal support:::1) The support can be made of metal such as copper or aluminum: an exfoliating film, an insulating film, a release paper, etc., especially using a gold film. At least one selected from the group consisting of insulating films is preferred. Take one-methyl ethanediester (hereinafter referred to as palpitations), polythene and other polyglycans, polyamidamine, polyamine, ..., benzene sulfide, polyether ketone, triethylene sulfonate For example, cellulose or the like is preferable, and a film of a material such as an anthracene, a polyene or a polyimine is preferable. The release film may be a phase film as exemplified in the above-mentioned insulating film, and may be released by using a (four) rubber or the like. Preferably, the release agent is used for the manufacture of the adhesive sheet (1), such as at least the surface of the support body containing the coating of the first or second adhesive composition, and then forming an adhesive layer by drying or the like. _ The agent layer is preferably semi-hardened by heat treatment. Special conditions, such as shortening the hardening time, embedding the conductor pattern, etc., inhibiting the mobility and foaming ▲, so it is better to properly control the semi-hardened state. It is better to control the method in the semi-hardened state and the helmet is particularly controlled. L is particularly limited, and the thickness after aging d-drying is preferably in the range of 3 to 4 μm. 5 to ΙΟΟμιη. The adhesive sheet of the present invention which forms an adhesive layer on at least one side of the support (1) 'When it is stored, the releasable film is adhered to the adhesive layer, and it can be made. * 317818 34 1W/:) It is better to prevent the adhesive from being subjected to (4). Therefore, the peelable film can be used. When the sheet is peeled off and the adhesive layer is used alone in the semiconductor device, the peelable film on the upper side can be used as long as it is peeled off from the adhesive side. 1) Peeling Next, the second semiconductor of the present invention The device is characterized in that the adhesive sheet (7) is characterized in that the first or second semiconductor device of the present invention has an adhesive layer formed by the sequential product 1 and an insulating film or stripping layer on at least one side of the metal layer. The film (the heart, and the object is as above == two, the same description of the homogenous layer, the synthetic 臈 and the detachable film. The viscous adhesive sheet (2) has this composition, and secondly, the present invention The third semiconductor device adhesive bonding sheet (3) is characterized in that two layers of the adhesive layer on both sides of the insulating film, and the adhesive composition of the body device are shaped and the % edge Sexual or peeling film. Sheet = layer branch = edge (four) the same description of the film The adhesive layer, the insulating film and the peeling property exemplified above. The adhesive sheet (3) has an excellent electrical stability device because of the composition, and is particularly suitable for a human composition and an adhesive sheet. The circuit board of the 317818 35 or the bottom area of the IC substrate of the various semiconductor Ί&quot;edge layer and conductor circuit structure, or the specific example of the first haptic device can be 4. The semiconductor example For example, a T-BGA using a TAB technology, a screen of a glass epoxy substrate, a 4-layer substrate, a chip-on-package type csp semiconductor, etc. The adhesive composition and the adhesive sheet of the present invention are more specifically used. It is suitable as a protective film between the insulator layer of the IC chip and the ic substrate and/or the adhesive or circuit board which adheres to or forms a circuit, and the protective film of the protection of the semiconductor device as described above. Adhesive. EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the invention should not be construed as limited. Examples 1-28 and Comparative Examples 1-7 [Preparation of Coating Material from Adhesive Composition] The components (A), (b), (c) and (C') were represented by the abbreviations shown in Table 1. , (D) component, decane coupling agent, epoxy hardener, filler, and copolymer containing diene. According to the respective amounts in Table 1 (% by mass of total solids), at room temperature to about 80 ° C Dissolved in toluene to form a coating containing an adhesive composition (solid content concentration: 35 mass%). I The content of the filler is the parts (parts by mass) of the component (A), the component (B), the component (C) or the component (C'), and the component (D) in a total amount of 100 parts by mass. Abbreviations of the respective component classes used in Examples 1 to 28 and Comparative Examples 1 to 7 in Table 1 are shown in Table 2. 36 3J7818 -1】1323275 表哒骟w者爱琪一#: 砌接w叫铋-B-ZTwli^i§铋I丨一术(质量份) Filling CO 丄er» c〇o I (14%费 Ί Φ ♦ money hardener eja I er> C3 1 C9 03⁄4 C9 03⁄4 C3 en C3 er&gt; o er&gt; C3 cr&gt; decane coupling agent « cL oa Cz3 〇&gt; cn c〇〇&gt; e^3 « &lt;7&gt; 09 en ΰϋ CQ (D) component Λ \n CO ό m era· CM 卜 Bub ^- U9 Bub (C) or (C') ingredient ra ώ ϊ〇c〇甘to 1/9 « « £» «〇c〇%t9 «Ο ς-&gt; o 6 \n CO &lt;〇(B)componentΙΑ 1A 一U9 卜60 cc 00 βτ» σ&gt; e^i lA ΙΛ ΙΑ : (A) Component U7 4; N Ξ 5 inch Jc to σ&gt; c*^ CO Λ e&lt; 04 5 rg e&lt;Q CSJ e»ao I ύ • cs ri Cs&gt; CO c〇t-- «0 O o βΝ)

317818V 1323275 [Table 1-2]

Enough to build?噶鹖-fi-ezWHcoif in the series 1-1: surgery (mass parts) Filling material CO ώ ώ era PQ 5 U5 (% by mass) Diene-containing polymer i Hardener Pu 0.19 0.19 0.19 0.19 X A 0.1S j 0.19 Decane coupling agent eo CX2 e*〇ύ σ&gt;e&gt;g·&lt;* Φ% «*« Z cs c〇Ρΐ (D) component order ά LA ά ά CjS Ο ca ca » * 面 face eo M (C) Or (C') ingredient?〇o ώ s 56.4 56.5 56.4 : 56.5 56.5 —H 47.1 58.3 (Β)Component C«3 £β ,丨― ή still en i£&gt; oo: 寸卜OO u» CO 〇 %S (Α) component U7 c— ui inch i 26.3 CM 24.2 i: U3 (A CN 03⁄4 CO CQ t- irt »_ * 20.1 u&gt; to 〇0 〇3 C^S ca 38 317818 -3]1323275

(parts by mass) Filler ec oa oc eo c〇 (% by mass) Diene-containing polymer BIS in σ» Hardener esi 丄0.19 0. L9 1 CV3 o «V9 C3 0.42 0.38 0.19 decane coupling agent ra ώ e«9 Cv 丄C〇03⁄4 c*5 kA CO mn (D) component work 03 Λ e— ή inch • «£&gt; CT5 (c) or (σ) component c〇Λ 〇芑ώ ry^ 47.1 5 〇CO U3 o 34.3 IA (〇(Β) component CN GQ σ&gt; O) O〇id 1/3 9 i «0 X cs 26.7 12.4 14.5 en a 44-4 (Α)Component I______ X LA «0 ea r·* CO 4 : 57.3 f· 24.2 c*〇26.5 t—· «〇&lt;〇28.7 c—lA 38.8 〇0 One GO CQ LT3 CO C~ ugly « S 39 317818θ 丄 [Table 2]

-------------------- Ethylene-glycidyl methacrylate copolymer (trade name: B〇NDFAST 7^Sumitomo Chemical Co., Ltd.)

**'V 40 317818 1323275 Next, the following evaluation was carried out using the obtained coating. &quot;(1) Pre-hardening evaluation 5 [Minimum melt viscosity] The coating of the adhesive composition prepared, and the lowest melt viscosity of the dynamic viscoelasticity measured before hardening is measured in the following order. The results are shown in Table 3. The coating materials prepared by the adhesive compositions of the above Examples 1-15 and Comparative Example 6 were applied to a peeled and treated 38 μm thick polyester film to a hot air after drying to a thickness of 25 μm. The adhesive was dried in a circulating dryer at 130 C for 5 minutes to form an adhesive layer. Next, the single layer of the adhesive layer is peeled off from the polyester film, and the adhesive layer of the single layer is laminated, and then the adhesive layer on the polyester film is laminated on both sides of the laminated body to The laminator was bonded so that the entire adhesive layer became a layer having a thickness of 8 mm. When the temperature of the layered ink was applied to a polyimide film (trade name: Upilex 50S, manufactured by Sakamoto Ube Industries Co., Ltd.), it was within +3t to +13 °C, and the temperature at which the reverse side was melted was observed. The adhesion speed is 1 m/min. Next, the two sides of the vinegar are peeled off, and the uncured film of the plurality of layers of the adhesive layer is formed. The resulting uncured film was measured for its minimum melt viscosity by a dynamic viscoelasticity measuring machine (manufactured by HAAKE Co., Ltd., RS75). It can be seen from Table 3 that, as a result of Examples 1-15, the uncured film is in the range of 4 〇〇 Pa · s to 50,000 pa.s, which is the optimum minimum viscous viscosity. On the other hand, as a result of Comparative Examples 1, 3, 5 and 6, the lowest melt viscosity of the uncured film was outside the range of 400 Pa · s to 50,000 Pa · s. [Compatibility] 317818 41 The coating of the adhesive composition of the above Examples 1-28 and Comparative Examples 1-7 was dried to a thickness of 25 μm, and applied to a thickness of 38 μm of the peeled treatment. The ester film was dried by a hot air circulation type dryer at 13 ° C for 5 minutes, and then adhered to a peeled polyethylene film having a thickness of 5 μm. Thereafter, the dry adhesive layer was observed by a microscope to determine the compatibility state of the (Α) component, the (Β) component, and the (C) component or the (C') component. In the results, no separation into a linear pattern or a reticular pattern was observed, so that it was judged that the compatibility was good. When the separation into a linear pattern or a reticular pattern, it was judged that the compatibility was poor. The results are shown in Table 3 as those with good compatibility as 〇, and those with poor compatibility are recorded as X 0 . It can be seen from Table 3 that, according to the results of Examples 1-28, the adhesive of the present invention, the composition Good compatibility. In contrast, Comparative Examples 4 and 6 have poor compatibility. [Embedded (foamed and filled state)] The coatings of the adhesive compositions of the above Examples 1-28 and Comparative Examples 1-7' After drying to a thickness of 25 μm, it was applied to a polyester film having a thickness of 38 μm which was peeled off, and then dried at 13 ° C for 5 minutes in a hot air circulation type dryer, and then bonded to the thickness of the peeled treatment. On the polyethylene film, an adhesive sheet is formed. In addition, a photomask film is thermocompression-bonded on a flexible substrate (trade name: Espanex, manufactured by Nippon Steel Chemical Co., Ltd.), and the mask film is aged and peeled off to form a ladder-type circuit having a conductor/conductor distance of 25 μm/25 μm. The adhesive sheet produced by thermocompression bonding is peeled off on the circuit while peeling off the polyethylene film. Next, the polyester film was peeled off and then heated at 16 ° C for 1 hour to harden the adhesive layer as a sample for evaluation of foaming 317818 42 1323275 &lt;RTIgt; When the thermocompression bonding temperature was applied to a polyimide film (trade name:, Upilex 50s' manufactured by Ube Industries, Japan), the melting temperature of the reverse side was observed. Thereafter, the foaming and filling state were observed under a microscope, and the results were judged by the following criteria. The results are shown in Table 3. In terms of foaming, the unfoamed person is referred to as 〇, and the foaming person is referred to as the filling state, and the circuit can be fully filled as 〇, and the incompletely filled person is recorded as x. The problem with the poor adhesion of the circuit in Table 3 is recorded as "_". • As is apparent from Table 3, in Example 1-28, the adhesive sheet of the present invention is not foamed and filled with a circuit, and therefore has excellent embedding property. On the other hand, in the results of Comparative Examples 1, 2, and 4-7, at least one of the foaming and filling states is not preferable, and there is a problem in terms of embedding in practical use of the semiconductor device. (2) Evaluation after hardening * [Adhesion to polyimine film (PI adhesion)] (PI adhesion in an initial state) The adhesive compositions of Examples 1-28 and Comparative Examples 1-7 were used. The coating is applied to a polyester film having a thickness of 38 μm after being dried, and then dried by a hot air circulation type dryer at i3〇〇c for 5 minutes, and then attached thereto. Adhesive sheets were prepared by peeling off a polyethylene film having a thickness of 5 〇gm. Then, the adhesive sheet was heat-bonded to a polyimine film having a thickness of 5 μm (trade name: Upilex 50S, manufactured by Sakamoto Ube Industries Co., Ltd.) while peeling off the polyethylene film. The heat bonding temperature was measured at the temperature above the melting and discoloration of the surface of the anti-317818 43 1323275 when it was bonded to a polyimide film (trade name: Upilex 50S, manufactured by Ube Industries, Japan). &quot; Next, the polyester film was peeled off and thermobonded to a polyimide film of 5 μm μm thickness (trade name · UPilex 50S, manufactured by Ube Industries, Japan), and heated at 160 C for 1 hour to adhere The layer is hardened. The adhesion is determined by the polyimine film surface and then fixed on the table, from the other end of the polyimide film.

Tensilon (made by Shimadzu Corporation) is 18 baht. The results of the direction peeling measurement are shown in Table 3. (PI adhesion after constant temperature and humidity test (PCT)) Lu The same evaluation sample as above was used, and the following adhesion after PCT was measured. The PCT system was operated under the following conditions using a constant temperature and humidity chamber. Temperature · 121 ° C, humidity: l 〇 0% RH, time: 3 〇〇 hours. The adhesion was measured by fixing the polyimide film surface to the stage, and the other end of the polyimide film was 180 in a Tensilon (manufactured by Shimadzu Corporation). The direction was measured by peeling and the results are shown in Table 3. As is apparent from Table 3, in Examples 1 to 28, the adhesive sheet of the present invention had an adhesive force of $2 2 (four) (4) or more in the initial stage of φ and after PCT, and thus had sufficient adhesion to the polyimide film. Particularly in the examples, the adhesive sheet of the present invention has an adhesive force of 4.2 (N/cm or more), particularly preferably 1. In contrast, in the case of Comparative Example U7, the adhesive force after pCT was 〇, and thus it was unusable for use in a semiconductor device. [Adhesion to Copper Foil (Cu Adhesion)] (Cu Adhesion in Initial State) Coating of Adhesive Composition of Example (10) and Comparative Example, 317818 44

1JZJZ/J t is not applied to a thickness of 25 μm, and is applied to a polyester film having a peeling treatment of 3 mm, and then subjected to a hot air circulation type dry machine (10). c After drying for 5 minutes and forming an adhesive layer, the thickness of the bismuth peeling treatment is applied to the adhesive layer to form an adhesive sheet. After the '-face peeling polyethylene film-face thermocompression bonding the adhesion 1 (four) of the copper drop (trade name · Shen-A, Japan Ε gy gy c〇 system: heat calendar temperature and the above evaluation of the polyimide film (The product name: Upilex 50S, manufactured by Japan Ube Industries Co., Ltd.) is the same as the temperature above the melting and discoloration of the reverse side. Next, 'Peeling the polyester film and bonding the U-tube to the thickness of the copper On the foil (trade name. JTC-A' Japan Energy c〇. manufactured), and then (10) smashed down, the adhesive layer is hardened. The adhesion force is the (four) surface fixed two: from the other end of the copper box The results were as shown in Table 3 (manufactured by Shimadzu Corporation). The results are shown in Table 3. (Cu adhesion after PCT) The Cu adhesion after pct was measured using the same evaluation sample. The wet test system uses a constant temperature and humidity chamber and operates under the following conditions: temperature: urc, humidity: Satoshi RH, time: 3 hrs. The adhesion is determined by fixing the copper box surface on the table, and (4) One end was produced by Shimadzu Corporation, and the measurement was performed in the 180° direction. The result is shown in the clothes 3. The period t: It is understood that the adhesive sheet of the present invention in the first embodiment of the present invention has an adhesion of 2.6 (N/cm) or more to the Cu, and thus the adhesion to the copper knife. Particularly in the case of the seventh embodiment, the adhesive of the present invention has an adhesive strength of 5 1 (N/cm) or more in the initial state and after the constant temperature and humidity test, and particularly has sufficient adhesion. In contrast, in the results of Comparative Example 1-7, the adhesion after pct was 2.5 (N/cm) or less. In particular, in Comparative Example 1_3, Comparative Example 6, and Comparative Example 7, the adhesion after PCT was 2 (N/cm) or less, so it is unusable for use in a semiconductor device. [Reflow resistance] The coatings of the adhesive compositions of Examples 1 to 28 and Comparative Examples 1 to 7 were applied to a thickness of 25 μm, which was subjected to a peeling treatment, and a thickness of 38 μm. On the ester film, the film was then passed through a hot air circulation type dryer at ι 3 〇 &lt; 5 (: after drying for 5 minutes to form an adhesive sheet, and then attached to a polyethylene film having a thickness of 50 μm which was peeled off.) The adhesive sheet was thermocompression bonded to a copper-etched glass epoxy substrate (trade name: CCL-EL170, manufactured by Mitsubishi Gas Chemical Co., Ltd.) having a thickness of 200 μm and a size of 2.5 cm x 2.5 cm. When it is bonded to a glass epoxy substrate (trade name: φ CCL-EL170' 曰Mitsubishi Gas Chemical Co., Ltd.), the temperature at which the reverse side is melted or discolored is observed. Next, the polyester film is peeled off and 0.9 cmx is applied. 7·7cm glass wafer is thermocompression bonded at a thermocompression bonding temperature, heating for 3 minutes, O.IMPa pressure, and then heated at 90 ° C for 1 hour, and then heated at 160 ° C for 1 hour to harden the adhesive layer. A total of 5 are used in each of the examples and comparative examples. Sample for evaluation of reflow resistance. The sample for evaluation was exposed to a constant temperature and humidity of 46 317818 85 at 85 ° C and 85% RH. After 48 hours in the tank, the ir was set to 26 〇t&gt; Return to the Zen furnace, and observe whether there is delamination between the layers and the generation of air bubbles. The results are shown in Table 3. In Table 3, the number of defects in the number of layers without peeling and the number of bubbles generated in the five samples is recorded. 3 In the example 28, the adhesive sheet of the present invention has no interlayer peeling and bubble generation, and all of the adhesive sheets are good. In contrast, not all of the adhesive sheets in Comparative Example-7 were good, and at least two or more of them were peeled off or bubbles were generated. # [heat-resistant temperature cycle property (TCT property)] The coating composition of the adhesive compositions of Examples 1-28 and Comparative Example 1-7 was applied to the thickness of the coating after peeling treatment to a thickness of 25 μm. On the polyester film, it was dried by a hot air circulation type dryer for 13 minutes, and then dried to form an adhesive sheet. Then, while peeling off the polyethylene film, the adhesive sheet was thermocompression bonded to a steel portion having a thickness of 200 μm and a size of 2.5 cm x 2.5 cm. The etched glass epoxy-based plate (trade name: CCL-EL170, Mitsubishi Gas Chemical Co., Ltd., Japan) Made). When the thermocompression bonding temperature was applied to a glass epoxy substrate (trade name: CCL-EL170, manufactured by Mitsubishi Gas Chemical Co., Ltd.), the temperature at which the reverse side was melted or discolored was observed. Next, the polyester film was peeled off, and a glass film of 〇.9 cm x 0.7 Cin was thermocompression-bonded at a thermocompression bonding temperature of 〇1 MPa for 3 minutes, heated at 9 Torr &lt;t for 1 hour, and heated at 16 CTC for 1 hour. To harden the adhesive layer, and make a total of 5 samples for temperature cycle resistance evaluation in each of the examples and comparative examples 317818 47 1323275

The test sample is then tested. Temperature cycling from -65 ° C to 150 ° C: Under conditions, each must be 15 吖 and -6 汴 each. Minutes Γ ΤΓ: ^ 1,000 cycles of operation. After the temperature cycle test operation, observe whether there is no control, production = .... In Table 3, the number of excellent peelings/rollings in 5 samples was not recorded (i.e., the number of good ones was 5). As is apparent from Table 3, in the example j_28, the adhesive sheet of the present invention was not peeled off from the interlayer or line-forming, and all of the adhesive sheets were good. In contrast, in the adhesive sheets of Comparative Example/Second, interlayer peeling or bubble generation occurred, and none of the five were good. [Dynamic viscoelasticity] The coatings of the adhesives and compositions of the first and second comparative examples and the comparative examples were applied, and the thickness of the dried coatings was 25 μm, and applied to a polyester film having a peeling treatment of 38 Mm. The adhesive layer was further dried by a hot air circulation type dryer at 13 minutes for 5 minutes. Then, the obtained adhesive layer is peeled off from the polyester film and used as a single layer. After laminating a plurality of single-layer adhesive layers, an adhesive layer is further laminated on both sides of the laminated body, and the laminate is laminated to make the total adhesion. The layer of the agent becomes a layer having a thickness of 〇.lmm. When the temperature of the laminator was applied to the polyimide (trade name: Upilex 50S, manufactured by Ube Industries, Japan), the temperature at which the opposite side melted was observed at +3. (: to +13. Within the crucible. The laminating speed is lm/min. Secondly, the polyester film on both sides is peeled off to form an uncured film of a layer of adhesive layer of 48 317818 〇 '1323275 ^ layer. After heating at 160 ° C for 1 hour to harden the adhesive layer, a dynamic viscoelasticity evaluation sample of 4 mm x 5 mm was prepared to evaluate the dynamic viscoelasticity at 200 ° C to 280 ° C after hardening (for hardening) Post-dynamic viscoelasticity rate. The measurement conditions were the values of Rheviibron DDV-II manufactured by Orientech Co. at a frequency of 11 Hz and a temperature increase rate of 3.8%, and then the same evaluation sample was used to measure the hardening and then at 15 °. t: After standing for 24 hours in the environment, at 20〇1_280. (: Dynamic viscoelasticity rate (dynamic viscoelasticity rate after == thermal history). Temperature of heating phase. 150 C, time: After 24 hours (η), Rheviibron DDV-Π manufactured by Orientech Co. was measured at a frequency UHz and a temperature increase rate of 3 t/min. The results are shown in Table 3. As is apparent from Table 3, in Example 1 - i 5 For example, when comparing the dynamic viscoelasticity rate of the adhesive sheet of the present invention after hardening and the dynamic viscoelasticity rate after thermal experience, As a result, it was found that the heat deterioration resistance was good. On the other hand, the dynamic viscoelasticity of the adhesive sheet in Comparative Example I-4 and the dynamic viscoelasticity after the thermal history were large, and the heat deterioration resistance was not [Moisture absorption rate] The coating materials of the adhesive compositions of the above Examples 1 to 28 and Comparative Example 丨-7 were applied to a polyester film having a thickness of 38 μm which was subjected to release treatment after being dried to a thickness of 60 μm. 'The adhesive layer was made by drying in a hot air circulation type dryer at 13 ° C for 5 minutes to form an adhesive sheet, and then peeled off the polyethylene film by 5 〇 μηι. 〇 317818 / 49 I323275

Thereafter, the polyethylene film and the polyester film were peeled off, and the adhesive layer was further cured by heating at 160 ° C for 1 hour to make a moisture absorption rate evaluation sample of 5 cm x 5 cm, and the moisture absorption rate was measured. The moisture absorption conditions were carried out using a constant temperature and humidity chamber under the conditions shown below. Temperature: 121 ° C, humidity · · l〇〇% RH, time: 24 hours. The moisture absorption rate was calculated by the following formula, and the results are shown in Table 3. Moisture absorption rate (%) = (weight of sample after moisture absorption - weight of sample before moisture absorption) / weight of sample before moisture absorption xlOO As can be seen from Table 3, in Example 1-28, the adhesion of the present invention The film has a moisture absorption rate of 0.7% or less, and the result is practically no problem. On the other hand, in the comparative examples 1, 3, 5, and 7, the moisture absorption rate was 13% or more, and this result has practical problems in semiconductor devices. [Elongation ratio] The coating material of the above-mentioned Example 28 and the adhesive composition of Comparative Example 1-7 was dried to a thickness of 60 μm, and applied to a peel-treated polyester film having a thickness of 38 μm. Then, the adhesive layer was dried by a hot air circulation type dryer at 13 ° C for 5 minutes to form an adhesive sheet, and then a polyethylene film having a thickness of φ 5 〇 μηη was attached. Thereafter, the polyethylene film and the polyester film were peeled off, and the adhesive layer was cured by heating under the pressure of 16 Å to prepare a tensile strength evaluation sample of 1 cm x 12 cm, and the elongation was evaluated. The elongation rate was measured by Tensil(R) (Shimadzu Corporation) and the elongation was calculated by the following formula. The results are shown in Table 3. ', elongation (%) = (length of the sample after stretching) _ length of sample before stretching) / stretching

The length of the sample before it is xlOO 317838 50 1323275 It can be seen from Table 3 that in the embodiment U, the stretched sheet of the present invention has a tensile elongation of 30% or more, and it is confirmed that the stress relaxation property is excellent. In contrast, in the = and 3, the moisture absorption rate can be determined, and the stress relaxation can be determined. [Electrical characteristics] The above-mentioned application of the adhesive composition of J 1-28 and the comparison of mu is carried out, and after drying, The thickness is 25, and it is applied on a polylactic acid film having a thickness of 38 μm on a peeling place, and then an adhesive layer is formed by m/drying for 5 minutes through a hot air circulation type dryer to form an adhesive sheet, and then attached to a thick layer. 5 〇 μηη of the peeled polyethylene film to make an adhesive sheet. &quot;Previously, the flexible substrate (trade name: Espanex, manufactured by Xinyi Iron Chemical Co., Ltd.) is connected with the cover film, and after aging and peeling off the mask film, it is made into a conductor/guide B (4). The circuit's one side of the circuit is stripped of the poly-face heat and the adhesive sheet produced by it is repeatedly connected. Secondly, peeling off the characteristics of the polyester film after the test, heat 1 hour to harden the adhesive layer, as an evaluation of its electrical = sample and then temperature: 峨, humidity: _ Η 恒温 constant temperature and humidity ' 5V electric 之 DC and expose it to 300 hours of it. „After the constant temperature and humidity chamber is taken out, observe whether there is electrical decay on the conductor (copper=part) on the comb circuit, and the conductor (five) on the ladder circuit) “, Gaffney’s rot is 〇, There are people who have Gavigny; if there is a problem with the poor adhesion of the road, the sample is recorded as "_". As a result, as shown in Table 3, in the embodiment K28, the Lilass piece of the present invention has no Gaffani rot on the conductor (copper foil portion) of the comb type 317818 51 1323275 type circuit, so practically - no problem. In contrast, in Comparative Example 2-7, the Gaffini rot was generated, and this result was a problem when actually used for a semiconductor device. [Interesting] The coating of the adhesive composition of the above Examples 16-28 and Comparative Examples 1-7 was applied to the peeled and treated 38 μηι thick polyester in such a manner that the thickness of the coating of the adhesive composition was 6 Ο μηη after drying. On the film, an adhesive layer was prepared by drying at 13 ° C in a hot air circulation type dryer, and then a polyethylene film having a thickness of 5 μm μm was peeled off. Then, a polyethylene film and a polyester film were peeled off, and a polyimide film (trade name: Upilex 75S, manufactured by Ube Industries, Ltd., Japan) having a thickness of 75 μm was thermocompression bonded to both surfaces of the adhesive layer. After cutting into a width of 7 mm, the film was heated at 160 C for 1 hour to harden the adhesive layer to form a polyimide film. The hardened polyimide film laminate was further cut into 7 mm x 5 mm and used as a sample for evaluating warpage characteristics. The evaluation sample was placed on a horizontal platform to have a convex shape, and the height of the projection was measured by a digital measuring microscope (trade name: #STM-UM, manufactured by 〇lympus Co., Ltd.). The results are shown in Table 3. As is clear from Table 3, in Example 16·28, the warpage of the adhesive sheet of the present invention was 1.5 nm or less. This result is practically not problematic. In contrast, in Comparative Examples 2, 3, and 6, the light curvature was 3 mm or more, and this result was a problem when it was actually used for a semiconductor device. In Comparative Examples i and 7, the warpage could not be measured because the sample was curled. 317818 52 1323275 [Table 3-1] Determination of the lowest melt viscosity (Pa. s) Dynamic viscoelastic, hardened meal (Mpa)* 1 Thermal experience after Example 1 4,000 5 to 1〇6 to 11 2 5,000 6 to 11 7 to 12 3 3,000 4 to 8 5 to 9 4 4,000 10 to 15 12 to 18 5 1,000 20 to 1 to 30 to 300 6 500 |3〇^ 180 to 30 to 350 7 10,000 30 to 50 40 to 60 8 4,000 3 to 6 4 to 8 9 5,000 4 to 8 5 to 10 10 6,000 5 to 10 7 to 14 11 15,000 〇·8 to 2 1 to 4 12 40,000 30 to 50 30 to 60 13 30,000 0.6 to 2 0.8 to 4 14 15,000 5 to 20 10 to 30 15 8,000 5 to 20 10 to 30 *1 : Minimum to maximum value (MPa) at 200 to 280 ° C [Table 3-2] 1 Minimum melt viscosity (Pa . s) Dynamic viscoelasticity (Mpa)* 1 Comparative example after hardening. 1 100 20 to 60 5 to 10 2 1,500 50 to 80 5 to 10 3 100 30 to 60 5 to 10 4 3,000 30 to 60 5 to 10 5 90,000 10 to 15 5 To 10 6 200 5 to 10 5 to 10 *1 ·· 200 to 280C minimum to maximum (]y[pa) 53 317818 1323275

&lt;垅铋莨S丨Mti

Buried filling state 〇〇〇〇〇o 〇o 〇〇OO 〇〇〇 foaming 〇〇〇〇O 〇〇o 〇〇〇〇〇〇〇electric i * 〇〇Ο 〇〇〇O 〇〇〇o O 〇〇O stretch ratio SS Lf) g E sc〇S CQ moisture absorption rate 〇cO 〇cO 〇σ〇CP t— C=9 UC3 〇Lf3 CtS «=> CO CO CO LO CO — LO C3 TCT ΙΛ UT9 LT3 LTS LT3 ITS LT9 LfS LT3 ΙΛ Ln LA UQ ΙΛ ;A LT7 LA m L» tra ΙΛ LO LO LT2 L〇LT3 L〇ΙΛ LA Cu adhesion (Ν/αη) PCT after ua LC3 卜«SI 9S) r-^ ★ OO CO inch t*^ to 卜 DO LA Cn 09 «0 Initial status〇〇(0 Γ—Cn3 » oo OO • c^· oc » e» 卜oa 〇d cn c»a «5 (O σί oo : PI adhesion (N/cra) PCT after CO CO OO oo oo σι ίΡ «σ -«ί e&gt;a tTd Lf3 ui ui u? Initial state LT3 LC9 tra UP U9 Ln ΙΟ U9 CQ ΙΛ CD U3 οό 03 CO OQ UO CO CO a% compatible 〇〇〇〇 〇 〇〇〇〇〇〇0 〇〇CO CO U5 LO Bu OO σν = CO Inch LA 54 317818 1323275 4 - 3 Table buried filling state 〇〇〇〇o 〇o 〇〇〇〇〇〇 foaming 〇〇〇〇 〇〇〇〇〇0 〇〇O Electrical characteristics. 〇〇〇〇〇〇〇〇〇〇〇〇〇 曲 ( (mm) 1.5 or less 1. 5 or less 1.5 or less 1.5 or less i_5 or less 1.5 or less 1.5 or less 1.5 or less 1.5 or less 1.5 or less 1.5 or less 1.5 or less y- 3 in stretch ratio 〇c*a Ο csi SS r-^t ? C3 C^lo CO 1^-· 5 !··» » « &lt; o ς£&gt; g C&gt ;5 Moisture absorption rate & e &lt;=&gt; L0 〇un a LA b- C? LA o LfS CD Lfd o L/9 o LA c? c〇C? CO o TCT ΙΛ kT3 US LT3 uO u5 lA U9 Uz&gt; Cf5 ςΑ LT5 la «-〇ιΤΰ fcA iA to lA LC? LT3 m ΙΛ u? lA bTd u? must iSP bA U9 k(9 l.{^ Cu adhesion (N/cm) PCT after c--C 〇ΟΊ Γ — CO cc CO os CO oo e·^ oo LA 0*3 Initial state inch LT9 oo LT9 CO σΟ oo eo to eo oo oo to CO CO CO to cr&gt; to — PI adhesion (Ν/απ) PCT After c-^ e^a Eo C^Q 卜«»« oo oo CO CO CQ C^J oo un o oo initial state CO CO 〇〇c〇CO LTD inch LTD CO eo CC OO CO oo — oo compatible 〇〇〇〇〇〇〇 〇〇〇〇〇〇PO 2 c3 C&lt;l CO c&gt;a CO c^» 〇o 55 317818

- 'V 1323275 【Table 3-5】

Buried filling state X 〇〇1 1 〇X Foaming XX 〇1 XX Electrical characteristics 〇XX 1 1 XX 勉曲(mm) 1 CC3 CO oO ixi 1.5 or less 1.5 or less 1 Stretch rate (%) ο •r Ή CD Oo u? os Moisture absorption rate (%) e&lt;ac*it_ o -CO cn CO 1 〇Q 〇«〇cO TCT ΙΛ LO oo LA C^a in Μ 1X9 LA LC9 CSI IA CO IT9 e^a Cu Adhesion (Μ/cm) PCT post ca o o. Two Lft C^a 〇〇 initial state Ο〇ο CO c£ oo 〇oo C^3 CO c〇—PI adhesion (N/cm) 1 pct after Ca o CD o O 〇 initial state CO ο CNI 1 CO CO o css » miscibility 〇O o X 〇XO a C&gt;a cry inch LT3 us t- 56 317818

!J 罝右知' The adhesive sword composition and adhesive sheet of the present invention have excellent embedding property, electrical characteristics, adhesion, and property, 'low hygroscopicity, large stretch ratio, and the magic six protector c sound! ^, good strength, good quality, and excellent heat deterioration. Therefore, the adhesive group of the present invention, 4, and the adhesive and the adhesive sheet can suppress the occurrence of interlayer peeling, generation of blistering, warpage, etc. in the +conductor device, and the processing property is also good. Therefore, the stability of the semiconductor device can be improved.

317818 57

Claims (1)

13232 $95103025 Patent Application* (August 6th, 1998) ^Month U amends this kind of semi-conducting, device adhesive composition, which is characterized by: r group glycerol hydrazine, glycidol vinegar, glycidylamine, line An epoxy resin (A) having at least β or more, a resole type phenol resin, a phenol resin for phenol paint, and a resin for cresol paint 'fa1 benzene di(10) ester, xylene resin lanolin (8): contains ethylene and has the above epoxy resin (A) or epoxy hardener (the epoxy hardener is selected from the group consisting of an amine catalyst and a phosphorus catalyst) The reactive functional carboxylic acid of the reaction or a derivative thereof is selected from the group consisting of ethylene-(meth) acrylate-maleic anhydride copolymer, ethylene-alkyl (meth) acrylate-(mercapto) acrylate a glyceride copolymer, an ethylene (meth) propyl glycosyl glycidyl ester copolymer, an ethylene-(mercapto)acrylic acid copolymer, an acetamidine-(mercapto)acrylic acid glycidyl ester-vinyl acetate copolymer One or more kinds of ethylene-based copolymers (C'), and the following formula (1) or (2) The amine-based compound of the amine group (D) ' (3⁄4 CBs Cp &amp; N-R1 - Si - Ο - fSi - · - it1 - ΝΗ β (1) I. II CHa 03⁄4 CBa ψ -Ο ^ H2N—Si-0 # Si — An Ei N &amp; (2) (3⁄4 CHs 58 317818 (Revised) (wherein R1 represents a carbon atom number of 1 to 10 and the stretching base is 0 to 1 〇 (Integer); and, relative to the total solid content, the content of (A) component is 3 to 40 mass 〇 / 〇, the content of (B) component is 0.5 to 50 mass 0 / 〇, and the content of (C) component is 20 To 80% by mass, the content of the component (D) is 0.05 to 10% by mass, and the content of the φ epoxy hardener is 0 to 10% by mass. 2. The adhesive for the semiconductor device according to the first application of the patent scope is The composition, wherein the lowest melt viscosity in the dynamic viscoelasticity measured before hardening is in the range of 400 to 50,000 pa · s. 3. The adhesive composition for a semiconductor device according to the first aspect of the patent application, wherein the hardening After 200. (: to 280 之, the dynamic viscoelasticity is in the range of 500Pa to 200MPa. 4. The viscosity of the semiconductor device according to the scope of the patent application The composition of the coating agent, wherein the tensile ratio after hardening is 30 〇 / 。 or more. 5. The adhesive composition for a semiconductor device according to claim 1, wherein the moisture absorption rate after hardening is 1%. 6. The adhesive composition for a semiconductor device according to the first aspect of the patent application, wherein 'hardened and placed in an environment of 150 ° C for 24 hours, at 2 〇 0. (The dynamic viscoelasticity at a temperature of 280 ° C is in the range of 5 〇〇 to 50 MPa. 7. The adhesive composition for a semiconductor device according to claim 1, wherein the 'the aforementioned ethylene copolymer ( 59 M7818 (Revised Edition) of the unsaturated carboxylic acid derivative in C') is contained in an amount of 0.1 to 40% by mass. 8. As described in the first half of the patent application, the aforementioned ethylene-based copolymer (c, In the middle: use sticky two::^ 2,500. Lu Yueji prepared for 100 to I: please ^Γ1 of the semiconductor device adhesive agent can be used == (eight) and the aforementioned enzyme resin (Β) ratio, to the official base Tian Li Biye, at 1:6 to 1:1 claws, an adhesive sheet for a semiconductor device, characterized in that it is covered in the inner layer (9) - the surface is coated as claimed, and at least the next day in the support is occupied. The semiconductor device is an adhesive layer formed by adhering d and forming a substance. 11. A bonding device for a semiconductor device + - characterized by: sequentially laminating at least one side of the metal layer, such as applying for a special brake.. ^ ^ For the purpose of profit-seeking, the first layer of the semiconductor device is viscous η 'J layer, and insulating film or peeling film. η.- species + lead The adhesive sheet for the device is characterized in that: on both sides of the insulating film, the laminated layer is formed by the adhesive composition of the semiconductor device such as Shen Bao Zhidou丨# Adhesive layer of wind, and insulating film or peeling film. 3178] 8 (revision) 60