TWI761614B - Film-shaped semiconductor-sealing material - Google Patents

Abstract

The present invention is an object of the present invention to provide a film-like semiconductor sealing material that satisfies the required properties of NCF. By containing (A) a compound having a benzoxazine structure, (B) an epoxy resin that is liquid at room temperature, (C) a polymer compound having a mass average molecular weight (Mw) of 10,000 or more, (D) an average This problem can be solved by a filler having a particle size of 1 μm or less and (E) a compound having an acid group and having a compound whose weight loss on heating at 200° C. is 30% or less.

Description

Film-like semiconductor sealing material

The present invention relates to a film-like semiconductor sealing material used as NCF (Non Conductive Film) at the time of semiconductor mounting.

Conventionally, for semiconductor mounting, the surface of electrodes (bumps; bumps) on which IC (Integrated Circuit) wafers are formed face to face the surfaces of electrodes (electrode pads) on which substrates are formed, and the bumps of IC chips and the electrodes of substrates are connected. Flip chip method in which the pads are electrically connected. In this flip-chip method, the connection portion between electrodes is protected from the outside, and in order to relieve the stress caused by the difference in the linear expansion coefficients of the IC chip and the substrate, usually after the electrodes are connected, a liquid called an underfill agent is used. The thermosetting adhesive is poured between the semiconductor wafer and the substrate to be hardened.

In recent years, the miniaturization of IC wafers has rapidly progressed. Along with this, the distance between adjacent electrodes or the gap between the semiconductor wafer and the substrate tends to gradually narrow. Therefore, when the underfill agent is flowed between the IC chip and the substrate using the capillary phenomenon, there may be problems such as generation of voids, or longer time required for casting the underfill agent. Therefore, a liquid adhesive called NCP (Non Conductive Paste) or a thin film adhesive called NCF (Non Conductive Film) is applied or bonded on the substrate in advance, and then a flip chip bonder is used. Bonder) etc., the so-called first-in method of connecting the bumps of the IC chip and the electrode pads of the substrate by curing the resin by thermal compression bonding (TCB) has been tried (refer to Patent Document 1).

As a characteristic required for NCF, it is void free, and it is required to have excellent electrical connectivity and reliability. In addition, the laminate or the like must be conveyed in the form of a tape, and resistance to bending is required in order to ensure handling properties. In addition, if the resistance to bending is insufficient, there is a fear of causing cutting and burrs in the NCF in the dicing step performed after the TCB step. When determining the position at the start of the mounting operation, it is required to have excellent transparency in order to confirm the identification mark as the mark of the wafer or chip through the NCF attached to the wafer.

In the flip-chip method, the electrical connection is often performed using solder. Among the applicable solder materials, lead-free solder is often used, and its melting point tends to be higher than that of conventional lead solder. Along with this, the temperature at the time of flip-chip mounting using NCF also tends to be high. As the temperature increases, defects such as voids tend to be easily generated due to side reactions or volatilization of components, and it is difficult to balance the prevention of defects such as voids with connectivity.

Compounds with a benzoxazine structure are stable at room temperature because the hardening reaction is carried out at high temperature, and the reaction at the temperature of the melting point of the solder is difficult to start, which can suppress the outgassing caused by side effects. It is characterized by the ring-opening polymerization of the dihydrooxazine ring, which hardly causes outgassing even under the hardening mechanism. Patent Document 2 proposes an adhesive composition for semiconductor devices containing a compound having a benzoxazine structure. However, when the compound having a benzoxazine structure is used as a thin film, it is brittle and easily broken. Therefore, when used as a component of NCF, it was found that the resistance to bending was insufficient. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Specification of Patent No. 4752107 [Patent Document 2] Japanese Patent Laid-Open No. 2008-231287

[Problems solved by the invention]

The present invention is intended to solve the above-mentioned problems in the prior art, and aims to provide a film-like semiconductor sealing material that satisfies the required properties of the above-mentioned NCF. [Means to solve the problem]

In order to achieve the above object, the present invention provides a film-like semiconductor sealing material containing (A) a compound having a benzoxazine structure, (B) an epoxy resin that is liquid at room temperature, (C) a polymer compound having a mass average molecular weight (Mw) of 10,000 or more, (D) Fillers with an average particle size of 1 μm or less and (E) A compound having an acid group whose weight loss on heating at 200°C is 30% or less.

In the film-like semiconductor sealing material of the present invention, the compound having a benzoxazine structure of the component (A) is preferably a compound represented by the following formula (1) or (2).

The film-like semiconductor sealing material of this invention WHEREIN: It is preferable that the epoxy resin which the said (B) component is liquid at room temperature contains either a bisphenol A type epoxy resin, or a bisphenol F type epoxy resin.

In the film-like semiconductor sealing material of the present invention, the compound of the component (E) is preferably a carboxylic acid.

In the film-like semiconductor sealing material of this invention, it is preferable that the compound of the said (E) component is at least 1 sort(s) chosen from the group which consists of oleic acid, stearic acid, abietic acid, and maleic acid resin.

It is preferable that the film-like semiconductor sealing material of this invention further contains (F) a silane coupling agent.

In the film-like semiconductor sealing material of this invention, it is preferable that the silane coupling agent of the said (F) component contains any one compound of following formula (3) or formula (4).

In the film-like semiconductor sealing material of this invention, what further contains (G) an elastomer is preferable.

In the film-like semiconductor sealing material of this invention, it is preferable that the elastomer of the said (G) component contains a polybutadiene skeleton.

Furthermore, the present invention provides a semiconductor device using the film-like semiconductor sealing material of the present invention. [Effect of invention]

Since the film-like semiconductor sealing material of the present invention has excellent bending resistance, it is excellent in handling properties at the time of conveyance in devices such as laminates, or between devices, or attachment to devices. In addition, when used as NCF, there is no concern that cutting and burrs are generated in the dicing step performed after the TCB step. Since the film-like semiconductor sealing material of the present invention has excellent visibility, when used as an NCF, it can be confirmed as an identification mark for marking a wafer or a chip through the NCF attached to the wafer. When the film-like semiconductor sealing material of the present invention is used as an NCF, it has excellent mountability in the TCB step. When the film-like semiconductor sealing material of the present invention is used as an NCF, the moisture absorption reflow resistance is good.

[Type of carrying out the invention]

The present invention will be described in detail below. The film-like semiconductor sealing material of the present invention contains components (A) to (E) shown below as essential components. (A) Compounds having a benzoxazine structure The compound having a benzoxazine structure of the component (A) is stable at room temperature because the curing reaction proceeds at a high temperature, and it is difficult to start the reaction at the temperature of the melting point of the solder, which can suppress outgassing caused by side effects. It is characterized by the use of ring-opening polymerization of dihydrooxazine rings similar to epoxy resins, which hardly causes outgassing even under the hardening mechanism. When the film-like semiconductor sealing material of the present invention is used as NCF, It is a component that imparts storage stability and hardening properties to the film.

由薄膜特性的觀點來看，(A)成分的具有苯並噁嗪結構的化合物係以式(2)所示化合物為佳。In the film-like semiconductor sealing material of the present invention, the compound having a benzoxazine structure of the component (A) is preferably a compound represented by the following formula (1) or (2).

From the viewpoint of film properties, the compound having a benzoxazine structure of the component (A) is preferably a compound represented by formula (2).

(B) Epoxy resin that is liquid at room temperature (B) The epoxy resin that is liquid at room temperature (hereinafter referred to as "liquid epoxy resin") is a component that imparts handleability to the film when the film-like semiconductor sealing material of the present invention is used as an NCF. The compound having a benzoxazine structure of the component (A) has preferable characteristics for the above-mentioned NCF, but when used as a thin film, the compound is brittle and prone to collapse. When combined with the liquid epoxy resin as the component (B), it can be handled as a thin film by imparting moderate flexibility.

The liquid epoxy resin in the present invention preferably has a viscosity at room temperature (25° C.) of 100,000 mPa·s or less.

As the liquid epoxy resin in the present invention, bisphenol A epoxy resins with an average molecular weight of about 400 or less can be exemplified; The branched chain polyfunctional bisphenol A type epoxy resin of ether; bisphenol F type epoxy resin; the average molecular weight of phenol novolac type epoxy resin is about 570 or less; such as vinyl (3,4-cyclohexene) Dioxide, 3,4-epoxycyclohexylcarboxylic acid (3,4-epoxycyclohexyl)methyl, adipic acid bis (3,4-epoxy-6-methylcyclohexylmethyl), 2 Alicyclic epoxy resins of -(3,4-epoxycyclohexyl)5,1-spiro(3,4-epoxycyclohexyl)-m-dioxane such as 3,3',5,5'- Biphenyl type epoxy resin of tetramethyl-4,4'-diglycidyloxybiphenyl; such as hexahydrophthalic acid diglycidyl, 3-methylhexahydrophthalic acid diglycidyl Glycidyl, hexahydroterephthalic acid diglycidyl ester type epoxy resin; such as diglycidyl aniline, diglycidyl toluidine, triglycidyl-p-aminophenol, tetra Glycidyl-m-xylylenediamine, glycidylamine-type epoxy resins of tetraglycidylbis(aminomethyl)cyclohexane; and, for example, 1,3-diglycidyl-5-methyl A hydantoin type epoxy resin based on 5-ethyl hydantoin; an epoxy resin containing a naphthalene ring. Moreover, the epoxy resin which has a polysiloxane skeleton such as 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane can also be used. Further, for example, (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane diglycidyl ether can also be exemplified. Diepoxides of methanol diglycidyl ether; such as trimethylolpropane triglycidyl ether, triepoxides of glycerol triglycidyl ether, etc. Among them, bisphenol epoxy resin, aminophenol epoxy resin and polysiloxane modified epoxy resin are preferred. More preferably, they are bisphenol A type epoxy resin and bisphenol F type epoxy resin. The liquid epoxy resin as the component (B) may be used alone or in combination of two or more.

The content of the liquid epoxy resin of the component (B) is preferably 0.5 to 70 parts by mass, more preferably 1 to 67 parts by mass, with respect to 100 parts by mass of the compound of the (A) component.

(C) A polymer compound having a mass average molecular weight (Mw) of 10,000 or more (C) A polymer compound having a mass-average molecular weight (Mw) of 10,000 or more (hereinafter referred to as a "polymer compound") is a component that imparts film-forming energy, and helps prevent warping and sinking during film formation. The so-called deviation refers to the situation in which the film ends gradually shrink toward the center during the film forming step, and the so-called depression refers to the situation in which crater-like unevenness is generated on the film surface during the film forming step. When the mass-average molecular weight (Mw) of the component (C) is less than 10,000, sufficient thin-film forming energy cannot be obtained, and deviations, dents, etc. at the time of thin-film formation cannot be prevented. The upper limit of the mass average molecular weight (Mw) of the component (C) is not particularly limited, but it is preferable to use 500,000 or less from the viewpoint of solubility in paint, and 200,000 or less is more preferable.

As the polymer compound of the component (C), a phenoxy resin having a mass average molecular weight (Mw) of 10,000 or more or an acrylic copolymer having a mass average molecular weight (Mw) of 10,000 or more can be used. The phenoxy resin as the component (C) may only be one having a mass average molecular weight (Mw) of 10,000 or more, and is not particularly limited. Bisphenol A type phenoxy resin, bisphenol F type phenoxy resin, bisphenol F Phenol A-bisphenol F copolymerized phenoxy resin is preferred. The acrylic copolymer as the component (C) is not particularly limited as long as it has a mass average molecular weight (Mw) of 10,000 or more, and is preferably a copolymer having a soft segment and a hard segment, and has a polybutylene as a soft segment. Based on the acrylate structure, and the polymethacrylate structure as the hard segment is preferred.

The content of the polymer compound of the component (C) is preferably 15 to 450 parts by mass, more preferably 20 to 400 parts by mass, with respect to 100 parts by mass of the compound of the (A) component.

(D) Filler with an average particle diameter of 1 μm or less In the filler of the component (D), when the film-like semiconductor sealing material of the present invention is used as NCF, it is added for the purpose of improving the reliability of the mounted semiconductor package. As the filler of the component (D), one having an average particle diameter of 1 μm or less is used. The reason for this is that it has excellent thin film visibility and fluidity with respect to a narrow gap of about 5 to 80 μm. As the filler, when the average particle size exceeds 1 μm, the visibility of the film is reduced, and when used as NCF, the identification mark that is the mark of the wafer or the wafer cannot be confirmed through the NCF attached to the wafer. . As the filler of the component (D), one having an average particle diameter of 0.7 μm or less is preferably used.

The filler of the component (D) is not particularly limited as long as the average particle diameter is 1 μm or less, and an inorganic filler can be used. Specifically, amorphous silicon dioxide, crystalline silicon dioxide, aluminum oxide, boron nitride, aluminum nitride, silicon carbide, silicon nitride, and the like can be mentioned. Among these, silica, especially amorphous spherical silica, is preferable from the viewpoint of chemical stability, ease of particle size adjustment, and dispersibility to resin components. In addition, this so-called silica is an organic group derived from a production raw material, and may have an alkyl group such as a methyl group and an ethyl group, for example. Amorphous spherical silica can be obtained by known production methods such as melting method, combustion method, sol-gel method, etc., and the production method can be appropriately selected according to characteristics such as desired particle size, impurity content, and surface state. method. Moreover, as the silica used as a filler, the composition containing silica obtained by the manufacturing method of Unexamined-Japanese-Patent No. 2007-197655 can also be used.

In addition, the shape of the filler is not particularly limited, and may be any form such as a spherical shape, an amorphous shape, and a scaly shape. In addition, when the shape of the filler is other than spherical, the average particle diameter of the filler means the average maximum diameter of the filler.

Moreover, as a filler, what was surface-treated with a silane coupling agent etc. can be used. When a surface-treated filler is used, the effect of preventing aggregation of the filler can be expected.

The content of the filler of the component (D) is preferably 5 to 75% by mass, preferably 10 to 70% by mass, with respect to the total mass of each component of the film-like semiconductor sealing material of the present invention.

(E) Compounds having an acid group whose weight loss on heating at 200°C is 30% or less The acid group-containing compound of the component (E) is a component that becomes a flux when the film-like semiconductor sealing material of the present invention is used as an NCF. When the film-like semiconductor sealing material of the present invention contains the component (E), when it is used as an NCF, electrical connectivity and reliability can be improved.

As the compound having an acid group as the component (E), the generation of voids in the TCB step can be suppressed when used as NCF by using a compound having a weight loss of 30% or less on heating at 200°C. Heating loss at 200°C can be determined as follows. Using a thermogravimetric analyzer, the temperature is increased at a constant rate (for example, 10° C./min) from a low temperature to a high temperature, and can be obtained by measuring the heating loss per temperature unit in the temperature increase. Oleic acid or stearic acid can be used as a compound having an acid group whose weight loss on heating at 200°C is 30% or less.

The acid group-containing compound of the component (E) is preferably a carboxylic acid type. The compound having an acid group of the component (E) is preferably at least one selected from the group consisting of oleic acid, stearic acid, abietic acid, and maleic acid resins. As the maleic acid resin, a commercial item can be used. As an example, Malchito No. 32 (product name, manufactured by Arakawa Chemical Industry Co., Ltd.) can be mentioned.

The content of the acid group-containing compound of the component (E) is preferably 0.5 to 35 parts by mass, more preferably 1 to 32 parts by mass, with respect to 100 parts by mass of the compound of the (A) component.

The film-like semiconductor sealing material of the present invention may further contain any of the following components.

(F) Silane Coupling Agent The silane coupling agent of the component (F) is added for the purpose of improving the adhesion to an IC chip or a substrate when the film-like semiconductor sealing material of the present invention is used as an NCF. As the silane coupling agent of the component (F), various silane coupling agents such as epoxy-based, amine-based, vinyl-based, methacrylic-based, acrylic-based, and mercapto-based can be used. Among these, when any one of the compounds of the following formula (3) or formula (4) is contained, it is preferable for reasons such as high adhesiveness.

When a silane coupling agent is contained as the component (F), the content of the silane coupling agent is preferably 0.1 to 3.5 mass % in terms of mass % with respect to the total mass of each component of the film-like semiconductor sealing material of the present invention. 0.2-3.0 mass % is preferable.

(G) Elastomer The elastomer of the component (G) is added for the purpose of adjusting the elastic modulus or stress when the film-like semiconductor sealing material of the present invention is used as NCF. As the elastomer of the component (G), those containing a polybutadiene skeleton are preferred from the viewpoint of flexibility, handling properties, and compatibility. As the elastomer containing a polybutadiene skeleton, epoxy-modified polybutadiene and carboxyl-terminated acrylonitrile-butadiene can be used.

When the elastomer is contained as the component (G), the content of the elastomer is preferably 0.1 to 25 parts by mass, preferably 0.2 to 20 parts by mass, with respect to 100 parts by mass of the compound of the (A) component.

(other compounding agents) The film-like semiconductor sealing material of this invention may further contain components other than the said (A)-(G) component as needed. Specific examples of such components include hardening accelerators, rheology modifiers, dispersants, precipitation inhibitors, antifoaming agents, colorants, and surface conditioners. Moreover, other solid resin may be contained for the purpose of adjusting the viscosity, toughness, etc. of the film-like semiconductor sealing material of this invention. As the above-mentioned solid resin, a solid epoxy resin can be used. Moreover, thermosetting resin other than (A) component and (B) component, for example, phenol resin, bismaleimide resin, cyanate resin, amine resin, imide resin, unsaturated polyester can be added Resins, (meth)acrylate resins, urethane resins. The type and compounding amount of each compounding agent can be based on conventional methods.

(Manufacture of film-like semiconductor sealing material) The film-like semiconductor sealing material of the present invention can be produced by a conventional method. For example, in the presence or absence of a solvent, the above-mentioned components (A) to (E), and the above-mentioned components (F), (G) and other components required for further compounding are prepared by heating and vacuum mixing and kneading. After mixing, a resin composition was prepared. The above-mentioned components (A) to (E), and the above-mentioned components (F), (G) and other compounding agents required for further compounding are dissolved in a predetermined solvent concentration in a desired content ratio, and these are heated to 10- At 80°C, put the required amount into the reaction kettle, and rotate at 100-1000 rpm, and mix at normal pressure for 3 hours, and then mix and stir for 3-60 minutes under vacuum (maximum 1 Torr). The resin composition prepared in the above procedure is diluted with a solvent to become a varnish, which is coated on at least one side of the support, and dried to provide a film-like semiconductor sealing material attached to the support or a film formed by the support. The peeled film-like semiconductor sealing material.

Examples of solvents that can be used as paints include ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic solvents such as toluene and xylene; dioctyl phthalate, dibutyl phthalate, and the like. High boiling point solvents such as phthalates, etc. The usage-amount of a solvent is not specifically limited, Although the conventional amount can be used, 20-90 mass % is preferable with respect to each component of a film-form semiconductor sealing material.

The support can be appropriately selected according to the desired form in the production method of the film-like semiconductor sealing material, and is not particularly limited, and examples thereof include metal foils such as copper and aluminum, resin carrier films such as polyester and polyethylene, and the like. When the film-like semiconductor sealing material of the present invention is provided in the form of a film peeled off from the support, it is preferable that the support is subjected to release treatment with a release agent such as polysiloxane.

The method of applying the paint is not particularly limited, and for example, a slot die method, a gravure method, and a blade coating method can be mentioned, and it can be appropriately selected according to the thickness of the desired film. The coating is performed until the thickness of the film formed after drying becomes a desired thickness. Such a thickness can be estimated by the operator from the solvent content.

The drying conditions can be appropriately designed according to the type and amount of the solvent used for painting, the amount of paint used, and the thickness of the coating.

Next, the characteristics of the film-like semiconductor sealing agent of the present invention will be described.

The film-like semiconductor sealing material of the present invention has excellent visibility, and the evaluation results of the visibility in the initial mounted state are good in the examples described later. Therefore, when it is used as NCF, it can be confirmed as an identification mark for marking the wafer or chip through the NCF attached to the wafer.

The film-like semiconductor sealing material of the present invention has excellent bending resistance, and no cracks occurred in the evaluation of film properties in the examples described later. Therefore, it is excellent in handling when conveying in or between devices such as a laminate, or when attaching devices. In addition, when used as NCF, there is no concern that cutting and burrs are generated in the dicing step performed after the TCB step. When the film-like semiconductor sealing material of the present invention is used as an NCF, the mountability in the TCB step is excellent, and the evaluation of voids and the evaluation of connectivity in the initial mounting state in the examples described later are favorable. When the film-like semiconductor sealing material of the present invention is used as an NCF, the moisture absorption reflow resistance is good, and the void/delamination at the time of moisture absorption reflow is evaluated as good in the Examples described later. The film-like semiconductor sealing material of the present invention can be mounted in a short time, so the productivity is high. The film-like semiconductor sealing material of the present invention combines the fluxing effect and has excellent solder connection.

Since the film-like semiconductor sealing material of this invention has the above-mentioned characteristic, it is suitable for NCF.

Next, the usage procedure of the film-like semiconductor sealing material of this invention is as follows. When a semiconductor package is mounted using the film-like semiconductor sealing material of the present invention, the film-like semiconductor sealing material is bonded to a laminate or the like in a desired shape with respect to the position of the semiconductor wafer on the mounting substrate. In addition, the wafers on which the semiconductor circuits are formed are bonded together with a laminate or the like, and then individual wafers can be cut out with a dicer or the like. The lamination conditions are not particularly limited, and conditions such as heating, pressurization, and decompression can be appropriately combined. In particular, when fine concavities and convexities are to be bonded without defects such as voids, the heating temperature is preferably 40 to 120° C., the decompression degree is 1 hPa or less, and the pressure is preferably 0.1 MPa or more. After bonding the film-like semiconductor sealing material by lamination or the like, a semiconductor wafer is mounted by thermocompression bonding (TCB) on the wafer mounting position on the substrate by a flip chip bonding machine or the like. The TCB conditions are not particularly limited, and the TCB conditions can be appropriately selected according to the size of the semiconductor wafer, the bump material, the number of bumps, and the like. The heating temperature is 50-300°C, the time is 1-20 seconds, and the pressure is 5-450N.

The semiconductor device of the present invention may only use the film-like semiconductor sealing material of the present invention in the manufacture of the semiconductor device, and is not particularly limited. As a specific example of the semiconductor device of the present invention, a semiconductor device having a flip-chip structure can be mentioned. The flip chip has protruding electrodes called bumps, and is connected to electrodes such as a substrate via the electrodes. As the bump material, solder, gold, copper, etc. are exemplified, and each can be exemplified independently, or a structure in which a solder layer is formed on copper can be exemplified. As the substrate to be connected to the flip-chip, single-layer or laminated organic substrates such as FR-4, inorganic substrates such as silicon, glass, and ceramics, copper and gold plating or tin plating on copper, and OSP on copper are used. (Organic Solderability Preservative) processing to form electrodes such as solder layers. Examples of semiconductor devices having a flip-chip structure include memory devices such as DRAM (Dynamic Random Access Memory), processing devices such as CPU (Central Processing Unit) GPU (Graphics Processing Unit), light-emitting elements such as LED (Light Emitting Diode), Used in driver ICs such as LCD (Liquid Crystal Display), etc. [Example]

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.

(Examples 1 to 26, Comparative Examples 1 to 7) Each raw material was mixed in the mixing ratio shown in the following table, and the mixture was dissolved and dispersed in a solvent so that the concentration of the mixture was 50 wt % to prepare a paint for coating. As a solvent, methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.) was used. On the release agent-coated PET (polyethylene terephthalate) film (35 μm thick), the coating layer was painted to a dry thickness of about 20 μm or about 35 μm. After that, the coated PET (polyethylene terephthalate) film treated with release agent was dried in a dryer at 80°C for 10 minutes, and then the solvent was removed to produce a 20 μm thick and 35 μm thick film. Thick 2 films. In addition, the numerical value about each composition in the table|surface represents a mass part.

(A2)下述式(2)所示化合物(製品名F-a型、四國化成工業股份有限公司製)

(B)液狀環氧樹脂 (B1)雙酚F型液狀環氧樹脂･雙酚A型液狀環氧樹脂混合物(製品名EXA835LV、DIC股份有限公司製，黏度：2000～2500mPa･s) (B2)雙酚A型液狀環氧樹脂(製品名EXA850CRP、DIC股份有限公司製，黏度：3500～5500mPa･s) (B3)雙酚F型液狀環氧樹脂(製品名EXA830CRP、DIC股份有限公司製，黏度：1100～1500mPa･s) (B’)雙酚A型半固體環氧樹脂(製品名EPICRON860、DIC股份有限公司製，黏度：1180Pa･s) (C)高分子化合物 (C1)丙烯酸共聚物(製品名M52N、Arkema股份有限公司製，Mw：約80000) (C2)丙烯酸共聚物(製品名LA4258、股份有限公司kuraray製，Mw：約80000) (C3)雙酚A/雙酚F共聚合型苯氧基樹脂、製品名jER4250、三菱化學股份有限公司製，Mw：60000) (D)二氧化矽填充物 (D1)製品名Sciqas，平均粒徑0.05μm(堺化學工業股份有限公司製) (D2)製品名Sciqas，平均粒徑0.1μm(堺化學工業股份有限公司製) (D3)製品名Sciqas，平均粒徑0.4μm(堺化學工業股份有限公司製) (D4)製品名Sciqas，平均粒徑0.7μm(堺化學工業股份有限公司製) (D’)製品名SOE-5、平均粒徑1.5μm(股份有限公司Admatechs製) (E)具有酸基的化合物 (E1)油酸(和光純藥工業股份有限公司製)，在200℃的加熱減量：1.7% (E2)硬脂酸(和光純藥工業股份有限公司製)，在200℃的加熱減量：0.8% (E3)樅酸(東京化成工業股份有限公司製)，在200℃的加熱減量：0.9% (E4)馬來酸樹脂(製品名馬耳其朵No32、荒川化學工業股份有限公司製)，在200℃的加熱減量：0.8% (E’)p-苯甲酸(和光純藥工業股份有限公司製)，在200℃的加熱減量：32.5% (F)矽烷偶合劑 (F1)3-環氧丙氧基丙基三甲氧基矽烷(式(3))(製品名：KBM403、信越化學股份有限公司製)

(F2)N-苯基-3-胺基丙基三甲氧基矽烷(式(4))(製品名：KBM573、信越化學股份有限公司製)

(G)彈性體 (G1)環氧變性聚丁二烯(製品名PB3600、東亞合成股份有限公司製) (G2)羧基末端丙烯腈-丁二烯(製品名CTBN、CVC Thermoset Specialties製)The components used in the preparation of the film-like resin composition are shown below. (A) Compound having a benzoxazine structure (A1) A compound represented by the following formula (1) (product name Pd type, manufactured by Shikoku Chemical Industry Co., Ltd.)

(A2) A compound represented by the following formula (2) (product name Fa type, manufactured by Shikoku Chemical Industry Co., Ltd.)

(B) Liquid epoxy resin (B1) Bisphenol F type liquid epoxy resin and bisphenol A type liquid epoxy resin mixture (product name EXA835LV, manufactured by DIC Co., Ltd., viscosity: 2000 to 2500 mPa･s) (B2) Bisphenol A type liquid epoxy resin (product name EXA850CRP, manufactured by DIC Corporation, viscosity: 3500 to 5500 mPa･s) (B3) Bisphenol F type liquid epoxy resin (product name EXA830CRP, manufactured by DIC Corporation) Co., Ltd., viscosity: 1100～1500mPa･s) (B') Bisphenol A type semi-solid epoxy resin (product name EPICRON860, manufactured by DIC Co., Ltd., viscosity: 1180Pa･s) (C) Polymer compound (C1 ) Acrylic copolymer (product name M52N, manufactured by Arkema Co., Ltd., Mw: about 80,000) (C2) Acrylic copolymer (product name LA4258, manufactured by Kuraray Co., Ltd., Mw: about 80,000) (C3) Bisphenol A/bisphenol Phenol F copolymerized phenoxy resin, product name jER4250, manufactured by Mitsubishi Chemical Co., Ltd., Mw: 60000) (D) Silica filler (D1) Product name Sciqas, average particle size 0.05 μm (Sakai Chemical Industry Co., Ltd. Co., Ltd.) (D2) Product name Sciqas, average particle size 0.1 μm (manufactured by Sakai Chemical Industry Co., Ltd.) (D3) Product name Sciqas, average particle size 0.4 μm (Sakai Chemical Industry Co., Ltd. product) (D4) Product Name Sciqas, average particle diameter 0.7 μm (manufactured by Sakai Chemical Industry Co., Ltd.) (D') product name SOE-5, average particle diameter 1.5 μm (manufactured by Admatechs Co., Ltd.) (E) Compound having an acid group (E1) Oleic acid (manufactured by Wako Pure Chemical Industries, Ltd.), weight loss at 200°C: 1.7% (E2) Stearic acid (manufactured by Wako Pure Chemical Industries, Ltd.), weight loss at 200°C: 0.8% (E3 ) Abietic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), weight loss by heating at 200°C: 0.9% (E4) Maleic acid resin (product name Malchito No32, manufactured by Arakawa Chemical Industry Co., Ltd.) at 200°C Heating weight loss: 0.8% (E') p-benzoic acid (manufactured by Wako Pure Chemical Industries, Ltd.), heating weight loss at 200°C: 32.5% (F) Silane coupling agent (F1) 3-glycidoxypropane Trimethoxysilane (formula (3)) (product name: KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.)

(F2) N-phenyl-3-aminopropyltrimethoxysilane (formula (4)) (product name: KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.)

(G) Elastomer (G1) Epoxy-modified polybutadiene (product name PB3600, manufactured by Toagosei Co., Ltd.) (G2) Carboxyl-terminated acrylonitrile-butadiene (product name CTBN, manufactured by CVC Thermoset Specialties)

Using the films produced in the above procedure, the following evaluations were carried out.

(thin film) The film formed on the PET by the above procedure was cut into 10 mm×100 mm to prepare a test piece. The test piece was bent by 180 degrees to check whether or not cracks occurred. The above procedure was applied to N=5 for each film thickness of 20 μm and 35 μm. The case where no two-film-thickness cracks occurred in all the film thicknesses of N=5 was indicated by ○, and the case where only one test piece was cracked was indicated by ×.

(Initial installation state) Using the 20 μm-thick film produced in the above procedure as an NCF, a test wafer was mounted on a substrate by the following procedure. The used substrate was a silicon substrate with a size of 10 mm×10 mm×0.725 mm(t), which was plated with Ni and Au on Cu as an electrode material. The test wafer has a size of 7.3 mm×7.3 mm×0.125 mm(t), and 1048 bumps for forming a solder layer (10 μm) on a copper pillar of 42 μmφ×10 μm are provided. On the silicon wafer of the structure connected to the above-mentioned dimensional test chip, 20 μm thick NCF was laminated using a vacuum press laminate (manufactured by Meiki Seisakusho Co., Ltd., trade name MLP500/600) under the following conditions. Vacuum degree: below 1hPa Temperature: 70℃ Pressurization: 0.4MPa Time: 180sec After lamination, a dicer was used to join the silicon wafers into individual test chips of a predetermined size (7.3 mm×7.3 mm) containing NCF. Then, using a flip chip bonding machine (manufactured by Panasonic Factory Solutions Co., Ltd., trade name FCB3), the test chip and the silicon substrate were subjected to thermocompression bonding (TCB) by applying a temperature of 260° C. to the NCF. The above procedure is implemented with N=5. Visibility: In the step of adjusting the position of the flip-chip bonding machine, the case where no recognition error occurred in all N=5 was ○, and the case where the recognition error occurred even with only one test piece was ×. Cavities: The produced test pieces were observed by a reflection method using an ultrasonic flaw detector (Scanning Acoustic Tomography, SAT). The case where the shadow of the cavity was not observed in all the images of N=5 was marked as ◯, and the case where the shadow was observed even with only one test piece was marked as ×. Connection: Among the produced test pieces, one test piece was pulled out, and the cross-section of the connected cross-section was ground and ground to observe the cross-section of a row of peripheral equipment parts. Whether there is solder wetting on the interface between the solder of the test wafer and the Pad of the Bottom wafer is checked by a scanning electron microscope.

(hygroscopic reflux) The test piece produced by the above procedure was left to stand for 168 hours under the conditions of 85° C./60% RH (JEDEC level 2 hygroscopic condition). After that, it passed through a reflow oven with a maximum temperature of 260°C 3 times. The above procedure is implemented with N=4. After the implementation of the moisture absorption reflow, the test piece was observed by the reflection method using an ultrasonic flaw detector (Scanning Acoustic Tomography, SAT). The case where no shadow of void/delamination was observed on all the images with N=4 was ○, and the case where shadow was observed even for only one test piece was x.

(Adhesion strength) An FR-4 substrate dried at 150° C. for 20 minutes, and a Si wafer with a SiN film having a square side of 2 mm as a semiconductor wafer were prepared. A film-shaped semiconductor sealing agent of 1 mmφ was placed on a substrate, and a semiconductor wafer was mounted on the film-shaped semiconductor sealing agent. Then, it was performed at 175 degreeC for 2.5 hours, and the thin-film semiconductor sealing agent was hardened. Adhesion strength (unit: N/mm ² ) was measured in shear mode using a superior strength tester (model: 1605HTP) manufactured by Aiko-Engineering. N=10 was implemented, and the average value of the adhesion strength was obtained.

In Examples 1 to 26, film properties (cracks), initial mounting state (void, connection, visibility), and moisture reflow (void/delamination) were all good. In addition, Example 2 is the example which changed the compound which has a benzoxazine structure of (A) component with respect to Example 1. Examples 3 and 4 are examples in which the polymer compound of the component (C) was changed with respect to Example 2. Examples 5 to 7 are examples in which silica fillers having different average particle diameters are used as the component (D) with respect to Example 2. Examples 8 and 9 are examples of the liquid epoxy resin in which the component (B) was changed with respect to Example 2. Example 10 is an example in which the silane coupling agent of the component (F) was changed with respect to Example 2. Example 11 is an example in which the silane coupling agent of (F) component was not added to Example 2, and the mixing ratio of the liquid epoxy resin of (B) component was changed. Example 12 is an example in which the compounding ratio of the liquid epoxy resin of the component (B) and the polymer compound of the component (C) was changed with respect to the semi-solid epoxy resin of Example 2 without adding the component (B'). Example 13 is an example in which the mixing ratio of the silica filler of the component (D) is changed with respect to Example 2. Example 14 is an example in which the mixing ratio of the liquid epoxy resin of the component (B), the semi-solid epoxy resin of the component (B'), and the silica filler of the component (D) was changed with respect to the example 2. Example 15 Example 2 is an example in which the mixing ratio of the liquid epoxy resin of the component (B) was changed by using two types of polymer compounds of the component (C) in combination with the elastomer to which the component (G) was not added. Example 16 is an example in which the compounding ratio of the liquid epoxy resin of (B) component and the silane coupling agent of (F) component was changed with respect to Example 2. Example 17 is an example in which the compounding ratio of the silane coupling agent of the component (F) and the elastomer of the component (G) was changed with respect to the example 2. Example 18 is an example in which the compounding ratio of the compound of (E) component and the elastomer of (G) component was changed with respect to Example 2. Example 19 is an example in which the compounding ratio of the semi-solid epoxy resin of the component (B') and the compound of the component (E) was changed with respect to the example 2. Examples 20, 25, and 26 are examples of compounds in which the component (E) was changed with respect to Example 2. Example 21 is an example in which the compounding ratio of the liquid epoxy resin of (B) component and the compound of (E) component was changed with respect to Example 2. Example 22 is an example in which the mixing ratio of each component is changed with the use of two types of polymer compounds of the component (C) in combination with the semi-solid epoxy resin containing no (B') component added in Example 2. Example 23 is an example in which the polymer compound of the component (C) and the elastomer of the component (G) were changed with respect to the example 2. Example 24 For Example 2, which is an elastomer to which the (G) component is not added, the liquid epoxy resin of the (B) component, the semi-solid epoxy resin of the (B') component, the compound of the (C) component, and ( D) Example of the compounding ratio of the silica filler of the component. Comparative Example 1 is an example in which a silica filler having an average particle size exceeding 1 µm was used as the component (D'), and the visibility in the initial mounting state was x. Therefore, other evaluations in the initial installation state and moisture reflow evaluation were not carried out. Comparative Example 2 is an example of the compound to which the component (E) is not added, and the connectivity in the initial mounting state is ×. Therefore, no hygroscopic reflux assessment was performed. Comparative Example 3 is an example of the silica filler to which the component (D) is not added, and the moisture absorption reflow evaluation is x. Comparative Example 4 is an example in which a compound whose weight is reduced by more than 30% on heating at 200°C is used as the component (E'), and the void in the initial mounting state is x. Therefore, no hygroscopic reflux assessment was performed. Comparative Examples 5 and 6 are examples of the liquid epoxy resin to which the component (B) is not added, and the evaluation of the film properties is x. Therefore, the evaluation in the initial installation state and the evaluation of moisture recirculation were not carried out. From the results of Comparative Examples 5 and 6, even in the case of the elastomer containing the component (G), it was confirmed that the film properties deteriorated in the case of the liquid epoxy resin not containing the component (B). Comparative Example 7 is an example of the compound to which the component (A) is not added, and the void in the initial mounting state is x. Therefore, no hygroscopic reflux assessment was performed.

Claims (10)

A film-shaped semiconductor sealing material is characterized by containing (A) a compound having a benzoxazine structure, (B) an epoxy resin that is liquid at room temperature, (C) a polymer compound having a mass average molecular weight (Mw) of 10,000 or more, (D) Fillers with an average particle size of 1 μm or less and (E) A compound having an acid group whose heating loss at 200°C is 30% or less. The film-like semiconductor sealing material according to claim 1, wherein the compound having a benzoxazine structure of the component (A) is a compound represented by the following formula (1) or formula (2);

. The film-like semiconductor sealing material according to claim 1, wherein the epoxy resin of the component (B) which is liquid at room temperature is any one of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin. The film-like semiconductor sealing material according to claim 1, wherein the compound of the component (E) is a carboxylic acid. The film-like semiconductor sealing material according to claim 1, wherein the compound of the component (E) is at least one selected from the group consisting of oleic acid, stearic acid, abietic acid, and maleic acid resins. The film-like semiconductor sealing material of Claim 1 which further contains (F) a silane coupling agent. The film-like semiconductor sealing material according to claim 6, wherein the silane coupling agent of the component (F) is a compound containing any one of the following formula (3) or formula (4);

. The film-like semiconductor sealing material according to claim 1, which further contains (G) an elastomer. The film-like semiconductor sealing material according to claim 8, wherein the elastomer of the component (G) contains a polybutadiene skeleton. A semiconductor device characterized by using the film-like semiconductor sealing material according to any one of claims 1 to 9.