JPH11260839A - Adhesive composition for semiconductor device and adhesive sheet for semiconductor device using the adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To increase the reliability and processibility of a substrate for connecting semiconductor integrated circuits in high density mounting and of a semiconductor device, and thereby increase the profitability by industrially providing an adhesive composition for a semiconductor device which has superior processibility, adhesive force, high in insulating reliability and durability and an adhesive sheet for a semiconductor device manufactured using the adhesive composition. SOLUTION: In a substrate for connecting semiconductor integrated circuits, having a wiring board layer constituted of an insulator layer and a conductor pattern, a layer formed with no conductor pattern and an adhesive layer, each of at least one or more layers, an adhesive composition which forms the adhesive layer includes at least one kind of each thermoplastic resin and thermosetting resin and has such as property that 2N cm<-1> <=P1 <=30N cm<-1> , 2N cm<-1> <=P2 <=30N cm<-1> , 0.2<=P2 /P1 , where P1 is the adhesive force in an uncured state and P2 is the adhesive force lapse of after 100 hours at 30 deg.C. With the use of this adhesive composition, an adhesive sheet for a semiconductor device is manufactured.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive composition for forming a substrate (interposer) for connecting a semiconductor integrated circuit used when mounting and packaging a semiconductor integrated circuit and a semiconductor device using the same. It relates to an adhesive sheet. More specifically, a ball grid array (BG
A), a wiring board layer composed of an insulator layer and a conductor pattern constituting a substrate for connecting a semiconductor integrated circuit used in a land grid array (LGA) and a pin grid array (PGA) method, for example, a metal reinforcing plate (stiffener)
Adhesion between layers where conductor patterns such as etc. are not formed,
The present invention also relates to an adhesive composition having a function of relieving thermal stress generated between respective layers due to a temperature difference, and an adhesive sheet for a semiconductor device using the same.

[0002]

2. Description of the Related Art Conventionally, as a semiconductor integrated circuit (IC) package, a dual in-line package (DIP),
Package forms such as a small outline package (SOP) and a quad flat package (QFP) have been used. However, with the increase in the number of pins of the IC and the miniaturization of the package, the limit of the QFP that can increase the number of pins is approaching its limit. This is due to the difficulty in maintaining the flatness of the leads and the difficulty in obtaining solder printing accuracy on the printed circuit board, particularly when mounting on a printed circuit board.
Therefore, in recent years, BGA method, LGA method, PGA method and the like have been put to practical use as means for increasing the number of pins and reducing the size.
Above all, the BGA method has attracted attention because of its low cost, light weight, and thinness due to the use of plastic materials.

FIG. 1 shows an example of the BGA system. The BGA method is characterized by having solder balls 9 corresponding to the number of pins of an IC on a grid (grid array) as external connection portions of a semiconductor integrated circuit connection substrate in which the ICs 1 are connected by gold bumps 2. The connection to the printed board is performed by placing the solder ball surface on the conductor pattern 5 of the printed board on which the solder is already printed so as to melt the solder by reflow. The greatest feature is that since the surface of the substrate for connecting a semiconductor integrated circuit can be used, more terminals can be arranged in a smaller space as compared with a package such as QFP which can use only peripheral sides. A chip-scale package (CSP) has further advanced this miniaturization function.
-BGA). The present invention relates to these BGs.
The present invention can be applied to a CSP having an A structure.

On the other hand, the BGA method has the following problems. (A) maintaining the flatness of the solder ball surface; (b) improving the heat dissipation; (c) mitigating the thermal stress applied to the solder ball during temperature cycling and reflow; (d) higher due to the large number of reflows Requires reflow resistance. As a method of improving these, a method of laminating a material such as a metal plate for reinforcement, heat radiation, and electromagnetic shielding on a substrate for connecting a semiconductor integrated circuit is generally used. This is particularly important when a TAB tape or a flexible printed board is used for a wiring board layer including an insulator layer 3, an adhesive layer 4, and a conductor pattern 5 for connecting an IC. For this reason, as shown in FIG. 2, the substrate for connecting a semiconductor integrated circuit includes a wiring board layer including an insulator layer 11 and a conductor pattern 13 for connecting an IC, a reinforcing plate (stiffener), and a heat sink (heat spreader). ), A layer 15 on which a conductor pattern such as a shield plate is not formed, and at least one adhesive layer 14 for laminating these layers. These semiconductor integrated circuit connection substrates are prepared in advance by forming an intermediate product in which an adhesive layer is formed on either a wiring substrate layer or a layer on which no conductor pattern is formed. It is generally produced by laminating a layer and a layer on which a conductor pattern is not formed, heating and curing the adhesive layer and molding.

[0005] From the above points, the following characteristics are required as the characteristics required of the adhesive layer 14. (A) High adhesive strength that does not peel off even under reflow conditions (230 ° C. or higher)
(B) To reduce thermal stress applied between dissimilar materials such as a wiring board layer and a reinforcing plate during a temperature cycle or reflow,
Moderate elastic modulus and linear expansion coefficient characteristics, (c) low temperature of bonding and heating and curing, easy processability for short-time process, and (d) insulation when laminated on wiring.

In particular, in the processing step (c), a relatively thick metal plate is often used for a layer on which a conductor pattern is not formed, since the flatness is usually emphasized.
It is difficult to continuously and continuously perform a bonding step with a wiring board layer supplied as a continuous tape using a tape or a flexible printed board. Therefore, it is more common that these are punched into a sheet having a size close to the final semiconductor device (BGA package) and bonded to a continuous tape-shaped wiring board layer. Therefore, an appropriate adhesive force is required so as not to cause a positional shift in a process from bonding to heating curing.

From such a viewpoint, conventionally, a thermoplastic resin or a silicone elastomer (Japanese Patent Publication No.
-50448) and the like.

[0008]

However, the conventional adhesive composition does not always provide sufficient adhesive strength in the process from bonding to heating and curing. For example, an adhesive composition composed of a thermoplastic resin has the advantage that heating cure is unnecessary if the initial adhesive strength can be ensured, but has a high softening point to withstand solder reflow, so in the bonding step There is a problem that high heat and pressure exceeding the softening point of the resin are required. On the other hand, in the case of an adhesive sheet made of a thermosetting resin, misalignment in a process from bonding to heat curing is prevented by the adhesive force caused by the low-viscosity uncured resin component. However, since the adhesive strength is reduced even by a slight increase in viscosity due to the progress of the curing reaction, a defect due to displacement may occur even though the adhesive strength after heat curing is sufficiently exhibited.

The present invention solves the above problems and provides a novel semiconductor excellent in bonding workability at the time of preparing a substrate for connecting a semiconductor integrated circuit while maintaining excellent adhesive strength, insulation reliability and durability. An object of the present invention is to provide an adhesive composition for a device and an adhesive sheet for a semiconductor device using the same.

[0010]

Means for Solving the Problems In order to achieve the above object, the present inventors have conducted intensive studies on the curing reaction of the adhesive component of the adhesive composition for semiconductor devices, and found that By controlling the reactivity of the resin and skillfully combining the curing agent of the thermosetting resin, the bonding process when creating a substrate for connecting semiconductor integrated circuits while maintaining excellent adhesive strength, insulation reliability and durability. The present inventors have found that an adhesive composition for a semiconductor device having excellent properties and suitable for a substrate for connecting a semiconductor integrated circuit can be obtained, and the present invention has been accomplished.

That is, the present invention provides a semiconductor having at least one layer of (A) a wiring board layer comprising an insulator layer and a conductor pattern, (B) a layer having no conductor pattern formed thereon, and (C) an adhesive layer. An adhesive composition for a semiconductor device forming an adhesive layer (C) of an integrated circuit connection substrate, wherein the adhesive composition contains at least one or more of a thermoplastic resin and a thermosetting resin as essential components, respectively. When the adhesive strength in an uncured state is P _{1 and} the adhesive strength after 100 hours in an environment of 30 ° C. is P ₂ , ₂ Ncm
^-1 ≦ P ₁ ≦ 30 Ncm ⁻¹ , ₂ Ncm ⁻¹ ≦ P ₂ ≦ 30 Ncm
^-1 and 0.2 ≦ P ₂ / P ₁ , and an adhesive composition for a semiconductor device, and an adhesive sheet for a semiconductor device using the same.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The substrate for connecting a semiconductor integrated circuit according to the present invention is for connecting a semiconductor integrated circuit (bare chip) which has been separated after a device is formed on a semiconductor substrate such as silicon. (A) a wiring board layer comprising an insulator layer and a conductor pattern, (B) a layer having no conductor pattern formed thereon, and (C) an adhesive layer comprising the adhesive composition of the present invention, each having at least one or more layers. If so, the shape, material, and manufacturing method are not particularly limited. Therefore, the most basic structure is A / C / B, but this also includes a multilayer structure such as A / C / B / C / B.

(A) is a layer having a conductor pattern for connecting an electrode pad of a bare chip to the outside of a package (a printed circuit board or the like). The conductor pattern is formed on one or both sides of an insulator layer. is there. The insulator layer referred to here is made of a plastic such as polyimide, polyester, polyphenylene sulfide, polyether sulfone, polyether ether ketone, aramid, polycarbonate, polyarylate, or a composite material such as an epoxy resin impregnated glass cloth, and has a thickness of 10%. ~ 125μ
An insulating film having a flexibility of m, a ceramic substrate of alumina, zirconia, soda glass, quartz glass, or the like is suitable, and a plurality of layers selected from these may be laminated and used. If necessary, the insulator layer may be subjected to surface treatment such as hydrolysis, corona discharge, low-temperature plasma, physical surface roughening, and easy adhesion coating treatment. The formation of the conductor pattern is generally performed by either the subtractive method or the additive method, but any of them may be used in the present invention. In the subtractive method, a metal plate such as a copper foil is adhered to the insulator layer with an insulating adhesive (the adhesive composition of the present invention can also be used), or the metal plate is provided with the insulator layer. A pattern is formed by stacking precursors and etching a material prepared by a method of forming an insulator layer by heat treatment or the like by a chemical solution treatment. Specific examples of the material here include a copper-clad material for a rigid or flexible printed circuit board and the TAB tape shown in FIG. In FIG. 3, reference numeral 17 denotes an insulating film, 18 denotes an adhesive, 19 denotes a sprocket hole, 20 denotes a device hole, 21 denotes a conductor pattern, and 22 denotes a conductor for solder ball connection. On the other hand, in the additive method, a conductor pattern is directly formed on the insulator layer by electroless plating, electrolytic plating, sputtering, or the like. In any case, the formed conductor may be plated with a metal having high corrosion resistance to prevent corrosion. Via holes may be formed in the wiring board layer (A) formed as described above, if necessary, and the conductor patterns formed on both sides by plating may be connected by plating.

(B) is a uniform layer substantially independent of (A) or (C), for reinforcing and dimensionally stabilizing a substrate for connecting a semiconductor integrated circuit (generally referred to as a reinforcing plate or a stiffener). , Electromagnetic shielding between outside and IC, I
Heat dissipation of C (generally referred to as a heat sink, heat spreader, heat sink, etc.), imparting flame retardancy to a substrate for connecting a semiconductor integrated circuit, imparting discriminability by the shape of the substrate for connecting a semiconductor integrated circuit, etc. It carries the function. Therefore, the shape may be not only a layer shape but also a three-dimensional shape having a fin structure for heat dissipation. In addition, any insulator or conductor may be used as long as it has the above function, and the material is not particularly limited. Examples of metals include copper, iron, aluminum, gold, silver, nickel, and titanium.
Examples of the inorganic material include alumina, zirconia, soda glass, quartz glass, carbon, and the like, and examples of the organic material include polyimide, polyamide, polyester, vinyl, phenol, and epoxy polymer materials.
Further, a composite material obtained by combining these can also be used.
For example, those having a shape in which thin metal plating is formed on a polyimide film, those having conductivity by kneading carbon into a polymer, and those having a metal plate coated with an organic insulating polymer can be exemplified. Further, it is not limited that various surface treatments are performed in the same manner as in the above (A).

(C) is an adhesive layer mainly used for adhesion between (A) and (B). However, the use of (A) or (B) for bonding to another member (for example, an IC or a printed board) is not limited at all. This adhesive layer is usually laminated in a semi-cured state on the semiconductor integrated circuit connection substrate, and before or after lamination, 30 to 20 times.
The degree of curing can be adjusted by performing a pre-curing reaction at a temperature of 0 ° C. for an appropriate time. This adhesive layer is an adhesive composition for a semiconductor device of the present invention (hereinafter referred to as an adhesive composition).
Is formed from the adhesive composition when the adhesive force after adhesion 100 hours elapsed in an environment of P _1, 30 ° C. in an uncured state and P _2, preferably 2N cm ^-1 ≦ P ₁ ≦ 30
N cm ⁻¹ , 2 N cm ⁻¹ ≦ P ₂ ≦ 30 N cm ⁻¹ , and 0.2 ≦ P ₂ / P ₁ , more preferably 4 N cm ⁻¹ ≦
P ₁ ≦ 20 N cm ⁻¹ , 4 N cm ⁻¹ ≦ P ₂ ≦ 20 N cm
⁻¹ and 0.5 ≦ P ₂ / P ₁ .

P ₁ <2N cm ⁻¹ and P ₂ <2N cm ⁻¹
In the case of (1), the adhesive strength is too low and a positional shift occurs in the process from bonding to heating and curing, which is not preferable. When 30 N cm ^-1 ≤ P ₁ and 30 N cm ^-1 ≤ P ₂ , the adhesive strength is too strong, which hinders the laminating process. When P ₂ / P ₁ <0.2, the storage life is too short and the workability is reduced, which is not preferable.

The adhesive composition preferably has an adhesive strength after heat curing of 5 N cm ^-1 or more, more preferably ¹ N cm ^-1.
It is preferable that it is ⁰ N cm ^-1 or more. If the adhesive strength after heat curing is lower than 5 N cm ^-1 , it is not preferable because peeling occurs during handling of the package and reflow resistance is reduced.

The thickness of the adhesive layer can be appropriately selected depending on the relationship between the elastic modulus and the coefficient of linear expansion, but is preferably 2 to 500 μm, more preferably 20 to 200 μm.

It is essential that the adhesive composition of the present invention contains at least one type of thermoplastic resin and at least one type of thermosetting resin as essential components, but the type is not particularly limited. Thermoplastic resin has functions such as adhesion, flexibility, relaxation of thermal stress, and improvement of insulation due to low water absorption. Thermosetting resin has heat resistance, insulation at high temperatures, chemical resistance, and adhesion. It is necessary to achieve a balance between physical properties such as strength of the agent layer.

As the thermoplastic resin, acrylonitrile-butadiene copolymer (NBR), acrylonitrile-
Butadiene rubber-styrene resin (ABS), polybutadiene, styrene-butadiene-ethylene resin (SEB
S), acrylic, polyvinyl butyral, polyamide,
Known materials such as polyester, polyimide, polyamideimide, and polyurethane are exemplified. Further, these thermoplastic resins may have a functional group capable of reacting with a thermosetting resin described below. Specific examples include an amino group, a carboxyl group, an epoxy group, a hydroxyl group, a methylol group, an isocyanate group, a vinyl group, and a silanol group. These functional groups are preferable because the bond with the thermosetting resin is strengthened and the heat resistance is improved. As the thermoplastic resin, a copolymer containing butadiene as an essential copolymer component is particularly preferred from the viewpoint of adhesiveness to the material (B), flexibility, and an effect of relaxing thermal stress, and various types can be used. Particularly, acrylonitrile-butadiene copolymer (NBR), styrene-butadiene-ethylene resin (SEBS), styrene-butadiene resin (SBS), and the like are preferable from the viewpoints of adhesion to metals, chemical resistance, and the like. Further, a copolymer containing butadiene as an essential copolymer component and having a carboxyl group is more preferable. For example, NBR (NBR-C) and SEB
S (SEBS-C), SBS (SBS-C) and the like. Examples of NBR-C include acrylonitrile and butadiene copolymerized in a molar ratio of about 10/90 to 50/50, in which the end groups of a copolymer rubber are carboxylated, or acrylonitrile, butadiene and acrylic acid, maleic acid, etc. And a terpolymer rubber of a carboxyl group-containing polymerizable monomer. Specifically, PN
R-1H (Nippon Synthetic Rubber Co., Ltd.), "Nipol" 10
72J, "Nipole" DN612, "Nipole" DN6
31 (Nippon Zeon Co., Ltd.), "Hiker" CTB
N (manufactured by BF Goodrich) and the like. SEBS
MX-73 (manufactured by Asahi Kasei Corporation) as C
-C is D1300X (manufactured by Shell Japan Co., Ltd.)
Can be exemplified.

Examples of the thermosetting resin include known resins such as epoxy resin, phenol resin, melamine resin, xylene resin, furan resin and cyanate ester resin. Particularly, epoxy resin and phenol resin are preferable because of their excellent insulating properties.

The epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule, but is not limited to bisphenol F, bisphenol A, bisphenol S,
Diglycidyl ethers such as resorcinol, dihydroxynaphthalene, dicyclopentadiene diphenol, epoxidized phenol novolak, epoxidized cresol novolak, epoxidized trisphenylolmethane, epoxidized tetraphenylolethane, epoxidized metaxylenediamine, cyclohexane epoxide, etc. Alicyclic epoxy, and the like. Further, it is effective to use a halogenated epoxy resin, particularly a brominated epoxy resin, for imparting flame retardancy. At this time, although the use of only the brominated epoxy resin can impart flame retardancy, the heat resistance of the adhesive is greatly reduced, so that it is more effective to use a mixed system with a non-brominated epoxy resin. Examples of the brominated epoxy resin include a copolymerized epoxy resin of tetrabromobisphenol A and bisphenol A, or "BR
EN "-S (manufactured by Nippon Kayaku Co., Ltd.) and the like. These brominated epoxy resins are used in combination of two or more kinds in consideration of bromine content and epoxy equivalent. May be.

As the phenol resin, any known phenol resin such as a novolak phenol resin and a resol phenol resin can be used. For example, alkyl-substituted phenols such as phenol, cresol, pt-butylphenol, nonylphenol, and p-phenylphenol; cyclic alkyl-modified phenols such as terpene and dicyclopentadiene; and heterocycles such as nitro, halogen, cyano, and amino groups. Those having a functional group containing atoms, naphthalene, those having a skeleton such as anthracene,
Examples of resins include polyfunctional phenols such as bisphenol F, bisphenol A, bisphenol S, resorcinol, and pyrogallol.

The addition amount of the thermosetting resin is 10
5-400 parts by weight, preferably 50-400 parts by weight per 0 parts by weight
200 parts by weight. When the addition amount of the thermosetting resin is less than 5 parts by weight, the elastic modulus at a high temperature is remarkably reduced, and the semiconductor integrated circuit connection substrate is deformed during use of the device on which the semiconductor device is mounted, and is handled in a processing step. This is not preferable because of lack of workability. If the addition amount of the thermosetting resin exceeds 400 parts by weight, the modulus of elasticity is high, the coefficient of linear expansion is small, and the effect of relaxing thermal stress is small.

The addition of a curing agent and a curing accelerator for epoxy resin and phenol resin to the adhesive layer of the present invention is not limited at all. For example, 3,3'5,5'-tetramethyl-4,4'-diaminodiphenylmethane,
3,3'5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 3,3
'-Dichloro-4,4'-diaminodiphenylmethane,
2,2'3,3'-tetrachloro-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 3,3'-diaminobenzophenone, 3,3 '
-Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminobenzophenone, 3,4,4
Aromatic polyamines such as'-triaminodiphenylsulfone; amine complexes of boron trifluoride such as boron trifluoride triethylamine complex; imidazole derivatives such as 2-alkyl-4-methylimidazole and 2-phenyl-4-alkylimidazole; Organic acids such as phthalic anhydride and trimellitic anhydride, dicyandiamide and triphenylphosphine can be used. These may be used alone or in combination of two or more. The addition amount is preferably 0.1 to 50 parts by weight based on 100 parts by weight of the adhesive composition.

The curability of the curing agent in a normal temperature environment in which the adhesive composition and the adhesive sheet are handled, that is, the pot life is preferably 50 hours or more, and more preferably 100 hours or more. The pot life in the present invention is defined as 30 minutes when a system obtained by mixing 5 parts by weight of a curing agent with 100 parts by weight of bisphenol A diglycidyl ether is stored at 30 ° C.
It is defined as the time at which the viscosity η measured at ° C. becomes twice that immediately after preparation. Examples of such an amine include boron trifluoride amine complexes such as boron trifluoride triethylamine complex, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, DBU (1, 8-diazabicyclo (5,4,
0) Undecene-7) organic acid salt and the like. Regardless of the pot life, it is also possible to impart a latent curing property by microencapsulating the curing agent. Examples of such a substance include microencapsulated imidazole, HX-3741, HX-3088
(Manufactured by Asahi Kasei Corporation) and HX-3613 (manufactured by Asahi Kasei Corporation) which is a microencapsulated dicyandiamide.

On the other hand, when a mixture of two or more curing agents is used, at least one kind of each of a cationically polymerizable curing agent and an anionically polymerizable curing agent having a pot life of preferably at least 50 hours, more preferably at least 100 hours, is used. If you include the above,
The ratio of the storage life to the heat-curing rate of the adhesive composition and the adhesive sheet is preferably larger than when each is used alone. In this case, the addition ratio of the anionic polymerizable curing agent to the cationic polymerizable curing agent is preferably from 0.1 to 10.0, more preferably from 0.5 to 5.
More preferably, it is 0 or less. As an example of a combination of a cationic polymerizable curing agent and an anionic polymerizable curing agent,
Boron trifluoride monoethylamine complex and dicyandiamide, boron trifluoride monoethylamine complex and 2-heptadecylimidazole, antimony triethylamine pentafluoride complex and dicyandiamide, sulfonate of ammonium tetraphenylborate and DBU (manufactured by San Apro Corporation, UCAT-603), a sulfonium salt of antimony hexafluoride (manufactured by Sanshin Chemical Co., Ltd., Sun Aid SI-
100L) and dicyandiamide.

In addition to the above components, addition of organic or inorganic components such as an antioxidant and an ion scavenger is not limited as long as the properties of the adhesive are not impaired. Examples of fine inorganic components include aluminum hydroxide, magnesium hydroxide, metal hydroxides such as calcium aluminate hydrate, silica, alumina, zirconium oxide, zinc oxide, antimony trioxide, antimony pentoxide, and magnesium oxide. Titanium oxide, iron oxide, cobalt oxide, chromium oxide, metal oxides such as talc, inorganic salts such as calcium carbonate, aluminum, gold, silver, nickel, iron, metal fine particles such as, or carbon black, glass, Examples of the organic component include crosslinked polymers such as styrene, NBR rubber, acrylic rubber, polyamide, polyimide, and silicone. These may be used alone or in combination of two or more. The average particle diameter of the fine component is preferably 0.2 to 5 μm in consideration of dispersion stability. Also,
The compounding amount is suitably 2 to 50 parts by weight of the whole adhesive composition.

The adhesive sheet for a semiconductor device of the present invention is:
The adhesive composition for a semiconductor device of the present invention is used as an adhesive layer, and has at least one or more peelable protective film layers. For example, a two-layer configuration of a protective film layer / adhesive layer or a three-layer configuration of a protective film layer / adhesive layer / protective film layer corresponds to this.

The protective film layer referred to here is (A) a wiring board layer (TAB) composed of an insulator layer and a conductor pattern.
Before bonding the adhesive layer to a layer (stiffener or the like) on which no conductive pattern is formed (tape or the like), the adhesive layer is not particularly limited as long as it can be peeled off without impairing the form and function of the adhesive layer. Plastic films such as polyolefin, polyphenylene sulfide, polyvinyl chloride, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, polyvinyl butyral, polyvinyl acetate, polyvinyl alcohol, polycarbonate, polyamide, polyimide, polymethyl methacrylate, etc. Alternatively, a film coated with a release agent such as a fluorine compound, a paper laminated with such a film, a paper impregnated or coated with a resin having a release property, and the like can be given.

When a protective film layer is provided on both sides of the adhesive layer, when the peeling force of each protective film layer with respect to the adhesive layer is F ₁ , F ₂ (F ₁ > F ₂ ), F ₁ -F ₂
Is preferably 5 N m ^-1 or more, more preferably 15 N m ^-1 or more.
m ^-1 or more is required. If F ₁ -F ₂ is less than 5 N m ⁻¹ , it is not preferable because which protective film layer side the peeled surface is not stable, and it becomes a serious problem in use. Further, the peeling forces F ₁ and F ₂ are preferably both 1 to 1.
200 N m ^-1, more preferably 3 to 100 nm ^-1
It is. If it is lower than 1 N m ^{-1, the} protective film layer will fall off, and if it exceeds 200 N m ^-1 , peeling is unstable and the adhesive layer may be damaged, which is not preferable.

Next, examples of the adhesive composition of the present invention and a method for producing an adhesive sheet for a semiconductor device using the same will be described.

(A) A coating obtained by dissolving the adhesive composition of the present invention in a solvent is applied on a polyester film having releasability and dried. It is preferable to apply the adhesive layer so that the film thickness is 10 to 100 μm. Drying condition is 10
0 to 200 ° C for 1 to 5 minutes. The solvent is not particularly limited, but aromatic solvents such as toluene, xylene and chlorobenzene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and aprotic polar solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone alone or a mixture thereof are preferred. It is.

(B) The adhesive sheet of the present invention is obtained by laminating a polyester or polyolefin-based protective film layer having a releasability having a lower peel strength than the above to the film of (a). When the thickness of the adhesive is further increased, the adhesive sheet may be laminated plural times. After lamination, the degree of curing may be adjusted by heat treatment at 40 to 70 ° C. for about 20 to 200 hours.

[0035]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these examples. Before starting the description of the embodiments, an evaluation method will be described.

Evaluation method (1) Preparation of pattern tape for evaluation: An 18 μm electrolytic copper foil was laminated on a tape with an adhesive for TAB (# 7100, manufactured by Toray Industries, Inc.) at 140 ° C. and 0.1 MPa. Then, in an air oven at 80 ° C for 3 hours, 100
The tape was heated and cured sequentially at 150 ° C. for 5 hours at 150 ° C. to prepare a TAB tape with a copper foil. A photoresist film was formed on the copper foil surface of the obtained TAB tape with copper foil, etching, and resist peeling were performed by a conventional method to prepare a pattern tape sample for evaluation.

(2) Conductive pattern embedding and cure foaming: A pure copper plate having a thickness of 100 mm and having an adhesive layer of an adhesive composition and having a thickness of 0.1 mm was used as a conductor of the pattern tape for evaluation of (1). 130 ° C, 0.1
After laminating under the condition of MPa, 1
Heat curing treatment was performed at 50 ° C. for 2 hours. This was immersed in an etching solution containing ferric chloride as a main component to dissolve the pure copper plate. Finally, the exposed adhesive layer was observed under a microscope to evaluate the foaming during curing and the embedding property of the conductor pattern.

(3) Peel strength: A pure copper plate with an adhesive layer similar to that of (2) was applied to a polyimide film ("UPILEX" 75S, manufactured by Ube Industries, Ltd.) at 130 ° C. and 0.1 MPa.
After laminating under the conditions of a, 150
Heat curing treatment was performed at 2 ° C. for 2 hours. The polyimide film of the obtained sample was cut so as to have a width of 2 mm, and peeled at a speed of 50 mm / min in a 90 ° direction, and the peeling force at that time was measured.

(4) Insulation reliability: Conductor width 100 μm, distance between conductors 100 μm of pattern tape for evaluation in (1)
On the conductor pattern surface of the sample for evaluating the comb shape,
A pure copper plate with an adhesive layer similar to that of (2) was heated at 130 ° C.
After laminating under the condition of 0.1 MPa, a heat curing treatment was performed in an air oven at 150 ° C. for 2 hours. Using the obtained sample, in a state where a voltage of 100 V was continuously applied in a thermo-hygrostat at 85 ° C. and 85% RH, the resistance value was measured immediately after the measurement and after 200 hours.

(5) Solder heat resistance: A 30 mm square sample prepared by the above method (3) was conditioned for 48 hours in an atmosphere of 85 ° C. and 85% RH, and immediately placed on a solder bath for 60 seconds. The highest temperature without floating, swelling and peeling was measured.

(6) Heat cycle test: A 30 mm square sample prepared by the above method (3) was subjected to a heat cycle tester (PL-3 model, manufactured by Tabai Espec Co., Ltd.) at -20.
600 cycles of treatment were carried out at a temperature of 1 to 100 ° C and a minimum and maximum temperature of 1 hour each, and the occurrence of peeling was evaluated.

(7) Protective film layer peeling force: In the case of a protective layer having a low peeling force, an adhesive sheet having a width of 30 mm is attached to a stainless steel plate with a double-sided tape, and the protective film is removed in a 90 ° direction.
Peeling was performed at a speed of 00 mm / min, and the peeling force at that time was measured. On the other hand, in the case of a protective layer having a high peeling force, the width is 30 m.
The protective film layer having a low peeling force is peeled off from the adhesive sheet having a thickness of m, the adhesive layer side is adhered to a stainless steel plate with a double-sided tape, and peeled in a 90 ° direction at a speed of 300 mm / min. did.

Example 1 A silica dispersion was prepared by mixing spherical silica ("Excelica", manufactured by Tokuyama Corporation) with toluene, followed by sand mill treatment. To this dispersion, NBR-C (Nipol N1072, manufactured by Zeon Corporation), epoxy resin (Epicoat 1001, epoxy equivalent 470, manufactured by Yuka Shell Co., Ltd.), boron trifluoride monoethylamine complex , Dicyandiamide and methyl ethyl ketone of the same weight as the dispersion so as to have the composition ratios shown in Table 1, respectively.
Then, the mixture was stirred and mixed to prepare an adhesive solution. This adhesive solution was coated with a silicone coating agent with a thickness of 25 μm using a bar coater.
m polyethylene terephthalate film (Fujimori Industries
The film was applied to a film thickness of about 50 μm so as to have a dry thickness of about 50 μm, and dried at 170 ° C. for 5 minutes.
On the other hand, a 25 μm thick silicone release agent with a low release force
Polyethylene terephthalate film (Fujimori Industry Co., Ltd.)
An adhesive layer was formed in the same manner as described above except that “Film Binner” GT) was used to obtain a dry thickness of about 50 μm. The peeling force was NSC (F ₁ )> GT (F ₂ ). Then, these were laminated together with the adhesive surfaces together to prepare an adhesive sheet for a semiconductor device of the present invention having an adhesive thickness of 100 μm. FIG. 4 shows the configuration. This adhesive sheet is applied to a pure copper plate having a thickness of 0.1 mm at 100 ° C. and 0.1 MPa.
And a pure copper plate with an adhesive layer was obtained. Table 2 shows the characteristics.

Example 2 NBR-C (Nipol N107 manufactured by Zeon Corporation)
2), epoxy resin (manufactured by Yuka Shell Co., Ltd., "Epico-
"1001", epoxy equivalent 470, "Epicoat" 8
28, epoxy equivalent 186), imidazole-based microencapsulated curing agent (“NOVACURE” H, manufactured by Asahi Kasei Corporation)
X-3088) and the same amount of methyl ethyl ketone as the dispersion liquid so as to have the composition ratios shown in Table 1, respectively.
Then, the mixture was stirred and mixed to prepare an adhesive solution. Using this adhesive solution, a pure copper plate with an adhesive sheet and an adhesive layer was obtained in the same manner as in Example 1. Table 2 shows the characteristics.

Example 3 A mixture of spherical silica ("Excelica", manufactured by Tokuyama Corporation) and zinc oxide was mixed with toluene, followed by sand mill treatment to prepare a silica and zinc oxide dispersion. NBR-C (PNR-1 manufactured by Nippon Synthetic Rubber Co., Ltd.)
H), SEBS-C (MX-07, manufactured by Asahi Kasei Corporation)
3), epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd.)
"Epicoat" YX-4000, epoxy equivalent 19
0), a phenol resole resin (manufactured by Showa High Polymer Co., Ltd.
CKM1282), 4,4'-diaminodiphenylsulfone, boron trifluoride monoethylamine complex, and the same amount of methyl ethyl ketone as the dispersion liquid and the same weight ratio as in Table 1, and stirred at 30 ° C., mixed, and adhered. An agent solution was prepared. Using this adhesive solution, a pure copper plate with an adhesive sheet and an adhesive layer was obtained in the same manner as in Example 1. Table 2 shows the characteristics.

Example 4 Spherical silica ("Excelica", manufactured by Tokuyama Corporation) and magnesium oxide were mixed with toluene, followed by sand mill treatment to prepare a silica and magnesium oxide dispersion. NBR-C (Nippon Synthetic Rubber Co., Ltd.)
, PNR-1H and BF Goodrich Co., Ltd., Hiker CTBN 1300X13), epoxy resin (manufactured by Yuka Shell Co., Ltd., "Epicoat" 1001, epoxy equivalent 470, "Epicoat" 157, epoxy equivalent 20)
0), a phenol resole resin (manufactured by Showa High Polymer Co., Ltd.
CKM908), dicyandiamide, an aromatic sulfonium salt of antimony hexafluoride (manufactured by Sanshin Chemical Co., Ltd., "San Aid" SI100L) and methyl ethyl ketone having the same weight as the dispersion liquid were added so as to have the composition ratios shown in Table 1, respectively. The mixture was stirred and mixed at a temperature of ° C to prepare an adhesive solution. Using this adhesive solution, a pure copper plate with an adhesive sheet and an adhesive layer was obtained in the same manner as in Example 1. Table 2 shows the characteristics.

Comparative Example 1 Spherical silica ("Excelica", manufactured by Tokuyama Corporation) was mixed with toluene, followed by sand milling to prepare a silica dispersion. To this dispersion, NBR-C (Nipol N1072, manufactured by Zeon Corporation), epoxy resin (Epicoat 1001, epoxy equivalent 470, manufactured by Yuka Shell Co., Ltd.), metaphenylenediamine and a dispersion Equal weights of methyl ethyl ketone were added so as to have the composition ratios shown in Table 1, and stirred and mixed at 30 ° C. to prepare an adhesive solution. Using this adhesive solution, a pure copper plate with an adhesive sheet and an adhesive layer was obtained in the same manner as in Example 1. Table 2 shows the characteristics.

Comparative Example 2 NBR (Nipol DN300, manufactured by Zeon Corporation)
Epoxy resin ("Epicoat" 8 manufactured by Yuka Shell Co., Ltd.)
28, epoxy equivalent 186), 2-ethyl 4-methylimidazole and methyl ethyl ketone of the same weight as the dispersion liquid were added so as to have the composition ratios shown in Table 1, respectively, and stirred at 30 ° C.
The mixture was mixed to form an adhesive solution. Using this adhesive solution, a pure copper plate with an adhesive sheet and an adhesive layer was obtained in the same manner as in Example 1. Table 2 shows the characteristics.

Comparative Example 3 Spherical silica ("Excelica", manufactured by Tokuyama Corporation) was mixed with toluene, followed by sand milling to prepare a silica dispersion. An epoxy resin (Epicoat 828, manufactured by Yuka Shell Co., Ltd., epoxy equivalent 18
6) 2-ethyl 4-methylimidazole, phenol novolak resin (manufactured by Gunei Chemical Industry Co., Ltd., PSM426)
1) Hexamethylenetetramine and methyl ethyl ketone of the same weight as the dispersion were added so as to have the composition ratios shown in Table 1, respectively, and stirred and mixed at 30 ° C. to prepare an adhesive solution. Using this adhesive solution, a pure copper plate with an adhesive sheet and an adhesive layer was obtained in the same manner as in Example 1. Table 2 shows the characteristics
Shown in

[0050]

[Table 1]

In Table 1, BF ₃ MEA is boron trifluoride monoethylamine complex, DICY is dicyandiamide, MP
D is metaphenylenediamine, DDS is 4,4'-diaminodiphenylsulfone, C11Z is 2-undecylimidazole, 2E4MZ is 2-ethyl-4-methylimidazole, and HEXA is hexamethylenetetramine. All resin compositions are parts by weight.

[0052]

[Table 2]

From the examples and comparative examples in Tables 1 and 2, it can be seen that the adhesive compositions for semiconductor devices obtained by the present invention are excellent in processability, adhesive strength, insulation reliability and durability.

[0054]

Industrial Applicability The present invention industrially provides a novel adhesive composition for semiconductor devices excellent in processability, adhesive strength, insulation reliability and durability, and an adhesive sheet for semiconductor devices using the same. In addition, the semiconductor device adhesive composition of the present invention can improve the economics based on the reliability and processability of the semiconductor integrated circuit connection substrate for high-density mounting and the semiconductor device.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of one embodiment of a BGA type semiconductor device using a semiconductor device adhesive composition and a semiconductor device adhesive sheet of the present invention.

FIG. 2 is a cross-sectional view of one embodiment of a substrate for connecting a semiconductor integrated circuit before connecting the semiconductor integrated circuit using the adhesive composition for a semiconductor device of the present invention.

FIG. 3 is a perspective view of one embodiment of a pattern tape (TAB tape) constituting a substrate for connecting a semiconductor integrated circuit.

FIG. 4 is a cross-sectional view of one embodiment of the adhesive sheet for a semiconductor device of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Semiconductor integrated circuit 2 Gold bump 3,11,17 Flexible insulating film 4,12,18 Adhesive layer which comprises a wiring board layer 5,13,21 Conductor for connecting a semiconductor integrated circuit 6,14, 23 Adhesive layer composed of the adhesive composition of the present invention 7, 15 Layer on which no conductor pattern is formed 8, 16 Solder resist 9 Solder ball 10 Sealing resin 19 Sprocket hole 20 Device hole 22 Solder ball connection Conductor part 24 Protective film layer constituting adhesive sheet of the present invention

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI H01L 23/40 H01L 23/40 F

Claims (10)

[Claims] 1. A semiconductor integrated circuit connection comprising (A) a wiring board layer comprising an insulator layer and a conductor pattern, (B) at least one layer having no conductor pattern and (C) an adhesive layer. An adhesive composition for a semiconductor device forming an adhesive layer (C) of a substrate, wherein the adhesive composition contains at least one or more of a thermoplastic resin and a thermosetting resin as essential components, respectively, and is in an uncured state. When the adhesive force at 100 ° C. is P ₁ and the adhesive force after 100 hours in an environment of 30 ° C. is P ₂ , 2Ncm ⁻¹ ≦ P ₁ ≦ 30Nc
m ⁻¹ , ₂ Ncm ⁻¹ ≦ P ₂ ≦ 30 Ncm ⁻¹ , and 0.2
≦ P ₂ / P ₁ , wherein the adhesive composition for a semiconductor device is provided. 2. The adhesive composition for a semiconductor device according to claim 1, wherein the adhesive strength after heat curing is 5 N cm ⁻¹ or more. 3. The thermoplastic resin contained in the adhesive composition,
The adhesive composition for a semiconductor device according to claim 1, wherein the adhesive composition for a semiconductor device has at least one or more functional groups that can react with a coexisting thermosetting resin. 4. The adhesive composition for a semiconductor device according to claim 1, wherein the adhesive composition contains a copolymer containing butadiene as an essential copolymer component as a thermoplastic resin. 5. The adhesive composition for a semiconductor device according to claim 1, wherein the adhesive composition contains an epoxy resin and / or a phenol resin as the thermosetting resin. 6. The adhesive composition according to claim 1, wherein the adhesive composition contains at least one kind of a cationically polymerizable hardener and an anionic polymerizable hardener having a pot life at 30 ° C. of 50 hours or more. An adhesive composition for a semiconductor device. 7. The adhesive composition for a semiconductor device according to claim 1, wherein the adhesive composition contains a microencapsulated curing agent. 8. An adhesive sheet for a semiconductor device, comprising the adhesive composition for a semiconductor device according to claim 1 as an adhesive layer and having at least one or more peelable protective film layers. 9. The adhesive sheet for a semiconductor device according to claim 8, wherein the protective film layer is subjected to a release treatment. 10. A protective film layer is provided on both sides of an adhesive layer, and when the peeling force of each protective film layer from the adhesive layer is F ₁ , F ₂ (F ₁ > F ₂ ), F ₁ − F ₂
9. The adhesive sheet for a semiconductor device according to claim 8, wherein ≧ 5 N m ⁻¹ .