JP4691401B2 - Adhesive composition for semiconductor device and adhesive sheet for semiconductor device - Google Patents

Description

  The present invention relates to an adhesive composition for a semiconductor device and an adhesive sheet for a semiconductor device that are suitably used for a semiconductor device using various semiconductors.

As electronic devices such as mobile phones and notebook PCs become smaller, lighter, faster, and more functional, IC chips also become more integrated and faster, and the mounting technology is QFP (Quad Flat Package). Leads are provided on the four sides of the package. Type) to new mounting forms such as BGA (Ball Grid Array), CSP (Chip Scale Package), and MCP (Multi Chip Package).
Along with this, the substrate on which a semiconductor such as an IC chip is mounted has also changed from a lead frame to a tape substrate and a printed substrate, and a structure that can be miniaturized and densified. In particular, the role of a built-up substrate, which is a method of laminating wiring, has become important.
In these substrates, a wiring and an insulating layer that electrically insulates the wiring are usually provided on a support. It is important for such an insulating layer to ensure electrical insulation, and various other characteristics are required.

For example, as a generally used substrate manufacturing method, a support having a wiring circuit formed on the surface and an adhesive sheet having an adhesive layer mainly composed of an uncured adhesive are bonded to the wiring. There is a method in which bonding is performed so that the adhesive layer is in contact, the adhesive layer is embedded between wirings, and the adhesive layer is cured by heat or the like. Here, the cured adhesive layer functions as an insulating layer. At this time, if foaming occurs in the adhesive layer or if there is a gap between the wiring, insulation is not good, so the adhesive layer may foam or create a gap when embedding the wiring. There is a need for embedding between the wirings. Such embeddability becomes more important as the wiring becomes finer and denser.
As an adhesive used for the adhesive layer as described above, a polymer having a diene such as a polyimide resin, an epoxy resin, a phenol resin, a styrene-butadiene-styrene block copolymer (diolefin resin) is usually used. Thermosetting resins such as are used.

The adhesive further requires heat resistance, heat temperature cycleability, stress relaxation against stress change, and the like.
For example, when the IC package is driven, the temperature becomes 100 ° C. or higher due to heat generated by the IC. That is, the IC package is exposed to a temperature change from room temperature to high temperature (100 ° C. or more). Therefore, the IC package is required to have heat resistance against high temperatures generated in that case and heat resistance temperature cycle resistance against temperature changes.
In addition, since wires with different coefficients of thermal expansion, such as wiring made of metal, a support on which the wiring is formed, and an insulating layer are bonded together, the coefficient of thermal expansion is Stress relaxation is required to cope with stress changes caused by differences. In particular, in recent years, as the mounting density has increased and the proportion of wiring such as metal has increased, it has become important to improve stress relaxation.
Further, in the case of a built-up substrate on which wirings are laminated, since a plurality of insulating layers are provided at the same time, heating for curing the adhesive must be performed for the number of laminated layers, and heat resistance at that time is also required.

However, the conventional adhesives as described above do not sufficiently satisfy these characteristics.
Specifically, these adhesive layers have poor flow properties. For example, when the adhesive layer is embedded in wiring arranged at a high density, significant bubble entrainment occurs. If the viscosity of the adhesive layer is lowered in order to improve the flowability, there is a problem that the adhesive layer is excessively protruded and the workability is deteriorated during the pasting.
In addition, after a semiconductor device such as an IC chip, the stress generated by repeated temperature changes from room temperature to high temperature (100 ° C. or higher), between the insulating layer and the IC chip, or inside the substrate, In some cases, delamination caused by the insulating layer or warpage of the substrate may occur. Such a problem is particularly noticeable in a laminated substrate such as a built-up substrate in which a plurality of wirings and insulating layers are laminated. Further, delamination and warpage deteriorate the electrical reliability of the semiconductor device, and hence improvement is required.

Further, in the above-described laminated high-density mounting method, a TAB (Tape Automated Bonding) substrate in which a metal layer such as a copper foil is laminated on an insulating film via an adhesive layer for the purpose of thinning the substrate. In many cases, a flexible substrate (FPC) or the like is used, and a resin film such as a polyimide resin is often used as an insulating film.
However, conventional adhesives have problems such as insufficient adhesive strength to these insulating films and metal layers, and the adhesive strength tends to decrease due to subsequent temperature changes. In particular, it is very difficult to adhere to a polyimide film.
This adhesive force is greatly influenced by the state of the support interface, but also affects the hygroscopicity of the adhesive. For example, the lower the hygroscopicity, the more the change in adhesive force tends to be suppressed. An adhesive with low properties is desired.

Further, in recent years, the IR reflow temperature has increased due to the lead-free process. Therefore, the moisture contained in the adhesive layer is easily vaporized at the time of reflow, and the popcorn phenomenon that causes the adhesive to push away and swell (void) tends to occur.
Currently, in order to remove the water that causes the popcorn phenomenon, the semi-finished product before reflow is managed in a moisture-proof state.
However, since the management in the moisture-proof state requires a large amount of work and cost, the adhesive composition with excellent reflow resistance can suppress the occurrence of the popcorn phenomenon during reflow without requiring the management of the moisture-proof state. Is required.

  In addition, since the adhesive is a material that comes into contact with the wiring, it is also important to have electrical reliability that maintains high insulation even in harsh environments. There is also a problem that when exposed to heat, the insulating properties are reduced and problems such as electrolytic corrosion are likely to occur.

In response to such a demand, the present applicant has proposed an adhesive composition using an epoxidized styrene-butadiene-styrene block copolymer in Patent Document 1, for example.
JP 2002-241728 A

However, although such an adhesive composition has various excellent properties, the adhesive strength to an insulating film such as a polyimide film as described above and a metal layer such as a copper foil is not sufficient.
Further, when the temperature change is repeated or when exposed to heat for a long period of time, characteristics such as adhesive strength may be deteriorated, and there is a problem that the heat deterioration resistance is not sufficient.
The present invention has been made in view of the above circumstances, and has various excellent characteristics, in particular, an adhesive composition for semiconductor devices and an adhesive sheet for semiconductor devices, which are excellent in adhesive strength and heat deterioration resistance. The purpose is to provide.

（式中のＲ ^１ はそれぞれ独立に炭素数１〜１０のアルキレン基を表し、ｍおよびｎはそれぞれ独立に０〜１０の整数を示す。）
上記課題を解決する本発明の第二の態様は、支持体の少なくとも一面に、第一の態様の半導体装置用接着剤組成物からなる接着剤層が積層してなることを特徴とする半導体装置用接着シートである。
本発明の第三の態様は、金属層の少なくとも一面に、第一の態様の半導体装置用接着剤組成物からなる接着剤層と、絶縁性フィルムまたは剥離性フィルムとが順次積層してなることを特徴とする半導体装置用接着シートである。
本発明の第四の態様は、絶縁性フィルムの両面に、第一の態様の半導体装置用接着剤組成物からなる接着剤層と、絶縁性フィルムまたは剥離性フィルムとが順次積層してなることを特徴とする半導体装置用接着シートである。 The first aspect of the present invention that solves the above problems is an epoxy resin (A), a phenol resin (B), and a monomer component having ethylene and a glycidyl group or carboxyl group (including an anhydride group). At least one siloxane compound (D) selected from the group consisting of a vinyl copolymer (C) having a saturated carboxylic acid or a derivative thereof and a siloxane compound represented by the following general formula (1) or general formula (2) And the content of the epoxy resin (A) is 3 to 45% by mass of the total solid amount, and the content of the phenol resin (B) is 2 to 30% by mass of the total solid amount. The content of the vinyl copolymer (C) is 20 to 80% by mass of the total solid amount, and the content of the siloxane compound (D) is 0.05 to 10% by mass of the total solid amount. , and the and before curing Minimum melt viscosity in a dynamic viscoelasticity measurement 400～50000Pa. It is the adhesive composition for semiconductor devices characterized by being in the range of s.

(R ¹ in the formula independently represents an alkylene group having 1 to 10 carbon atoms, and m and n each independently represents an integer of 0 to 10)
According to a second aspect of the present invention for solving the above-mentioned problems, a semiconductor device is characterized in that an adhesive layer made of the adhesive composition for a semiconductor device according to the first aspect is laminated on at least one surface of a support. It is an adhesive sheet for use.
In the third aspect of the present invention, an adhesive layer composed of the adhesive composition for a semiconductor device of the first aspect and an insulating film or a peelable film are sequentially laminated on at least one surface of the metal layer. It is the adhesive sheet for semiconductor devices characterized by these.
According to a fourth aspect of the present invention, an adhesive layer made of the adhesive composition for a semiconductor device of the first aspect and an insulating film or a peelable film are sequentially laminated on both surfaces of the insulating film. It is the adhesive sheet for semiconductor devices characterized by these.

According to the present invention, it has excellent various characteristics such as excellent embedding property, heat resistance, heat resistance temperature cycle property, stress relaxation property, electrical reliability, adhesion property, reflow resistance property, etc. An adhesive composition and an adhesive sheet excellent in heat resistance and heat deterioration resistance can be provided.
Therefore, according to the adhesive composition and adhesive sheet of the present invention, defects such as delamination and warpage due to repeated temperature changes can be solved. Therefore, the reliability of the semiconductor device can be improved by the adhesive composition and the adhesive sheet of the present invention.
Also, the moisture resistance is high, and for example, the popcorn phenomenon generated when the moisture contained in the adhesive is vaporized at the time of reflow can be improved. Therefore, the trouble of managing the semi-finished product before reflow in a moisture-proof state is reduced.
Furthermore, the adhesive sheet of the present invention is excellent in processability and can be easily provided industrially.

Hereinafter, the present invention will be described in detail.
<Adhesive composition for semiconductor device>
The adhesive composition for a semiconductor device according to the first aspect of the present invention (hereinafter sometimes simply referred to as an adhesive composition) comprises an epoxy resin (A) (hereinafter referred to as component (A)) and a phenol resin ( B) (hereinafter referred to as component (B)), a vinyl copolymer (C) (hereinafter referred to as component (C)) containing at least two specific types as monomer components, and a thermosetting type It is an adhesive composition.

Further, the adhesive composition of the present invention has a minimum melt viscosity of 400 Pa.s in dynamic viscoelasticity measurement before curing. s to 50000 Pa. It must be s.
The minimum melt viscosity in the measurement of dynamic viscoelasticity before curing is 400 Pa. s or more, the resin flow during processing is small, and 50000 Pa. If it is s or less, the wiring is easily buried and hardly affected by the unevenness of the bonding surface. That is, the minimum melt viscosity is 400 to 50000 Pa. By being in the range of s, the adhesive composition of the present invention has good embeddability in wiring, particularly wiring arranged at high density. In addition, processing becomes very easy.
The minimum melt viscosity can be adjusted by adjusting the type and blending amount of the component (A), the component (B) and the component (C). For example, as will be described later, the minimum melt viscosity can be adjusted by adjusting the blending amount of the component (C) in the composition within a range of 20 to 80% by mass of the total solid content.

In addition, in this invention, the minimum melt viscosity in the dynamic viscoelasticity measurement before hardening is the minimum value of the viscosity at the time of measuring a viscosity change on the following conditions.
[Minimum melt viscosity measurement conditions]
・ Apparatus: Shear modulus measuring device (Rheo Stress RS75 (product name) manufactured by HAAKE)
Measurement temperature range: -10 ° C to 300 ° C
・ Rise rate: 3 ° C / min
・ Measurement frequency: 1Hz
・ Weight: 15N
-Strain rate: 0.01% ± 0.0025%

The adhesive composition of the present invention preferably has a dynamic elastic modulus at 200 to 280 ° C. after curing in the range of 500 Pa to 200 Mpa, and more preferably in the range of 1 MPa to 100 Mpa.
That is, an adhesive sheet obtained by forming an adhesive layer on a support using the adhesive composition of the present invention is applied (temporary adhesion) to an adherend and then heated to cure the adhesive composition. To adhere to the adherend. The cured adhesive composition is heated to 200 to 280 ° C. during a reflow process (soldering process) when mounting a BGA, a laminated substrate or the like on a main substrate via solder balls. Therefore, when the dynamic elastic modulus at 200 to 280 ° C. after curing is in the range of 500 Pa to 200 Mpa, the generation of voids during the reflow process is suppressed, and the reflow resistance is improved. In addition, the stress relaxation property is excellent.
In addition, the said dynamic elastic modulus hardened the adhesive composition about the adhesive sheet which provided the adhesive layer whose thickness after hardening is 100 micrometers using the said adhesive composition on a peelable film. Thereafter, the peelable film was removed, and a value measured at a frequency of 11 Hz and a heating rate of 3 ° C./min using Leovibron DDV-II manufactured by Orientech.

In the adhesive composition of the present invention, voids are generated in the reflow process and the like, and moisture is the main cause of the popcorn phenomenon. Therefore, in order to improve the reflow resistance, the moisture absorption after curing is 1% or less. It is preferable that
There is no restriction | limiting in particular as a minimum of a moisture absorption rate, and the said effect is excellent and preferable, so that a moisture absorption rate is small.
The moisture absorption rate can be adjusted by adjusting the type and amount of the component (A), the component (B), the component (C), and the like. For example, as will be described later, the ratio of the component (A) to the component (B) is adjusted so that the amount of the component (C) in the composition is adjusted within the range of 20 to 80% by mass of the total solid content. The moisture absorption rate can be adjusted by adjusting the equivalent ratio within the range of 1: 0.6 to 1: 1.4.

The adhesive composition of the present invention preferably has a tensile elongation after curing of 30% or more. If the tensile elongation is 30% or more, the stress relaxation property is improved. For example, when different materials are bonded together, the difference in thermal expansion between the materials at high temperature or temperature change is alleviated, and thermal expansion is reduced. Substrate warpage and delamination due to the difference can be suppressed.
The tensile elongation can be adjusted by adjusting the type and blending amount of the component (A), the component (B), the component (C), and the like. For example, as will be described later, the ratio of the component (A) to the component (B) is adjusted so that the amount of the component (C) in the composition is adjusted within the range of 20 to 80% by mass of the total solid content. The ratio of the unsaturated carboxylic acid or its derivative in the component (C) is adjusted within the range of 0.1 to 40% by mass, adjusted in an equivalent ratio within the range of 1: 0.6 to 1: 1.4. The tensile elongation can be adjusted by adjusting the functional group equivalent of the component (C) within the range of 100 to 2500.

Furthermore, the adhesive composition of the present invention preferably has a dynamic elastic modulus at 200 ° C. to 280 ° C. after being allowed to stand in an environment of 150 ° C. for 24 hours after curing, within a range of 500 Pa to 500 MPa. More preferably, it is in the range of -200 MPa.
For example, when a substrate is manufactured by a built-up method, a plurality of adhesive layers are stacked, and thus a curing temperature corresponding to the number of stacked layers must be applied in order to cure the adhesive. For this reason, the heat deterioration resistance with respect to the curing temperature repeatedly exposed at that time is also important. Accordingly, even after an accelerated test that is allowed to stand at 150 ° C. for 24 hours after curing, if the dynamic elastic modulus at 200 ° C. to 280 ° C. is in the range of 500 Pa to 500 MPa, the heat deterioration resistance is very excellent.
Here, the dynamic elastic modulus is measured in the same manner as the dynamic elastic modulus at 200 to 280 ° C. after curing, except that the adhesive composition is cured and then left in an environment of 150 ° C. for 24 hours. Can be measured.
The dynamic elastic modulus can be adjusted by adjusting the type and blending amount of the component (A), the component (B), the component (C), and the like. For example, as described later, the dynamic elastic modulus can be adjusted by adjusting the functional group equivalent of the component (C) within the range of 100 to 2500.

  Furthermore, the adhesive composition of the present invention is 4.5 N / in the case where the adhesive strength between the cured polyimide film (trade name: Upilex 50S, manufactured by Ube Industries) is peeled in the 180 ° direction. When the adhesive strength with the polyimide film after being cured for 300 hours in an environment of temperature 121 ° C. and humidity 100% after peeling is 180 N ° or more, it is 2 N / cm or more. Preferably there is. Thereby, stress relaxation property, heat-resistant temperature cycle property, adhesive force, etc. improve, and hygroscopicity can also be reduced. For this reason, resistance to physical impact, particularly physical impact during the reflow process is improved, and resistance to generation of voids due to moisture and the like is improved when manufacturing a substrate such as a BGA or a laminated substrate.

Hereinafter, the composition of the adhesive composition of the present invention will be described in more detail.
In the adhesive composition of the present invention, the component (A) reacts with the component (B) and / or the component (C) by heating to form a three-dimensional network structure. And the effect of this invention is acquired by the combination of these components and the said minimum melt viscosity. In particular, the component (A) and the component (B) greatly contribute to heat-resistant temperature cycle performance, electrical reliability, adhesion to copper, polyimide film, etc., reflow resistance, and the like. In addition, the component (C) has a large contribution to stress relaxation, heat-resistant temperature cycle performance, electrical reliability, adhesion to copper, polyimide film, etc., moisture resistance, and the like.

[(A) component]
The epoxy resin is a resin having two or more epoxy groups in the molecule.

As the component (A), for example, any structure such as glycidyl ether, glycidyl ester, glycidyl amine, linear aliphatic epoxide, alicyclic epoxide can be used. These may be used alone or in combination of two or more.
Specifically, bifunctional epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, naphthalene type epoxy resin, triglycidyl isocyanurate type epoxy resin, triglycidyl-p-aminophenol Type epoxy resin, tetraglycidyldiaminodiphenylmethane type epoxy resin, tetraglycidylmetaxylenediamine type epoxy resin, tetraglycidyl-1,3-bisaminomethylcyclophene type epoxy resin, etc., polyfunctional glycidylamine type epoxy resin, tetraphenylglycidyl Polyfunctional glycidyl ether type epoxy resin such as ether ethane type epoxy resin, triphenyl glycidyl ether methane type epoxy resin, phenol type epoxy resin, alkylphenol Multifunctional resol type epoxy resins such as Nord type epoxy resin, cyclopentadiene type epoxy resin, biphenyl type epoxy resin, phenol epoxy resins, such as a polyfunctional novolak epoxy resins and cresol type epoxy resins.
Among these, bisphenol type epoxy resins are preferably used in the present invention because they are inexpensive. In addition, the polyfunctional epoxy resin is suitably used in the present invention because of its excellent insulation and heat resistance.

  As the component (A) suitably used in the present invention, specifically, bisphenol types such as Epicoat 806, 828, 834, and 1001 manufactured by Yuka Shell Epoxy Co., Ltd., trade names: YX-4000, YX Bifunctional epoxy resin such as biphenyl type such as -4000H; Trade name: Epicoat 152, 154, 180S65, 1032H60, 157S70, etc., polyfunctional novolac type, trade name: 604 etc. tetraglycidyl diphenylmethane manufactured by Yuka Shell Epoxy Co., Ltd. Type, product name: polyfunctional epoxy resin such as dicyclo type such as HP-7200, HP-7200H, etc .; product name: o-cresol novolak type such as EOCNI02S, 103S, 104S, 1020 manufactured by Nippon Kayaku Co., Ltd., product name : Multifunctional such as triphenylmethane type such as EPPN501H and 502H Epoxy resins and the like.

  Moreover, it is preferable to use a halogenated epoxy resin, particularly a brominated epoxy resin, as the component (A) because it is effective for imparting flame retardancy to the adhesive composition. Specific examples of brominated epoxy resins include trade names: Epicoat 5045, 5046, 5050 manufactured by Yuka Shell Epoxy Co., Ltd., trade names: BREN-S, BREN-105, BREN-301 manufactured by Nippon Kayaku Co., Ltd. Is mentioned. Further, there is no problem even if a phosphide epoxy resin or the like is used instead of the halogenated epoxy resin.

  The component (A) preferably has an epoxy equivalent (molecular weight per epoxy group) of 100 to 4000, more preferably 100 to 2000, and particularly preferably 100 to 1000. When the epoxy equivalent is 100 or more, when cured, the uncured (A) component is unlikely to remain, and therefore it is difficult to foam. When the epoxy equivalent is 4000 or less, the resin is easily soluble in a solvent and has good compatibility with other resins.

  In the adhesive composition of the present invention, the content of the component (A) is preferably 3 to 45% by mass, more preferably 5 to 25% by mass, based on the total solid content of the adhesive composition.

[Component (B)]
The phenol resin is a resin obtained by addition / condensation of phenols and aldehydes.
Specific examples of the component (B) include phenol derivatives such as a resole phenol resin, a phenol novolac resin, a cresol novolac resin, a resorcinol resin, and a xylene resin. Among these, phenol novolac resins are preferable because they are excellent in reactivity and have excellent moisture resistance and heat resistance in semiconductor device applications.
The component (B) preferably has a hydroxyl equivalent (molecular weight per hydroxyl group) of 50 to 4000, more preferably 100 to 2000, and particularly preferably 100 to 1000. When the hydroxyl equivalent is less than 50, the adhesive after curing tends to be brittle, and when it exceeds 4000, it is difficult to dissolve in an organic solvent, which tends to cause a problem in production.

  In the adhesive composition of the present invention, the content of the component (B) is preferably 2 to 30% by mass and more preferably 5 to 25% by mass with respect to the total solid content of the adhesive composition.

Further, in the adhesive composition of the present invention, the ratio of the component (A) to the component (B) is preferably a functional group equivalent ratio in the range of 1: 0.6 to 1: 1.4. More preferably, the ratio is in the range of 1: 0.7 to 1: 1.1. That is, when the content of the component (B) when the component (A) is 1 is 0.6 or more, the cured adhesive composition has no brittleness and excellent strength, and stress Good relaxation. Further, when the content of the component (B) is 1 or less when the component (A) is 1, the deterioration of the adhesive strength is suppressed, for example, the decrease in the adhesive strength after being exposed to a high temperature is suppressed. Is done.
Moreover, the tensile elongation rate of the adhesive composition after hardening also improves because the ratio of (A) component and (B) component exists in the said range. In addition, the dynamic elastic modulus at 200 ° C. to 280 ° C. after being allowed to stand in an environment of 150 ° C. for 24 hours after curing is also a suitable range for a semiconductor device.
Here, the functional group equivalent ratio of the component (A) and the component (B) is the number of epoxy groups in the component (A) (the functional group of the component (A)) and the hydroxyl group in the component (B) ( (B) the ratio to the number of functional groups).

[Component (C)]
Component (C) is an unsaturated carboxylic acid having at least ethylene and a functional group capable of reacting with component (A) or a derivative thereof (hereinafter simply referred to as an unsaturated carboxylic acid or a derivative thereof) as a monomer component. And a vinyl copolymer. By containing the component (C), flexibility is imparted to the adhesive composition of the present invention, and stress relaxation properties are improved. Also, moisture resistance is improved. Further, as described above, the combination with the component (A) and the component (B) improves the heat resistance temperature cycle property, the electrical reliability, and the adhesive force to copper, polyimide film, and the like.
Here, the “monomer component” means a compound that forms a repeating unit of a polymer when the polymer is produced by polymerization reaction. For example, a polymer containing ethylene as a monomer component contains a repeating unit represented by the formula — [CH ₂ —CH ₂ ] — formed by cleavage of a double bond of ethylene.

(C) In component, it is preferable that the total amount of ethylene and unsaturated carboxylic acid or its derivative (s) is 40-98 mass% with respect to the sum total of all the monomer components.
(C) It is preferable that the ratio of ethylene in a component is 40 mass% or more with respect to the sum total of all the monomer components, and 50-98 mass% is more preferable.

The functional group that can react with the component (A) of the unsaturated carboxylic acid or derivative thereof includes amino group, isocyanate group, glycidyl group, carboxyl group (including anhydride group), silanol group, hydroxyl group, vinyl group , Methylol group, mercapto group, ester group and the like. Of these, amino groups, carboxyl groups, glycidyl groups, and hydroxyl groups are preferred because of their high reactivity. Particularly preferred functional groups are glycidyl and carboxyl groups.
Specific examples of the unsaturated carboxylic acid or derivative thereof having these groups include the following. Examples of those having a carboxyl group include olefins such as acrylic acid, methacrylic acid, (anhydrous) maleic acid, and propylene having a carboxyl group. Examples of those having a glycidyl group include glycidyl acrylate and glycidyl methacrylate. Examples of those containing a hydroxyl group include hydroxymethyl acrylate, hydroxymethyl methacrylate, hydroxyethyl acrylate, and hydroxyethyl methacrylate.

  (C) It is preferable that the ratio of unsaturated carboxylic acid or its derivative (s) in a component is 0.1-40 mass% with respect to the sum total of all the monomer components, and 0.8-20 mass% is more preferable. When the proportion of the unsaturated carboxylic acid or derivative thereof in component (C) is 0.1% by mass or more, the reactivity with component (A) is high, the tensile elongation after curing, and the substrate after curing. Adhesive strength between the two is improved. In addition, it has high solubility in organic solvents and is easy to use as a paint. Further, when the ratio is 40% by mass or less, the stability in the paint state is good.

(C) A component may contain other monomers other than ethylene and unsaturated carboxylic acid or its derivative (s) as a monomer component in the range which does not impair the effect of this invention.
Other monomers may be any monomers that can be copolymerized with the above-mentioned ethylene and unsaturated carboxylic acid or derivatives thereof. For example, (meth) acrylic acid such as methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate Alkyl ester or aryl ester, vinyl acetate and the like.
(C) When a component contains the said other monomer, it is preferable that the content is 40 mass% or less with respect to the sum total of all the monomer components, and 30 mass% or less is more preferable.

In the present invention, the (C) component is particularly preferably a vinyl copolymer containing ethylene and (meth) acrylic acid ester as monomer components. Since such a vinyl copolymer does not contain a diene bond in the main chain, there is almost no thermal deterioration (no elasticity) when left at high temperatures, and stress relaxation can be maintained over a long period of time. In addition, since it has an ester bond in the side chain, it has relatively high solubility in organic solvents and is difficult to hydrolyze, so corrosion of the electrode bonded to the adhesive composition in a high temperature and high humidity environment It is suppressed and has high electrical reliability.
As a vinyl copolymer containing ethylene and (meth) acrylic acid ester as monomer components, specifically, ethylene- (meth) acrylic acid ester-maleic anhydride copolymer, ethylene- (meth) acrylic acid alkyl ester -Glycidyl (meth) acrylate copolymer, ethylene-glycidyl (meth) acrylate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene-glycidyl (meth) acrylate-vinyl acetate copolymer are mentioned. Among them, ethylene- (meth) acrylic acid alkyl ester-maleic anhydride copolymer, ethylene- (meth) acrylic acid alkyl ester-glycidyl (meth) acrylate copolymer, ethylene-glycidyl (meth) acrylate copolymer are mentioned. It is done.
Any of these vinyl copolymers may be used alone or in combination of two or more. In the adhesive composition of the present invention, it is also preferable to use two or more of the above vinyl copolymers in combination.
The ratio of the acrylic acid ester in the copolymer containing ethylene and (meth) acrylic acid ester as the monomer component is preferably 5 to 40 mol% with respect to the total of all the monomer components. If it is 5 mol% or more, the solubility in an organic solvent is good, and it is easy to obtain a coating solution (paint). Moreover, the effect which suppresses the fall of the electrical property by hydrolysis as it is 40 mol% or less is high.

The mass average molecular weight of the component (C) is preferably in the range of 1,000 to 2,000,000, more preferably 100,000 to 1,000,000. The mass average molecular weight is a value measured by gel permeation chromatography (GPC) using styrene as a standard.
Particularly, when the functional group equivalent of the component (C) (molecular weight per functional group (value obtained by dividing the mass average molecular weight by the number of functional groups)) is in the range of 100 to 2500, the tensile elongation after curing Moreover, the adhesive force between the base material after curing is good.
Here, the functional group of (C) component means the functional group which the said unsaturated carboxylic acid or its derivative has and can react with the said (A) component.

In this invention, it is preferable that content of (C) component is 20-80 mass% of the total solid of the said adhesive composition, and 30-70 mass% is more preferable. When the content of the component (C) is within the above range, the effect of the present invention is excellent, and particularly stress relaxation, heat-resistant temperature cycle property, adhesion between copper and polyimide films, moisture resistance, etc. are good. is there.
Moreover, it is preferable that content of (C) component exists in the range of 20-200 mass parts with respect to 100 mass parts of (A) component, and 50-150 mass parts is more preferable. When the content is 200 parts by mass or less, the film formability of the adhesive layer is good, and when it is 20 parts by mass or more, the strength of the adhesive layer is high.

[Siloxane compound (D)]
The adhesive composition of the present invention preferably further contains a siloxane compound (D) (hereinafter referred to as component (D)). Thereby, the compatibility of each component at the time of melt | dissolving the said (A)-(C) component in an organic solvent and using it as a coating material improves. Further, there is an advantage that the moisture absorption after curing can be reduced.
(D) As a component, what has the reactive group which has the reactivity with respect to an epoxy group is preferable. Examples of such a reactive group include a hydroxyl group, an alkoxy group, an amino group, a methacryl group, and an epoxy group.

  The component (D) is preferably a siloxane compound having an amino group at both ends, and is particularly at least one selected from the group consisting of siloxane compounds represented by the following general formula (1) or general formula (2). It is preferable.

（式中のＲ^１はそれぞれ独立に炭素数１〜１０のアルキレン基を表し、ｍおよびｎはそれぞれ独立に０〜１０の整数を示す。）

(R ¹ in the formula independently represents an alkylene group having 1 to 10 carbon atoms, and m and n each independently represents an integer of 0 to 10)

In formula (1), the alkylene group for R ¹ may be linear or branched, and is particularly preferably a linear alkylene group having 2 to 5 carbon atoms.
As m, the integer of 3-8 is preferable.
n is preferably an integer of 0 to 8.

  As a siloxane compound having an amino group at both ends represented by the above general formula (1) or (2), product names: TSL9306 (diaminodisiloxane) manufactured by Toshiba Silicone Co., Ltd., product names: TSL9886 (diaminopoly) Siloxane), trade name: TSF4706 (diaminodisiloxane), trade name: XF42-A2645 (diaminopolysiloxane), and the like.

  In the adhesive composition of the present invention, the content of the component (D) is preferably 0.05 to 10% by mass, more preferably 0.3 to 5% by mass, based on the total solid content of the adhesive composition. When the content is 0.05% by mass or more, the compatibility of the components (A) to (C) when the adhesive composition of the present invention is used as a paint is good, and the moisture absorption after curing is also low. The fall of adhesive force is suppressed as it is 10 mass% or less.

[Other optional ingredients]
Moreover, in order to improve adhesiveness with a to-be-adhered body, it is preferable to add a coupling agent to the adhesive composition of this invention.
As the coupling agent, a silane coupling agent, a titanium coupling agent and an aluminum coupling agent are preferably used.

The adhesive composition of the present invention preferably contains an epoxy curing agent together with the component (A). Thereby, the curing reaction of the adhesive composition of the present invention is promoted, and the heat resistance is improved.
As the epoxy curing agent, commonly used ones can be used. Specifically, amine catalysts such as imidazoles, 1,8-diazabicyclo (5,4,0) undecene, triphenylphosphine and the like can be used. A phosphorus catalyst etc. can be illustrated.
In the adhesive composition of the present invention, the content of the epoxy curing agent is preferably from 0.1 to 10 mass%, more preferably from 0.1 to 3 mass%, based on the total solid content of the adhesive composition.

The adhesive composition of the present invention preferably contains a filler such as an inorganic filler or an organic filler for the purpose of adjusting the thermal expansion coefficient, thermal conductivity, or controlling workability.
Examples of inorganic fillers include silica, alumina, titanium oxide, beryllium oxide, magnesium oxide, calcium carbonate, titanium nitride, silicon nitride, boron nitride, titanium boride, tungsten boride, silicon carbide, titanium carbide, zirconium carbide, molybdenum carbide, Examples thereof include mica, clay, zinc oxide, carbon black, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, antimony trioxide, and those whose surfaces are treated with a trimethylsiloxyl group.
Examples of the organic filler include polyimide, polyamideimide, polyetheretherketone, polyetherimide, polyesterimide, nylon, and silicone.
In the adhesive composition of the present invention, the filler content is 2 with respect to 100 parts by mass of the total of the component (A), the component (B), the component (C), and the component (D), which is an optional component. It is preferable to be within the range of -95 parts by mass, and more preferably 5-50 parts by mass.

The adhesive composition of the present invention can be used for forming an adhesive layer as a paint in which the components (A) to (C), which are essential components, are dissolved in an organic solvent and the component (D) is optionally added. it can.
Preferred organic solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, pyridine, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, 1,4-dioxane, tetrahydrofuran Several types and amounts such as ethanol, methanol, methyl cellosolve and the like can be appropriately selected and used.
The paint is preferably prepared so that the solid content concentration is 5% by mass or more, and more preferably 10 to 50% by mass. When the solid content concentration is 5% by mass or more, an adhesive sheet having a uniform adhesive layer thickness can be easily produced.

<Semiconductor device adhesive sheet>
The adhesive sheet for a semiconductor device according to the second aspect of the present invention (hereinafter sometimes referred to as an adhesive sheet (2)) has an adhesive layer made of the adhesive composition of the present invention on at least one surface of a support. It is characterized by being laminated.

In the adhesive sheet (2), as the support, a metal layer made of a metal such as copper or aluminum, a peelable film, an insulating film, a release paper, etc. can be used, and in particular, the metal layer, the peelable film and the insulating film. At least one selected from the group consisting of
Preferred insulating films include polyesters such as polyethylene terephthalate (hereinafter abbreviated as PET), polyolefins such as polyethylene, polyimide, polyamide, polyethersulfone, polyphenylene sulfide, polyetherketone, and triacetylcellulose. More preferably, films made of materials such as polyesters, polyolefins, and polyimide are used.
As the peelable film, a film made of the same material as that mentioned as the insulating film and subjected to a release treatment with a release agent such as silicone is preferably used.

The adhesive sheet (2) of the present invention can be produced, for example, by forming an adhesive layer by applying a coating containing the adhesive composition on at least one surface of a support and drying.
The adhesive layer is preferably heat-treated to be in a semi-cured state. In particular, the semi-cured state is appropriately controlled in order to suppress flowability and foaming by processing and use conditions such as shortening of the curing time and embedding of the conductor pattern. The method for controlling the semi-cured state is not limited, but is preferably controlled by aging or the like.
The thickness of the adhesive layer after drying is preferably in the range of 3 to 400 μm, and more preferably 5 to 100 μm.

In the adhesive sheet (2) of the present invention formed by forming an adhesive layer on at least one surface of the support, when the peelable film is further adhered on the adhesive layer during storage, the adhesive layer It is preferable because it is not contaminated. Such an adhesive sheet can be used by peeling the peelable film at the time of use.
Moreover, when using only an adhesive bond layer for a semiconductor device, it can also use as a peelable film also about a support body, and can peel and use the peelable film of both sides of an adhesive bond layer at the time of use.

Next, the adhesive sheet for a semiconductor device according to the third aspect of the present invention (hereinafter sometimes referred to as an adhesive sheet (3)) is formed on at least one surface of the metal layer. It is characterized in that an adhesive layer made of and an insulating film or a peelable film are sequentially laminated.
About description of a metal layer, an adhesive bond layer, an insulating film, and a peelable film, in the said adhesive sheet (2), it is the same as description of the metal layer illustrated as a support body, an adhesive bond layer, an insulating film, and a peelable film. It is.
By having such a configuration, the adhesive sheet (3) can be used as a wiring board as it is.

Next, the adhesive sheet for a semiconductor device according to the fourth aspect of the present invention (hereinafter sometimes referred to as an adhesive sheet (4)) is formed on both sides of the insulating film. It is characterized in that an adhesive layer made of and an insulating film or a peelable film are sequentially laminated.
About description of an adhesive bond layer, an insulating film, and a peelable film, it is the same as that of description of the adhesive bond layer in the said adhesive sheet (2), an insulating film, and a peelable film.
The adhesive sheet (4) has excellent electrical reliability due to such a configuration.

The adhesive composition and adhesive sheet of the present invention can be applied to various semiconductor devices, and in particular, an IC chip is laminated on the circuit surface or the back surface of an IC substrate comprising an insulator layer and a conductor circuit. It is particularly suitable for a semiconductor device. Specific examples of such a semiconductor device include T-BGA using TAB technology, a build-up substrate using a FPC or a glass epoxy substrate, or a surface-mount type CSP semiconductor.
As a more specific application of the adhesive composition and adhesive sheet of the present invention, in the semiconductor device described above, an adhesive that bonds or forms a circuit between the IC chip and the insulator layer and / or conductor circuit of the IC substrate. It is suitable as an adhesive for bonding between circuit boards and a protective film for protecting the circuit boards.

EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these.
Examples 1-15, Comparative Examples 1-6
[Preparation of paint for adhesive composition]
Copolymers having (A) component, (B) component, (C) component, (D) component, silane coupling agent, epoxy curing agent, filler, and diene shown in abbreviations in Table 1, respectively, 1 was dissolved in toluene at about room temperature to about 80 ° C. so that the blending amount shown in FIG. 1 (mass% relative to the total solid content) was obtained to obtain a paint (solid content concentration 35 mass%) containing the adhesive composition.
In addition, content of a filler is the number of parts (mass part) with respect to 100 mass parts of sum total of (A) component, (B) component, (C) component, and (D) component.
Moreover, the meaning of the symbol in Table 1 which shows the kind of each component used in Examples 1-15 and Comparative Examples 1-6 was shown in Table 2.

Next, the following evaluation was performed using the obtained paint.
(1) Evaluation before curing [minimum melt viscosity]
The minimum melt viscosity in the measurement of dynamic viscoelasticity before curing was measured by the following procedure using the obtained paint of the adhesive composition. The results are shown in Table 3.
The coating compositions of the adhesive compositions of Examples 1 to 15 and Comparative Examples 1 to 6 were applied onto a polyester film having a thickness of 38 μm subjected to a peeling treatment so that the thickness after drying was 25 μm. It dried for 5 minutes at 130 degreeC in the circulation type dryer, and formed the adhesive bond layer. Next, the obtained adhesive layer is peeled from the polyester film to form a single layer, and a plurality of the single-layer adhesive layers are stacked, and then an adhesive layer on the polyester film is further formed on both sides of the laminate. The laminate was laminated with a laminator so that the thickness of the entire adhesive layer was 0.8 mm. The laminator temperature was set to a temperature within + 3 ° C. to + 13 ° C. when the film was bonded to a polyimide film (trade name: Upilex 50S, manufactured by Ube Industries Co., Ltd.). The bonding speed was 1 m / min. Next, the polyester films on both sides were peeled to obtain an uncured film in which a plurality of adhesive layers were laminated.
About the obtained uncured film, the minimum melt viscosity was measured using the dynamic measuring machine (RS75 by HAAKE).
As is clear from Table 3, the uncured films based on Examples 1 to 15 entered the range of 400 Pa · s to 50000 Pa · s and had an appropriate minimum melt viscosity. On the other hand, the uncured film based on Comparative Examples 1, 3, 5, and 6 had a minimum melt viscosity outside the range of 400 to 50000 Pa · s.

[Compatibility]
The coating compositions of the adhesive compositions of Examples 1 to 15 and Comparative Examples 1 to 6 were applied onto a polyester film having a thickness of 38 μm subjected to a peeling treatment so that the thickness after drying was 25 μm. After drying for 5 minutes at 130 ° C. in a circulation dryer, a polyethylene film having a thickness of 50 μm subjected to a peeling treatment was bonded. Thereafter, the dried adhesive layer was observed with a microscope, and the compatibility state of the component (A), the component (B) and the component (C) was confirmed. As a result, it was judged that compatibility was good for those in which no separation such as a group pattern or a striped pattern was found, and that in which separation such as a group pattern or a striped pattern was seen was judged to be incompatible. . The results are shown in Table 3 with “Good” indicating good compatibility and “Poor” indicating poor compatibility.
As is clear from Table 3, the adhesive composition of the present invention based on Examples 1 to 15 had good compatibility. On the other hand, those in Comparative Examples 4 and 6 had poor compatibility.

[Embeddability (foamed and filled)]
The coating compositions of the adhesive compositions of Examples 1 to 15 and Comparative Examples 1 to 6 were applied onto a polyester film having a thickness of 38 μm subjected to a peeling treatment so that the thickness after drying was 25 μm. After drying for 5 minutes at 130 ° C. in a circulation type dryer to form an adhesive layer, a peeling treatment was performed to bond a polyethylene film having a thickness of 50 μm to produce an adhesive sheet.
In addition, a photoresist film is thermocompression-bonded to a flexible substrate (trade name: Espanex, manufactured by Nippon Steel Chemical Co., Ltd.), etched, and the resist film is peeled off to produce a ladder type circuit having a conductor / conductor distance of 25 μm / 25 μm. The produced adhesive sheet was thermocompression-bonded on the circuit while peeling the polyethylene film. Next, the polyester film was peeled off and heated at 160 ° C. for 1 hour to cure the adhesive layer, thereby obtaining a foam and embedding evaluation sample. The thermocompression bonding temperature was set to a temperature at which the color changes when wet when viewed from the opposite side when bonded to a polyimide film (trade name: Upilex 50S, manufactured by Ube Industries).
Thereafter, the foaming and filling states were determined by a microscope according to the following criteria, and the results are shown in Table 3. Regarding foaming, the case where foaming did not occur was marked with ◯, and the case where foaming occurred was marked with ×. In addition, regarding the filling state, the case where the circuit was sufficiently filled was marked with ◯, and the case where the circuit was not filled was marked with x. In Table 3, “−” indicates that the adhesion to the circuit is poor and there is a problem as a sample.
As is clear from Table 3, the adhesive sheets of the present invention based on Examples 1 to 15 did not cause foaming, had good filling into the circuit, and had good embeddability. On the other hand, in Comparative Examples 1, 2, 4 to 6, at least one of the foaming state and the filling state was bad, and as a result for semiconductor devices, there was a problem in terms of embedding properties.

(2) Evaluation after curing [Adhesive strength with polyimide film (PI adhesive strength)]
(Initial PI adhesion)
The adhesive composition paints of Examples 1 to 15 and Comparative Examples 1 to 6 were applied onto a 38 μm thick polyester film that had been subjected to a release treatment so that the thickness after drying was 25 μm, and hot air circulation was performed. After drying for 5 minutes at 130 ° C. in a mold dryer to form an adhesive layer, a 50 μm-thick polyethylene film with a release treatment was bonded to the surface of the adhesive layer to prepare an adhesive sheet.
Then, this adhesive sheet was thermocompression bonded to a polyimide film having a thickness of 50 μm (trade name: Upilex 50S, manufactured by Ube Industries) while peeling the polyethylene film. The thermocompression bonding temperature was set to be equal to or higher than the temperature at which the color changes when wet from the opposite side when bonded to a polyimide film (trade name: Upilex 50S, manufactured by Ube Industries).
Next, the polyester film was peeled off, thermocompression bonded to a polyimide film having a thickness of 50 μm (trade name: Upilex 50S, manufactured by Ube Industries), and further heated at 160 ° C. for 1 hour to cure the adhesive layer. The adhesive force was measured by fixing the polyimide film surface to a base and peeling off the end of another polyimide film in a 180 ° direction with Tensilon (manufactured by Shimadzu Corporation). The results are shown in Table 4.
(PI adhesive strength after constant temperature and humidity test (PCT))
Moreover, the adhesive force after the following PCT was measured using the sample for evaluation similar to the above.
PCT was performed using the constant temperature and humidity chamber under the following conditions. Temperature: 121 ° C., humidity: 100% RH, time: 300 hours. The adhesive force was measured by fixing the polyimide film surface to a base and peeling off the end of another polyimide film in a 180 ° direction with Tensilon (manufactured by Shimadzu Corporation). The results are shown in Table 4.
As is clear from Table 4, the adhesive sheets of the present invention based on Examples 1 to 15 have an initial state and an adhesive force after PCT of 4.2 (N / cm) or more, and are sufficiently bonded to the polyimide film. Had power.
On the other hand, in Comparative Examples 1 to 6, the adhesive strength after PCT was 0, and it could not be used for semiconductor devices.

[Adhesive strength with copper foil (Cu adhesive strength)]
(Initial Cu adhesion)
The adhesive composition paints of Examples 1 to 15 and Comparative Examples 1 to 6 were applied onto a 38 μm thick polyester film that had been subjected to a release treatment so that the thickness after drying was 25 μm, and hot air circulation was performed. After forming an adhesive layer by drying at 130 ° C. for 5 minutes in a mold dryer, an adhesive sheet was prepared by laminating a 50 μm-thick polyethylene film with a release treatment on the surface of the adhesive layer. .
Then, this adhesive sheet was thermocompression bonded to a copper foil (trade name: JTC-A, manufactured by Japan Energy Co., Ltd.) having a thickness of 18 μm while peeling the polyethylene film. The thermocompression bonding temperature is set to a temperature equal to or higher than the temperature at which the color changes when viewed from the opposite side, similarly to the case where the film is bonded to a polyimide film (trade name: Upilex 50S, manufactured by Ube Industries) in the previous evaluation.
Next, the polyester film was peeled off and thermocompression bonded to a 18 μm thick copper foil (trade name: JTC-A, manufactured by Japan Energy Co., Ltd.), and further heated at 160 ° C. for 1 hour to cure the adhesive layer. The adhesive strength was measured by fixing the copper foil surface to a base and peeling off the end of another copper foil in a 180 ° direction with Tensilon (manufactured by Shimadzu Corporation). The results are shown in Table 4.
(Cu adhesive strength after PCT)
Moreover, the adhesive force after PCT was measured using the same sample for evaluation.
The constant temperature and humidity test was performed using a constant temperature and humidity chamber under the following conditions. Temperature: 121 ° C., humidity: 100% RH, time: 300 hours. The adhesive strength was measured by fixing the copper foil surface to a base and peeling off the end of another copper foil in a 180 ° direction with Tensilon (manufactured by Shimadzu Corporation). The results are shown in Table 4.
As is apparent from Table 4, in the adhesive sheets of the present invention based on Examples 1 to 15, the initial state and the Cu adhesive force after PCT are 5.1 (N / cm) or more, which is sufficient for the copper foil. It had adhesive strength.
On the other hand, in the comparative examples 1-6, the adhesive force after PCT is 2.5 (N / cm) or less, and it cannot be used for semiconductor devices.

[Reflow resistance]
The adhesive composition paints of Examples 1 to 15 and Comparative Examples 1 to 6 were applied onto a 38 μm thick polyester film that had been subjected to a release treatment so that the thickness after drying was 25 μm, and hot air circulation was performed. An adhesive sheet was prepared by drying at 130 ° C. for 5 minutes in a mold dryer, and then a polyethylene film having a thickness of 50 μm subjected to a peeling treatment was bonded.
Then, while peeling the polyethylene film, this adhesive sheet was applied to a glass epoxy substrate (trade name; CCL-EL170, manufactured by Mitsubishi Gas Chemical Co., Ltd.) with a copper part having a thickness of 200 μm and a size of 2.5 cm × 2.5 cm etched. Thermocompression bonding was performed. The thermocompression bonding temperature was set to be equal to or higher than the temperature at which the color changes when wet from the opposite side when bonded to a glass epoxy substrate (trade name; CCL-EL170, manufactured by Mitsubishi Gas Chemical Company).
Next, the polyester film is peeled off, and a glass chip of 0.9 cm × 0.7 cm is thermocompression bonded at a thermocompression temperature for 3 minutes at a pressure of 0.1 MPa, and heated at 90 ° C. for 1 hour and further at 160 ° C. for 1 hour. Then, the adhesive layer was cured, and five reflow resistance evaluation samples were obtained for each of the examples and comparative examples.
This evaluation sample was exposed to a constant temperature and humidity chamber at 85 ° C. and 85% RH for 48 hours, then passed through an IR reflow furnace set at 260 ° C., and observed for delamination and foaming. The results are shown in Table 4. Table 4 shows the number of samples having no delamination and foaming among the five samples (the number of good ones / 5).
As is clear from Table 4, the adhesive sheets of the present invention based on Examples 1 to 15 were free from delamination and foaming, and all five were good.
On the other hand, none of the five adhesive sheets of Comparative Examples 1 to 6 were satisfactory, and at least two of the adhesive sheets had either delamination or foaming.

[Heat-resistant temperature cycle (TCT)]
The coating compositions of the adhesive compositions of Examples 1 to 15 and Comparative Examples 1 to 6 were applied on a polyester film having a thickness of 38 μm subjected to a peeling treatment so that the thickness after drying was 50 μm. An adhesive sheet was prepared by drying at 130 ° C. for 5 minutes in a circulation dryer, and then a polyethylene film having a thickness of 50 μm subjected to a peeling treatment was bonded.
Then, while peeling the polyethylene film, this adhesive sheet was applied to a glass epoxy substrate (trade name: CCL-EL170, manufactured by Mitsubishi Gas Chemical Co., Ltd.) obtained by etching a copper part having a thickness of 200 μm and a size of 2.5 cm × 2.5 cm. Thermocompression bonding was performed. The thermocompression bonding temperature was set to be equal to or higher than the temperature at which the color changes when wet from the opposite side when bonded to a glass epoxy substrate (trade name; CCL-EL170, manufactured by Mitsubishi Gas Chemical Company).
Next, the polyester film is peeled off, and a glass chip of 0.9 cm × 0.7 cm is thermocompression bonded at a thermocompression temperature for 3 minutes at a pressure of 0.1 MPa, and heated at 90 ° C. for 1 hour and further at 160 ° C. for 1 hour. Then, the adhesive layer was cured, and five temperature cycle resistance evaluation samples were obtained in each example and comparative example.
Using this evaluation sample, a temperature cycle test of −65 ° C. to 150 ° C. was performed.
However, in this case, a temperature history of 30 minutes was essential at 150 ° C. and −65 ° C., and [high temperature-low temperature] was set as one cycle, and the test was performed under conditions of 1000 cycles.
After the temperature cycle test, the presence or absence of delamination and foaming was observed, and the results are shown in Table 4. Table 4 shows the number of good samples without delamination and foaming among the five samples (good number / 5 pieces).
As is clear from Table 4, the adhesive sheets of the present invention based on Examples 1 to 15 were free from delamination and foaming, and all five were good. On the other hand, in the adhesive sheets of Comparative Examples 1 to 6, either delamination or foaming occurred and none of the five sheets was satisfactory.

[Dynamic elastic modulus]
The coating compositions of the adhesive compositions of Examples 1 to 15 and Comparative Examples 1 to 6 were applied onto a polyester film having a thickness of 38 μm subjected to a peeling treatment so that the thickness after drying was 25 μm. It dried for 5 minutes at 130 degreeC in the circulation type dryer, and formed the adhesive bond layer. Next, the obtained adhesive layer is peeled from the polyester film to form a single layer, and a plurality of the single-layer adhesive layers are stacked, and then an adhesive layer on the polyester film is further formed on both sides of the laminate. The laminate was laminated with a laminator so that the thickness of the entire adhesive layer was 0.1 mm. The laminator temperature was set to a temperature within + 3 ° C. to + 13 ° C. when the film was bonded to a polyimide film (trade name: Upilex 50S, manufactured by Ube Industries Co., Ltd.). The bonding speed was 1 m / min. Next, the polyester films on both sides were peeled to obtain an uncured film in which a plurality of adhesive layers were laminated.
Thereafter, the uncured film is further heated at 160 ° C. for 1 hour to cure the adhesive layer, to prepare a 4 mm × 5 cm sample for dynamic elastic modulus evaluation, and after curing, the dynamic elastic modulus at 200 ° C. to 280 ° C. (Dynamic elastic modulus after curing) was evaluated.
The measurement conditions are values measured at a frequency of 11 Hz and a heating rate of 3 ° C./min using Leovibron DDV-II manufactured by Orientech.
Moreover, using the same sample for evaluation, after curing, the dynamic elastic modulus at 200 ° C. to 280 ° C. (dynamic elastic modulus after thermal history) after standing in an environment of 150 ° C. for 24 hours was measured.
After measurement in an oven at a temperature of 150 ° C. and a time of 24 hours (H), the measurement was performed at a frequency of 11 Hz and a heating rate of 3 ° C./min using a Leo Vibron DDV-II manufactured by Orientec.
These results are shown in Table 4.
As is apparent from Table 4, the adhesive sheets of the present invention based on Examples 1 to 15 showed little change when compared between the dynamic elastic modulus after curing and the elastic modulus after thermal history. From this result, it can be seen that the heat resistance deterioration was good.
On the other hand, in the adhesive sheet based on Comparative Examples 1-4, the change with the dynamic elastic modulus after hardening and the elastic modulus after a heat history was large, and its heat-resistant deterioration property was bad.

[Hygroscopic rate]
The coating compositions of the adhesive compositions of Examples 1 to 15 and Comparative Examples 1 to 6 were applied on a polyester film having a thickness of 38 μm subjected to a release treatment so that the thickness after drying was 60 μm. After drying for 5 minutes at 130 ° C. in a circulation type dryer to form an adhesive layer and preparing an adhesive sheet, a polyethylene film having a thickness of 50 μm subjected to a release treatment was bonded.
Thereafter, the polyethylene film and the polyester film were peeled off, and further heated at 160 ° C. for 1 hour to cure the adhesive layer, thereby preparing a 5 cm × 5 cm moisture absorption rate evaluation sample and measuring the moisture absorption rate. Hygroscopic conditions were performed under the following conditions using a constant temperature and humidity chamber. Temperature: 121 ° C., humidity: 100% RH, time: 24 hours. Thereafter, the moisture absorption rate was calculated by the following formula, and the results are shown in Table 4.
Moisture absorption rate (%) = (sample weight after moisture absorption−sample weight before moisture absorption) / sample weight before moisture absorption × 100
As is apparent from Table 4, the adhesive sheets of the present invention based on Examples 1 to 15 had a moisture absorption rate of 0.7% or less, and there were no practical problems.
On the other hand, Comparative Examples 1 and 3 had a moisture absorption rate of 1.3% or more, which was a practically problematic result for semiconductor devices.

[Growth rate]
The coating compositions of the adhesive compositions of Examples 1 to 15 and Comparative Examples 1 to 6 were applied on a polyester film having a thickness of 38 μm subjected to a release treatment so that the thickness after drying was 60 μm. After drying for 5 minutes at 130 ° C. in a circulation type dryer to form an adhesive layer and preparing an adhesive sheet, a polyethylene film having a thickness of 50 μm subjected to a peeling treatment was bonded.
Thereafter, the polyethylene film and the polyester film were peeled off, and further heated at 160 ° C. for 1 hour to cure the adhesive layer, and a 1 cm × 12 cm elongation rate evaluation sample was prepared to evaluate the elongation rate.
The elongation percentage was measured with Tensilon (manufactured by Shimadzu Corporation), the elongation percentage was calculated according to the following formula, and the results are shown in Table 4.
Elongation rate (%) = (sample length after tension−length of sample before tension) / length of sample before tension × 100
As is clear from Table 4, it was confirmed that the adhesive sheets of the present invention based on Examples 1 to 15 had an elongation rate of 30% or more and excellent stress relaxation properties. In contrast, in Comparative Examples 1 and 3, the elongation was 10% or less, and it was confirmed that the stress relaxation properties were inferior.

[Electrical characteristics]
The coating compositions of the adhesive compositions of Examples 1 to 15 and Comparative Examples 1 to 6 were applied onto a polyester film having a thickness of 38 μm subjected to a peeling treatment so that the thickness after drying was 25 μm. After drying for 5 minutes at 130 ° C. in a circulation type dryer to form an adhesive layer, a 50 μm-thick polyethylene film having been subjected to a release treatment was bonded to prepare an adhesive sheet.
Further, a photoresist circuit is thermocompression-bonded to a flexible substrate (trade name: Espanex, manufactured by Nippon Steel Chemical Co., Ltd.), etched, and the resist film is peeled off to produce a comb-type circuit having a conductor / conductor distance of 25 μm / 25 μm. The adhesive sheet was thermocompression bonded while peeling the polyethylene film on the circuit. Next, the polyester film was peeled off and heated at 160 ° C. for 1 hour to cure the adhesive layer, thereby obtaining an electrical property evaluation sample.
Next, this sample was exposed to a constant temperature and humidity chamber having a temperature of 130 ° C. and a humidity of 85% RH for 300 hours while applying a DC voltage of 5V. Then, take out from the constant temperature and humidity chamber, observe the presence or absence of electrolytic corrosion on the conductor (copper foil portion) of the comb-shaped circuit, ○ It was set to x with electric corrosion. In Table 4, “−” indicates that the adhesiveness to the circuit is poor and there is a problem as a sample. The results are shown in Table 4.
As is apparent from Table 4, the adhesive sheets of the present invention based on Examples 1 to 15 had no electrical corrosion on the conductor (copper foil portion) of the comb circuit, and had no practical problems. On the other hand, in Comparative Examples 2 to 6, electrolytic corrosion occurred, and there were practically problematic results for semiconductor devices.

As is apparent from the above results, the adhesive composition and adhesive sheet of the present invention are excellent in embedding property, electrical property, adhesive force, reflow resistance and TCT property, have a low moisture absorption rate, a high elongation rate, and a stress relaxation. Excellent in heat resistance and heat deterioration resistance. Therefore, according to the adhesive composition and the adhesive sheet of the present invention, the occurrence of defects such as delamination, foaming and warping in the semiconductor device is suppressed, and the processability is excellent, so that the reliability of the semiconductor device can be improved. Can be improved.

Claims (10)

A vinyl copolymer having an epoxy resin (A), a phenol resin (B), ethylene as a monomer component, and an unsaturated carboxylic acid having a glycidyl group or a carboxyl group (including an anhydride group) or a derivative thereof ( C) and at least one siloxane compound (D) selected from the group consisting of siloxane compounds represented by the following general formula (1) or general formula (2) :
The content of the epoxy resin (A) is 3 to 45% by mass of the total solid amount, the content of the phenol resin (B) is 2 to 30% by mass of the total solid amount, and the vinyl copolymer The content of the coalescence (C) is 20 to 80% by mass of the total solid content, the content of the siloxane compound (D) is 0.05 to 10% by mass of the total solid content, and before curing The minimum melt viscosity in the dynamic viscoelasticity measurement is 400 to 50000 Pa. It is in the range of s, The adhesive composition for semiconductor devices characterized by the above-mentioned.

(R ¹ in the formula independently represents an alkylene group having 1 to 10 carbon atoms, and m and n each independently represents an integer of 0 to 10)   2. The adhesive composition for a semiconductor device according to claim 1, wherein the dynamic elastic modulus at 200 ° C. to 280 ° C. after curing is in the range of 500 Pa to 200 MPa.   The adhesive composition for semiconductor devices according to claim 1, wherein the tensile elongation after curing is 30% or more.   The adhesive composition for a semiconductor device according to claim 1, wherein the moisture absorption after curing is 1% or less.   2. The adhesive composition for a semiconductor device according to claim 1, wherein a dynamic elastic modulus at 200 ° C. to 280 ° C. after being left in an environment of 150 ° C. for 24 hours after curing is in a range of 500 Pa to 500 MPa.   2. The semiconductor device according to claim 1, wherein a ratio of the epoxy resin (A) to the phenol resin (B) is a functional group equivalent ratio in a range of 1: 0.6 to 1: 1.4. Adhesive composition.   The adhesive composition for a semiconductor device according to claim 1, wherein the vinyl copolymer (C) has a functional group equivalent of 100 to 2500. An adhesive sheet for a semiconductor device, wherein an adhesive layer made of the adhesive composition for a semiconductor device according to any one of claims 1 to 7 is laminated on at least one surface of a support. An adhesive layer made of the adhesive composition for a semiconductor device according to any one of claims 1 to 7 , and an insulating film or a peelable film are sequentially laminated on at least one surface of the metal layer. An adhesive sheet for a semiconductor device. An adhesive layer made of the adhesive composition for a semiconductor device according to any one of claims 1 to 7 , and an insulating film or a peelable film are sequentially laminated on both surfaces of the insulating film. An adhesive sheet for a semiconductor device.