JP4691365B2 - Adhesive composition for semiconductor device and adhesive sheet for semiconductor device - Google Patents

Description

  The present invention relates to a semiconductor device using various semiconductors, in particular, a semiconductor device having a structure in which an IC chip is laminated on an IC substrate composed of an IC insulator layer and a conductor circuit, a surface-mount type semiconductor device, and a built-in semiconductor device. In particular, the present invention relates to an adhesive composition and an adhesive sheet suitable for an up substrate, etc., in particular, for bonding an IC chip, for bonding a heat sink, or for stacking an IC substrate at a higher density. IC chips and circuit boards, insulating layers for stacking circuit boards at higher density, circuit-formed FPCs, FPC and circuit boards, circuit boards and protective films, IC chips and heat sinks, heat sinks and circuit boards The present invention relates to an adhesive composition and an adhesive sheet.

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 from QFP (types with leads on the four sides of the package). , BGA, CPS, MCM, etc., have been developed. Along with this, the IC chip mounting side has also changed from a lead frame to a tape substrate and printed circuit board 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.
By the way, a substrate material using polyimide resin, epoxy resin, phenol resin, or the like is usually used for the insulator layer constituting the IC substrate. Since the temperature of the IC package becomes 100 ° C. or higher due to heat generated by the IC during driving, the IC package is exposed to a temperature change from room temperature to high temperature (100 ° C. or higher). Therefore, IC packages are required to have heat resistance that can withstand changes in the stress generated in that case, humidity resistance at high temperatures, and stress relaxation properties. Since the ratio increases and different thermal expansion coefficients are bonded together, it is necessary to withstand the stress in that case. However, the properties of the materials are not sufficient for long-term temperature changes and high temperatures and high temperatures.

  Specifically, due to the stress generated when the temperature change from room temperature to high temperature (100 ° C. or higher) is repeated, the insulating layer constituting the IC substrate and the interlayer caused by the adhesive layer inside the IC chip or the laminated substrate May cause peeling. Further, as a method for increasing the mounting density, there is a method in which an insulating layer is laminated to form a three-dimensional wiring pattern, and this case also has the same problem. In this stacked type high-density mounting method, in addition to a glass epoxy substrate, a TAB substrate, a flexible substrate, and the like are often used in addition to a glass epoxy substrate. Material.

Generally, polyimide resin or the like is very difficult to adhere. For this reason, when the layers are laminated, moisture absorption, the state of the interface, and the like have a great influence, and thus an adhesive composition having low hygroscopicity and excellent adhesive force has been demanded. In addition, this stacked type high-density mounting method also needs to embed a wiring pattern when stacked. Therefore, there has been a demand for an adhesive composition that does not cause foaming during embedding and flowability for embedding.
Further, in recent years, when the IR reflow temperature is increased due to the lead-free process, a water vapor explosion called popcorn phenomenon, which causes the swelling of the adhesive when the moisture contained in the adhesive is vaporized during reflowing and the swelling occurs. Therefore, in order to remove the water causing the popcorn phenomenon, the semi-finished product before reflowing is managed in a moisture-proof state. However, since management in a moisture-proof state requires a great deal of work and cost, an adhesive composition that does not require the management of the moisture-proof state and does not cause popcorn phenomenon has been demanded. Furthermore, since it is necessary to use it for a conductor part, electrical reliability is also required.
In response to the demand for such an adhesive composition, it has been proposed to use a diolefin resin composed of an epoxidized styrene-butadiene-styrene block copolymer (for example, see Patent Document 1). However, an adhesive composition using such a diolefin-based resin has a problem that it deteriorates when exposed to heat for a long period of time, resulting in a decrease in insulation.

JP 2002-241728 A

The present invention has been made to solve the above-mentioned problems, and is used for a semiconductor device in a new mounting form such as BGA, CSP, MCM, etc., and insulation caused by repeated temperature changes, which is a problem of conventional adhesives. The object is to solve the problem of delamination that occurs between the body layer and the adhesive layer and between the IC chip and the adhesive layer, and to solve defects such as warping and embedding. That is, to provide an adhesive composition for a semiconductor device and an adhesive sheet for a semiconductor device that have excellent stress relaxation properties, excellent heat cycle resistance, electrical reliability, and excellent adhesion between copper, a polyimide film, and the like. is there.
Furthermore, the adhesive composition for a semiconductor device and a semiconductor device, which have improved humidity resistance, improve the popcorn phenomenon that occurs when the moisture contained in the adhesive is vaporized during reflow, which is a problem of conventional adhesives It is to provide an adhesive sheet for use.

（式中のＲ¹は、炭素数１〜１０のアルキレン基を表し、ｍ及びｎは０〜１０の整数を示す）
また、前記（Ａ）エポキシ樹脂と（Ｂ）フェノール樹脂の比率が官能基当量比で１：０．６〜１：１．４であることが好ましい。
また、ビニル共重合体中の不飽和カルボン酸誘導体の含有率が０．１〜４０重量％であることが好ましい。また、前記ビニル共重合体の官能基当量が１００〜２５００であることが好ましい。 The adhesive composition for a semiconductor device of the present invention (hereinafter referred to as an adhesive composition) has (A) an epoxy resin, (B) a phenol resin, (C) a glycidyl group or a carboxyl group (including an anhydride group) . An unsaturated carboxylic acid derivative having a vinyl copolymer containing ethylene and (D) a siloxane compound having amino groups at both ends represented by the following general formula (1) or general formula (2), or the following general formula ( 1) and a siloxane compound containing both siloxane compounds having amino groups at both ends represented by the general formula (2) , wherein (A) the epoxy resin is 3 to 40% by weight of the total solid content, (C) The vinyl copolymer contains 20 to 80% by weight of the total solid amount, and the (D) siloxane compound contains 0.05 to 10% by weight of the total solid amount .

(R ¹ in the formula represents an alkylene group having 1 to 10 carbon atoms, and m and n represent an integer of 0 to 10)
Moreover, it is preferable that the ratio of said (A) epoxy resin and (B) phenol resin is 1: 0.6-1: 1.4 by functional group equivalent ratio.
Further, it is preferable that the content of the unsaturated carboxylic acid derivatives of vinyl-copolymer is 0.1 to 40 wt%. Moreover, it is preferable that the functional group equivalent of the said vinyl copolymer is 100-2500.

The adhesive sheet for a semiconductor device of the present invention (hereinafter referred to as an adhesive sheet) is characterized in that the adhesive composition described above is laminated on at least one surface of a support.

  According to the present invention, the problem of delamination that occurs between an insulator layer and an adhesive layer and an IC chip and an adhesive layer due to repeated temperature changes, which is a problem of conventional adhesives, is solved and warped. And defects such as embedding can be solved. That is, it is possible to provide an adhesive composition and an adhesive sheet that are excellent in stress relaxation properties and heat-resistant temperature cycle properties, and have electrical reliability and excellent adhesion between copper, polyimide film, and the like. Moreover, the popcorn phenomenon which generate | occur | produces when the water | moisture content contained in an adhesive vaporizes at the time of reflow can be improved, and the adhesive composition and adhesive sheet excellent in moisture resistance can be provided. Furthermore, it is possible to industrially provide an adhesive sheet with excellent electrical characteristics and adhesive strength, PCT resistance, reflow resistance and processability, and the reliability of the semiconductor device is improved by the adhesive composition of the present invention. Can be made.

Hereinafter, the present invention will be described in detail.
The adhesive composition of the present invention comprises (A) an epoxy resin, (B) a phenol resin, (C) an epoxy resin or an unsaturated carboxylic acid derivative having a functional group capable of reacting with an epoxy curing agent, and a vinyl copolymer containing ethylene. It is a curable adhesive composition containing a polymer and (D) a siloxane compound as essential components.
Each component used in the adhesive composition of the present invention will be described.

[(A) Epoxy resin]
The epoxy resin may have any structure such as a resin having two or more oxysilane rings in the molecule, for example, glycidyl ether, glycidyl ester, glycidyl amine, linear aliphatic epoxide, alicyclic epoxide. However, two or more types can be used in combination.
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 mold an 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.
Of these, bisphenol-type epoxy resins are particularly inexpensive, and polyfunctional epoxy resins are preferably used because of their excellent insulation and heat resistance.

The epoxy equivalent of these epoxy resins is preferably from 100 to 4000, more preferably from 100 to 2000, particularly preferably from 100 to 1000. When the epoxy equivalent is less than 100, an uncured portion tends to remain and easily causes foaming. If the epoxy equivalent is greater than 4000, it is difficult to dissolve in a solvent, and compatibility with other resins tends to deteriorate.
Specifically, the epoxy resin suitably used in the present invention is manufactured by Yuka Shell Epoxy Co., Ltd .: trade name; bisphenol type such as Epicoat 806, 828, 834, 1001, YX-4000, YX-4000H (biphenyl type), etc. Bifunctional epoxy resins such as Epicoat 152, 154, 180S65, 1032H60, 157S70 (polyfunctional novolac type), 604 (tetraglycidyldiphenylmethane type), HP-7200, HP-7200H (dicyclo type), Japan Product name: EOCNI02S, 103S, 104S, 1020 (o-cresol novolac type), EPPN501H, 502H (triphenylmethane type), etc. The use of halogenated epoxies, especially brominated epoxies, to impart flame retardancy is an effective means. Specific examples of brominated epoxies include: Yuka Shell Epoxy Co., Ltd .: trade name; Epicoat 5045, 5046, 5050, Nippon Kayaku Co., Ltd .: trade name: BREN-S, BREN-105, BREN-301, and the like. . There is no problem even if phosphide epoxy or the like is used.
In addition, content of an epoxy resin is 3 to 40 weight% with respect to the resin solid whole quantity, Preferably it is 5 to 25 weight%.

  In order to accelerate the curing reaction of the adhesive composition of the present invention, epoxy such as imidazoles, amine catalysts such as 1,8-diazabicyclo (5,4,0) undecene, phosphorus catalysts such as triphenylphosphine, etc. It is preferable to contain a curing agent.

[(B) Phenolic resin]
The phenol resin reacts with the epoxy resin to form a three-dimensional network structure.
Specifically, phenol derivatives such as resol phenol resin, phenol novolac resin, cresol novolac resin, resorcinol resin, xylene resin, etc. Among them, phenol novolac resin is preferable because it has excellent reactivity and moisture resistance and heat resistance in semiconductor device applications. . The epoxy resin and phenol resin are used in a functional group equivalent ratio of 1: 0.6 to 1: 1.4, preferably 1: 0.7 to 1: 1.1. If the ratio of the epoxy resin to the phenol resin is less than 1: 0.6 in terms of the functional group equivalent ratio, the cured product tends to be brittle. When the ratio of the phenol resin is larger than 1: 1.4, the adhesive force tends to decrease.

[(C) Unsaturated carboxylic acid derivative having functional group capable of reacting with epoxy resin or epoxy curing agent and vinyl copolymer containing ethylene]
The vinyl copolymer constituting the present invention contains at least ethylene and an unsaturated carboxylic acid derivative having a functional group capable of reacting with the epoxy resin or the epoxy curing agent as main monomer components. A small amount of the third monomer described below may be contained. Functional groups that can react with the epoxy resin or epoxy curing agent include amino groups, isocyanate groups, glycidyl groups, carboxyl groups (including anhydride groups), silanol groups, hydroxyl groups, vinyl groups, methylol groups, mercapto groups, esters. Among them, an amino group, a carboxyl group, a glycidyl group, and a hydroxyl group are preferable because of their high reactivity. Particularly preferred functional groups are glycidyl and carboxyl groups. Specific examples of the unsaturated carboxylic acid derivative having these groups include the following. Those having a carboxyl group include olefins such as acrylic acid, methacrylic acid, (anhydrous) maleic acid and propylene having a carboxyl group, and those having a glycidyl group include glycidyl acrylate, glycidyl methacrylate and the like. Examples of those containing a hydroxyl group include hydroxymethyl acrylate, hydroxymethyl methacrylate, hydroxyethyl acrylate, and hydroxyethyl methacrylate. The third monomer copolymerizable with the ethylene and the unsaturated carboxylic acid derivative having a functional group may be an alkyl (meth) acrylate such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, or the like. Examples include aryl esters and vinyl acetate.

  The content of the unsaturated carboxylic acid derivative in the vinyl copolymer is preferably 0.1 to 40% by weight, and more preferably 0.8 to 20% by weight. When the content of the unsaturated carboxylic acid derivative component in the copolymer is less than 0.1% by weight, the reactivity with the component (A) or (B) is low, and the solubility in an organic solvent is low. If the content exceeds 40% by weight, the stability in the paint state tends to deteriorate. Further, when the third monomer component is present, its content is 40% by weight or less, more preferably 30% by weight or less.

  In the present invention, the vinyl copolymer is preferably an ethylene- (meth) acrylic acid ester-maleic anhydride copolymer, an ethylene- (meth) acrylic acid alkyl ester-glycidyl (meth) acrylate copolymer, Examples include ethylene-glycidyl (meth) acrylate copolymer, ethylene- (meth) acrylic acid copolymer, and ethylene-glycidyl (meth) acrylate-vinyl acetate copolymer. Among these, ethylene- (meth) acrylic acid alkyl ester-maleic anhydride copolymer, ethylene- (meth) acrylic acid alkyl ester-glycidyl (meth) acrylate copolymer, and ethylene-glycidyl (meth) acrylate copolymer are preferable. . 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 vinyl copolymer is added for the purpose of imparting flexibility to the adhesive composition, and preferably contains an ethylene- (meth) acrylate as described above. A copolymer containing ethylene- (meth) acrylic acid ester does not contain a diene bond in the main chain, so there is almost no thermal deterioration (no elasticity) when left at high temperature, 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. In this case, the monomer ratio of the acrylic ester is preferably 5 to 40 mol%. If it is less than 5 mol%, the solubility in an organic solvent is extremely reduced, and is unsuitable for a coating solution (paint). If it exceeds 40 mol%, the electrical properties are degraded by hydrolysis. End up. The weight average molecular weight of the vinyl copolymer is 1,000 to 2,000,000, preferably 100,000 to 1,000,000. The weight average molecular weight is a value measured by gel permeation chromatography (GPC) using styrene as a standard. The functional group equivalent of the vinyl copolymer is preferably 100-2500.

In the present invention, the vinyl copolymer preferably has a tensile elongation at break of 500% or more. More preferably, it is 700% or more. In the present invention, the tensile elongation at break means a value measured in accordance with JIS K6760 with a thickness of 2 mm. If the tensile elongation at break is less than 500%, the film formability is inferior, and the flexibility of the adhesive composition layer after the resin is cured is also lowered. The vinyl copolymer preferably has a solubility in an organic solvent of 5% or more, more preferably 10% or more, and still more preferably 60% or more. When the solubility is less than 5%, the thickness during film formation tends to be extremely thin. The solubility was determined by adding 100 g of a sample to 100 g of a toluene solution, stirring and dissolving at 80 ° C. for 12 hours, cooling to room temperature, and then filtering the solution through a nylon 600 mesh filter to obtain an insoluble residue ( x) g can be obtained and obtained by the following formula.
Solubility (%) = [(100 g− (x) g) / 100 g] × 100

  In the present invention, the vinyl copolymer is contained in an amount of 20 to 200 parts by weight, preferably 50 to 150 parts by weight, based on 100 parts by weight of the total of the epoxy resin and the epoxy curing agent. When the content is more than 200 parts by weight, the film forming property tends to deteriorate. On the other hand, if the amount is less than 20 parts by weight, the film tends to be brittle.

[(D) Siloxane compound]
The siloxane compound preferably has a reactive group, and examples of the reactive group include a hydroxyl group, an alkoxy group, an amino group, a methacryl group, and an epoxy group. More preferably, it is a siloxane compound having amino groups at both ends represented by the following general formula (1) or general formula (2). Moreover, the siloxane compound containing both the siloxane compound which has an amino group in the both terminal shown by following General formula (1) and General formula (2) may be sufficient.

（式中のＲ¹は、炭素数１〜１０のアルキレン基を表し、ｍ及びｎは０〜１０の整数を示す。）
上記一般式(１)又は一般式（２）で示される両末端にアミノ基を有するシロキサン化合物としては、東芝シリコ−ン社製の商品名：ＴＳＬ９３０６（ジアミノジシロキサン）、商品名：ＴＳＬ９８８６（ジアミノポリシロキサン）、商品名：ＴＳＦ４７０６（ジアミノジシロキサン）、商品名：ＸＦ４２−Ａ２６４５（ジアミノポリシロキサン）等を挙げることができる。

(R ¹ in the formula represents an alkylene group having 1 to 10 carbon atoms, and m and n represent an integer of 0 to 10)
As a siloxane compound having an amino group at both ends represented by the above general formula (1) or general formula (2), a product name: TSL9306 (diaminodisiloxane) manufactured by Toshiba Silicone Co., Ltd., a product name: TSL9886 (diamino) Polysiloxane), trade name: TSF4706 (diaminodisiloxane), trade name: XF42-A2645 (diaminopolysiloxane), and the like.

  The ratio of the siloxane compound in the adhesive composition is 0.05 to 10% by weight, preferably 0.3 to 5% by weight of the total solid content. If it is less than 0.3% by weight, the compatibility as a paint and the moisture absorption after curing are not good, and if it exceeds 10% by weight, the adhesive strength in a normal state tends to be significantly reduced.

  In the adhesive composition of the present invention, the component (A) is preferably 3 to 40% by weight of the component (A), (B), (C) and the epoxy curing agent added as required. B) is 0.5 to 50% by weight, component (C) is 30 to 80% by weight, and epoxy curing agent is in the range of 0 to 10% by weight.

  The adhesive composition of the present invention preferably contains an inorganic or 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, Mica, clay, zinc oxide, carbon black, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, antimony trioxide or those whose surfaces are treated with a trimethylsiloxyl group or the like can be mentioned. Examples include polyimide, polyamideimide, polyetheretherketone, polyetherimide, polyesterimide, nylon, and silicone. Content of the said filler is 2-95 weight part with respect to 100 weight part of total of said component (A), (B), (C), and (D), Preferably it is the range of 5-50 weight part. .

  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 essential components (A) to (D) and other additives are dissolved in an organic solvent and used in the form of an adhesive solution. 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 selected and used as appropriate. Further, using these solvents, at least the solid content is adjusted to 5% or more. Preferably it is 5% or more. If the solid content is less than 10%, it is difficult to produce a uniform adhesive sheet.

  The adhesive sheet of the present invention has a structure in which a layer made of the adhesive composition is laminated on at least one surface of a support, and is produced by applying and drying the adhesive solution on at least one surface of the support. Is done. As the support, a metal layer made of a metal such as copper or aluminum, a peelable film, an insulating film, a release paper, and the like can be used. In particular, a metal layer, a peelable film, and an insulating film are preferably used.

  Film materials used for the peelable film and the insulating film include polyesters such as polyethylene terephthalate (hereinafter abbreviated as PET), polyolefins such as polyethylene, polyimide, polyamide, polyethersulfone, polyphenylene sulfide, and polyether. Preferred examples include ketones and triacetyl cellulose, and more preferred examples include polyesters, polyolefins, and polyimides. As the peelable film, a film made of any of these film materials and subjected to a release treatment with a release agent such as silicone is preferably used.

An adhesive solution obtained by dissolving the adhesive composition in an organic solvent is applied to one or both surfaces of these films, and dried to form an adhesive layer. Preferably, the adhesive layer is in a semi-cured state. To do.
In particular, the semi-cured state is appropriately controlled in order to suppress flowability and foaming by processing 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 3 to 400 μm, preferably 5 to 100 μm.
At the time of storage of the film on which the adhesive layer is formed, a peelable film is attached if necessary, and is peeled off at the time of use. Moreover, when using an adhesive agent by a single layer, it is desirable to make a support body into a peelable film, and also peels off and uses the support body side.
As the adhesive sheet of the present invention, the adhesive composition and the insulating film or peelable film are sequentially laminated on at least one surface of the metal layer, or the adhesive composition and the adhesive composition on both surfaces of the insulating film. The thing formed by laminating | stacking an insulating film or a peelable film sequentially can be mentioned.

  The adhesive composition and adhesive sheet of the present invention can be applied to various electronic components, but a semiconductor in which 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. Is particularly suitable. Specifically, there are T-BGA using TAB technology, FPC, a build-up substrate using a glass epoxy substrate, or a surface mount type CSP semiconductor. Specifically, in the semiconductor device, an adhesive that bonds the IC chip and an insulating layer and / or a conductor circuit of the IC substrate or forms a circuit, an adhesion between the circuit boards, and a protective film that protects the adhesive It is suitable as an adhesive.

EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these.
[Preparation of paint for adhesive composition]
(A) an epoxy resin, (B) a phenol resin, (C) an epoxy resin or an unsaturated carboxylic acid derivative having a functional group capable of reacting with an epoxy curing agent, and a vinyl copolymer containing ethylene, (D) a siloxane compound, A silane coupling agent, an epoxy curing agent, and other compounds are dissolved in toluene at room temperature to about 80 ° C. so as to have the weight% (solid content) shown in Table 1, respectively. The coating composition of the adhesive composition of the present invention and a comparative adhesive composition was obtained by containing 35% by weight. In addition, what was shown in Table 2 was used for each compound in Examples 1-24 shown in Table 1 and Comparative Examples 1-7. Moreover, content of a filler is the number of parts with respect to 100 weight part of sum total of a component (A), (B), (C), and (D).

Next, the following characteristic evaluation was performed using the adhesive composition.
[Compatibility]
The coating compositions of the adhesive compositions of Examples 1 to 24 and Comparative Examples 1 to 7 were applied onto a polyester film having a thickness of 38 μm subjected to a release 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 composition was confirmed with a microscope to confirm the compatibility of the (A) epoxy resin, (B) phenol resin, and (C) vinyl copolymer, and separation such as a strip pattern or a stripe pattern was observed. The results were shown in Table 3 as being judged to be incompatible. Good compatibility was marked with ◯, and poor quality with x. As is apparent from Table 3, the adhesive composition of the present invention based on Examples 1 to 24 had a good compatibility state. On the other hand, the compatibility state was bad in the comparative example 4 and the comparative example 7.

[Adhesive strength]
[Adhesive strength with polyimide film (PI adhesive strength)]
The adhesive composition paints of Examples 1 to 24 and Comparative Examples 1 to 7 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, 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.
Next, the polyester film is peeled off, thermocompression-bonded to a 50 μm-thick polyimide film (trade name: Upilex 50S, manufactured by Ube Industries, Ltd.), and further heated at 150 ° C. for 1 hour to cure the adhesive layer and evaluate the adhesive strength. A polyimide film was prepared and the initial adhesive force was measured.
Moreover, the adhesive force after a constant temperature and humidity test 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 method for measuring the adhesive force was measured by fixing the polyimide film surface to a table 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 3.
As is clear from Table 3, the adhesive sheets of the present invention based on Examples 1 to 24 have a sufficient adhesive force with an adhesive strength of 2.2 (N / cm) or more after the initial and constant temperature and humidity tests. It was. On the other hand, in Comparative Examples 1 to 7, the adhesive strength after the constant temperature and humidity test was 0, so that it could not be used for semiconductor devices.

[Adhesive strength with copper foil (Cu adhesive strength)]
The adhesive composition paints of Examples 1 to 24 and Comparative Examples 1 to 7 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, 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 copper foil (trade name: JTC-A, manufactured by Japan Energy Co., Ltd.) having a thickness of 18 μm while peeling the polyethylene film.
Next, the polyester film is peeled off, thermocompression bonded to a 18 μm thick copper foil (trade name: JTC-A, manufactured by Japan Energy Co., Ltd.), and further heated at 150 ° C. for 1 hour to cure the adhesive layer, and the adhesive strength A copper foil sample for evaluation was prepared and the initial adhesive force was measured.
Moreover, the adhesive force after a constant temperature and humidity test 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 method for measuring the adhesive force was measured by fixing the copper foil surface to a table 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 3.
As is apparent from Table 3, the adhesive sheets of the present invention based on Examples 1 to 24 have a sufficient adhesive force with an adhesive force of 2.6 (N / cm) or more after the initial and constant temperature and humidity tests. It was. On the other hand, in Comparative Examples 1 to 3, Comparative Example 5 and Comparative Example 7, the adhesive strength after the constant temperature and humidity test is less than 2 (N / cm), and it cannot be used as a semiconductor device. There wasn't.

[Reflow resistance]
The adhesive composition paints of Examples 1 to 24 and Comparative Examples 1 to 7 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, 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.
Next, the polyester film is peeled off, and a 0.9 cm × 0.7 cm glass chip is thermocompression bonded at 140 ° C. for 3 minutes at a pressure of 0.1 MPa, heated at 90 ° C. for 1 hour, and further at 150 ° C. for 2 hours. 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 3. Table 3 shows the number of good samples without delamination and foaming among the five samples (good number / 5 pieces).
As is clear from Table 3, the adhesive sheets of the present invention based on Examples 1 to 24 were free from delamination and foaming, and all five were good. On the other hand, in the adhesive sheets of Comparative Examples 1 to 7, either delamination or foaming occurred and none of the five sheets was satisfactory.

[Temperature cycle resistance (TCT)]
The coating compositions of the adhesive compositions of Examples 1 to 24 and Comparative Examples 1 to 7 were applied onto 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.
Next, the polyester film is peeled off, and a glass chip of 0.9 cm × 0.7 cm is thermocompression bonded at 140 ° C. for 3 minutes at a pressure of 0.1 MPa, heated at 90 ° C. for 1 hour, and further at 150 ° C. for 1 hour. Then, the adhesive layer was cured, and five temperature cycle resistance evaluation samples were obtained for each of the examples and comparative examples.
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 3. Table 3 shows the number of good samples without delamination and foaming among the five samples (good number / 5 pieces).
As is clear from Table 3, the adhesive sheets of the present invention based on Examples 1 to 24 were free from delamination and foaming, and all five were good. On the other hand, in the adhesive sheets of Comparative Examples 1 to 7, either delamination or foaming occurred and none of the five sheets was satisfactory.

[Hygroscopic rate]
The coating compositions of the adhesive compositions of Examples 1 to 24 and Comparative Examples 1 to 7 were applied onto 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 150 ° 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 according to the following formula, and the results are shown in Table 3.
Moisture absorption rate (%) = (sample weight after moisture absorption−sample weight before moisture absorption) / sample weight before moisture absorption × 100
As is clear from Table 3, the adhesive sheets of the present invention based on Examples 1 to 24 had a moisture absorption rate of 0.7% or less, and there were no practical problems. On the other hand, Comparative Examples 1, 3, 5 and 6 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 24 and Comparative Examples 1 to 7 were applied onto 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 to produce 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 by the following formula, and the results are shown in Table 3.
Elongation rate (%) = (sample length after tension−length of sample before tension) / length of sample before tension × 100
As apparent from Table 3, the adhesive sheets of the present invention based on Examples 1 to 24 were confirmed to have an elongation of 130% or more and excellent stress relaxation properties. On the other hand, in Comparative Examples 1-3, 5 and 7, the elongation was less than 100%, and it was confirmed that the stress relaxation properties were inferior.

[warp]
The coating compositions of the adhesive compositions of Examples 1 to 24 and Comparative Examples 1 to 7 were applied onto 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 to produce an adhesive sheet, a polyethylene film having a thickness of 50 μm subjected to a peeling treatment was bonded.
Thereafter, a polyimide film (trade name: Upilex 75S, manufactured by Ube Industries) with a thickness of 75 μm was thermocompression bonded to both surfaces of the adhesive layer while peeling the polyethylene film and the polyester film. After cutting it to a width of 70 mm, the adhesive layer was cured by heating at 160 ° C. for 1 hour to prepare a polyimide film laminate. The cured polyimide film laminate was cut into 70 mm × 5 mm to obtain a warpage characteristic evaluation sample. This evaluation sample was placed in a convex state on a horizontal base, and the height of the convex part was measured with a digital measurement microscope (trade name: STM-UM, manufactured by Olympus Corporation). The results are shown in Table 3.
As is clear from Table 3, the adhesive sheets of the present invention based on Examples 1 to 24 had a warp of 1.5 mm or less, and there were no practical problems. On the other hand, in Comparative Examples 2, 3 and 7, the warp was 3 mm or more, which was a practically problematic result for semiconductor devices. In Comparative Examples 1 and 5, it was impossible to measure the warp because the sample was wound.

[Foaming and embedding]
The coating compositions of the adhesive compositions of Examples 1 to 24 and Comparative Examples 1 to 7 were applied onto a polyester film having a thickness of 38 μm subjected to a release 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.
A ladder circuit with a conductor / conductor distance of 25 μm / 25 μm is manufactured by thermocompression bonding, etching, and resist film peeling on a flexible substrate (trade name: Espanex, manufactured by Nippon Steel Chemical Co., Ltd.). 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 a foam and embedding evaluation sample.
Thereafter, the foaming and embedding states were determined with a microscope, 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 ×. Further, regarding the embedding property, “◯” indicates that the circuit was sufficiently filled, and “×” indicates that the circuit cannot be filled.
As is apparent from Table 3, the adhesive sheets of the present invention based on Examples 1 to 24 did not cause foaming, had good filling into the circuit, and had no problem with respect to embedding, whereas Comparative Example 1 Nos. 4 to 6 were poor in foaming or embedding properties, and had practically problematic results for semiconductor devices.

[Electrical characteristics]
The coating compositions of the adhesive compositions of Examples 1 to 24 and Comparative Examples 1 to 7 were applied onto a polyester film having a thickness of 38 μm subjected to a release 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, it took out from the constant temperature and humidity chamber, and observed the presence or absence of the electrolytic corrosion to the conductor (copper foil part) of a comb-type circuit, and the result was shown in Table 3. The thing without the electrolytic corrosion to the conductor (copper foil part) of a comb-type circuit was set as (circle) and the thing with electrolytic corrosion x.
As is apparent from Table 3, the adhesive sheets of the present invention based on Examples 1 to 24 had no pitting 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 7, galvanic corrosion was generated, which was a practically problematic result for semiconductor devices.

  As shown in the above table, the adhesive composition and the adhesive sheet of the present invention are excellent in electrical properties, adhesive strength, reflow resistance and TCT properties, have a large moisture absorption rate and elongation rate, and are excellent in stress relaxation properties, warping, foaming, Since the processability such as embedding is excellent, the reliability of the semiconductor device can be improved.

Claims (7)

(A) an epoxy resin, (B) a phenol resin, (C) an unsaturated carboxylic acid derivative having a glycidyl group or a carboxyl group (including an anhydride group) and a vinyl copolymer containing ethylene, and (D) the following general formula Both a siloxane compound having amino groups at both ends represented by (1) or general formula (2), or a siloxane compound having amino groups at both ends represented by the following general formula (1) and general formula (2) containing siloxane compound comprising the 3-40 wt% of (a) an epoxy resin total solids weight, (C) 20 to 80 wt% of a vinyl copolymer the total solid content and (D) a siloxane compound total An adhesive composition for a semiconductor device comprising 0.05 to 10% by weight of a solid amount .

(R ¹ in the formula represents an alkylene group having 1 to 10 carbon atoms, and m and n represent an integer of 0 to 10)   2. The adhesive composition for a semiconductor device according to claim 1, wherein the ratio of the (A) epoxy resin to the (B) phenol resin is 1: 0.6 to 1: 1.4 in terms of functional group equivalent ratio. object.   The adhesive composition for a semiconductor device according to claim 1, wherein the content of the unsaturated carboxylic acid derivative in the vinyl copolymer is 0.1 to 40% by weight.   The adhesive composition for a semiconductor device according to claim 1, wherein a functional group equivalent of the vinyl copolymer is 100 to 2500. An adhesive sheet for a semiconductor device, wherein the adhesive composition for a semiconductor device according to any one of claims 1 to 4 is laminated on at least one surface of a support. An adhesive sheet for a semiconductor device, wherein the adhesive composition for a semiconductor device according to any one of claims 1 to 4 and an insulating film or a peelable film are sequentially laminated on at least one surface of a metal layer. An adhesive sheet for a semiconductor device, wherein the adhesive composition for a semiconductor device according to any one of claims 1 to 4 and an insulating film or a peelable film are sequentially laminated on both surfaces of the insulating film.