JP2008231235A - Adhesive composition for semiconductor device, adhesive sheet for semiconductor device using the same, cover-lay film and copper-clad laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive composition for semiconductor devices having excellent adhesiveness and keeping high adhesiveness even in a high-temperature environment. <P>SOLUTION: The adhesive composition for semiconductor devices contains (A) a tetrazole compound, (B) an epoxy resin containing phosphorus in the repeating unit and (C) a curing agent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an adhesive composition for a semiconductor device, an adhesive sheet for a semiconductor device, a coverlay film, and a copper clad laminate using the same.

  A flexible printed circuit board (FPC) is generally formed by lithography on a copper clad laminate (CCL) in which a copper foil is provided on one or both sides of a base film typified by a polyimide film or a polyethylene terephthalate film via an adhesive layer. A pattern circuit is formed by applying a technique or the like, and a coverlay film serving as a protective layer is provided thereon. The FPC has an overall thickness of about 100 μm or less and can be bent, so that it has been adopted in various electronic devices that have been made lighter and thinner in recent years.

  In recent years, as the components and elements used in electronic devices and the performance and size of CPUs become smaller, the amount of heat generated has increased significantly, and the average temperature in electronic devices tends to increase. For example, it may reach 80 ° C. or more in a notebook computer or a vehicle-mounted device that is continuously used. The conventional FPC material premised on use at room temperature has a problem that performance such as adhesiveness decreases due to thermal deterioration of the adhesive layer when the use environment temperature rises to 50 to 80 ° C.

On the other hand, while the impact on the environment is regarded as an important social issue, the flame retardant regulations required for electrical and electronic products are shifting to higher safety considering safety for human bodies. In other words, electrical and electronic products are not only difficult to burn, but are also required to generate less harmful gases and fumes. Conventionally, derivatives that mainly contain tetrabromobisphenol A as a flame retardant for glass epoxy boards, copper-clad laminates, flexible printed wiring boards, and encapsulants for mounting electronic components, for safety reasons such as fire prevention and delay. (Brominated epoxy resins, etc.) were widely used in general. However, although such brominated epoxy resins have excellent flame retardancy, they not only generate corrosive bromine and hydrogen bromide by thermal decomposition, but are also highly toxic when decomposed in the presence of oxygen. Polybrominated dibenzofurans and polybrominated dibenzodioxins can be produced. For these reasons, flame retardant resin compositions containing phosphorus-containing epoxy resins have been widely studied as alternatives to conventional brominated epoxy resins (see, for example, Patent Documents 1 to 3). Since the phosphorus-containing epoxy resin is obtained by reacting a phosphorus compound and an epoxy resin, there is no problem that the heat resistance and bleedability of the FPC material is lowered unlike the additive type flame retardant, and the flame retardant effect is exhibited. This is a flame-retardant resin composition containing no halogen and having excellent solder heat resistance and adhesion of the FPC material. However, when such a flame retardant resin composition is used at an environmental temperature of 50 to 80 ° C. for a long time as described above, there is a problem that the adhesiveness with the copper foil is lowered due to thermal deterioration of the adhesive layer. It was.
JP 2001-151990 A JP 2001-123049 A JP 2003-105167 A

  In view of the above problems, an object of the present invention is to provide an adhesive composition for a semiconductor device that is excellent in adhesiveness and can maintain good adhesiveness even in a high temperature environment.

  The present invention includes (A) a tetrazole-based compound, (B) an epoxy resin containing phosphorus in a repeating unit, and (C) a curing agent, and an adhesive composition for a semiconductor device, which uses the same. An adhesive sheet for semiconductor devices, a coverlay film, and a copper clad laminate.

  The adhesive composition for a semiconductor device of the present invention is excellent in adhesiveness and can maintain good adhesiveness even under high temperature and high humidity. By using the adhesive composition for a semiconductor device of the present invention, it is possible to obtain an adhesive sheet for a semiconductor device, a cover lay film, and a copper clad laminate excellent in adhesiveness under high temperature and high humidity.

  The present invention is described in detail below.

  The adhesive composition for a semiconductor device of the present invention (hereinafter referred to as an adhesive composition) contains (A) a tetrazole-based compound, (B) an epoxy resin containing phosphorus in a repeating unit, and (C) a curing agent. By containing a combination of the component (A) and the component (B), the adhesion is improved, and high adhesion can be maintained even under high temperature and high humidity.

  (A) A tetrazole compound is a compound having a 5-membered ring composed of 4 atoms of nitrogen and 1 atom of carbon. Examples of (A) tetrazole compounds used in the present invention include tetrazole, tetrazole salts, bistetrazole, and tetrazole derivatives in which a hydrogen atom is substituted with a lower alkyl group having 1 to 3 carbon atoms. Specifically, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 5,5′-bi-1H-tetrazole, and metals of the tetrazole compounds Examples thereof include various inorganic and organic salts such as salts, amine salts, ammonium salts, piperazine salts, and guanidine salts. Further, a 2H-tetrazole compound derivative which is a tautomer of the 1H-tetrazole compound may be used. These can be used alone or in combination of two or more.

  In the present invention, among the tetrazole compounds, an inorganic salt or an organic salt is preferably used because the thermal decomposition temperature can be increased. An amine salt of 5,5'-bi-1H-tetrazole is preferable from the viewpoint of excellent adhesiveness and solder heat resistance in a high temperature environment.

  In this invention, it is preferable that the thermal decomposition point of (A) tetrazole type compound is 300 degreeC or more. By containing a tetrazole compound having a high thermal decomposition point, the solder heat resistance can be improved.

  Examples of amine salts of bistetrazole compounds having a thermal decomposition point of 300 ° C. or higher include, for example, 5,5′-bi-1H-tetrazole diammonium (thermal decomposition temperature 325 to 380 ° C.), 5,5′- Examples thereof include bi-1H-tetrazole / piperazine (thermal decomposition temperature: 350 to 375 ° C.) and 5,5′-bi-1H-tetrazole / guanidine (thermal decomposition temperature: 340 to 370 ° C.).

  In the present invention, the content of the (A) tetrazole compound is preferably 1% by weight or more in the adhesive composition. Moreover, 10 weight% or less is preferable from a fluid viewpoint at the time of forming an adhesive bond layer, and 5 weight% or less is more preferable.

  The adhesive composition of the present invention contains (B) an epoxy resin containing phosphorus in the repeating unit. Such an epoxy resin may be a conventional reactive phosphorus-based difficulty such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, resorcyl diphenyl phosphate, phenylphosphinic acid, diphenylphosphinic acid and the like. Unlike the flame retardant, the repeating unit in the epoxy resin which is the base of the adhesive composition contains phosphorus. Therefore, adjustment of adhesive force etc. is easy, and phosphorus can be fixed in the resin matrix without leaving an unreacted phosphorus compound. Therefore, the water absorption is smaller than that of the conventional reactive phosphorus-based flame retardant, and there is almost no adverse effect due to the hydrolysis of phosphorus.

  (B) The epoxy resin containing phosphorus in the repeating unit is not particularly limited. For example, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and derivatives thereof; Examples include compounds obtained by reacting an epoxy resin in advance with a compound obtained by reacting 1,4-benzoquinone, 1,2-benzoquinone, tolquinone, 1,4-naphthoquinone, and the like.

  Since phosphorus has a high flame retardant effect and also has hygroscopicity, it is preferable that the component (B) has a chemical structure in which the amount of phosphorus contained is small and it is difficult to burn. In this invention, it is preferable that the epoxy resin of (B) component has a structure represented by the following general formula (1) or (2) in a repeating unit.

  Further, the phosphorus content in the component (B) is preferably 4% by weight or more, more preferably 4.2% by weight or more from the viewpoint of flame retardancy. Further, from the viewpoint of storage stability and solvent solubility of the obtained adhesive composition, it is preferably 5% by weight or less, and more preferably 4.8% by weight or less.

  Moreover, the adhesive composition of this invention contains (C) hardening | curing agent. Examples of the curing agent include 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′- which is an aromatic polyamine. Diaminodiphenylmethane, 3,3′-dimethyl-5,5′-diethyl-4,4′-diaminodiphenylmethane, 3,3′-dichloro-4,4′-diaminodiphenylmethane, 2,2 ′, 3,3′- Tetrachloro-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminobenzophenone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4 ' -Diaminodiphenyl sulfone, 4,4'-diaminobenzophenone, 3,4,4'-triaminodiphenyl sulfone, etc., phenol Such as novolac resin and the like. Further, a curing agent such as dicyandiamide or an acid anhydride may be used in order to adjust the curing speed and appropriate flexibility of the adhesive film. In the case of an adhesive layer having a high elastic modulus, it is preferable to use dicyandiamide having excellent adhesiveness and a flexible structure.

  Further, the phosphorus content in the adhesive composition of the present invention is preferably 2% by weight or more, more preferably 3% by weight or more from the viewpoint of flame retardancy. Moreover, 10 weight% or less is preferable from a viewpoint of adjusting the crosslinking density after hardening to an appropriate range, and 7 weight% or less is more preferable. In the adhesive composition, a reactive phosphorus compound may be contained in addition to the component (B). In order to further improve solder heat resistance, adhesiveness, insulation, and processability, it is preferable that 12% or more of the phosphorus in the adhesive composition is phosphorus derived from the component (B). The phosphorus content can be measured by elemental analysis.

  Further, the nitrogen content in the adhesive composition of the present invention is preferably 0.5% by weight or more, more preferably 1% by weight or more from the viewpoint of flame retardancy. Moreover, in order to suppress the hygroscopicity after hardening, 10 weight% or less is preferable and 8 weight% or less is more preferable. The nitrogen content can be measured by elemental analysis.

  Moreover, the adhesive composition of this invention may contain the epoxy resin, phenol resin, hardening accelerator, elastomer, etc. which do not contain phosphorus as needed.

  The epoxy resin not containing phosphorus is not particularly limited as long as it has two or more epoxy groups in one molecule. For example, bisphenol F, bisphenol A, bisphenol S, resorcinol, dihydroxynaphthalene, dicyclopentadiene diphenol, etc. Examples thereof include alicyclic epoxies such as diglycidyl ether, epoxidized phenol novolak, epoxidized cresol novolak, epoxidized trisphenylol methane, epoxidized tetraphenylol ethane, epoxidized metaxylene diamine, and cyclohexane epoxide. Specific examples include YD-128 (manufactured by Toto Kasei Co., Ltd.), “Epicoat” (registered trademark) 828, “Epicoat” (registered trademark) 180 (manufactured by Yuka Shell Epoxy Co., Ltd.), and the like.

  As a phenol resin, well-known phenol resins, such as a novolak type phenol resin and a resol type phenol resin, are mentioned. For example, aralkyl-substituted phenols such as phenol, cresol, p-t-butylphenol, nonylphenol and p-phenylphenol, cyclic alkyl-modified phenols such as terpene and dicyclopentadiene, and heteroatoms such as nitro group, cyano group and amino group Resins composed of functional groups, those having skeletons such as naphthalene and anthracene, polyfunctional phenols such as bisphenol F, bisphenol A, bisphenol S, resorcinol, pyrogallol, and nitrogen-containing phenols such as melamine-modified or triazine-modified phenol Can be mentioned.

  Further, examples of the curing accelerator include boron trifluoride amine complexes such as boron trifluoride triethylamine complex, 2-alkyl-4-methylimidazole, imidazole derivatives such as 2-phenyl-4-alkylimidazole, phthalic anhydride, Examples include organic acids such as trimellitic anhydride, dicyandiamide, and the like. These may be used alone or in combination of two or more.

  Examples of the elastomer include modified types such as acrylic rubber, acrylonitrile butadiene rubber, and carboxyl group-containing acrylonitrile butadiene rubber (hereinafter referred to as NBR-C). For example, as an example of NBR-C, the terminal group of a copolymer rubber obtained by copolymerizing acrylonitrile and butadiene at a molar ratio of about 10/90 to 50/50, or acrylonitrile, butadiene and acrylic acid, maleic acid And terpolymer rubbers of carboxyl group-containing polymerizable monomers such as As specific NBR-C, PNR-1H (manufactured by Nippon Synthetic Rubber Co., Ltd.), “Nipol” (registered trademark) 1072J, “Nipol” (registered trademark) DN612, “Nipol” (registered trademark) DN631J (above) Nippon Zeon Co., Ltd.), “Hiker” (registered trademark) CTBN (manufactured by BF Goodrich), and the like. The content of NBR-C is preferably 16.7 parts by weight or more with respect to 100 parts by weight of the total epoxy resin in the adhesive composition. Further, from the viewpoint of solder heat resistance, 200 parts by weight or less is preferable.

  The adhesive composition of the present invention preferably contains imidazole silane. By containing imidazole silane, the heat resistance, the antirust effect on the metal surface, and the adhesion to the metal can be improved. If necessary, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, etc. It may contain.

  Furthermore, you may contain an inorganic particle other than the said component as needed. Inorganic particles include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium aluminate hydrate, zinc oxide, magnesium oxide, silica, alumina, zirconium oxide, antimony trioxide, antimony pentoxide, and oxidation. Examples include metal oxides such as titanium, iron oxide, cobalt oxide, chromium oxide, and talc, metal fine particles such as aluminum, gold, silver, nickel, and iron, carbon black, and glass. Aluminum oxide is preferred. These may be used alone or in combination of two or more. The average particle diameter of the inorganic particles is preferably 0.2 to 5 μm in consideration of transparency and dispersion stability. Here, the average particle diameter refers to the diameter at which the cumulative weight becomes 50% in the particle size distribution obtained by the laser diffraction scattering method or the like. The content is suitably 30 to 300 parts by weight with respect to 100 parts by weight of NBR-C.

  In addition, antioxidants, ion-supplementing agents, melamine and derivatives thereof, phosphorus compounds such as various phosphate esters, phosphorus nitrogen-containing compounds such as phosphazene compounds, and organic compounds of silicone compounds as long as the properties of the adhesive composition are not impaired. The addition of the inorganic component is not limited at all. Specific examples of phosphorus compounds such as the above-mentioned various phosphate esters include “ADK STAB” PFR, FP-600, FP-700 (above, manufactured by ADEKA), SP-703, SP-670 (above, Shikoku Kasei Kogyo Co., Ltd.) ), PX-200, CR-733S, CR-741 (manufactured by Daihachi Chemical Industry Co., Ltd.) and the like.

  Next, the adhesive sheet for semiconductor devices (hereinafter referred to as an adhesive sheet) of the present invention will be described. The adhesive sheet of the present invention has an adhesive layer formed from the adhesive composition of the present invention and at least one peelable protective film.

  The peelable protective film is not particularly limited as long as it can be peeled without impairing the form of the adhesive layer and the coverlay film using the adhesive layer. For example, a polyester film, a polyolefin film, and a paper obtained by laminating these with a silicone or fluorine compound coating treatment may be mentioned.

  Examples of the configuration of the adhesive sheet include a peelable polyester protective film (12.5 to 150 μm) / an adhesive layer (10 to 100 μm) / a peelable polyester protective film (12.5 to 150 μm). It is done. Moreover, when the peeling force with respect to the adhesive bond layer of each protective film is set to F1 and F2 (F1> F2), F1-F2 is preferably 5 N / m or more, more preferably 10 N / m or more. If F1-F2 is 5 N / m or more, one protective film can be peeled stably. Moreover, as for peeling force F1, F2, all are 1-200 N / m, More preferably, it is 3-150 N / m, More preferably, it is 3-100 N / m.

  The protective film may be colored with a pigment, for example, for visibility during processing. Thereby, since the protective film of the side which peels previously can be recognized easily, misuse can be avoided.

  Next, the coverlay film of the present invention will be described. The coverlay film of this invention has an insulating film, the adhesive bond layer formed from the adhesive composition of this invention, and the peelable protective film in this order. Examples of the insulating film include films made of plastics such as polyimide, polyester, polyphenylene sulfide, polyether sulfone, polyether ketone, aramid, polycarbonate, and polyarylate, and a plurality of films may be laminated. The thickness of the insulating film is preferably 5 to 200 μm. Further, it may be subjected to surface treatment such as hydrolysis, corona discharge, low-temperature plasma, physical roughening, and easy adhesion coating treatment as necessary.

  As a main structure of the coverlay film of the present invention, for example, an insulating film (12.5 to 125 μm) such as polyimide film or aramid film / adhesive layer (5 to 50 μm) / peelable protective film (12. 5 to 125 μm).

  Next, the copper clad laminate of the present invention will be described. The copper clad laminated board of this invention has an insulating film, the adhesive bond layer formed from the adhesive composition of this invention, and copper foil in this order. As the insulating film, those exemplified as the insulating film of the coverlay film can be used. In general, rolled copper foil, electrolytic copper foil, and the like can be used as the copper foil, but rolled copper foil is preferable from the viewpoint of further stabilizing the bending characteristics of the obtained copper-clad laminate. The main configuration of the copper-clad laminate of the present invention is, for example, single-sided product: copper foil (9 to 35 μm) / adhesive layer (5 to 20 μm) / polyimide film (12.5 to 125 μm), double-sided product: copper Examples include foil (9 to 35 μm) / adhesive layer (5 to 20 μm) / polyimide film (12.5 to 125 μm) / adhesive layer (5 to 20 μm) / copper foil (9 to 35 μm).

  Next, a tape with an adhesive for tape automated bonding (TAB) obtained from the adhesive sheet of the present invention will be described. As tape with adhesive for TAB, peelable polyester protective film (12.5 to 150 μm) / adhesive layer (5 to 200 μm) / releasable polyester protective film (12.5 to 150 μm) and the like are specified standards. An adhesive sheet slit to a width (29.7 to 60.6 mm) is heated in a central portion of an insulating film having a standard width of 35 to 70 mm at 100 to 160 ° C., 10 N / cm, and 5 m / min. Examples produced by laminating are exemplified.

  Next, the manufacturing method of the adhesive sheet of this invention, a copper clad laminated board, a coverlay film, and the tape with an adhesive for tape automated bonding (TAB) using the same is given, giving an example.

  (1) Fabrication of adhesive sheet for semiconductor device: A paint prepared by dissolving the adhesive composition of the present invention in a solvent is applied on a polyester film subjected to a release treatment on both sides and dried to form an adhesive layer. . The film thickness of the adhesive layer is preferably 10 to 100 μm. Drying conditions are generally 100 to 200 ° C. and 1 to 5 minutes. Solvents are not particularly limited, but aromatics such as toluene, xylene and chlorobenzene, ketones such as methyl ethyl ketone and methyl ethyl isobutyl ketone (MIBK), aprotic such as dimethylformamide (DMF), dimethylacetamide and N-methylpyrodoline Mention may be made of system polar solvents. Two or more of these may be used.

  On the dried adhesive layer, a polyester or polyolefin protective film having higher releasability is laminated to obtain the adhesive sheet of the present invention. In order to further increase the adhesive thickness, the adhesive layer may be laminated a plurality of times. Moreover, you may adjust the hardening degree of an adhesive bond layer, for example after aging at 40-100 degreeC for about 1 to 200 hours after a lamination.

  (2) Production of copper clad laminate: An adhesive solution in which the adhesive composition of the present invention is dissolved in a solvent is produced. Examples of the solvent include MEK (methyl ethyl ketone), MIBK (methyl isobutyl ketone), CB (chlorobenzene), BA (benzyl alcohol) and the like. This adhesive solution was applied to a 25 μm-thick polyimide film (“Kapton” (registered trademark) 100V-P, manufactured by Toray DuPont Co., Ltd.) with a bar coater to a dry thickness of about 10 μm, and at 150 ° C. for 5 minutes. Dry to form an adhesive layer. A 25 μm thick polyester film with a silicone release agent is laminated on this adhesive layer to obtain an adhesive sheet. Thereafter, the polyester film of the adhesive sheet is peeled off, laminated to the non-glossy surface of a 1/2 oz rolled copper foil at 100 ° C. and 2.7 MPa, and then heated at 150 ° C. for 5 hours in an air oven. Then, a copper clad laminate is produced. When producing a double-sided copper-clad laminate, after producing a single-sided adhesive sheet as described above, an adhesive layer is again formed on the opposite side in the same manner to produce a double-sided adhesive sheet. What is necessary is just to laminate a copper foil.

  (3) Production of coverlay film: 25 μm-thick polyimide film (“Kapton” (registered trademark) manufactured by Toray DuPont Co., Ltd.) using an adhesive solution produced by the same method as in (2) above, using a bar coater 100V-P) so as to have a dry thickness of about 30 μm, and dried at 150 ° C. for 5 minutes to form an adhesive layer. A coverlay film is obtained by laminating a 25 μm thick polyester film with a silicone release agent on this adhesive layer. Then, it is common to perform the aging of 50 degreeC and 20 to 50 hours so that the amount of oozing out of an adhesive agent may become appropriate, and to adjust the hardening degree of an adhesive bond layer.

  (4) Production of tape with adhesive for tape automated bonding (TAB): After applying an adhesive composition solution to an insulating film such as polyimide by a coating method and drying to form an adhesive layer, a predetermined adhesive layer is formed. Slit to width to get tape with adhesive. In addition, the adhesive composition solution is applied by a coating method on a protective film such as a polyester film having a releasability and dried to form an adhesive layer, and then the standard width is 29.7 to 60.6 mm. Tape with adhesive for TAB by a method of laminating the slit tape with adhesive on the central part of an insulating film with a standard width of 35 to 70 mm under conditions of 100 to 160 ° C., 10 N / cm, 5 m / min. It may be used as a shape.

  Examples of the use of the adhesive sheet, cover lay film, and copper clad laminate of the present invention include, for example, a flexible printed circuit board composed of a copper clad laminate and a cover lay film, and a plurality of flexible printed circuit boards using an adhesive sheet. Examples include laminated multilayer copper-clad polyimide film circuit boards, flex-rigid circuit boards obtained by laminating rigid laminate boards and flexible printed circuit boards using adhesive sheets, TAB boards, and various package applications (CSP, BGA). .

  Hereinafter, a general method for manufacturing a TAB substrate and a method for manufacturing a circuit board for semiconductor connection will be described with examples.

(5) Manufacturing method example of TAB substrate A 3-35 μm electrolytic or rolled copper foil is applied to a tape with an adhesive for TAB obtained by the method described in (4) above, at 110 to 180 ° C., 30 N / cm, Laminate at 1 m / min. If necessary, a stepwise heat curing treatment is performed in an air oven at 80 to 300 ° C. for 1 to 24 hours to produce a TAB substrate. At this time, device holes and solder ball holes may be drilled in the TAB adhesive-attached tape before the copper foil is laminated.

(6) Manufacturing method example of circuit board for semiconductor connection Copper-clad laminate obtained by the method described in the above (2), copper foil surface of the TAB substrate obtained by the method described in (5) Then, photoresist film formation, etching, resist stripping, electrolytic gold plating, and solder resist film formation are performed to produce a circuit board for semiconductor connection.

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Each evaluation method of the copper clad laminate will be described before the description of the examples.

(1) Evaluation method of each characteristic Peel strength (peel)
This was performed according to JIS-C6481. When a 2 mm wide copper foil pattern is produced on a copper clad laminate by etching and the 2 mm wide copper foil is peeled off in a 90-degree direction using Tensilon (Orientec Co., Ltd., UTM-11-5HR type) Was measured (tensile speed: 50 mm / min).
B. Solder heat resistance It carried out by the method based on JIS-C6481. Cut the copper-clad laminate into 20 mm squares, adjust the humidity for 24 hours in an atmosphere of 40 ° C. and 90% RH, immediately float on a solder bath at a predetermined temperature for 30 seconds, and the polyimide film does not swell or peel off The maximum temperature was measured.
C. Flame retardancy A sample obtained by etching the entire copper foil of the copper clad laminate was prepared, and the evaluation method was based on the UL94 flame retardancy test.
D. Heat-resistant peel strength (heat-resistant peel)
After heat-treating the copper clad laminate at 170 ° C. for 5 hours, the peel strength was measured in the same manner as A described above.

Example 1
Tetrazole compounds (“Certetra” BHT-PIPE manufactured by Eiwa Chemical Industries, Ltd., nitrogen content 62.5%), bisphenol A epoxy resin (Japan Epoxy Resin Co., Ltd., Ep834), phosphorus-containing epoxy resin (Toto Kasei Co., Ltd., ZX-1548-4, phosphorus content 4%), carboxylated NBR (Nippon Synthetic Rubber Co., PNR-1H), curing agent (4,4′-diaminodiphenylsulfone, 4, 4′DDS), a flame retardant (manufactured by Otsuka Chemical Co., Ltd., SPB-100, phosphorus content 13%, nitrogen content 6%) is added so as to have the composition ratio (unit: solid part by weight) shown in Table 1 Benzyl alcohol was added to adjust to 3 Pa · s or less, and the mixture was stirred and mixed at 30 ° C. to prepare an adhesive solution. This adhesive solution was applied to a 25 μm-thick polyimide film (“Kapton” (registered trademark) 100V-P, manufactured by Toray DuPont Co., Ltd.) with a bar coder so as to have a dry thickness of about 10 μm. After drying for a minute, a 25 μm thick polyester film with a silicone release agent was laminated to obtain an adhesive sheet. The adhesive sheet for double-sided copper-clad laminate obtained by repeating the same operation once again is laminated so that the non-glossy surface of 1 / 2oz rolled copper foil (BHY foil, manufactured by Nikko Gould Foil Co., Ltd.) is matched. A copper-clad laminate was prepared. The properties of the obtained copper clad laminate are shown in Table 1.

Examples 2-5, Comparative Examples 1-3
A copper-clad laminate was prepared in the same manner as in Example 1 using the adhesive prepared with the raw materials and the composition ratio (unit: solid weight part) shown in Table 1. The properties of the obtained copper clad laminate are shown in Table 1.

In addition, each component described in Table 1 is as follows.
BHT-PIPE: 5,5′-bi-1H-tetrazole / piperazine (manufactured by Eiwa Chemical Industry Co., Ltd., nitrogen content 62.5%)
BHT-2NH3: 5,5′-bi-1H-tetrazole diammonium (manufactured by Eiwa Chemical Industry Co., Ltd., nitrogen content 81.4%)
1H-TZ: 1H-tetrazole (manufactured by Tokyo Chemical Industry Co., Ltd., nitrogen content 79.9%)
ZX-1548-4: Phosphorus-containing epoxy resin (Toto Kasei Co., Ltd., phosphorus content 4%)
Ep834: Bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd.)
PNR-1H: Carboxylated NBR (manufactured by Nippon Synthetic Rubber Co., Ltd.)
SPB-100: Phosphazene (Otsuka Chemical Co., Ltd., phosphorus content 13%, nitrogen content 6%)
4,4′DDS: 4,4′-diaminodiphenylsulfone (manufactured by Wakayama Seika Co., Ltd.)

  From Examples 1 to 5 and Comparative Examples 1 to 3 in Table 1, it can be seen that the copper-clad laminate of the present invention is excellent in adhesiveness and adhesiveness in a high temperature environment.

Claims (8)

An adhesive composition for a semiconductor device comprising (A) a tetrazole-based compound, (B) an epoxy resin containing phosphorus in a repeating unit, and (C) a curing agent. 2. The semiconductor device according to claim 1, wherein the (B) epoxy resin containing phosphorus in the repeating unit includes an epoxy resin having a structure represented by the general formula (1) or (2) in the repeating unit. Adhesive composition.

The adhesive composition for a semiconductor device according to claim 1 or 2, wherein the thermal decomposition point of the (A) tetrazole-based compound is 300 ° C or higher. The adhesive composition for a semiconductor device according to claim 1, wherein the (A) tetrazole-based compound contains an amine salt of a bistetrazole-based compound. The phosphorus content in the adhesive composition for a semiconductor device is 2 to 10% by weight, and the nitrogen content is 0.5 to 10% by weight. Adhesive composition for semiconductor devices. An adhesive sheet for a semiconductor device, comprising an adhesive layer formed from the adhesive composition for a semiconductor device according to any one of claims 1 to 5 and at least one peelable protective film. A coverlay film comprising an insulating film, an adhesive layer formed from the adhesive composition for a semiconductor device according to claim 1, and a peelable protective film in this order. . A copper-clad laminate comprising an insulating film, an adhesive layer formed from the adhesive composition for a semiconductor device according to any one of claims 1 to 5, and a copper foil in this order.