JP2008231286A - Adhesive composition for semiconductor device and copper-clad laminate, coverlay film and adhesive sheet each using the composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive composition which is free of halogen components, excellent in flame retardancy, without deteriorating heat-resistant adhesive force; and to provide a copper-clad laminate, a coverlay film and an adhesive sheet each using the composition. <P>SOLUTION: This adhesive composition for a semiconductor device comprises a thermoplastic resin (A), an epoxy resin (B) and a curing agent (C), characterized in that the epoxy resin (B) contains a phosphorus-containing epoxy resin and triglycidyl isocyanurate. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

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

  As a typical example of a laminated board used for an electric / electronic device printed circuit board, there is a flexible printed circuit board (hereinafter sometimes referred to as FPC). The FPC is composed of a copper-clad laminate (hereinafter also referred to as CCL) and a coverlay film (hereinafter also referred to as CL). CCL has three types of layers: a low-cost three-layer type consisting of three layers of copper foil, polyimide base film, and epoxy thermosetting adhesive layer, and a polyimide adhesive that is the same quality as the polyimide base film. There are types, and also a two-layer type without an adhesive layer. Moreover, CL is laminated | stacked in order to protect the copper wiring of CCL, and is comprised with a polyimide base film and an epoxy-type thermosetting adhesive layer. FPC material that is flexible and has excellent flexibility is suitable as a substrate for movable parts such as HDDs, CDs, DVDs, hinge parts of various electronic devices, etc. It is indispensable for space saving.

  On the other hand, in recent years, the environmental impact of materials used for electrical and electronic equipment has been regarded as a social issue, and material design that considers safety for the human body has been demanded. In particular, it is desired that the generation of harmful gases and smoke generated during combustion is small. Conventionally, in addition to FPC on which electronic components are mounted, hard printed wiring boards such as glass epoxy boards and sealants also have derivatives (bromine bromide) mainly composed of tetrabromobisphenol A as a flame retardant to prevent fires and delay the spread of fire. Halogen-containing chemical substances such as halogenated epoxy resins) have been widely used (see, for example, Patent Document 1).

However, flame retardant adhesives and flame retardant adhesive sheets using such bromine-containing flame retardants have good flame retardancy, but corrosive hydrogen halide over time after bonding. May generate (hydrogen bromide) gas. In particular, aromatic bromine compounds not only generate corrosive bromine and hydrogen bromide by thermal decomposition, but can form highly toxic polybrominated dibenzofurans and polybrominated dibenzodioxins when decomposed in the presence of oxygen. There is sex. In addition, the corrosive gas causes problems such as corrosion and fogging in the printed circuit, and its use is currently being suppressed. For these reasons, phosphorus compounds have been widely studied as an alternative to bromine-containing flame retardants. For example, a flame retardant adhesive composition containing a phosphorus-containing epoxy resin (for example, see Patent Document 2) or a flame retardant adhesive composition containing a phosphorus-containing epoxy resin and a phosphazene compound (for example, see Patent Document 3). It is disclosed. Since the phosphorus-containing epoxy resin is obtained by reacting a phosphorus compound and an epoxy resin, the heat resistance and bleedability of the FPC material, which are disadvantages of the additive-type flame retardant, can be minimized. However, there is a problem that the adhesive strength (hereinafter referred to as heat-resistant adhesive strength) after receiving a heat history over a long period of time is lowered, and a characteristic that is fully satisfactory cannot be obtained.
JP 62-96580 A Japanese Patent Laid-Open No. 2002-020715 JP 2005-2294 A

  The present invention provides an adhesive composition for a semiconductor device which does not contain a halogen component and has excellent flame retardancy without reducing heat-resistant adhesive strength, a copper-clad laminate, a coverlay film and an adhesive sheet using the same The purpose is to do.

  The present invention is an adhesive composition for a semiconductor device containing (A) a thermoplastic resin, (B) an epoxy resin, and (C) a curing agent, wherein (B) the epoxy resin is a phosphorus-containing epoxy resin and triglycidyl. An adhesive composition for a semiconductor device comprising isocyanurate.

  According to the present invention, it is possible to obtain an adhesive sheet, a cover lay film, and a copper-clad laminate having flame retardancy required for electric / electronic devices and excellent in heat-resistant adhesion.

  Details of the present invention will be described below. The adhesive composition of the present invention comprises (A) a thermoplastic resin, (B) an epoxy resin, and (C) a curing agent as essential components, and (B) the epoxy resin contains a phosphorus-containing epoxy resin and triglycidyl isocyanurate. . Thermoplastic resin has functions such as adhesion, flexibility, relaxation of thermal stress, and improvement of insulation due to low water absorption, and epoxy resin reacts with a curing agent to provide heat resistance and insulation at high temperature. Property balance such as property, chemical resistance and strength of the adhesive layer can be realized. That is, even if any of the thermoplastic resin, the epoxy resin, and the curing agent is lacking, characteristics that sufficiently satisfy performance as an adhesive composition for semiconductor devices cannot be obtained.

  Examples of the thermoplastic resin (A) used in the present invention include acrylonitrile-butadiene copolymer (NBR), acrylonitrile-butadiene rubber-styrene resin (ABS), polybutadiene, styrene-butadiene-ethylene resin (SEBS), acrylic resin, Examples include known materials such as polyvinyl butyral, polyamide, polyester, polyimide, polyamideimide, and polyurethane. Further, these thermoplastic resins preferably have a functional group capable of reacting with an epoxy resin described later. Specific examples include amino groups, carboxyl groups, epoxy groups, hydroxyl groups, methylol groups, and isocyanate groups. These functional groups are preferable because the bond with the epoxy resin becomes strong and the heat resistance is improved.

  Among these, copolymers containing butadiene as a copolymer component such as acrylonitrile-butadiene copolymer (NBR), styrene-butadiene-ethylene resin (SEBS), and styrene-butadiene resin (SBS) are adhesive to metal. It is preferably used from the viewpoint of chemical resistance and the like. Furthermore, copolymers having butadiene as a copolymer component and having a carboxyl group are more preferably used. For example, carboxylated NBR (NBR-C), carboxylated SEBS (SEBS-C), and carboxylated SBS (SBS-C). ) And the like. Examples of NBR-C include those obtained by carboxylating terminal groups 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, etc. And terpolymer rubbers of carboxyl group-containing polymerizable monomers. Specifically, PNR-1H (manufactured by JSR Corporation), “Nipol” (registered trademark) 1072J, “Nipol” (registered trademark) DN612, “Nipol” (registered trademark) DN631 (manufactured by Nippon Zeon Co., Ltd.) ), “Hiker” (registered trademark) CTBN (manufactured by BF Goodrich). Moreover, MX-073 (made by Asahi Kasei Co., Ltd.) can be illustrated as SEBS-C, and D1300X (made by Shell Japan Co., Ltd.) can be exemplified as SBS-C.

  The (B) epoxy resin used in the present invention contains a phosphorus-containing epoxy resin and triglycidyl isocyanurate.

  The epoxy resin containing phosphorus in the molecule is not particularly limited. For example, diglycidyl ethers such as bisphenol A, bisphenol F, bisphenol S, resorcinol, dihydroxynaphthalene, dicyclopentadiene diphenol, and epoxidation Aliphatic epoxy resins such as phenol novolak, epoxidized cresol novolak, epoxidized trisphenylol methane, epoxidized tetraphenylol ethane, biphenol type epoxy resin or novolac type epoxy resin, 9,10-dihydro-9-oxa- An epoxy compound is obtained by reacting 10-phosphaphenanthrene-10-oxide or a derivative thereof with 1,4-benzoquinone, 1,2-benzoquinone, tolquinone, 1,4-naphthoquinone, or the like. Those pre-reacted with butter, and the like, and the like. Among them, a novolac type epoxy resin is preferably used in order to enhance the effect on flame retardancy.

  This phosphorus-containing epoxy resin is 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 a flame retardant, it contains phosphorus as a structural unit in an epoxy resin serving as a base of an adhesive composition. 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.

  Triglycidyl isocyanurate is a compound called 1,3,5-tris (2,3-epoxypropyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, It has a structure represented by the following formula. It is a trifunctional epoxy compound having a strong triazine in the skeleton, and an excellent flame retardant effect can be exhibited by the strong skeleton and nitrogen.

  The adhesive composition for a semiconductor device of the present invention may contain a general-purpose non-brominated epoxy resin in addition to the above-described phosphorus-containing epoxy resin and triglycidyl isocyanurate as the (B) epoxy resin. The type is not particularly limited, but includes at least two epoxy groups in the molecule, for example, diglycidyl ethers such as bisphenol A, bisphenol F, bisphenol S, resorcinol, dihydroxynaphthalene, dicyclopentadiene diphenol, Examples thereof include alicyclic epoxy resins such as epoxidized phenol novolak, epoxidized cresol novolak, epoxidized trisphenylol methane, and epoxidized tetraphenylol ethane, or biphenol type epoxy resin or novolak type epoxy resin. In particular, a bisphenol A type epoxy resin or a bisphenol F type epoxy resin is preferable in terms of improving the flexibility of the adhesive layer and improving the adhesive force.

  (B) As for content of an epoxy resin, 90 to 200 weight part is preferable with respect to 100 weight part of (A) thermoplastic resins. Among them, triglycidyl isocyanurate is preferably 70 parts by weight or more and 150 parts by weight or less.

  The phosphorus content in the adhesive composition for a semiconductor device of the present invention is preferably 0.2% by weight or more in order to further improve the flame retardancy. Further, the nitrogen content in the adhesive composition for a semiconductor device is preferably 0.5% by weight or more in order to further improve the flame retardancy, and is preferably 10% by weight or less in order to reduce the hygroscopicity after curing. . The phosphorus content and nitrogen content can be generally measured by a method such as elemental analysis.

  The (C) curing agent used in the present invention is not particularly limited. For example, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, which is an aromatic polyamine, , 3′5,5′-tetraethyl-4,4′-diaminodiphenylmethane, 3,3′-dimethyl-5,5′-diethyl-4,4′-diaminodiphenylmethane, 3,3′-dichloro-4,4 '-Diaminodiphenylmethane, 2,2'3,3'-tetrachloro-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminobenzophenone, 3,3'-diaminodiphenylsulfone 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 4,4′-diaminobenzophenone, 3,4,4 ′ Triamino diphenyl sulfone, phenol novolak resins, dicyandiamide, and acid anhydrides thereof.

  The adhesive composition for a semiconductor device of the present invention may contain a curing accelerator. Curing accelerators include boron trifluoride amine complexes such as boron trifluoride triethylamine complex, imidazole derivatives such as 2-alkyl-4-methylimidazole and 2-phenyl-4-alkylimidazole, phthalic anhydride, And organic acids such as merit acid. Two or more of these may be used.

  The adhesive composition for a semiconductor device of the present invention may contain an inorganic particle agent as necessary. Examples of inorganic particles include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium aluminate hydrate, and metal oxides such as zinc oxide and magnesium oxide. These may be used alone or in combination of two or more. Also good. In consideration of transparency and dispersion stability, the average particle size of the inorganic particulate agent is preferably 0.2 to 5 μm. Moreover, 30-300 weight part is suitable with respect to 100 weight part of (A) thermoplastic resins. In addition to the above components, it is not limited to contain organic and inorganic components such as antioxidants, ion scavengers, nitrogen flame retardants (melamine modified phenolic resin, etc.) within the range that does not impair the properties of the adhesive. It is not something.

  The copper-clad laminate of the present invention has an insulating film, an adhesive layer formed from the adhesive composition, and a copper foil in this order. Moreover, the coverlay film of this invention has an insulating film, the adhesive bond layer formed from the said adhesive composition, and the peelable protective film in this order. Moreover, the adhesive sheet of this invention has a protective film which can peel on both surfaces of the adhesive bond layer formed from the said adhesive composition.

  Examples of the insulating film include plastic films such as polyimide, polyester, polyphenylene sulfide, polyethersulfone, polyetheretherketone, aramid, polycarbonate, and polyarylate. A plurality of films selected from these may be laminated and used. The thickness of the insulating film is preferably 5 to 200 μm. If necessary, surface treatments such as hydrolysis, corona discharge, low temperature plasma, physical roughening, and easy adhesion coating treatment can be applied.

  As the copper foil, either a rolled foil or an electrolytic foil can be suitably used depending on the application. The thickness and surface roughness of the copper foil are not particularly limited.

  The release film is not particularly limited as long as it can be peeled without impairing the form of the adhesive layer and the adhesive sheet using the adhesive layer. For example, a polyester film, a polyolefin film subjected to a coating treatment with silicone or a fluorine compound, and The paper which laminated these is mentioned.

  Applications of the adhesive composition for semiconductor devices, copper-clad laminates, coverlay films, and adhesive sheets of the present invention are not particularly limited, and are suitably used for electronic devices, substrates for connecting semiconductor integrated circuits, and semiconductor devices. can do. Examples include flexible printed circuit boards (FPC), tape automated bonding (TAB), and various package applications (CSP, BGA).

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

A. Sample preparation method for evaluation (single-sided CCL)
An adhesive solution was applied to a polyimide film “Kapton” (registered trademark) 50EN having a thickness of 12.5 μm with a bar coater and cured to form an adhesive layer having a thickness of 10 μm. Next, the adhesive layer was laminated at 100 ° C. and 2.7 MPa so that the non-glossy surface of 1/3 oz electrolytic copper foil (manufactured by Mitsui Kinzoku Co., Ltd., 3EC-M3S-HTE foil, 12 μm thickness) was matched. Thereafter, heat treatment was performed at 150 ° C. for 5 hours in a hot-air circulating air oven, and a single-sided CCL having an adhesive layer with a degree of cure of 90% or more was produced.

B. Sample preparation method for evaluation (double-sided CCL)
An adhesive solution was further applied to the polyimide film surface of the single-sided CCL obtained by the method described in A above with a bar coater and cured to 1/3 oz electrolytic copper foil (Mitsui Metals Co., Ltd., 3EC- The non-glossy surface of M3S-HTE foil (thickness 12 μm) was laminated under the same conditions. This was subjected to heat treatment at 150 ° C. for 5 hours in a hot-air circulating air oven to prepare a double-sided CCL having a degree of cure of the adhesive layer of 90% or more.

C. Normal-state adhesive strength Using a single-sided CCL sample prepared by the method described in A above, the adhesion was performed according to JIS-C6481. That is, a copper foil pattern having a width of 2 mm was produced by etching the copper foil on one side, and the strength when only 2 mm width of the copper foil was peeled in the direction of 90 degrees using Tensilon was measured as a normal adhesive force ( (Tensile speed: 50 mm / min). The normal state adhesive strength is preferably 10 N / cm or more, more preferably 15 N / cm.

D. Heat-resistant adhesion (single-sided pattern)
Using a double-sided CCL sample produced by the method described in B above, the measurement was performed according to UL796. However, the copper foil pattern was produced with a width of 2 mm only on one side, and the other copper foil was etched on the entire surface. The strength when only 2 mm-wide copper foil was peeled off in the 90-degree direction using Tensilon was measured to determine the heat-resistant adhesive strength (tensile speed: 50 mm / min). The heat resistant adhesive force is preferably 3.5 N / cm or more.

E. Heat resistant adhesive strength (double-sided pattern)
Using the CCL sample prepared by the method described in B above, the measurement was performed according to UL796. However, the copper foil pattern was produced with a width of 2 mm so as to be paired on both sides. Using Tensilon, the strength when only a 2 mm-wide copper foil was peeled off in the 90-degree direction was measured (tensile speed: 50 mm / min). The adhesive strength is preferably 3.5 N / cm or more.

F. Solder heat resistance It carried out by the method based on JIS-C6481. A single-sided CCL sample prepared by the method described in A above is cut into a 20 mm square, conditioned for 24 hours in an atmosphere of 40 ° C. and 90% RH, and immediately floated on a solder bath at a predetermined temperature for 30 seconds. The maximum temperature at which the polyimide film did not swell and peel was measured. The solder heat resistance is preferably 260 ° C. or higher, more preferably 280 ° C. or higher.

G. Flame Retardancy A sample was prepared by etching a double-sided CCL copper foil produced by the method described in B above on both sides, and measured according to UL94V-0.

Example 1
NBR (manufactured by JSR Corporation, PNR-1H) 100 parts by weight, triglycidyl isocyanurate (Nissan Chemical Industry Co., Ltd., TEPIC-S) 70 parts by weight, phosphorus-containing epoxy resin (manufactured by Toto Kasei Co., Ltd., FX) -289B, phosphorus content 2% by weight) 50 parts by weight and curing agent (Sumitomo Chemical Co., Ltd., 4,4′-diaminodiphenylsulfone) 25 parts by weight are dissolved in methyl ethyl ketone, and stirred and mixed at 30 ° C. A 28 wt% adhesive solution was prepared.

Example 2
100 parts by weight of NBR (manufactured by JSR Corporation, PNR-1H), 100 parts by weight of triglycidyl isocyanurate (manufactured by Nissan Chemical Industries, Ltd., TEPIC-S), phosphorus-containing epoxy resin (manufactured by Toto Kasei Co., Ltd., FX) -289B, phosphorus content 2% by weight) 50 parts by weight and curing agent (Sumitomo Chemical Co., Ltd., 4,4′-diaminodiphenylsulfone) 35 parts by weight are dissolved in methyl ethyl ketone, and stirred and mixed at 30 ° C. A 28 wt% adhesive solution was prepared.

Example 3
NBR (manufactured by JSR Corporation, PNR-1H) 100 parts by weight, triglycidyl isocyanurate (manufactured by Nissan Chemical Industries, Ltd., TEPIC-S) 150 parts by weight, phosphorus-containing epoxy resin (manufactured by Toto Kasei Co., Ltd., FX) -289B, phosphorus content 2% by weight) 50 parts by weight and curing agent (Sumitomo Chemical Co., Ltd., 4,4'-diaminodiphenylsulfone) 45 parts by weight are dissolved in methyl ethyl ketone, and stirred at 30 ° C and mixed. A 28 wt% adhesive solution was prepared.

Example 4
80 parts by weight of an inorganic filler (manufactured by Showa Denko KK, aluminum hydroxide, H-42I) was dispersed in toluene, and sand milled to prepare an aluminum hydroxide dispersion. To this dispersion, 100 parts by weight of NBR (manufactured by JSR Corporation, PNR-1H), 80 parts by weight of triglycidyl isocyanurate (manufactured by Nissan Chemical Industries, Ltd., TEPIC-S), phosphorus-containing epoxy resin (Tohto Kasei ( Co., Ltd., EXA-9710, phosphorous content 3% by weight) 120 parts by weight, and curing agent (Sumitomo Chemical Co., Ltd., 4,4′-diaminodiphenylsulfone) 30 parts by weight are added and stirred at 30 ° C. A 28 wt% adhesive solution was made by mixing.

Example 5
80 parts by weight of an inorganic filler (manufactured by Showa Denko KK, aluminum hydroxide, H-42I) was dispersed in toluene, and sand milled to prepare an aluminum hydroxide dispersion. To this dispersion, 100 parts by weight of NBR (manufactured by JSR Corporation, PNR-1H), 70 parts by weight of triglycidyl isocyanurate (manufactured by Nissan Chemical Industries, Ltd., TEPIC-S), a phosphorus-containing epoxy resin (Tohto Kasei ( Co., Ltd., EXA-9710, phosphorus content 3% by weight) 130 parts by weight, and curing agent (Japan Epoxy Resin Co., Ltd., dicyandiamide, DICY7) 8 parts by weight are added and stirred at 30 ° C. and mixed to 28 parts. A weight percent adhesive solution was prepared.

Example 6
NBR (manufactured by JSR Corporation, PNR-1H) 100 parts by weight, triglycidyl isocyanurate (Nissan Chemical Industry Co., Ltd., TEPIC-S) 70 parts by weight, phosphorus-containing epoxy resin (manufactured by Toto Kasei Co., Ltd., FX) -289B, phosphorus content 2% by weight) 70 parts by weight, epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., “jER” (registered trademark) 834, epoxy equivalent 250), 20 parts by weight, curing agent (Sumitomo Chemical Co., Ltd.) , 4,4'-diaminodiphenylsulfone) and 2 parts by weight of a curing accelerator (manufactured by Nikko Metal Co., Ltd., imidazolesilane, IS-1000) are dissolved in methyl ethyl ketone, and stirred and mixed at 30 ° C. A 28 wt% adhesive solution was prepared.

Example 7
NBR (manufactured by JSR Corporation, PNR-1H) 100 parts by weight, triglycidyl isocyanurate (Nissan Chemical Industry Co., Ltd., TEPIC-S) 70 parts by weight, phosphorus-containing epoxy resin (manufactured by Toto Kasei Co., Ltd., FX) -289B, phosphorus content 2% by weight) 30 parts by weight, epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., "jER" (registered trademark) 834, epoxy equivalent 250) 100 parts by weight, curing agent (Sumitomo Chemical Co., Ltd.) , 4,4'-diaminodiphenylsulfone) and 2 parts by weight of a curing accelerator (manufactured by Nikko Metal Co., Ltd., imidazolesilane, IS-1000) are dissolved in methyl ethyl ketone, and stirred and mixed at 30 ° C. A 28 wt% adhesive solution was prepared.

Example 8
80 parts by weight of an inorganic filler (manufactured by Showa Denko KK, aluminum hydroxide, H-42I) was dispersed in toluene, and sand milled to prepare an aluminum hydroxide dispersion. To this dispersion, 100 parts by weight of NBR (manufactured by JSR Corporation, PNR-1H), 70 parts by weight of triglycidyl isocyanurate (manufactured by Nissan Chemical Industries, Ltd., TEPIC-S), a phosphorus-containing epoxy resin (Tohto Kasei ( Co., Ltd., FX-289B, phosphorus content 2% by weight) 30 parts by weight, and curing agent (Japan Epoxy Resin Co., Ltd., dicyandiamide, DICY7) 8 parts by weight are added and stirred at 30 ° C. and mixed to 28 parts. A weight percent adhesive solution was prepared.

Example 9
80 parts by weight of an inorganic filler (manufactured by Showa Denko KK, aluminum hydroxide, H-42I) was dispersed in toluene, and sand milled to prepare an aluminum hydroxide dispersion. To this dispersion, 100 parts by weight of NBR (manufactured by JSR Corporation, PNR-1H), 150 parts by weight of triglycidyl isocyanurate (manufactured by Nissan Chemical Industries, Ltd., TEPIC-S), phosphorus-containing epoxy resin (Tohto Kasei ( Co., Ltd., FX-289B, phosphorus content 2 wt%) 50 parts by weight, and curing agent (Japan Epoxy Resin Co., Ltd., dicyandiamide, DICY7) 15 parts by weight are added and stirred at 30 ° C. and mixed 28 A weight percent adhesive solution was prepared.

Example 10
NBR (manufactured by JSR Corporation, PNR-1H) 100 parts by weight, epoxy resin (Nissan Chemical Industry Co., Ltd., TEPIC-S) 60 parts by weight, phosphorus-containing epoxy resin (manufactured by Toto Kasei Co., Ltd., FX-289B) 20 parts by weight of phosphorus content 2%) and 15 parts by weight of a curing agent (Sumitomo Chemical Co., Ltd., 4,4′-diaminodiphenylsulfone) were dissolved in methyl ethyl ketone and stirred and mixed at 30 ° C. A weight percent adhesive solution was prepared.

Example 11
NBR (manufactured by JSR Corporation, PNR-1H) 100 parts by weight, epoxy resin (Nissan Chemical Industry Co., Ltd., TEPIC-S) 60 parts by weight, phosphorus-containing epoxy resin (manufactured by Toto Kasei Co., Ltd., FX-289B) 80 parts by weight of phosphorus content 2%) and 20 parts by weight of a curing agent (manufactured by Sumitomo Chemical Co., Ltd., 4,4′-diaminodiphenylsulfone) were dissolved in methyl ethyl ketone and stirred and mixed at 30 ° C. A weight percent adhesive solution was prepared.

Example 12
NBR (manufactured by JSR Corporation, PNR-1H) 100 parts by weight, epoxy resin (manufactured by Nissan Chemical Industries, Ltd., TEPIC-S) 160 parts by weight, phosphorus-containing epoxy resin (manufactured by Toto Kasei Co., Ltd., FX-289B) 80 parts by weight of phosphorus content 2%) and 45 parts by weight of a curing agent (manufactured by Sumitomo Chemical Co., Ltd., 4,4′-diaminodiphenylsulfone) were dissolved in methyl ethyl ketone, and stirred and mixed at 30 ° C. 28 A weight percent adhesive solution was prepared.

Comparative Example 1
NBR (manufactured by JSR Corporation, PNR-1H) 100 parts by weight, epoxy resin (manufactured by Nissan Chemical Industries, Ltd., TEPIC-S) 120 parts by weight, and curing agent (manufactured by Sumitomo Chemical Co., Ltd., 4, 4 ' -Diaminodiphenylsulfone) 30 parts by weight was dissolved in methyl ethyl ketone and stirred and mixed at 30 ° C. to prepare a 28% by weight adhesive solution.

Comparative Example 2
NBR (manufactured by JSR Corporation, PNR-1H) 100 parts by weight, phosphorus-containing epoxy resin (manufactured by Toto Kasei Co., Ltd., FX-289B, phosphorus content 2% by weight) 120 parts by weight, and curing agent (Sumitomo Chemical ( Co., Ltd., 4,4′-diaminodiphenylsulfone) 10 parts by weight was dissolved in methyl ethyl ketone and stirred and mixed at 30 ° C. to prepare a 28 wt% adhesive solution.

Comparative Example 3
100 parts by weight of NBR (manufactured by JSR Corporation, PNR-1H), 170 parts by weight of a phosphorus-containing epoxy resin (manufactured by Toto Kasei Co., Ltd., EXA-9710, phosphorus content 3% by weight), and a curing agent (Sumitomo Chemical ( Co., Ltd., 4,4′-diaminodiphenylsulfone) 10 parts by weight was dissolved in methyl ethyl ketone and stirred and mixed at 30 ° C. to prepare a 28 wt% adhesive solution.

Comparative Example 4
100 parts by weight of NBR (manufactured by JSR Corporation, PNR-1H), 120 parts by weight of epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., “jER” (registered trademark) 834, epoxy equivalent 250), curing agent (Sumitomo Chemical ( Co., Ltd., 4,4′-diaminodiphenylsulfone) 15 parts by weight, and a curing accelerator (Nikko Metal Co., Ltd., imidazolesilane, IS-1000) 2 parts by weight were dissolved in methyl ethyl ketone and stirred at 30 ° C. A 28 wt% adhesive solution was made by mixing.

Comparative Example 5
NBR (manufactured by JSR Corporation, PNR-1H) 100 parts by weight, phosphorus-containing epoxy resin (manufactured by Toto Kasei Co., Ltd., EXA-9710, phosphorus content 3% by weight), epoxy resin (Japan Epoxy Resin ( "JER" (registered trademark) 834, epoxy equivalent 250) 120 parts by weight, curing agent (Sumitomo Chemical Co., Ltd., 4,4'-diaminodiphenylsulfone) 15 parts by weight, and curing accelerator (Nikko) 2 parts by weight of Metal Co., Ltd. (Imidazolesilane, IS-1000) was dissolved in methyl ethyl ketone and stirred and mixed at 30 ° C. to prepare a 28 wt% adhesive solution.

  Samples for evaluation were prepared using the adhesive solutions described in Examples 1 to 12 and Comparative Examples 1 to 5, and the results of evaluation of normal adhesive strength, heat resistant adhesive strength, solder heat resistance, and flame retardancy are shown in Tables 1 to 1. It is shown in 2.

Claims (5)

(A) A thermoplastic resin, (B) an epoxy resin, and (C) an adhesive composition for a semiconductor device containing a curing agent, wherein (B) the epoxy resin contains a phosphorus-containing epoxy resin and triglycidyl isocyanurate. An adhesive composition for semiconductor devices. (A) The content of the epoxy resin is 90 to 200 parts by weight and the content of triglycidyl isocyanurate is 70 to 150 parts by weight with respect to 100 parts by weight of the thermoplastic resin. The adhesive composition for a semiconductor device according to claim 1. A copper-clad laminate comprising an insulating film, an adhesive layer formed from the adhesive composition for a semiconductor device according to claim 1, and a copper foil in this order. 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. An adhesive sheet comprising a peelable protective film on both sides of an adhesive layer formed from the adhesive composition for a semiconductor device according to claim 1.