JP2002188066A - Adhesive composition for semiconductor device and adhesive sheet and cover lay film for semiconductor devices - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new-adhesive composition for semiconductor devices that includes no halogen as a flame retardant, satisfies the flame retardancy regulations which electric and electronic appliances are required with reduced emission of hazardous gas and smoke, and provide adhesive sheets and cover lay films for semiconductor devices including the same. SOLUTION: This adhesive composition for semiconductor devices is characteristically a thermosetting adhesive and includes the following chemicals (A) through (D) as essential components: (A) 100 pts.wt. of carboxyl group-bearing acrylonitrile-butadiene rubber, (B) 50-400 pts.wt. of epoxy resin, (C) a curing agent mixture including at least one kind of an aromatic polyamine with a reactivity factor Rg of 3-13 and an aromatic polyamine with a reactivity factor of 15-30 and (D) 0.1-5.0 pts.wt. of a hardening accelerator and additionally contains a polyfunctional phosphorus compound directly reactive with epoxy resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive composition for a non-halogen flame-retardant semiconductor device which does not use halogen as a flame-retarding method and does not generate hydrogen bromide which is a harmful gas during combustion. The present invention relates to an adhesive sheet for semiconductor devices and a coverlay film containing the same.

[0002]

2. Description of the Related Art In recent years, flexible printed wiring boards, flat cables, and the like that are lightweight and compact and can be bent have been incorporated into electronic devices in order to meet demands for miniaturization, weight reduction, and space reduction. For example, in the case of a flexible printed wiring board, it is common to bond a printed circuit on an insulating film with an adhesive.

[0003] On the other hand, as the influence on the environment is regarded as a social problem, the regulation of flame retardancy required for electric and electronic products is shifting to higher safety in consideration of safety for the human body. That is, it is demanded that not only electric and electronic products are not easily burned but also generate less harmful gas and smoke. Flame retardants conventionally used in printed wiring boards (copper-clad laminates) such as glass-epoxy boards, flexible printed boards, and encapsulants, on which electronic components are mounted, are used for safety reasons such as fire prevention and delay. In particular, derivatives mainly based on tetrabromobisphenol A (brominated epoxy resins and the like) are widely and generally used. Examples of the flame-retardant adhesive used in such applications include, for example, a saturated copolymerized polyester resin as a main component, and a brominated organic flame retardant and an inorganic filler added thereto (Japanese Patent Application Laid-Open No. Sho 62-62).
Japanese Patent Application Laid-Open No. 6-177520) and a flame-retardant adhesive sheet using a brominated epoxy resin and a brominated polyvinyl phenol (JP-A-6-177520).

[0004]

However, such brominated epoxy resins have good flame retardancy,
With the passage of time after bonding, corrosive hydrogen halide (hydrogen bromide) gas may be generated. Particularly, aromatic bromine compounds not only generate corrosive bromine and hydrogen bromide by thermal decomposition, but also When decomposed in the presence of oxygen, highly toxic polybromodibenzofuran and polybromodibenzodioxin may be formed. In addition, there has conventionally been a problem that the corrosive gas causes corrosion or fogging in a printed circuit, and its use is being suppressed at present.

For these reasons, phosphorus compounds have been widely studied as alternatives to bromine-containing flame retardants.
When using phosphate ester etc. in epoxy resin system, due to problems of bleeding and hydrolysis, it is fully satisfactory in printed wiring boards (copper-clad laminates) such as glass epoxy boards on which electronic components are mounted, flexible printed boards, and sealing materials. Possible properties have not been obtained. That is, free phosphoric acid is generated by the hydrolysis, and harmful gases such as phosphine are generated, and the product reliability such as heat resistance, adhesiveness, and electrical characteristics is significantly deteriorated. Therefore, JP
As disclosed in Japanese Patent Application Laid-Open No. 000-129090, there is an attempt to newly combine a phosphorus compound with a resin matrix by using a reactive phosphoric acid ester to achieve both flame retardancy and electrical characteristics and to eliminate the disadvantages. Although it is made with molding materials for semiconductor encapsulation and rigid copper-clad laminates, it still has adhesiveness on coverlays and flexible printed boards, etc.
Sufficient effects have not been obtained on solder heat resistance.

The present invention has been made in order to solve the above-mentioned drawbacks, and shows a good flame retardancy by using a halogen-free, multifunctional phosphorus-based flame retardant as a flame-retarding technique. It is an object of the present invention to provide an adhesive composition for a semiconductor device excellent in adhesiveness, solder heat resistance and laminating processability, and an adhesive sheet for a semiconductor device and a coverlay film containing the same.

[0007]

That is, the present invention relates to a thermosetting adhesive containing the following (A) to (D) as essential components, and a polyfunctional phosphorus compound which directly reacts with an epoxy resin. It is an adhesive composition for semiconductor devices characterized by including, and is an adhesive sheet and a coverlay film using the same. (A) 100 parts by weight of acrylonitrile butadiene rubber containing a carboxyl group, (B) epoxy resin 50 to 40
0 parts by weight, (C) a curing agent mixture containing at least one kind of an aromatic polyamine having a reactivity index Rg of 3 to 13 and at least one aromatic polyamine having a reactivity index Rg of 15 to 30; , Reactivity index R
g is the gel time at 150 ° C. of the mixture of bisphenol A diglycidyl ether and the aromatic polyamine.
h and the ratio between the gelation time td of the mixture of bisphenol A diglycidyl ether and 4,4 ′ diaminodiphenylmethane under the same conditions, and is defined by the following formula (1). Rg = th / td (1) (D) 0.1 to 5 parts by weight of a curing accelerator.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
Carboxyl group-containing acrylonitrile butadiene rubber (hereinafter referred to as NBR-C) used in (A) of the present invention
For example, acrylonitrile and butadiene are mixed in about 1
Carboxylated end groups of a copolymer rubber copolymerized in a molar ratio of 0/90 to 50/50, or ternary of acrylonitrile, butadiene and carboxyl group-containing polymerizable monomers such as acrylic acid and maleic acid. And copolymer rubber. Carboxyl group content is 1 to 8 mol%
Is desirable. If it is less than 1 mol%, the number of reaction points with the epoxy resin is small, and the heat resistance of the finally obtained cured product is poor. On the other hand, if it exceeds 8%, the viscosity increases and the stability decreases when an adhesive solution is used during coating. The amount of acrylonitrile must be 10 to 50 mol%, and if it is less than 10%, the cured product has poor chemical resistance. On the other hand, if it exceeds 50 mol%, it becomes difficult to dissolve in a usual solvent, which leads to a decrease in workability. Specific NBR-C includes PNR-1H
(Manufactured by Nippon Synthetic Rubber Co., Ltd.), "Nipol" 1072J,
"Nipole" DN612, "Nipol" DN631 (all made by Nippon Zeon Co., Ltd.), "Hiker" CTBN (BF
Goodrich Co., Ltd.).

The epoxy resin used in (B) of the present invention is a non-brominated epoxy resin, and is not particularly limited as long as it contains at least two or more epoxy groups in a molecule. For example, bisphenol A, bisphenol F, bisphenol S, resorcinol, dihydroquinaphthalene, diglycidyl ether such as dicyclopentadiene diphenol, epoxidized phenol novolak,
Epoxidized cresol novolak, epoxidized cresol novolak, epoxidized trisphenylolmethane,
An alicyclic epoxy resin such as epoxidized tetraphenylolethane, or a biphenol-type epoxy resin or a novolak-type epoxy resin is exemplified.

The phosphorus compound used in the present invention for imparting flame retardancy is not particularly limited as long as it is a polyfunctional phosphorus compound which directly reacts with an epoxy resin, and preferably has two or more functional groups. .

In the polyfunctional phosphorus compound, a functional group having an active hydrogen capable of reacting with an epoxy resin and capable of polyaddition (amino group, carboxyl group, epoxy group, hydroxyl group, methylol group, isocyanate group, vinyl group, silanol group) Group, phenolic hydroxyl group, etc.) in one molecule, or a compound having at least two P--H bonds in one molecule having active hydrogen capable of reacting with an epoxy resin and capable of polyaddition. There is no particular limitation as long as it exists. Further, the types of two or more functional groups present in one molecule may be the same or different, and in one molecule of a polyfunctional phosphorus-based flame retardant,
Functional groups such as an amino group, a carboxyl group, an epoxy group, a hydroxyl group, a methylol group, an isocyanate group, a vinyl group, a silanol group, and a phenolic hydroxyl group may be mixed with a PH bond.

Further, the polyfunctional phosphorus compound used in the present invention for imparting flame retardancy is directly bonded to an epoxy resin and firmly bonded to a resin matrix, thereby increasing the crosslink density to provide high heat resistance and high adhesion. The bifunctional type is more preferable in terms of the properties. For example, 9,10-dihydro-9-
Examples include compounds obtained by reacting oxa-10-phosphaphenanthrene-10-oxide or a derivative thereof with 1,4-benzoquinone, 1,2-benzoquinone, tolquinone, 1,4-naphthoquinone, or the like. More than one kind may be mixed. Further, these bifunctional phosphorus compounds may be compounds having two or more epoxy groups obtained by previously reacting with the epoxy resin used in (B) of the present invention.

In particular, a polyfunctional phosphorus compound obtained by previously reacting a bifunctional phosphorus compound represented by the following general formula (1) with the epoxy resin used in (B) of the present invention is a semiconductor adhesive composition: From the viewpoint of adhesiveness and high soldering heat resistance, the cured product after heat curing has a high glass transition temperature (Tg) and high mechanical properties (bending properties), especially high heat resistance and high bending properties in a high temperature environment. , A coverlay, an adhesive sheet and the like are obtained. The glass transition temperature (Tg) of the adhesive composition for a semiconductor device after curing is 8
Preferably it is higher than 0 ° C. At 80 ° C or lower, a substrate for connecting a semiconductor integrated circuit, a flexible printed wiring board,
When used as an adhesive layer such as coverlay film,
Since the ambient temperature may rise to about 80 ° C. in the case of in-vehicle use or the like, the mechanical strength and the bending characteristics are reduced. The term “after heat curing” as used herein refers to a state in which, after applying an adhesive to form an adhesive layer, a predetermined cure such as 50 ° C. and 30 hours is performed, and at least the curing reaction of the adhesive proceeds by 80% or more. That means. The progress of the curing reaction can be determined by measuring the calorific value by a differential scanning calorimeter method (DSC method).

[0014]

Embedded image

Further, a bifunctional phosphorus compound represented by the general formula (2) is preferable. In other words, utilizing the reaction between two phenolic hydroxyl groups in the molecule and the epoxy group, and further strongly bonded to the resin matrix by the epoxy group,
By increasing the crosslink density, both flame retardancy and reliability can be achieved. The compound represented by the general formula (2) undergoes a reaction with an epoxy group in the resin composition in the process of preparing and curing the resin composition and forming an adhesive layer. In order to improve electrical reliability, the phosphorus compound obtained by previously reacting with the epoxy resin used in (B) of the present invention may be added to the resin composition. When the phosphorus compound reacted in advance has a high viscosity and affects workability such as impregnation and flowability, it can be avoided by using a low-viscosity epoxy resin.

The phosphorus compound obtained by previously reacting the phosphorus compound represented by the general formula (2) with the epoxy resin used in (B) of the present invention has an adhesive property as a semiconductor adhesive composition, More preferable in terms of high solder heat resistance,
The cured product after heat curing has a high glass transition temperature (Tg), and provides a mechanical property (bending property), particularly, a coverlay and an adhesive sheet having good heat resistance and good bending property under a high temperature environment.

Further, in a system in which the compound represented by the general formula (2) does not dissolve in the organic solvent system for dissolving the resin composition but exists as particles, the melting point of the compound is as high as 260 ° C. Can be used as an organic filler having the action of In this case, it may be used in combination with the inorganic particle agent (inorganic filler) or may be used alone.

[0018]

Embedded image

[0019] The phosphorus content in the adhesive composition is preferably from 0.3 to 30% by weight, more preferably from 0.3 to 5% by weight. If the amount is less than 0.3% by weight, sufficient flame retardancy cannot be obtained. If the amount is more than 30% by weight, the crosslink density of the cured epoxy resin decreases, and the physical properties such as heat resistance and adhesiveness decrease. The phosphorus content can be generally measured by a method such as elemental analysis.

The mixing ratio of NBR-C and epoxy resin is 50 to 400 parts by weight, preferably 150 to 250 parts by weight of epoxy resin per 100 parts by weight of NBR-C. If the amount is less than 50 parts by weight, the solder heat resistance when used for a substrate for connecting a semiconductor integrated circuit, a coverlay film or the like is reduced. On the other hand, if it exceeds 400 parts by weight, the adhesiveness is undesirably reduced.

The curing agent mixture used in (C) is an aromatic polyamine having a reactivity index Rg of 3 or more and 13 or less, preferably 5 or more and 12 or less and Rg of 15 or more and 30 or less, preferably 17 or more and 28 or less. And at least one or more aromatic polyamines. If the Rg does not contain an aromatic polyamine having a value of 3 to 13, or one of the Rg's exceeds 30, the curing reactivity is too low and the curing cannot be performed sufficiently under appropriate heat treatment conditions. Solder heat resistance when used for substrates for substrates, coverlay films, etc., is reduced.
On the other hand, when the aromatic polyamine having an Rg of 15 to 30 is not contained, or when one of the Rg is less than 3, the curing reactivity is too high, the life is shortened, the adhesiveness, the substrate for connecting a semiconductor integrated circuit, the coverlay, Solder heat resistance when used for films and the like is reduced. In addition, a reduction in workability due to curl or the like also occurs.

The type of the aromatic polyamine is not limited as long as it satisfies the above range of Rg, but aromatic diamine is particularly preferred.

For example, aromatic polyamines having an Rg of 3 to 13 include 3,3'5,5'-tetramethyl-
4,4'-diaminodiphenylmethane, 3,3'5,5
'-Tetraethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-5,5'-diethyl-4,4
'-Diaminodiphenylmethane, 3,3'-dichloro-
4,4'-diaminodiphenylmethane, 2,2'3,3
'-Tetrachloro-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3
'-Diaminobenzophenone and the like.

The aromatic polyamine having an Rg of 15 to 30 is 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4 '.
-Diaminodiphenylsulfone, 4,4'-diaminobenzophenone, 3,4,4'-triaminodiphenylsulfone and the like.

As a curing accelerator, an amine complex of boron trifluoride, such as triethylamine boron trifluoride complex;
Alkyl-4-methylimidazole, 2-phenyl-4
-Imidazole derivatives such as alkyl imidazole; organic acids such as phthalic anhydride and trimellitic anhydride; dicyandiamide; and the like, and these may be used alone or as a mixture of two or more.

In addition to the above-mentioned essential components, fine inorganic particles can be added as required. Examples of the fine inorganic particle agent include metal hydroxides such as aluminum hydroxide, magnesium hydroxide and calcium aluminate hydrate, and metal oxides such as zinc oxide and magnesium oxide. These may be used in combination. The average particle diameter of the fine inorganic particle agent is preferably 0.2 to 5 μm in consideration of transparency and dispersion stability. The amount of addition is N
30 to 300 parts by weight to BR-C is suitable.

In addition to the above components, addition of organic or inorganic components such as an antioxidant and an ion scavenger as long as the properties of the adhesive are not impaired is not limited at all.

The adhesive composition of the present invention is preferably used as an adhesive sheet for a semiconductor device which is constituted as a layer and has at least one or more peelable protective films. Further, the adhesive composition of the present invention is preferably used as a coverlay constituted as a laminate of an insulating film coated with the composition and a peelable protective film.

The insulating film referred to in the present invention is a film having a thickness of 5 to 200 μm made of a plastic such as polyimide, polyester, polyphenylene sulfide, polyether sulfone, polyether ether ketone, aramid, polycarbonate, polyarylate, etc. A plurality of films selected from these may be laminated and used. If necessary, a surface treatment such as hydrolysis, corona discharge, low-temperature plasma, physical surface roughening, and easy adhesion coating treatment can be performed.

The peelable protective film (release film) referred to in the present invention is not particularly limited as long as it can be peeled off without damaging the form of an adhesive layer and an adhesive sheet and a coverlay film using the same. Alternatively, there may be mentioned a polyester film, a polyolefin film coated with a fluorine compound and a paper laminated with these.

The cover lay film obtained as described above has an insulating film / adhesive layer / release film configuration, and both sides of the adhesive layer are used as release film layers to form an adhesive sheet. Also available. In this case, in addition to the insulating film, it is possible to use a metal, ceramics, or an organic film that is not suitable for the coating substrate due to the problem of solvent resistance, and only protection for the purpose of surface insulation and environmental resistance. In addition, there is an advantage that new functions such as heat radiation, electromagnetic shielding, reinforcement, and identification can be provided.

The use of the adhesive composition and the adhesive sheet of the present invention is not particularly limited, and the adhesive composition and the adhesive sheet can be suitably used for electronic devices, substrates for connecting semiconductor integrated circuits, and semiconductor devices. For example, a flexible printed circuit board (FP
C), Tape automated bonding (TA
B), various packaging applications (CSP, BGA), and the like.

[0033]

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

Evaluation method (1) Method of preparing sample for evaluation A coverlay film was used as one form of an adhesive sheet.
μm electrolytic copper foil (manufactured by Nikko Gould Foil Co., Ltd., J
160 ° C, 30 kg / cm ² , 3
Lamination was performed under a 0 minute press condition to prepare a sample for evaluation.

(2) Peel Strength The peel strength was measured in accordance with JIS-C6481 using a sample pressed on an electric field copper foil by the method of (1).

(3) Solder heat resistance The solder heat resistance was measured in accordance with JIS-C6481. The sample of 25 mm square pressed on the electrolytic copper foil by the method of the above (1) was conditioned for 24 hours in an atmosphere of 22 ° C. and 90% RH, and then immediately floated on a solder bath for 30 seconds to prevent swelling and peeling. Not the highest temperature measured.

(4) Curl After releasing the release film from the 150 mm square cover lay, place it on a flat plate so that the four corners float, and measure the maximum distance from the flat plate.

(5) Adhesiveness After the release film was peeled off from the coverlay having a width of 25 mm, the above-mentioned electrolytic copper foil was applied at 20 ° C. under a pressure of 1 kg / cm ² .
Pressing for 1 minute and measuring the strength per unit length when peeled off at a speed of 50 mm / min in the direction of 90 degrees.

(6) Flame Retardancy A copper-clad polyimide film (1F2-EG44, manufactured by Toray Industries, Inc.) was etched on both sides, and the cover lay film having an adhesive thickness of 30 μm obtained by the present invention was applied to both sides thereof.
Lamination was performed under the pressing conditions of 0 ° C., 30 kg / cm ² , and 30 minutes to prepare a sample for evaluation. The evaluation method was measured according to UL94.

(7) Gelation time (th and td) Measured according to IPC-L110. The sample was mixed so that the mole number of the total number of aromatic polyamine active hydrogens to the mole number of the epoxy group of bisphenol A diglycidyl ether was equal.

(8) The glass transition temperature (T
g) The DSC heating curve and the 1 were measured by differential scanning calorimetry (DSC method).
DSC cooling curve and DS after short-time pre-heat treatment at 80 ° C
The C heating curve was measured. This short-time pre-heat treatment was performed in order to restore the glass dislocation signal deformed (enthalpy relaxed) due to dehydration and change with time of the attached water.

(Conditions) Apparatus: DSC821 manufactured by METTLER, temperature range: -20 ° C to 300 ° C (pre-heat treatment sample: -50 ° C to 2 ° C)
(00 ° C) Heating rate: 20 ° C / min (pre-heat treatment sample: 10 ° C /
Min) Temperature drop rate: 10 ° C / min (Pretreatment sample) Sample: Approx. 5mg Pretreatment condition: Treated at 180 ° C for 0.1 minute.

(9) Bending test A pattern of a bending resistance test material disclosed in JIS C 6471 was prepared on a copper-clad polyimide sample (1F1-RN50, manufactured by Toray Industries, Inc.).
The sample was hot-pressed at 0 ° C., 30 kg / cm 2 and 30 minutes to obtain a test sample. This was tested with a FPC high-speed bending tester (Shin-Etsu Engineering Co., Ltd.) at a vibration frequency of 150.
The change in the resistance value was measured at 80 ° C. in an atmosphere of 0 cpm, a stroke of 20 mm, a curvature of 2.5 mmR, and the outside of the coverlay.
If a crack such as a crack is formed in the copper foil due to bending, the volume is reduced and the resistance is increased.
The bending characteristics were confirmed by measuring the number of times of increase in%.

Example 1 Aluminum hydroxide (H-43, manufactured by Showa Denko KK) was converted into a toluene solution, followed by sand milling to prepare an aluminum hydroxide dispersion. The NBR-C
(Manufactured by Nippon Synthetic Rubber Co., Ltd., PNR-1H), polyfunctional phosphorus compound (manufactured by Toto Kasei Co., Ltd., FX-279BEK, phosphorus content 2 wt%), epoxy resin (Yukaka Shell Co., Ltd.)
"Epicoat" 834, epoxy equivalent 250),
3,3'5,5'-Tetramethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, boron trifluoride monoethylamine complex, and a dispersion, each having the same weight of methyl ethyl ketone as in Table 1 The mixture was added so as to have a ratio, and stirred and mixed at 30 ° C. to prepare an adhesive solution. Apply this adhesive with a bar coater to a thickness of 25μ.
m of a polyimide film ("Kapton" 100H manufactured by Toray DuPont Co., Ltd.) to a dry thickness of about 35 .mu.m, and dried at 150.degree. C. for 5 minutes. Lamination was performed to obtain an adhesive sheet (coverlay film). Table 3 shows the characteristics.

[0045]

[Table 1]

In Table 1, (1) Ep828, Ep834, Ep1001: bisphenol A type epoxy resin (the epoxy equivalent is
190, 250, 475) (2) HCA-HQ: bifunctional phosphorus-based flame retardant (manufactured by Sanko Co., Ltd., phosphorus content: 9.5 wt%), FX-279B
EK75: polyfunctional phosphorus compound (manufactured by Toto Kasei Co., Ltd., epoxy equivalent 308.2, phosphorus content 2 wt%), ZX-
1548-3: Polyfunctional phosphorus compound (Toto Kasei Co., Ltd.)
(3) TMDM: 3,3 ', 5,5'-tetramethyl-
4,4'-diaminodiphenylmethane, TEDM: 3
3 ′, 5,5′-Tetraethyl-4,4′-diaminodiphenylmethane, MEDM: 3,3′-dimethyl-5
5'-diethyl-4,4'-diaminodiphenylmethane, DDM: 4,4'-diaminodiphenylmethane (4) 4,4'DDS: 4,4'-diaminodiphenylsulfone, 3,3'DDS: 3,3 ''-Diaminodiphenylsulfone,3,4' DDS: 3,4 ''-diaminodiphenylsulfone, 4,4'DBP: 4,
4′-diaminobenzophenone (5) BTF: boron trifluoride monoethylamine complex,
PMHZ: 2-phenyl-4-methyl-5-hydroxymethylimidazole (6) ATH: aluminum hydroxide

[0047]

[Table 2]

Here, in Table 2, (1) FBAP: 1,1,3,3-tetrafluoro-
2,2-bis (4-aminophenyl) propane) (2) TMDS: 3,3 ′, 5,5′-tetramethyl-
4,4′-diaminodiphenyl sulfone (3) RDP-T: reactive monofunctional phosphorus compound (manufactured by Ajinomoto Fine Techno Co., phosphorus content 9 wt%), HC
A: Reactive monofunctional phosphorus compound (manufactured by Sanko Co., Ltd., phosphorus content: 14.29 wt%) Other abbreviations are the same as in Table 1.

[0049]

[Table 3]

Examples 2 to 5 and Comparative Examples 1 to 7 In the same manner as in Example 1, an adhesive sheet (coverlay) was prepared by using the raw materials and adhesives prepared at the composition ratios shown in Tables 1 and 2, respectively. Film). Table 3 shows the characteristics.

The adhesive sheet (coverlay film) obtained by the present invention from the examples and comparative examples in Tables 1 to 3
It can be seen that it has good flame retardancy and is excellent in adhesiveness, solder heat resistance and bonding workability.

[0052]

As described above, the present invention shows good flame retardancy by using a polyfunctional phosphorus flame retardant which does not contain halogen and reacts directly with an epoxy resin as a method of flame retardation, as well as adhesion and heat resistance. The present invention provides a novel adhesive composition for a semiconductor device excellent in workability of a laminating process without lowering the mechanical properties, a semiconductor device adhesive sheet containing the same, and a coverlay film, It is possible to provide a material that satisfies the flame-retardant regulations required for electric and electronic products and that generates less harmful gas and smoke.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (Reference) H01L 21/60 311 H01L 21/60 311W F term (Reference) 4F100 AH03A AK27A AK27J AK29A AK29J AK53A AL01A AL05A BA03 BA07 BA10B BA10C CA02A CB EH46 GB41B JA05A JB13A JG04B JL14C YY00A 4J004 AA05 AA13 AB05 CA06 CB03 CD08 DA02 DA04 FA05 4J040 CA071 EC041 EC061 EC071 EC091 GA07 HB44 HC06 HC12 HC16 HC23 HD23 HD38 KA16 KA17 KA36 LA10 LA04

Claims (6)

[Claims] 1. A thermosetting adhesive containing the following (A) to (D) as essential components, and containing a polyfunctional phosphorus compound which directly reacts with an epoxy resin. Adhesive composition. (A) 100 parts by weight of acrylonitrile butadiene rubber containing a carboxyl group, (B) epoxy resin 50 to 40
0 parts by weight, (C) a curing agent mixture containing at least one kind of an aromatic polyamine having a reactivity index Rg of 3 to 13 and at least one aromatic polyamine having a reactivity index Rg of 15 to 30; ) Hardening accelerator
1 to 5 parts by weight (however, the reactivity index Rg is 150 parts by weight of a mixture of bisphenol A diglycidyl ether and the aromatic polyamine).
It is the ratio between the gelation time th at ° C and the gelation time td of a mixture of bisphenol A diglycidyl ether and 4,4'-diaminodiphenylmethane under the same conditions, and is defined by the following formula (1). ) Rg = th / td (1) 2. The adhesive composition for a semiconductor device according to claim 1, wherein the glass transition temperature (Tg) of the resin composition after thermosetting is Tg> 80 ° C. 3. The adhesive for a semiconductor device according to claim 1, wherein the polyfunctional phosphorus compound is a compound obtained by reacting the phosphorus compound represented by the general formula (1) with an epoxy resin. Composition. Embedded image 4. The adhesive composition for a semiconductor device according to claim 1, wherein the polyfunctional phosphorus compound is a bifunctional phosphorus compound represented by the general formula (2). Embedded image 5. An adhesive sheet for a semiconductor device, wherein the adhesive composition for a semiconductor device according to claim 1 or 2 is used as an adhesive layer and has at least one or more peelable protective film layers. 6. A coverlay film comprising a laminate of an insulating film coated with the adhesive composition for a semiconductor device according to claim 1 or 2 and a peelable protective film.