KR101401162B1 - Liquid adhesive for electronic parts and adhesive tape - Google Patents

Abstract

(C) is a liquid adhesive obtained by dissolving a component (a) acrylonitrile-butadiene copolymer, (b) a phenol resin, and (c) a compound containing at least two maleimide groups in an organic solvent, ), And a compound represented by the following formula (2).

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a liquid adhesive for an electronic component,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid adhesive for an electronic part and an adhesive tape for use in adhesion between members around a lead frame constituting a semiconductor device, for example, a lead pin, a substrate for mounting a semiconductor chip, a heat sink, .

The present application claims priority based on Japanese Patent Application No. 2010-069063 filed on March 25, 2010, the contents of which are incorporated herein by reference.

Conventionally, as the adhesive tape used in the resin encapsulation type semiconductor device, there are a lead frame fixing tape, a TAB tape and the like.

For example, an adhesive tape for fixing a lead frame is used to fix the lead pin of the lead frame, thereby contributing to improvement of the production yield and productivity of the lead frame itself and the semiconductor assembly process as a whole.

The fixing adhesive tape is usually taped on a lead frame in a lead frame maker, and then the semiconductor maker shipped from a semiconductor maker mounts an IC and is then sealed with resin.

Therefore, the lead frame fixing adhesive tape is required to have general reliability at a semiconductor level and workability at the time of taping, a sufficient room temperature adhesive force immediately after taping, and sufficient heat resistance to withstand heating in a semiconductor device assembling process.

Conventionally, as the adhesive tape used for such a purpose, for example, there can be used a film of a synthetic resin such as polyacrylonitrile, polyacrylic acid ester or acrylonitrile-butadiene copolymer on a support film such as a polyimide film, A resin modified with another resin, or an adhesive mixed with another resin is applied and the resin is in a B-stage state.

Recently, a resin encapsulation type semiconductor device (semiconductor package) having a structure as shown in Figs. 1 to 3 has been developed or manufactured.

1, the lead pin 3 and the plane 2 are connected by an adhesive layer 6, the semiconductor chip 1 is mounted on the plane 2, and the semiconductor chip 1 is mounted on the plane 2, And the resin 5 together with the bonding wire 4 between the lead pin 3 and the bonding wire 4.

2 has a structure in which the lead pins 3 and the semiconductor chip 1 are fixed by the adhesive layer 6 and are sealed with the resin 5 together with the bonding wires 4. [

3, the semiconductor chip 1 is mounted on the die pad 7, the electrode 8 is fixed by the adhesive layer 6, and furthermore, between the semiconductor chip 1 and the electrode 8, And the electrode 8 and the lead pin 3 are connected to each other by the bonding wire 4 and they are sealed by the resin 5.

An adhesive having a sufficient heat resistance and reliability, which can be adhered and cured at a relatively low temperature, is known as an adhesive layer in the resin encapsulated semiconductor device having the structures shown in Figs. 1 to 3 (see, for example, Patent Document 1 ).

In addition, reliability means that leakage or short of current does not occur even if the temperature is kept under the conditions of a migration test (PCBT: Pressure Cooker Biased Test) described later.

However, for such an adhesive, it has been required to further improve migration resistance.

My migrability means that there is no shot in the migration test and no growth of the dendrite.

Japanese Patent Application Laid-Open No. 09-176593

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object of the present invention is to provide a liquid adhesive for an electronic part and an adhesive tape which can be adhered and cured at a low temperature and have sufficient heat resistance and reliability and excellent migration resistance .

The present invention can solve the above problems by the following technical constructions.

(1) A liquid adhesive obtained by dissolving a component (a) acrylonitrile-butadiene copolymer, a component (b) a phenol resin and a component (c) a compound containing at least two maleimide groups in an organic solvent, (1) and a compound represented by the following formula (2): " (1) "

(2) The liquid adhesive for electronic parts according to (1), wherein the component (a) has a Mooney viscosity of 50 to 90 M _{1 +4} 100 캜 and a content of acrylonitrile of 5 to 50% .

(3) The liquid adhesive for electronic parts according to (1), wherein the component (a) is an acrylonitrile-butadiene copolymer having a carboxyl group.

(4) The liquid adhesive for electronic parts according to (1), wherein the component (b) is a phenol resin containing a resol-type alkylphenol.

(5) The liquid adhesive for electronic parts according to (1), wherein the component (b) is a combination of a resol-type phenol and a novolak-type phenol.

(6) The liquid adhesive for electronic parts according to (1), wherein the weight ratio of the component (c) to the compound represented by the formula (1) or (2) is 3: 3 to 3:45.

(7) A positive resist composition comprising 10 to 900 parts by weight of the total of the components (b) and (c) relative to 100 parts by weight of the component (a) The liquid adhesive for electronic parts according to (1), wherein the weight ratio is 10 to 90% by weight.

(8) Component (d) The liquid adhesive for electronic parts according to (1), further comprising a diamine compound.

(9) The liquid adhesive for electronic parts according to (8), wherein the component (d) is a compound represented by the formula (3) described later.

(10) The liquid adhesive for electronic parts according to (8), wherein the component (d) is a compound represented by the formula (4) described later and has a weight average molecular weight of 200 to 7,000.

(11) The liquid adhesive for electronic parts according to (1), wherein the filler having a particle diameter of 1 占 퐉 or less contains 4 to 40% by weight of the total solid content.

(12) The adhesive tape according to (1), wherein an adhesive layer is formed on at least one surface of the heat resistant film by applying and drying the liquid adhesive for electronic components.

(13) The adhesive tape according to (12), wherein the heat resistant film is a polyimide film.

(14) The adhesive tape according to (1), wherein an adhesive layer is formed on at least one surface of the peelable film by applying and drying the liquid adhesive for electronic parts.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a liquid adhesive for an electronic part and an adhesive tape which can be bonded and cured at a low temperature, have sufficient heat resistance and reliability, and have excellent migration resistance.

That is, the liquid adhesive for electronic parts of the present invention can be bonded or cured at a low temperature, has sufficient heat resistance, reliability, and excellent migration resistance, so that the adhesive tape of the present invention using the same can be used, for example, For example, a lead pin, a substrate for mounting a semiconductor chip, a heat sink, a semiconductor chip itself, and the like between the members around the lead frame constituting the semiconductor device.

1 is a cross-sectional view of an example of a resin encapsulated semiconductor device (semiconductor package) using the present invention or a conventional adhesive tape.
2 is a cross-sectional view of another example of a resin encapsulated semiconductor device using the present invention or a conventional adhesive tape.
3 is a sectional view of still another example of the resin encapsulated semiconductor device using the adhesive tape of the present invention or the conventional adhesive tape.

Hereinafter, the present invention will be described in detail.

First, a preferable example of the liquid adhesive for electronic components will be described. However, the present invention is not limited to these examples.

The liquid adhesive for electronic parts of the present invention is a liquid adhesive in which an acrylonitrile-butadiene copolymer component (a), a phenol resin component (b), and a compound containing two or more maleimide groups (c) The component (c) is characterized by using the compounds represented by the following formulas (1) and (2) in combination.

Each component will be described below.

Component (a):

As the acrylonitrile-butadiene copolymer which is the component (a), all known acrylonitrile-butadiene copolymers may be used, but an acrylonitrile-butadiene copolymer having a carboxyl group is preferable.

The reason for this is that the melt viscosity at the time of heating is increased, the thermal stability is improved, the compatibility with other resins is high, the insulating property is stabilized, and the tensile strength of the resin is increased.

The equivalent of the carboxyl group in the acrylonitrile-butadiene copolymer having a carboxyl group is preferably from 1,000 to 20,000.

The carboxyl group equivalent is calculated by the number average molecular weight.

It is also preferable that the Mooney viscosity is 50 to 90 M _{1 + 4} (100 ° C).

The reason is that when the Mooney viscosity is within the above range, the thermal stability is improved and the heat resistance is improved.

In addition, when it is used as an adhesive due to an improvement in solvent solubility and a decrease in melt viscosity, workability and adhesiveness are favorable, which is preferable.

When the Mooney viscosity is lower than the lower limit of the above range, the heat resistance of the resin is lowered and the heat resistance necessary for the semiconductor assembly process can not be obtained. Further, the melt viscosity of the adhesive in the B-stage is lowered, the outflow of the adhesive agent during processing for the lead frame is increased, and the workability is lowered. On the other hand, if the Mooney viscosity exceeds the upper limit of the above range, the adhesive is hardly melted, the fluidity is lowered, and the taping property to the lead frame is lowered. In addition, the solubility in a solvent is lowered, and workability in making an adhesive deteriorates, which is not preferable.

Next, the acrylonitrile content of the copolymer is preferably 5 to 50% by weight, more preferably 10 to 40% by weight.

When the content of acrylonitrile is within the above range, heat resistance and solvent solubility are in a preferable range, and the insulating property is stable and reliability is improved.

Below the lower limit of the above range, the heat resistance of the resin is lowered and heat resistance necessary for the semiconductor assembly process can not be obtained. On the other hand, when the upper limit of the above range is exceeded, the solubility in a solvent is lowered (the workability of preparing an adhesive is lowered), which is not preferable. Also, the migration performance is degraded.

Component (b):

As the phenol resin as the component (b), a known phenol resin can be used, but a phenol resin containing a resol-type alkylphenol is preferable because it can lower the bonding temperature and the curing temperature of the adhesive, Do.

It is more preferable to use a combination of a resol-type phenol and a novolak-type phenol.

Further, the weight ratio of the resol-type phenol resin to the novolac-type phenol resin is preferably 100: 5 to 100: 100, more preferably 100: 10 to 100: 50.

This is because the use of the resol-type phenol and the novolak-type phenol together can suppress the surface adhesiveness, and it is possible to suppress the defective conveyance at the time of the lead frame processing.

In addition, since the novolak type phenol resin alone has poor curability, if the weight ratio of the novolak type phenol resin to the resol type phenol is excess, the curability of the adhesive is lowered and migration resistance is lowered.

Specifically, resol-type p-t-butylphenol and novolac-type p-t-butylphenol can be exemplified.

Component (c):

As the compound containing two or more maleimide groups as the component (c), it is necessary to use the compounds represented by the above-mentioned formulas (1) and (2) in combination.

The reason is that the bonding temperature and the curing temperature of the adhesive can be lowered, and a high adhesive force can be obtained. In combination, thermal stability is improved and adhesion upon heating is improved. Further, compatibility with other resins is enhanced, and migration resistance is excellent.

The weight ratio of the compounds represented by the formulas (1) and (2) is preferably 3: 3 to 3:45, more preferably 3: 3.9 to 3: 19.5, ~ 1: 7.

The liquid adhesive for electronic parts of the present invention preferably further contains a component (d): a diamine compound, and the component (d) preferably contains a compound represented by the following formula (3) or (4).

(Wherein R < ¹ > represents a divalent aromatic group)

(Wherein R ² represents a propylene group or a phenoxymethylene group, and n represents an integer of 0 to 7)

This is because the curing temperature can be adjusted by using it as a curing agent for a maleimide group.

Examples of the compound represented by the above formula (3) include the following compounds. In the present invention, the bivalent aromatic group is not particularly limited. The divalent aromatic group means a divalent group containing an aromatic group, and any aromatic group can be selected as necessary. For example, the number of phenyl groups is not limited and may have a substituent as required. 3,3'-diaminobiphenyl, 3,4'-diaminobiphenyl, 4,4'-diaminobiphenyl, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenyl Methane, 4,4'-diaminodiphenylmethane, 2,2- (3,3'-diaminodiphenyl) propane, 2,2- (3,4'-diaminodiphenyl) propane, 2,2 - (4,4'-diaminodiphenyl) propane, 2,2- (3,3'-diaminodiphenyl) hexafluoropropane, 2,2- Fluoropropane, 2,2- (4,4'-diaminodiphenyl) hexafluoropropane, 3,3'-oxydianiline, 3,4'-oxydianiline, 4,4'-oxydianiline , 3,3'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfone, 3,4'- Diaminodiphenylsulfone, 1,3-bis [1- (3-aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- Benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis [1- (Aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) diphenyl ether, 3,4'-bis (4-aminophenoxy) diphenyl ether, 3,4'- Phenyl ether, 4,4'-bis (3-aminophenoxy) diphenyl ether, 4,4'-bis (4-aminophenoxy) diphenyl ether, Bis (3-aminophenoxy) biphenyl, 3,3'-bis (4-aminophenoxy) biphenyl, 3,4'- 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, Bis [3- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2- Bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- Bis [3- (4-aminophenoxy) phenyl] propane, 2,2-bis [3- (3- aminophenoxy) phenyl] hexafluoropropane, 2,2- Propane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, Bis (3-aminophenyl) fluorene, 9,9-bis (4-aminophenyl) fluorene and the like.

The compound represented by the formula (4) preferably has a weight average molecular weight of 200 to 7,000.

The reason for this is that it is easy to dissolve in a solvent and therefore easy to handle.

Examples of the compound represented by the formula (4) include bis (3-aminopropyl) tetramethyldisiloxane, aminopropyl-terminated dimethylsiloxane tetramer or octamer, bis (3-aminophenoxymethyl) tetramethyl Disiloxane, and the like, and they may be mixed and used.

The blend ratio of the liquid adhesive is preferably 10 to 900 parts by weight in total of the component (b) and the component (c) based on 100 parts by weight of the component (a). More preferably, the total amount of the component (b) and the component (c) is in the range of 20 to 800 parts by weight, more preferably 50 to 400 parts by weight, particularly preferably 100 to 400 parts by weight.

When the sum of the components (b) and (c) is within the above range, the adhesive layer has improved heat resistance, particularly T _g and Young's modulus, after coating and curing.

Further, when the adhesive layer is cured to the B-stage, the adhesive layer itself is not squeezed, the workability is good, and adhesion with the heat resistant film as a support tends to be good.

The weight ratio of the component (b) to the total amount of the component (b) and the component (c) is preferably 10 to 90% by weight, more preferably 20 to 53% to be.

The mixing ratio of the component (c) to the component (d) is preferably such that the amino group of the component (d) is 0.01 to 2.0 molar equivalents relative to 1 molar equivalent of the maleimide group of the component (c) Is set in the range of 0.1 to 1.0 molar equivalent.

When the amino group equivalent of the component (d) is within the above range, the adhesive layer itself is not slackened when the adhesive layer is cured to the B stage, and the workability is improved, and adhesion with the heat resistant film as a support is improved.

In addition, since the gelation does not occur during mixing, the adhesive can be adjusted.

The mixing of component (a), component (b), component (c) and component (d) is carried out in a solvent which dissolves them.

The solvent may be selected as required and may be, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, sulfolane, hexamethylphosphoric triamide , 1,3-dimethyl-2-imidazolidinone, hexane, benzene, toluene, xylene, methyl ethyl ketone, acetone, diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, It is preferable to use an organic solvent such as methanol, ethanol, propanol, isopropanol, methyl acetate, ethyl acetate, acetonitrile, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene, dichloroethane, trichloroethane, . Among them, the kind and the amount can be appropriately selected so as to dissolve each component.

If necessary, a reaction accelerator may be added to the liquid adhesive in order to promote addition reaction between the components (a) and (b).

Examples of the reaction accelerator include diazabicyclooctane or methyl ethyl ketone peroxide, cyclohexane peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide (T-butylperoxy) -3,3,5-trimethylhexane, 1,1-bis (t-butylperoxy) -cyclohexane, 2,2- ) Octane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane, t- butyl hydroperoxide, cumene hydroperoxide, Propylbenzene hydroperoxide, p-menthydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di- (T-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) ) Hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne, acetylperoxide, isobutylperoxide, octanoylperoxide, decanoylperoxide, benzoylperoxide, , 3,5,5-trimethylhexanoyl peroxide, succinic acid peroxide, 2,4-dichlorobenzoyl peroxide, m-toluoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, (4-t-butylcyclohexyl) peroxydicarbonate, di-myristyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di- Butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypivalate, t-butyl peroxypivalate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, - butyl peroxyneodecanate, cumyl peroxyneodeca Butylperoxy-2-ethylhexanate, t-butylperoxy-3,5,5-trimethylhexanate, t-butylperoxy laurate, t-butylperoxybenzoate, di- Butylperoxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t-butylperoxyisopropylcarbonate, cumylperoxyoctoate, t- Butyl peroxyneohexanoate, acetylcyclohexylsulfonyl peroxide, t-butyl peroxyallylcarbonate and the like, organic peroxides such as 1,2-dimethylimidazole, t-butyl peroxyneodecanoate, t- 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2- Benzyl-2-phenylimidazole, 1-benzyl-2-phenylimidazole trimellitate, 1-benzyl-2-ethylimidazole Benzyl-2-ethyl-5-methylimidazole, 2-ethylimidazole, 2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, Cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methyl < RTI ID = 0.0 > 2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] - ethyl-s- Triazine, 2,4-diamino-6- [2'-ethyl-4-methylimidazolyl- (1 ')] - undecylimidazolyl- (1 ')] - ethyl-s-triazine, 2-methylimidazolium isocyanuric acid adduct, 2-phenylimidazolium isocyanuric acid adduct, 2,4-diamino (1 ')] - ethyl-s-triazine-isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl 4-benzyl-5-hydroxymethylimidazole, 4,4'-methylene-bis- (2-ethyl- 2-methylimidazole, 1-cyanoethyl-2-phenyl-4,5-di (cyanoethoxymethyl) imidazole, 1-dodecyl- Methylimidazole benzotriazole adduct, 1-aminoethyl-2-ethylimidazole, 1- (cyanoethylaminoethyl) -2-methyl- (2-methylimidazolyl-1-ethyl) urea, N, N'-bis N '- [2-methylimidazolyl- (1) -ethyl] dodecanedioleamide, N, N' - [2- Imidazoles such as 1-benzyl-2-phenylimidazole and hydrochloride, and triphenylphosphine may be used as the reaction accelerator. They may be used alone or in combination of two or more.

The liquid adhesive may include a filler having a particle diameter of 1 占 퐉 or less in order to stabilize taping characteristics when applied to an adhesive tape.

Stability of the taping property means that the adhesive tape is prevented from coming out from the end face of the tape due to melting when the adhesive tape is thermocompression bonded on the lead and the adhesive layer is kept in a proper thickness by holding the adhesive layer .

The content of the filler is preferably set in a range of 4 to 40% by weight, preferably 9 to 24% by weight of the total solid content.

When the content is within the above range, the effect of stabilizing the taping property is increased, the adhesive strength of the adhesive tape is improved, and the workability of the laminate is improved.

As the filler, for example, silica, quartz powder, alumina, calcium carbonate, magnesium oxide, diamond powder, mica, fluororesin, zircon powder and the like can be used.

If necessary, the liquid adhesive may be removed after completion of the reaction, that is, after drying, washed with an organic solvent, water or a mixture of an organic solvent and water, and then dissolved again in an organic solvent, May be used.

Examples of the organic solvent that can be used for the washing include acetone, methyl ethyl ketone, hexane, benzene, toluene, xylene, methanol, ethanol, propanol, diethyl ether, tetrahydrofuran, methyl acetate, ethyl acetate, acetonitrile, , Carbon tetrachloride, chlorobenzene, dichlorobenzene, dichloroethane, trichloroethane and the like.

Next, the adhesive tape of the present invention will be described.

The adhesive tape of the present invention is characterized in that an adhesive layer formed by applying and drying the above liquid adhesive for electronic parts is formed on at least one surface of a heat resistant film or a peelable film.

At that time, the coating thickness is preferably in the range of 5 to 100 mu m, particularly 10 to 50 mu m.

Examples of the heat resistant film include films of heat resistant resins such as polyimide, polyphenylene sulfide, polyether, polyparabanic acid and polyethylene terephthalate, epoxy resin-glass cloth, epoxy resin-polyimide- A composite heat-resistant film such as a glass fabric, and the like, and a polyimide film is particularly preferable.

The thickness of the heat resistant film is preferably set in the range of 7.5 to 130 탆, preferably in the range of 12.5 to 75 탆. The shape and size of the heat-resistant film can be selected as required.

Within this range, the elasticity of the adhesive tape becomes sufficient, and the hole drilling operation becomes easy.

The peelable film preferably has a thickness of 1 to 200 占 퐉, preferably 10 to 100 占 퐉, and acts as a temporary support. Peelability The shape and size of the film can be selected as needed. Examples of the peelable film that can be used include a polypropylene film, a fluororesin film, a polyethylene film, a polyethylene terephthalate film, paper, and, in some cases, a film obtained by imparting releasability thereto with a silicone resin.

The peelable film preferably has a 90 占 peel strength in the range of 0.01 to 7.0 g / cm.

When the peel strength is within the above range, the peelable film is not easily peeled off from the adhesive layer at the time of conveying the adhesive tape, and the peelable film is peeled off from the adhesive layer at the time of use.

When an adhesive layer is formed on the heat resistant film, a protective film may be further provided on the adhesive layer.

The protective film may be the same as the peelable film.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples.

≪ Example 1 >

Component (a):

Acrylonitrile-butadiene copolymer (containing no carboxyl group, Mooney viscosity 70 M _{1 +4} 100 ° C, acrylonitrile content: 27%) 100 parts by weight

Component (b):

50 parts by weight of a p-t-butylphenol type resolphenol resin (trade name: "CKM-1282 ", trade name,

Copolymerization of p-t-butylphenol and Bis-A 20 parts by weight of novolak phenol resin (CKM-2400, manufactured by Showa Highpolymer Co., Ltd.)

Component (c):

30 parts by weight of a commercially available compound represented by the above formula (1)

50 parts by weight of a commercially available compound represented by the above formula (2)

Component (d):

0.25 parts by weight of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane

The above components were added to tetrahydrofuran, sufficiently mixed and dissolved, and the solid content was adjusted to 30% by weight to obtain a liquid adhesive for electronic parts of Example 1.

Further, the molar equivalent of the amino group based on 1 molar equivalent of the maleimide group is 0.51.

≪ Example 2 >

Component (a) was changed as follows.

Component (a):

100 parts by weight of a carboxyl group-modified butadiene-acrylonitrile copolymer (carboxyl equivalent 100, Mooney viscosity 60 M _{1 +4} 100 ° C, acrylonitrile content 27%)

A liquid adhesive for electronic parts of Example 2 was obtained in the same manner as in Example 1 except for the above.

≪ Example 3 >

The component (b) was changed as follows.

Component (b):

70 parts by weight of p-t-butylphenol type resolphenol resin (CKM-1282, manufactured by Showa Highpolymer Co., Ltd.)

A liquid adhesive for electronic parts of Example 3 was obtained in the same manner as in Example 1 except for the above.

<Example 4>

The component (b) was changed as follows.

Component (b):

50 parts by weight of a p-t-butylphenol type resolphenol resin (trade name: "CKM-1282 ", trade name,

40 parts by weight of a copolymerized novolac phenol resin (CKM-2400: manufactured by Showa Highpolymer Co., Ltd.) copolymerized with p-t-butylphenol and Bis-A

The liquid adhesive for electronic parts of Example 4 was obtained in the same manner as in Example 1 except for the above.

&Lt; Example 5 >

Component (c) was changed as follows.

Component (c):

15 parts by weight of a commercially available compound represented by the above formula (1)

65 parts by weight of a commercially available compound represented by the above formula (2)

A liquid adhesive for electronic parts of Example 5 was obtained in the same manner as in Example 1 except for the above.

&Lt; Example 6 >

The component (d) was changed as follows.

Component (d):

A liquid adhesive for electronic parts of Example 6 was obtained in the same manner as in Example 1 except for the above.

&Lt; Example 7 >

The components (b) and (c) were changed as follows.

Component (b):

16.6 parts by weight of p-t-butylphenol type resolphenol resin (trade name: "CKM-1282 ", manufactured by Showa Highpolymer Co.,

6.7 parts by weight of a copolymerized novolak phenol resin (CKM-2400: manufactured by Showa Highpolymer Co., Ltd.) of p-t-butylphenol and Bis-A

Component (c):

10 parts by weight of a commercially available compound represented by the above formula (1)

16.7 parts by weight of a commercially available compound represented by the above formula (2)

The liquid adhesive for electronic parts of Example 7 was obtained in the same manner as in Example 1 except for the above.

&Lt; Example 8 >

The components (b) and (c) were changed as follows.

Component (b):

33.3 parts by weight of p-t-butyl phenol type resolphenol resin (trade name: "CKM-1282 ", manufactured by Showa High Polymer Co.,

Copolymerization of p-t-butylphenol and Bis-A 13.4 parts by weight of novolak phenol resin (CKM-2400, manufactured by Showa Highpolymer Co., Ltd.)

Component (c):

20 parts by weight of a commercially available compound represented by the above formula (1)

33.3 parts by weight of a commercially available compound represented by the above formula (2)

A liquid adhesive for electronic parts of Example 8 was obtained in the same manner as in Example 1 except for the above.

&Lt; Example 9 >

The components (b) and (c) were changed as follows.

Component (b):

p-t-butylphenol type resolphenol resin (trade name: "CKM-1282", manufactured by Showa High Polymer Co., Ltd.) 133.3 parts by weight

Copolymerization of p-t-butylphenol and Bis-A 53.4 parts by weight of novolak phenol resin (CKM-2400, manufactured by Showa Highpolymer Co., Ltd.)

Component (c):

80 parts by weight of a commercially available compound represented by the above formula (1)

133.3 parts by weight of the commercially available compound represented by the above formula (2)

A liquid adhesive for electronic parts of Example 9 was obtained in the same manner as in Example 1 except for the above.

&Lt; Example 10 >

The components (b) and (c) were changed as follows.

Component (b):

266.6 parts by weight of p-t-butylphenol type resolphenol resin (trade name: "CKM-1282 ", trade name,

Copolymerization of p-t-butylphenol and Bis-A Novolak phenol resin (CKM-2400: manufactured by Showa Highpolymer Co., Ltd.) 106.7 parts by weight

Component (c):

160 parts by weight of the commercially available compound represented by the above formula (1)

266.7 parts by weight of the commercially available compound represented by the above formula (2)

A liquid adhesive for electronic parts of Example 10 was obtained in the same manner as in Example 1 except for the above.

&Lt; Example 11 >

The components (b) and (c) were changed as follows.

Component (b):

85.7 parts by weight of a p-t-butylphenol type resolphenol resin (trade name: "CKM-1282 ", manufactured by Showa Highpolymer Co.,

34.3 parts by weight of a copolymerized novolak phenol resin (CKM-2400, manufactured by Showa Highpolymer Co., Ltd.) copolymerized with p-t-butylphenol and Bis-A

Component (c):

11.2 parts by weight of the commercially available compound represented by the above formula (1)

18.8 parts by weight of the commercially available compound represented by the above formula (2)

The liquid adhesive for electronic parts of Example 11 was obtained in the same manner as in Example 1 except for the above.

&Lt; Example 12 >

The components (b) and (c) were changed as follows.

Component (b):

32.1 parts by weight of a p-t-butylphenol type resolphenol resin (trade name: "CKM-1282 ", manufactured by Showa Highpolymer Co.,

12.9 parts by weight of a copolymerized novolak phenol resin (CKM-2400, manufactured by Showa Highpolymer Co., Ltd.) copolymerized with p-t-butylphenol and Bis-A

Component (c):

39.4 parts by weight of a commercially available compound represented by the above formula (1)

65.6 parts by weight of the commercially available compound represented by the above formula (2)

A liquid adhesive for electronic parts of Example 12 was obtained in the same manner as in Example 1 except for the above.

&Lt; Example 13 >

The components (b) and (c) were changed as follows.

Component (b):

21.4 parts by weight of p-t-butylphenol type resolphenol resin (trade name: "CKM-1282 ", manufactured by Showa Highpolymer Co.,

Copolymerization of p-t-butylphenol and Bis-A Novolak phenol resin (CKM-2400: manufactured by Showa High Polymer Co., Ltd.) 8.6 parts by weight

Component (c):

45 parts by weight of a commercially available compound represented by the above formula (1)

75 parts by weight of a commercially available compound represented by the above formula (2)

A liquid adhesive for electronic parts of Example 13 was obtained in the same manner as in Example 1 except for the above.

&Lt; Example 14 >

The components (b) and (c) were changed as follows.

Component (b):

10.7 parts by weight of a p-t-butylphenol type resolphenol resin (trade name: "CKM-1282 ", manufactured by Showa High Polymer Co.,

Copolymerization of p-t-butylphenol and Bis-A 4.3 parts by weight of novolak phenol resin (CKM-2400, manufactured by Showa Highpolymer Co., Ltd.)

Component (c):

50.6 parts by weight of a commercially available compound represented by the above formula (1)

A commercially available 84.4 parts by weight of the compound represented by the above formula (2)

The liquid adhesive for electronic parts of Example 14 was obtained in the same manner as in Example 1 except for the above.

&Lt; Example 15 >

Component (c) was changed as follows.

Component (c):

5 parts by weight of a commercially available compound represented by the above formula (1)

75 parts by weight of a commercially available compound represented by the above formula (2)

A liquid adhesive for electronic parts of Example 15 was obtained in the same manner as in Example 1 except for the above.

&Lt; Example 16 >

Component (c) was changed as follows.

Component (c):

10 parts by weight of a commercially available compound represented by the above formula (1)

A commercially available 70 weight part of the compound represented by the above formula (2)

The liquid adhesive for electronic parts of Example 16 was obtained in the same manner as in Example 1 except for the above.

&Lt; Example 17 >

Component (c) was changed as follows.

Component (c):

20 parts by weight of a commercially available compound represented by the above formula (1)

60 parts by weight of a commercially available compound represented by the above formula (2)

A liquid adhesive for electronic parts of Example 17 was obtained in the same manner as in Example 1 except for the above.

&Lt; Example 18 >

Component (c) was changed as follows.

Component (c):

40 parts by weight of a commercially available compound represented by the above formula (1)

40 parts by weight of a commercially available compound represented by the above formula (2)

A liquid adhesive for electronic parts of Example 18 was obtained in the same manner as in Example 1 except for the above.

&Lt; Comparative Example 1 &

Component (c) was changed as follows.

Component (c):

80 parts by weight of a commercially available compound represented by the above formula (1)

In the same manner as in Example 1 except for this, a liquid adhesive for electronic parts of Comparative Example 1 which did not contain the compound represented by the formula (2) was obtained.

&Lt; Comparative Example 2 &

Component (c) was changed as follows.

Component (c):

80 parts by weight of a commercially available compound represented by the above formula (2)

In the same manner as in Example 1 except for this, a liquid adhesive for electronic parts of Comparative Example 2 containing no compound represented by the formula (1) was obtained.

Table 1 shows the main conditions of Examples and Comparative Examples.

Component (a) Component (b) Component (c) Component (d) Example 1 Acrylonitrile-butadiene copolymer Resolphenol +
Novolak phenol
(Weight ratio 50:20) The compound of formula (1) +
The compound of formula (2)
(Weight ratio 30:50) 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane Example 2 Carboxyl group-modified butadiene-acrylonitrile copolymer Same as Example 1 Same as Example 1 Same as Example 1 Example 3 Same as Example 1 Resolephenol Same as Example 1 Same as Example 1 Example 4 Same as Example 1 Resolphenol +
Novolak phenol
(Weight ratio 50:40) Same as Example 1 Same as Example 1 Example 5 Same as Example 1 Same as Example 1 The compound of formula (1) +
The compound of formula (2)
(Weight ratio 15:65) Same as Example 1 Example 6 Same as Example 1 Same as Example 1 Same as Example 1 The compound of formula (5) Example 7 Same as Example 1 Resolphenol +
Novolak phenol
(Weight ratio 16.6: 6.7) The compound of formula (1) +
The compound of formula (2)
(Weight ratio 10: 16.7) Same as Example 1 Example 8 Same as Example 1 Resolphenol +
Novolak phenol
(Weight ratio 33.3: 13.4) The compound of formula (1) +
The compound of formula (2)
(Weight ratio 20: 33.3) Same as Example 1 Example 9 Same as Example 1 Resolphenol +
Novolak phenol
(Weight ratio 133.3: 53.4) The compound of formula (1) +
The compound of formula (2)
(Weight ratio 80: 133.3) Same as Example 1 Example 10 Same as Example 1 Resolphenol +
Novolak phenol
(Weight ratio 266.6: 106.7) The compound of formula (1) +
The compound of formula (2)
(Weight ratio 160: 266.7) Same as Example 1 Example 11 Same as Example 1 Resolphenol +
Novolak phenol
(Weight ratio 85.7: 34.3) The compound of formula (1) +
The compound of formula (2)
(Weight ratio 11.2: 18.8) Same as Example 1 Example 12 Same as Example 1 Resolphenol +
Novolak phenol
(Weight ratio 32.1: 12.9) The compound of formula (1) +
The compound of formula (2)
(Weight ratio 39.4: 65.6) Same as Example 1 Example 13 Same as Example 1 Resolphenol +
Novolak phenol
(Weight ratio 21.4: 8.6) The compound of formula (1) +
The compound of formula (2)
(Weight ratio 45:75) Same as Example 1 Example 14 Same as Example 1 Resolphenol +
Novolak phenol
(Weight ratio 10.7: 4.3) The compound of formula (1) +
The compound of formula (2)
(Weight ratio 50.6: 84.4) Same as Example 1 Example 15 Same as Example 1 Same as Example 1 The compound of formula (1) +
The compound of formula (2)
(Weight ratio 5:75) Same as Example 1 Example 16 Same as Example 1 Same as Example 1 The compound of formula (1) +
The compound of formula (2)
(Weight ratio 10:70) Same as Example 1 Example 17 Same as Example 1 Same as Example 1 The compound of formula (1) +
The compound of formula (2)
(Weight ratio 20:60) Same as Example 1 Example 18 Same as Example 1 Same as Example 1 The compound of formula (1) +
The compound of formula (2)
(Weight ratio 40:40) Same as Example 1 Comparative Example 1 Same as Example 1 Same as Example 1 The compound of formula (1) Same as Example 1 Comparative Example 2 Same as Example 1 Same as Example 1 The compound of formula (2) Same as Example 1

The liquid adhesives for electronic parts of Examples 1 to 18 and Comparative Examples 1 and 2 were applied on both sides of the polyimide film so that the thickness of the adhesive layer after drying was 20 占 퐉 and dried in a hot air circulating dryer at 160 占 폚 for 5 minutes Thus, an adhesive tape using the adhesives of Examples 1 to 18 and Comparative Examples 1 and 2 was produced.

Next, by using the adhesive tape using the adhesives of Examples 1 to 18 and Comparative Examples 1 and 2, a lead frame bonded with a plane usable in the semiconductor package shown in Fig. 1 was assembled in the following order.

Perforation of adhesive tape: The adhesive tape was drilled in a ring shape by a mold.

Adhesion of Adhesive Tape: A plane was placed on a hot plate, and a ring-shaped perforated tape was pressed against the plane by a metal rod to be adhered.

In addition, the condition of the adhesion was 140 DEG C / 2 sec / 4 kgf / cm &lt; 2 &gt;.

Assembly of the lead frame: The lead frame (Cu material) and the lead frame (Cu material) main body are aligned with the adhesive tape adhered by the above process and heated and pressed on the heated hot plate, Lt; / RTI &gt;

In addition, the cohesion condition was set at 140 ° C / 2 sec / 4 kgf / cm 2.

Adhesive Tape Curing: A hot-air circulating type oven replaced with nitrogen was used to thermally cure.

The conditions of the thermal curing were 200 占 폚 / 1 hour.

Next, the semiconductor package was assembled in the following procedure by using a lead frame (Cu material) bonded to the plane produced.

Die bonding: The semiconductor chip was adhered to the plane portion of the lead frame which was joined to the plane by using a silver paste for die bonding, and cured at 150 占 폚 for 2 hours.

Wire Bonding: The wire pads on the semiconductor chip and the silver lead portion of the inner lead wire of the lead pin were wired by gold wire by gold wire.

Molding: Epoxy-based mold transfer mold was used.

Finishing process: homing, die cutting, outer lead plating, etc., and finished with a package.

(evaluation)

&Lt; Low-temperature bonding, hardening &

Evaluation was made as to whether the adhesive tapes of Examples 1 to 18 and Comparative Examples 1 and 2 could be easily and quickly adhered to an adherend, that is, a plane or a lead pin.

Specifically, a 90 ° peel strength (adhesive force) at a room temperature of a 10 mm wide tape after the adhesive tape was attached (taped) to a copper plate at 100 캜, 140 캜 or 180 캜 was measured.

The results are shown in Table 2.

The adhesive strength of 4.2 N / cm or more was evaluated as &quot; low-temperature adhesion and curing &quot; under the following criteria.

◎: Bonding at 100 ℃. Practically excellent.

○: Adhesion at 140 ° C. No problem in practical use.

?: Adhesion at 180 占 폚. Practical.

X: Adhesion at 180 ° C is not possible. There is a problem in practical use.

The evaluation results of the low-temperature bonding and curing are shown in Table 5.

<Heat resistance>

And evaluated based on the void and shear adhesive strength as described below.

(Boyd)

Whether or not voids generated in the adhesive when curing the adhesive is at a level at which it is practically problematic is visually determined by a microscope.

Specifically, an adhesive tape was attached (taped) to a copper plate at 140 占 폚, and then kept at 30 占 폚 / 70% RH for 72 hours to prepare a test sample.

Then, the test sample was placed on a heater block of 160 ° C for 1 minute, and the state of the void between the tape and the copper plate was visually judged by a microscope.

(Shear adhesive force)

[Production of test body]

The adhesive tape cut in a width of 5 mm and a length of 75 mm was affixed (taping) at 140 DEG C to an end portion (one central portion) of a 20 mm x 20 mm copper plate.

The adhesive area was 25 mm 2 (5 mm × 5 mm in size), and the length of the tape which did not adhere to the copper material was 70 mm.

[Shear bond strength measurement]

After the test piece was fixed on the heater block at 160 ° C, the portion of the tape not bonded to the copper plate was connected to a universal tensile tester to measure shear bond strength.

The zipper distance of the copper plate tensile tester at the time of measurement was 50 mm and the tensile speed was 50 mm / min.

Further, in order to stabilize the measurement temperature, the test piece was fixed on the heater block, and measurement was started after 5 seconds passed.

The results are shown in Table 3.

Then, evaluation of <heat resistance> was carried out based on the following criteria.

◎: No void, shear adhesive strength 40 N / ㎠ or more (practically no problem at all)

?: No void, nor more than 20 N / cm2 and not more than 40 N / cm2 (no problem in practice)

?: No voids, nor a shear bond strength of less than 20 N / cm 2 (practically no problem)

X: With voids, and a shear bond strength of less than 20 N / cm 2 (Practical problem)

The evaluation results of the heat resistance are shown in Table 5.

<Dimensional Stability of Lead Pins>

Evaluation was made based on whether or not the misalignment of the lead pins at the time of curing the adhesive is at a level at which practical problems are caused.

Specifically, the adhesive tape was punched with a square (ring) having an outer dimension of 22 mm and an inner dimension of 20 mm using a metal mold, and then attached to a predetermined position of the evaluation lead frame (QFP 208 pin) with a hot press .

The heat press condition was a pressure of 5 kgf / cm 2, and a compression time of 0.3 seconds. (The temperature at which the thickness of the adhesive on the lead pin was 15 to 18 占 퐉 was regarded as the attachable temperature).

The lead pitch of the lead frame used is 168 mu m.

[Measurement of positional displacement of lead pin]

Immediately after tape bonding and after treatment in a hot air circulating oven at 200 DEG C for 1 hour, the fin pitch of the lead frame was measured with a microscope.

The compression temperature and the measurement result are shown in Table 4.

Thus, the dimensional stability of the lead pin was evaluated based on the following criteria.

?: The fin pitch immediately after tape bonding and the fin pitch after treatment at 200 占 폚 for 1 hour in the hot air circulating type oven were all within 168 占 퐉 占 10%.

?: The pin pitch immediately after the tape attaching and the fin pitch after treatment at 200 占 폚 for 1 hour in the hot air circulating type oven exceed 168 占 퐉 占 10% and are within 168 占 퐉 占 15%.

X: the value of the pin pitch immediately after the tape attaching and the fin pitch after treatment at 200 占 폚 for 1 hour in the hot air circulating type oven exceed 168 占 퐉 占 15%.

The evaluation results of the dimensional stability of the lead pin are shown in Table 5.

<Reliability>

The package obtained as described above was subjected to a PCBT test (Pressure Cooker Biased Test).

Electrical reliability tests were carried out under conditions of 100 volts, 130 ° C, 2 atm, and 85% RH.

Then, the reliability was evaluated based on the following criteria.

○: No shot at 240 hours

×: Short in 240 hours

The evaluation results of reliability are shown in Table 5.

<My Migration Ability>

After the reliability test, the package was polished to expose the adhesive surface and observed with a microscope.

Then, <Migration ability> evaluation was conducted based on the following criteria.

◎: Dendrite can not be confirmed, and there is no discoloration of the lead pin.

○: Dendrite can not be confirmed, but there is discoloration of the lead pin.

X: With dendrites

Table 5 shows the evaluation results of the migration performance.

<Workability>

(Workability) evaluation was performed on the handling property (curl, running property) at the time of use, such as taping of the adhesive tape at the time of assembling the lead frame, and the tackiness of the adhesive surface of the adhesive tape, according to the following criteria.

○: Very easy to work because it is not sticky.

△: Easy to work because of low stickiness

X: Difficult to work due to stickiness

The evaluation results are shown in Table 5.

(Evaluation results)

As shown in Table 5, all of the adhesive tapes of Examples 1 to 18 are?

Particularly, Example 5, Example 9, Example 16, and Example 17 were excellent in low temperature bonding, curing, heat resistance, and migration resistance. Example 2 was more excellent in low temperature bonding, hardening, heat resistance and migration resistance.

In contrast, the adhesive tape of Comparative Example 1 was short in the reliability test, and there was a problem in practical use due to the presence of dendrites in terms of migration resistance.

In addition, the adhesive tape of Comparative Example 2 had practical problems with respect to heat resistance and dimensional stability of the lead pin.

Industrial availability

It is possible to provide a liquid adhesive for an electronic part and an adhesive tape which can be adhered and cured at a low temperature, have sufficient heat resistance and reliability, and have excellent migration resistance.

1 semiconductor chip
2 planes
3 lead pins
4 bonding wires
5 resin
6 adhesive layer
7 die pad
8 electrodes

Claims (14)

In an organic solvent
Component (a) Acrylonitrile-butadiene copolymer,
Component (b) Phenolic resin,
Component (c) is a liquid adhesive in which a compound containing two or more maleimide groups is dissolved. The component (c) comprises a compound represented by the following formula (1) and a compound represented by the following formula (2)
Wherein the weight ratio of the component (c) to the compound represented by the formula (1) or (2) is 3: 3 to 3:45.

The method according to claim 1,
Wherein the component (a) has a Mooney viscosity of 50 to 90 M _{1 +4} 100 ° C and a content of acrylonitrile of 5 to 50% by weight. The method according to claim 1,
Wherein the component (a) is an acrylonitrile-butadiene copolymer having a carboxyl group. The method according to claim 1,
Wherein the component (b) is a phenol resin including a resol-type alkylphenol. The method according to claim 1,
Wherein the component (b) is a combination of a resol-type phenol and a novolac-type phenol. delete The method according to claim 1,
The total amount of the component (b) and the component (c) is 10 to 900 parts by weight based on 100 parts by weight of the component (a), and the weight ratio of the component (b) And 10 to 90% by weight of the liquid adhesive. The method according to claim 1,
Component (d) A liquid adhesive for electronic parts, further comprising a diamine compound. The method of claim 8,
Wherein the component (d) is a compound represented by the following formula (3).

(Wherein R &lt; ¹ &gt; represents a divalent aromatic group) The method of claim 8,
Wherein the component (d) is a compound represented by the following formula (4) and has a weight average molecular weight of 200 to 7,000.

(Wherein R ² represents a propylene group or a phenoxymethylene group, and n represents an integer of 0 to 7) The method according to claim 1,
Wherein the filler having a particle size of 1 占 퐉 or less contains 4 to 40% by weight of the total solid content. Wherein an adhesive layer is formed on at least one surface of the heat-resistant film by applying and drying the liquid adhesive for electronic parts according to claim 1. The method of claim 12,
Wherein the heat resistant film is a polyimide film. Wherein an adhesive layer is formed on at least one surface of the peelable film by applying a liquid adhesive for electronic parts according to claim 1 and drying the adhesive layer.

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