JP5914123B2 - Adhesive for electronic parts and adhesive film for electronic parts - Google Patents

Description

The present invention relates to an adhesive for electronic parts that is excellent in fast curing property and storage stability and has high adhesive strength. Moreover, this invention relates to the adhesive film for electronic components manufactured using this adhesive agent for electronic components.

When manufacturing a semiconductor device using a semiconductor chip, a process (die bonding process) of bonding and fixing the semiconductor chip to a substrate or the like using an adhesive is performed.
As an adhesive used in the die bonding process, for example, Patent Document 1 discloses a die attach paste containing an epoxy resin, a phenol aralkyl resin, and an imidazole compound. The die attach paste described in Patent Document 1 is said to be excellent in adhesiveness, fast curability, and reliability, and it is described that high adhesion reliability can be obtained particularly by curing in a short time. In the Example of patent document 1, the adhesive strength at the time of making it harden | cure at 200 degreeC, 30 second, and 60 second is evaluated.

In recent years, there has been an increasing demand for higher integration of semiconductor devices, and semiconductor chips are being stacked in multiple layers. For this reason, using an adhesive that requires several tens of seconds for curing, such as the die attach paste described in Patent Document 1, there is a problem that the time required to manufacture one semiconductor device becomes longer. It was happening. In addition, due to the multi-layer stacking, a slight shift of the semiconductor chip can be a fatal defect as a stacked body, but there is also a problem that the shift is likely to occur if it takes too much time for curing.

In order to eliminate the lengthening of the manufacturing time of the semiconductor device, for example, the use of a fast-curing adhesive has been studied. However, in general, a fast-curing type adhesive uses a highly reactive curing agent and curing accelerator, and thus has a problem of poor storage stability.

JP 2004-172443 A

An object of this invention is to provide the adhesive for electronic components which is excellent in quick-curing property and storage stability, and has high adhesive force. Moreover, an object of this invention is to provide the adhesive film for electronic components manufactured using this adhesive agent for electronic components.

The present invention is an adhesive for electronic parts containing an epoxy resin, a curing agent, an anionic curing accelerator, and 1 to 60 parts by weight of a sulfonium salt compound with respect to 100 parts by weight of the anionic curing accelerator.
The present invention is described in detail below.

The inventor of the present invention has an epoxy resin, a curing agent, and an adhesive for electronic components containing a curing accelerator, and is fast curable by using an anionic curing accelerator and a sulfonium salt compound in combination as a curing accelerator. The present inventors have found that an adhesive for electronic parts having excellent storage stability can be obtained. Furthermore, the present inventor not only decreases the fast curability or storage stability but also lacks adhesive strength depending on the blending ratio of the anion curing accelerator and the sulfonium salt compound, while the blending ratio is within a predetermined range. As a result, it was found that an adhesive for electronic components having excellent fast curing properties and storage stability and having high adhesive strength was obtained, and the present invention was completed.

The adhesive for electronic components of the present invention contains an epoxy resin.
The said epoxy resin is not specifically limited, For example, an aromatic epoxy resin, an aliphatic epoxy resin, etc. are mentioned. These epoxy resins may be used independently and 2 or more types may be used together. The said aromatic epoxy resin is not specifically limited, For example, the aromatic epoxy resin whose softening point is 150 degrees C or less, the aromatic epoxy resin of a liquid or crystalline solid at normal temperature, etc. are mentioned.

Examples of the aromatic epoxy resin having a softening point of 150 ° C. or lower include phenol novolac epoxy resin, bisphenol A novolac epoxy resin, cresol novolac epoxy resin, dicyclopentadienephenol novolac epoxy resin, biphenylphenol novolac epoxy resin, and the like. . Examples of the aromatic epoxy resin that is liquid or crystalline solid at room temperature include, for example, bisphenol type epoxy resins such as bisphenol A type, bisphenol F type, bisphenol AD type, bisphenol S type, resorcinol type epoxy resin, biphenyl type epoxy resin, anthracene Type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, aniline type epoxy resin and the like. Of these, naphthalene type epoxy resins and aniline type epoxy resins are preferred because of their high curing speed. These aromatic epoxy resins may be used alone or in combination of two or more.

Of the aromatic epoxy resins, commercially available products include, for example, YL-980, 1004AF (manufactured by Mitsubishi Chemical Corporation), HP-4032, HP-4700 (manufactured by DIC), EP-3900 (manufactured by ADEKA). ) And the like.

The aliphatic epoxy resin may be an aliphatic chain compound or an alicyclic compound. Examples of the aliphatic chain compound include (poly) ethylene glycol type epoxy resin, (poly) propylene glycol type epoxy resin, bisphenol A- (poly) propylene oxide type epoxy resin, and bisphenol F- (poly) propylene oxide type epoxy. Examples thereof include resins. Examples of the alicyclic compound include hydrogenated resorcinol type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated biphenyl type epoxy resin, hydrogenated naphthalene type epoxy resin, and hydrogenated anthracene type. Examples thereof include an epoxy resin, a dicyclopentadiene type epoxy resin, an adamantane type epoxy resin, and the like. Especially, since the elasticity modulus of the hardened | cured material of the adhesive for electronic components becomes high, an alicyclic compound is preferable and a dicyclopentadiene type epoxy resin is more preferable. These aliphatic epoxy resins may be used alone or in combination of two or more.

Among the aliphatic epoxy resins, commercially available products include, for example, EP-4000S, EP-4010S, ED-502S, ED-501, EP-4080S, EP-4088S, EP-4088L (manufactured by ADEKA), YX-8000. YX-8040, YL-6753, YL-7410 (manufactured by Mitsubishi Chemical Corporation), EXA-7015 (manufactured by DIC Corporation), and the like.

The epoxy resin may contain a polymer compound having a functional group capable of reacting with the epoxy resin (hereinafter also simply referred to as a polymer compound having a functional group capable of reacting).
The polymer compound having a reactive functional group plays a role as a film forming component. Moreover, the cured | curing material of the adhesive agent for electronic components obtained by having the said high molecular compound which has a functional group which can react has toughness, and can express the outstanding impact resistance.

The polymer compound having a reactive functional group is not particularly limited, and examples thereof include a polymer compound having an amino group, a urethane group, an imide group, a hydroxyl group, a carboxyl group, an epoxy group, and the like. Among these, a polymer compound having an epoxy group is preferable.
By containing the polymer compound having the epoxy group, the cured product of the adhesive for electronic components obtained has excellent mechanical strength, heat resistance and moisture resistance derived from the aromatic epoxy resin and the like, and the epoxy By combining excellent toughness derived from a polymer compound having a group, high joint reliability and connection reliability can be expressed.

The polymer compound having an epoxy group is not particularly limited as long as it is a polymer compound having an epoxy group at the terminal and / or side chain (pendant position). For example, an epoxy group-containing acrylic rubber, an epoxy group-containing butadiene rubber, Examples thereof include bisphenol type high molecular weight epoxy resin, epoxy group-containing phenoxy resin, epoxy group-containing acrylic resin, epoxy group-containing urethane resin, and epoxy group-containing polyester resin. Among them, an epoxy group-containing acrylic resin is preferable because it contains a large amount of epoxy groups and the resulting cured product of the adhesive for electronic components can exhibit excellent mechanical strength, heat resistance, toughness, and the like. These polymer compounds having an epoxy group may be used alone or in combination of two or more.

When the polymer compound having an epoxy group, particularly an epoxy group-containing acrylic resin, is used as the polymer compound having a reactive functional group, the preferred lower limit of the weight average molecular weight of the polymer compound having an epoxy group is 10,000. The preferred upper limit is 200,000. When the weight average molecular weight is less than 10,000, the film-forming property when the resulting adhesive for electronic parts is made into a film becomes insufficient, the film shape may not be maintained, and there are many low molecular weight compounds. Therefore, voids are likely to occur. When the weight average molecular weight exceeds 200,000, the obtained adhesive for electronic parts has low fluidity and may not be conductive after bonding.

When the polymer compound having an epoxy group, particularly an epoxy group-containing acrylic resin, is used as the polymer compound having a functional group capable of reacting, the preferred lower limit of the epoxy equivalent of the polymer compound having an epoxy group is 200, preferably The upper limit is 1000. When the epoxy equivalent is less than 200, a cured product of the obtained adhesive for electronic components may be hard and brittle. When the said epoxy equivalent exceeds 1000, the mechanical strength, heat resistance, etc. of the hardened | cured material of the adhesive agent for electronic components obtained may become inadequate.

When the epoxy resin contains a polymer compound having a functional group capable of reacting, the content of the polymer compound having a functional group capable of reacting is not particularly limited, but the preferred lower limit in the epoxy resin is 5% by weight. %, And a preferable upper limit is 80% by weight. When the content of the polymer compound having a functional group capable of reacting is less than 5% by weight, the film forming property when the resulting adhesive for electronic parts is formed into a film becomes insufficient, and the film shape cannot be maintained. In addition, tack may become strong. When the content of the polymer compound having a functional group capable of reacting exceeds 80% by weight, the obtained adhesive for electronic parts may be cracked during handling in an uncured state.

The adhesive for electronic components of the present invention contains a curing agent.
The said hardening | curing agent is not specifically limited, For example, an acid anhydride hardening | curing agent, a phenol hardening | curing agent, an amine hardening | curing agent, a thiol hardening | curing agent etc. are mentioned. The acid anhydride curing agent is not particularly limited, but a bifunctional acid anhydride curing agent is preferable. The bifunctional acid anhydride curing agent is not particularly limited, and examples thereof include phthalic acid derivative anhydrides and maleic anhydride. Among the acid anhydride curing agents, examples of commercially available products include YH-306 (manufactured by Mitsubishi Chemical Corporation).

The phenol curing agent is not particularly limited. For example, bisphenol A, bisphenol F, phenol novolac, cresol novolac, dicyclopentadiene phenol, aralkylphenol, trisphenol, tetrakisphenol, resol type phenol, biphenyldimethylene type phenol, phenol resin -Silica hybrid, derivatives thereof, modified products, and the like. Of these, phenol novolak, cresol novolak, dicyclopentadiene phenol, biphenyldimethylene type phenol, phenol resin-silica hybrid, and derivatives and modified products thereof are preferable. Among the above-mentioned phenol curing agents, examples of commercially available products include MEH-8000H (manufactured by Meiwa Kasei Co., Ltd.), TD-2131 (manufactured by DIC), Matrimid (manufactured by Huntsman), and KA-1160 (manufactured by DIC). It is done.

The amine curing agent is not particularly limited, and examples thereof include modified aliphatic amines such as diethylenetriamine and triethylenetetramine, modified aromatic amines such as diaminodiphenylsulfone, and derivatives and modified products thereof. Of these, modified aliphatic amines such as diethylenetriamine and triethylenetetramine, and derivatives and modified products thereof are preferable. Among the amine curing agents, as commercial products, for example, DICY (manufactured by Nacalai Tesque), epoxy resin curing agent T, TO184, U (above, manufactured by Mitsubishi Chemical Corporation), EH540-5 (manufactured by ADEKA) and the like can be mentioned. It is done.

Although the said thiol hardening | curing agent is not specifically limited, Thioglycolic acid, (beta) -mercapto propanoic acid, 3-mercapto butanoic acid, these derivatives, a modified body, etc. are preferable. Among the above thiol curing agents, as commercial products, for example, BMPA, MPM, PEMP, TMMP, TEMPIC (above, SC Organic Chemical Co., Ltd.), Karenz MT PE1, BD1, NR1 (above, Showa Denko Co., Ltd.) and the like can be mentioned. It is done.

Although content of the said hardening | curing agent is not specifically limited, The preferable minimum with respect to 100 weight part of said epoxy resins is 20 weight part, and a preferable upper limit is 200 weight part. When the content of the curing agent is less than 20 parts by weight, the obtained adhesive for electronic parts may not be sufficiently cured. When content of the said hardening | curing agent exceeds 200 weight part, the connection reliability of the adhesive agent for electronic components obtained may fall. The content of the curing agent is more preferably 25 parts by weight with respect to 100 parts by weight of the epoxy resin, more preferably 150 parts by weight, still more preferably 30 parts by weight, and still more preferably 120 parts by weight.

The adhesive for electronic components of the present invention contains an anionic curing accelerator and 1 to 60 parts by weight of a sulfonium salt compound with respect to 100 parts by weight of the anionic curing accelerator.
By containing the anion curing accelerator and the sulfonium salt compound, the adhesive for electronic components of the present invention is excellent in storage stability while being fast curable. Furthermore, depending on the blending ratio of the anion curing accelerator and the sulfonium salt compound, not only the fast curability or storage stability is lowered but also the adhesive strength is insufficient, whereas the blending ratio is within the above range. The adhesive for electronic parts of the present invention is excellent in fast curability and storage stability and can have high adhesive strength.

Examples of the anionic curing accelerator include imidazole compounds, amines and amine derivatives. Especially, since the adhesive force of the adhesive agent for electronic components obtained increases more, an imidazole compound is preferable.

The imidazole compound is not particularly limited. For example, 1-cyanoethyl-2-phenylimidazole in which the 1-position of imidazole is protected with a cyanoethyl group, an imidazole compound in which basicity is protected with isocyanuric acid (trade name “2MAOK”, Shikoku Chemical Industries, Ltd.) 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid addition salt (trade name “2MAOK-PW”, manufactured by Shikoku Kasei Kogyo Co., Ltd.) 2,4-Diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine (trade name “2MZA”, manufactured by Shikoku Chemicals), 2-phenyl-4-methyl-5 Hydroxymethylimidazole (trade name “2P4MHZ”, manufactured by Shikoku Chemicals), 2-ethyl-4-methylimidazole (trade name “2E4 Z ”, manufactured by Shikoku Kasei Kogyo Co., Ltd., core-shell type latent imidazole compound (trade name“ HX-3792 ”, manufactured by Asahi Kasei Co., Ltd.), liquid imidazole compound (trade name“ Fujicure 7000 ”, manufactured by Fuji Kasei Co., Ltd.), epoxy-imidazole Adduct (trade name “Cure Duct P-0505”, manufactured by Shikoku Kasei Co., Ltd.) and the like. These imidazole compounds may be used independently and 2 or more types may be used together.

Examples of the amine and amine derivative include JER Cure 3010 (manufactured by Mitsubishi Chemical Corporation), Adeka Hardener EH4351S, EH4388S, EH3636AS (manufactured by ADEKA), Amicure PN-23J, PN-40J, MY-24, VDH, UDH (Above, Ajinomoto Fine Techno Co., Ltd.), Novacure HX-3742, HX-3792 (above Asahi Kasei Co., Ltd.) and the like. These amines and amine derivatives may be used alone or in combination of two or more.

Examples of other anionic curing accelerators other than the imidazole compound, the amine and the amine derivative include DBU (1,8-diazabicyclo (5.4.0) undecene-7), DBN (1,5-diazabicyclo (4. 3.0) Nonene-5), U-CAT SA1 (DBU-phenol salt), U-CAT SA31, U-CAT 5002 (DBU-based tetraphenylborate salt) (manufactured by San Apro). These other anionic curing accelerators may be used alone or in combination of two or more.

Although content of the said anion hardening accelerator is not specifically limited, The preferable minimum with respect to 100 weight part of said epoxy resins is 0.3 weight part, and a preferable upper limit is 20 weight part. When the content of the anionic curing accelerator is less than 0.3 parts by weight, the obtained adhesive for electronic parts may not be sufficiently cured, the curing rate may be slow, or the adhesive force may be decreased. is there. When the content of the anionic curing accelerator exceeds 20 parts by weight, in the obtained adhesive for electronic parts, unreacted anionic curing accelerator oozes out to the adhesive interface, and thus the bonding reliability may be lowered. .

The sulfonium salt compound is a cationic curing accelerator and acts as a curing accelerator together with the anionic curing accelerator.
The sulfonium salt compound is not particularly limited as long as it is a sulfonium salt compound that acts as a curing accelerator, and examples thereof include aromatic sulfonium salt compounds having a structure represented by the following general formula (I) or (II). It is done. In addition, when other cationic hardening accelerators are used instead of the sulfonium salt compound, the rapid curability or the storage stability of the adhesive for electronic components is lowered.

In general formulas (I) and (II), R represents hydrogen, halogen, an alkyl group, a benzoyl group or an alkylated benzoyl group. R ′ and R ″ each represents an alkyl group, a benzyl group or an alkylated benzyl group. R ″ ″ represents a benzoyl oxide group or an alkylated benzoyl oxide group.

Specific examples of the sulfonium salt compounds include 4-hydroxyphenylbenzylmethylsulfonium hexafluoroantimonate, 4-benzoyloxyphenyldimethylsulfonium hexafluorophosphate, and benzyl-4- (4-toluoyloxy) phenylmethylsulfonium. Examples include hexafluorophosphate. These sulfonium salt compounds may be used independently and 2 or more types may be used together.

Among the sulfonium salt compounds, examples of commercially available products include Sun Aid SI-45, SI-80, SI-110, SI-180 (manufactured by Sanshin Chemical Co., Ltd.) and the like.

The lower limit of the content of the sulfonium salt compound is 100 parts by weight and the upper limit is 60 parts by weight with respect to 100 parts by weight of the anion curing accelerator. When the content of the sulfonium salt compound is less than 1 part by weight, the storage stability of the obtained adhesive for electronic parts is lowered. When the content of the sulfonium salt compound exceeds 60 parts by weight, the obtained adhesive for electronic parts is not sufficiently cured, the curing rate is slowed, or the adhesive force is decreased. The content of the sulfonium salt compound is preferably 2 parts by weight with respect to 100 parts by weight of the anionic curing accelerator, 55 parts by weight with a preferred upper limit, 3 parts by weight with a more preferred lower limit, and 50 parts by weight with a more preferred upper limit. .

The adhesive for electronic components of the present invention may contain an inorganic filler.
By containing the inorganic filler, the coefficient of linear expansion of the resulting cured product of the adhesive for electronic components is reduced, and it is possible to satisfactorily prevent the generation of stress on the semiconductor chip and the generation of cracks in the conductive parts such as solder. Can do.
The inorganic filler is not particularly limited, and examples thereof include silica such as fumed silica and colloidal silica, alumina, aluminum nitride, boron nitride, silicon nitride, glass powder, and glass frit.

When a particulate inorganic filler is used as the inorganic filler, the preferable lower limit of the average particle diameter is 1 nm, and the preferable upper limit is 30 μm. When the average particle diameter of the particulate inorganic filler is less than 1 nm, the adhesive for electronic components may be thickened and conduction may not be achieved after bonding. When the average particle diameter of the particulate inorganic filler exceeds 30 μm, the inorganic filler may be bitten between the electrodes when the semiconductor chip is pressure bonded using the obtained adhesive for electronic components.

When the adhesive for electronic parts of the present invention contains the inorganic filler, the content of the inorganic filler is not particularly limited, but a preferable lower limit with respect to 100 parts by weight of the epoxy resin is 5 parts by weight, and a preferable upper limit is 500 parts by weight. is there. If the content of the inorganic filler is less than 5 parts by weight, the effect of adding the inorganic filler may be hardly obtained. When the content of the inorganic filler exceeds 500 parts by weight, the linear expansion coefficient of the cured product of the obtained adhesive for electronic components decreases, but at the same time the tensile elastic modulus increases, stress on the semiconductor chip, solder, etc. There are cases where cracks in the conductive portion are likely to occur.
The content of the inorganic filler is more preferably 10 parts by weight with respect to 100 parts by weight of the epoxy resin, more preferably 400 parts by weight, still more preferably 15 parts by weight, and even more preferably 300 parts by weight.

The adhesive for electronic components of the present invention may contain additives such as an anti-bleeding agent, a silane coupling agent, an adhesion imparting agent such as an imidazole silane coupling agent, and a thickener as necessary. .

The method for producing the adhesive for electronic components of the present invention is not particularly limited. For example, a predetermined amount of an epoxy resin, a curing agent, an anion curing accelerator, a sulfonium salt compound, and other materials blended as necessary. Examples of the method include blending and mixing using a homodisper, a universal mixer, a Banbury mixer, a kneader, and the like.

The adhesive for electronic components of the present invention is suitably used for the production of a semiconductor device, and particularly suitably used in a process (die bonding process) in which a semiconductor chip is bonded and fixed to a substrate or the like. Moreover, a semiconductor device can also be manufactured using the adhesive film for electronic components which has the adhesive bond layer which consists of an adhesive agent for electronic components of this invention.
The adhesive film for electronic parts which has the adhesive bond layer which consists of an adhesive agent for electronic parts of this invention is also one of this invention.

The method for producing the adhesive film for electronic parts of the present invention is not particularly limited, for example, on a substrate obtained by releasing the adhesive solution containing the adhesive for electronic parts of the present invention and a solvent, such as a PET film. And a method of forming a film by applying an applicator or the like and drying and removing the solvent.
The adhesive film for electronic parts obtained in this way may be cut into a desired shape and used in the method for manufacturing a semiconductor device as described above.

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in quick-hardening property and storage stability, and can provide the adhesive agent for electronic components which has high adhesive force. Moreover, according to this invention, the adhesive film for electronic components manufactured using this adhesive agent for electronic components can be provided.

The embodiments of the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

( Examples 1-12 and Comparative Examples 1-5, 11 )
According to the composition of Table 1, the materials shown below were stirred and mixed using a homodisper to prepare an adhesive for electronic parts.

( Examples 14 to 24 and Comparative Examples 6 to 10 and 12 )
According to the composition of Table 2, each material shown below was added to 50 parts by weight of methyl ethyl ketone as a solvent using a homodisper and mixed by stirring to prepare an adhesive solution. This adhesive solution was applied onto a release-treated PET film using an applicator, and the solvent was removed by drying to form a film, whereby an adhesive film for electronic parts having an adhesive layer with a thickness of 50 μm was obtained.

(1) Epoxy resin glycidyl group-containing acrylic resin (weight average molecular weight 200,000, trade name “G-2050M”, manufactured by NOF Corporation)
Bisphenol A type epoxy resin (trade name “1004AF”, manufactured by Mitsubishi Chemical Corporation)
Bisphenol A type epoxy resin (trade name “YL-980”, manufactured by Mitsubishi Chemical Corporation)

(2) Curing agent trialkyltetrahydrophthalic anhydride (trade name “YH-306”, manufactured by Mitsubishi Chemical Corporation)
Liquid phenol novolak (trade name “MEH-8000H”, manufactured by Meiwa Kasei Co., Ltd.)
Dicyandiamide (trade name “DICY”, manufactured by Nacalai Tesque)
Trimethylolpropane tris (3-mercaptopropionate) (trade name “TMMP”, manufactured by SC Organic Chemical Co., Ltd.)

(3) Inorganic filler silica filler (trade name “SE-4050”, manufactured by Admatechs)

(4) Anionic curing accelerator 2-ethyl-4-methylimidazole (trade name “2E4MZ”, manufactured by Shikoku Kasei Kogyo Co., Ltd.)
Liquid imidazole compound (trade name “Fujicure 7000”, manufactured by Fuji Kasei Co., Ltd.)
Core-shell type latent imidazole compound (trade name “HX-3792”, manufactured by Asahi Kasei Corporation)
2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine (trade name “2MZA”, manufactured by Shikoku Kasei Kogyo Co., Ltd.)
2,4-Diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid addition salt (trade name “2MAOK-PW”, manufactured by Shikoku Kasei Kogyo Co., Ltd.)

(5) Cationic curing accelerator (5-1) Sulfonium salt compound A salt of an aromatic sulfonium compound and an antimony compound (trade name “Sun-Aid SI-45”, manufactured by Sanshin Chemical Co., Ltd.)
Salt of aromatic sulfonium compound and antimony compound (trade name “Sun-Aid SI-80”, manufactured by Sanshin Chemical Co., Ltd.)
Salt of aromatic sulfonium compound and phosphorus hexafluoride compound (trade name “Sun-Aid SI-110”, manufactured by Sanshin Chemical Co., Ltd.)
Salt of aromatic sulfonium compound and phosphorus hexafluoride compound (trade name “Sun-Aid SI-180”, manufactured by Sanshin Chemical Co., Ltd.)
(5-2) Other triphenylphosphine (trade name “TPP”, manufactured by Hokuko Chemical Co., Ltd.)
Tetraphenylphosphonium tetraphenylborate (trade name “TPP-S”, manufactured by Hokuko Chemical Co., Ltd.)
Tetraphenylphosphonium tetra-p-triborate (trade name “TPP-MK”, manufactured by Hokuko Chemical Co., Ltd.)

<Evaluation>
The following evaluation was performed about the adhesive agent for electronic components and the adhesive film for electronic components obtained by the Example and the comparative example. The results are shown in Tables 1 and 2.

(1) Storage stability ( Examples 1-12 and Comparative Examples 1-5, 11 )
The obtained adhesive for electronic parts and the one obtained by removing the cationic curing accelerator from the adhesive for electronic parts are allowed to stand at 25 ° C., and the viscosity measured at 25 ° C. and 10 rpm using an E-type viscometer is initial. The time for which the value was doubled (25 ° C. standing time) was measured, and this was defined as storage stability. The storage stability multiple of the adhesive for electronic components was determined by dividing the storage stability of the adhesive for electronic components by the storage stability of the adhesive for electronic components excluding the cationic curing accelerator.
( Examples 14 to 24 and Comparative Examples 6 to 10 and 12 )
The obtained adhesive film for electronic parts and the one obtained by removing the cationic curing accelerator from the adhesive film for electronic parts were allowed to stand at 25 ° C., and a rheometer (STRESSTECH, manufactured by REOLOGICA) was used. Control (1 rad), frequency 10 Hz, temperature increase rate 10 ° C / min, measurement temperature range 60-300 ° C, measure the time (25 ° C standing time) when the lowest complex viscosity is twice the initial value This was designated as storage stability. The storage stability multiple was determined by dividing the storage stability of the adhesive film for electronic parts by the storage stability of the adhesive film for electronic parts except the cationic curing accelerator.

(2) Gel time The obtained adhesive for electronic parts or the adhesive film for electronic parts was placed on a hot plate at 260 ° C., the adhesive was flowed with a spatula or the like, and the time when the adhesive stopped flowing was defined as gel time.

(3) Adhesive force Using an obtained adhesive for electronic parts or an adhesive film for electronic parts, a 3 mm x 3 mm silicon chip was bonded to a 20 mm x 20 mm silicon chip and cured at 190 ° C for 30 minutes, Immediately, the adhesive force at 260 ° C. was measured using a bond tester (Dage series, Dage series 4000).

(4) MRT, TCT
The adhesive for electronic components obtained in Examples 1 to 13 and Comparative Examples 1 to 5 was a full array TEG chip (10 mm × 10 mm × 10 mm) in which 3136 solder balls (height 85 μm) were formed on the entire surface of the chip at intervals of 150 μm. A TEG chip with an adhesive was obtained. The adhesive films for electronic components obtained in Examples 14 to 25 and Comparative Examples 6 to 10 were full array TEG chips (10 mm × 10 mm) in which 3136 solder balls (height 85 μm) were formed on the entire surface of the chip at intervals of 150 μm. 10 mm × thickness 725 μm), and then the electronic component adhesive film was cut according to the chip size to obtain a TEG chip with adhesive.
Solder of the obtained adhesive TEG chip and soldered pre-coated glass epoxy TEG substrate wired to form one daisy chain, stage temperature 120 ° C, head temperature 140 ° C 20 seconds, 280 ° C 5 seconds, head TEG chip with adhesive was flip-chip bonded at a pressure of 100N. Thereafter, post-cure (post-curing) was performed at 190 ° C. for 30 minutes to obtain a test sample.
Eight test samples were prepared, the conduction resistance value (hereinafter referred to as the initial resistance value) was measured in advance, moisture was absorbed at 60 ° C. and 60% RH for 40 hours, and three times in a reflow oven with a peak temperature of 260 ° C. After performing a reflow test through (MRT), -55 to 125 ° C. (30 minutes / 1 cycle), and 1000 cycles of TCT were performed. The conduction resistance value after MRT and TCT (1000 cycles) was measured, and the case where the conduction resistance value changed by 10% or more from the initial resistance value was regarded as defective (NG), and the NG number was evaluated.

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in quick-hardening property and storage stability, and can provide the adhesive agent for electronic components which has high adhesive force. Moreover, according to this invention, the adhesive film for electronic components manufactured using this adhesive agent for electronic components can be provided.

Claims (3)

An adhesive for electronic parts containing an epoxy resin, a curing agent, an anionic curing accelerator, and a sulfonium salt compound that is a cationic curing accelerator ,
Containing 0.3 to 20 parts by weight of the anionic curing accelerator with respect to 100 parts by weight of the epoxy resin, and
An adhesive for electronic parts, comprising 1 to 10 parts by weight of a sulfonium salt compound with respect to 100 parts by weight of the anionic curing accelerator. The adhesive for electronic parts according to claim 1, wherein the anionic curing accelerator is an imidazole compound. An adhesive film for electronic parts, comprising an adhesive layer comprising the adhesive for electronic parts according to claim 1.