JP2005307037A - Film-shaped epoxy resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a film-shaped epoxy resin composition and a film-shaped adhesive that have high flowability at melt and can secure sufficient adhesion at a pressure lower than a conventional pressure. <P>SOLUTION: This film-shaped epoxy resin composition comprises not less than 50 wt.% of a liquid epoxy resin with a dynamic viscosity at 25°C of not more than 100 Pa-s, a solid curing agent with a softening point of not more than 125°C and having at least two hydroxy groups in the molecule, and 5-45 pts.wt. of a seat forming agent having a molecular weight of 10,000-1,000,000, based on the total 100 pts.wt. of the epoxy resin and the curing agent, wherein the dynamic viscosity of the resin composition when heating/melting is 100-5,000 Pa-s. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a film-like epoxy resin composition, and particularly to a highly fluid film-like epoxy resin composition at the time of melting suitable for a film-like adhesive used for manufacturing a semiconductor component or a semiconductor device.

  In recent years, various electronic devices such as mobile phones have been miniaturized, and semiconductor components and semiconductor devices incorporated therein have been increasingly required to be thinner and lighter. As a result, semiconductor chips, which are constituent elements, Mounting boards and the like are also in the trend of further thinning. For this reason, the rigidity and strength of the semiconductor chip and the like are lower than those of the previous one, and it is necessary to refrain from applying an external force as much as possible when mounting or packaging the semiconductor chip.

  On the other hand, film adhesives are widely used in the manufacture of semiconductors. For example, in the packaging of semiconductor chips, film adhesives are conventionally used to fix the chip to the substrate before wire bonding. Yes. This film adhesive is generally called a die bond film or a die bonding film. Also, when connecting the bump and the circuit board in flip chip connection etc., a film adhesive having a function of sealing the bump is used while ensuring the conduction between the wiring of the board and the wiring of the chip. Yes.

  By the way, as a film-like or sheet-like epoxy resin composition, there exists a sheet-like thing formed by shape | molding the epoxy resin composition which consists of a liquid epoxy resin, a latent hardening | curing agent, a sheeting agent, and a highly heat conductive filler, for example ( For example, see Patent Document 1.) However, this is for a high thermal conductive substrate and is not suitable for adhesive use. Moreover, the dynamic viscosity at the time of melting exceeds 10,000 Pa · s, and the fluidity is low. Moreover, as a film-like adhesive for die bonding, for example, there is an adhesive formed by blending a thermoplastic resin, an epoxy resin and its curing agent, and silica (for example, see Patent Document 2). However, this material needs to contain a large amount of silica and has low fluidity when melted. Thus, the film-form epoxy resin composition, especially the film-form epoxy resin composition for adhesives for semiconductors, has usually had a high melt viscosity. In such a conventional adhesive having low fluidity at the time of melting, a certain amount of pressure must be applied when the chip or the like is bonded at the time of mounting or packaging. It is difficult to avoid giving, and the wrinkle at the time of manufacture of a thin semiconductor component etc. cannot be disregarded. Therefore, it has been necessary to reduce the rate of production of semiconductor components and semiconductor devices while avoiding the application of external force as much as possible during mounting and packaging.

JP 2002-179886 A JP 2003-261833 A

  In view of the above-mentioned present situation, the present invention provides a film-like epoxy resin composition and a film-like adhesive that have high fluidity at the time of melting and can ensure sufficient adhesiveness at a lower pressure than conventional. With the goal.

As a result of intensive studies to solve the above problems, the present inventors have found a film-like epoxy resin composition having a low dynamic viscosity at the time of heating and melting, and have completed the present invention based on this finding.
That is, this invention is a film-form epoxy resin composition (henceforth the composition of this invention) whose dynamic viscosity at the time of heat-melting is 100-5,000 Pa.s.

One embodiment of the present invention contains a solid curing agent having a softening point of 125 ° C. or lower and having at least two hydroxyl groups in the molecule, and further has a weight average molecular weight based on 100 parts by weight of the total of the epoxy resin and the curing agent. It is a composition containing 5 to 45 parts by weight of a sheeting agent of 10,000 to 1,000,000.
In another aspect of the present invention, the curing agent is at least one selected from the group consisting of a phenol novolak resin, an aralkylphenol novolak resin, a naphthol novolak resin, and a terpene phenol resin.
In another aspect of the present invention, 50% by weight or more of the epoxy resin is a liquid epoxy resin having a dynamic viscosity at 25 ° C. of 100 Pa · s or less.
In still another embodiment of the present invention, the inorganic filler is further contained in an amount of 30 to 80% by weight based on the total amount of the composition.
The present invention is also a film adhesive comprising any one of the above compositions.
The present invention is also a semiconductor component or semiconductor device using the above adhesive.

The present invention can provide a film-form epoxy resin composition and a film-form adhesive that have a high fluidity at the time of melting and can secure a sufficient adhesive force with a lower pressure than conventional pressures. .
Hereinafter, the present invention will be described in detail.

  The composition of the present invention is a film-like composition having a dynamic viscosity of 100 to 5,000 Pa · s when heated and melted. Dynamic viscosity is the complex viscosity measured by dynamic viscoelasticity. If the dynamic viscosity at the time of heating and melting is less than 100 Pa · s, bleeding of the adhesive occurs, and if it exceeds 5,000 Pa · s, the fluidity is lowered, and there is a possibility of damaging the chip or the like with a high pressure at the time of pressure bonding. is there. Preferably, the upper limit is 3,000 Pa · s. In addition, although the film-form epoxy resin composition and film-form adhesive of this invention are a film-form thing which does not have a support tape layer, what has a release sheet removed at the time of use is included.

  In the composition of the present invention, the epoxy resin is not particularly limited, and may be solid or liquid at room temperature. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol type epoxy resin such as bisphenol AD type epoxy resin, biphenyl novolak type epoxy resin, hydrogenated bisphenol A type epoxy resin, phenol novolak type Epoxy resin, cresol novolac type epoxy resin, naphthol novolac type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene epoxy resin, sulfide modified epoxy resin, dimer acid modified epoxy resin, alkyl modified triphenolmethane type epoxy resin, amino epoxy resin, Preferable examples include polyfunctional epoxy resins such as triglycidyl isocyanurate and poly (epoxidized cyclohexene oxide). These epoxy resins may be used alone or in combination of two or more.

  However, in the present invention, 50 wt% or more, more preferably 70 wt% or more of the epoxy resin is preferably a liquid epoxy resin having a dynamic viscosity at 25 ° C. of 100 Pa · s or less. Therefore, it goes without saying that the case where the entire epoxy resin is the liquid epoxy resin is included. In addition, even if a single epoxy resin does not have the above-described characteristics, those having the above-described characteristics by mixing two or more kinds can be used as the liquid epoxy resin.

  Examples of the liquid epoxy resin include bisphenol-type epoxies such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol AD diglycidyl ether, and chain oligomer mixtures obtained by partial condensation thereof. 1 type, or 2 or more types of mixtures, such as resin, a naphthalene type epoxy resin, a sulfide modified epoxy resin, an amino epoxy resin, a dimer acid modified epoxy resin, can be used. Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin and the like are preferable because they are easily available.

  The blending amount of the epoxy resin is preferably 15 to 25% by weight, more preferably 17 to 23% by weight in the composition of the present invention.

  In the composition of the present invention, as the curing agent, a solid curing agent having a softening point of 125 ° C. or lower, preferably 120 ° C. or lower, more preferably 100 ° C. or lower, having at least two hydroxyl groups in the molecule is used. Examples of such a solid curing agent include phenol novolak resins, aralkylphenol novolak resins, naphthol novolak resins, terpene phenol resins, and the like having a softening point in the above range.

  The blending amount of the curing agent is preferably 0.5 to 1.5 mol, more preferably 0.9 to 1.1 mol, with respect to 1 mol of the epoxy group.

  The curing agent can be made into a B-stage sheet without substantially acting as a curing agent under the conditions for gelling the epoxy composition with a sheeting agent to be described later, but is cured under the subsequent curing conditions. Acts as an agent to form a C-stage cured product.

  Further, a curing accelerator (including what is called a curing catalyst) may be used. Such a curing accelerator is not particularly limited. For example, an imidazole curing accelerator, an amine adduct type curing accelerator (for example, Amicure (trade name) (manufactured by Ajinomoto Co., Inc.)), a phosphorus curing accelerator, a phosphonium salt type. Curing accelerators (eg tetraphenylphosphonium bromide, tetrabutylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide), bicyclic amidines and their derivatives (eg 1, Examples include 8-diazabicyclo (5,4,0) undecene-7), organometallic complexes, polyamine ureates (urea-modified polyamines), and the like. Of these, imidazole curing accelerators and phosphorus curing accelerators are preferable.

  Specific examples of the imidazole curing accelerator include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2,4-diamino-6-ethyl-S triazine isocyanuric acid adduct, 2-phenylimidazole, 2 -Phenyl-4-methylimidazole, those encapsulating them (for example, those marketed as Novacure (trade name) (manufactured by Asahi Kasei Epoxy Corporation)) and the like.

  Specific examples of the phosphorus curing accelerator include triphenylphosphine (TPP), tributylphosphine (TBP), triorthotolylphosphine (TOTP), and triphenylphosphine oxide (TPPO). be able to.

  0.5-20 weight is preferable with respect to 100 weight part of epoxy resins, and, as for the compounding quantity of the said hardening accelerator, More preferably, it is 2-10 weight part.

  In the present invention, 5 to 45 parts by weight of a sheeting agent having a weight average molecular weight of 10,000 to 1,000,000 is contained with respect to 100 parts by weight of the total of the epoxy resin and the curing agent.

  The above sheeting agent can form a solid sheet after applying a varnish obtained by dissolving the epoxy resin composition of the present invention in a solvent to a support by printing or the like and distilling off the solvent. As a specific example of the sheet agent having a weight average molecular weight of 10,000 to 1,000,000, a polyimide having a molecular weight in the above range (for example, Rika Coat SN-20 (trade name) (manufactured by Shin Nippon Rika Kogyo Co., Ltd.)) Etc.), polyamideimide (for example, MT5050 (trade name) (manufactured by Toyobo Co., Ltd.)), polyether sulfone (for example, PSE1010 (trade name) (manufactured by Mitsui Chemicals)), PES5003P (trade name) (manufactured by Sumitomo Chemical) Further, as a sheeting agent having a functional group, an epoxy group-containing acrylic resin (for example, Epofriend AT-501 (trade name) (manufactured by Daicel Chemical Industries), SG-P3-DR ( Product name) (manufactured by Nagase ChemteX), SG-80HDR (product name) (manufactured by Nagase ChemteX), etc.), hydroxyl group-containing acrylic resin (e.g. , SG-600LBDR (trade name) (manufactured by Nagase Chemtex Corporation), BPAM-01 (trade name) can be given (manufactured by Nippon Kayaku Co., Ltd.), and the like), and the like.

  The amount of the sheeting agent is 5 to 45 parts by weight, more preferably 8 to 35 parts by weight, and still more preferably 10 to 25 parts by weight with respect to 100 parts by weight as a total of the epoxy resin and the curing agent. It is. If the amount of the sheeting agent is too small, it tends to be difficult to make tack-free at a predetermined temperature. On the other hand, if the amount is too large, the viscosity of the compound becomes high and it becomes difficult to form a sheet-like material.

  The composition of the present invention may contain an inorganic filler. Examples of the inorganic filler include crystalline silica, fused silica, alumina, aluminum nitride, boron nitride, aluminum hydroxide, and calcium carbonate. These may be used alone or in combination of two or more. These preferably have an average particle size of 0.1 to 10 μm, more preferably 0.1 to 5 μm.

  The inorganic filler is preferably contained in an amount of 10 to 80% by weight in the composition of the present invention. The upper limit is more preferably 75% by weight, still more preferably 70% by weight, and the lower limit is more preferably 40% by weight.

  Other additives can be used in the composition of the present invention as long as the object of the present invention is not impaired. Examples of such additives include silane coupling agents, leveling agents, antifoaming agents, and pressure-sensitive adhesives. Examples of the silane coupling include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4- Epoxycyclohexyl) ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, mercaptosilane, sulfide silane, ureidosilane, aminosilane and the like. Examples of the leveling agent include TSF4445 manufactured by Toshiba Silicone Co., Ltd., examples of the antifoaming agent include ST86PA manufactured by Toray Dow Corning Co., Ltd., and examples of the adhesive include KE-311 manufactured by Arakawa Chemical Co., Ltd. D-100 (aliphatic hydrocarbon resin) etc. are mentioned.

  The method for producing the composition of the present invention is not particularly limited, and the composition may be mixed so that the raw materials are uniformly mixed. For example, a solid component such as a sheeting agent, a solid epoxy resin, and a solid curing agent is blended so that the solid content is 30 to 80% in a slurry in which an inorganic filler is dispersed in a solvent, and completely dissolved at 60 to 80 ° C. Let Examples of the solvent used at this time include methyl ethyl ketone, toluene, acetone, methyl isobutyl ketone, butyl cellosolve, ethanol, cyclohexanone, methanol, dimethylacetamide, dimethylformamide, and 2-methylpyrrolidone. These may be used alone or in combination. Liquid components, such as a liquid epoxy resin, a coupling agent, a leveling agent, an antifoamer, and an adhesive, are mixed with this at room temperature to create a varnish. This varnish is applied to a release substrate such as a PET film that has been subjected to a release treatment with a coating machine such as a roll coater so that the dry film thickness is, for example, 10 to 60 μm, and dried by heating to form a tack-free film. It can be an adhesive. The film adhesive may be processed into a predetermined shape and then used for manufacturing a semiconductor component / semiconductor device.

  In the manufacture of semiconductor components / semiconductor devices, chips and the like can be mounted on a substrate using the film adhesive as a die bonding film. Also, when connecting bumps and circuit boards in flip-chip connection, etc., it is used as a so-called non-conductive film etc. that has the function of sealing the bumps while ensuring the continuity between the wiring of the board and the wiring of the chip. The circuit can be connected by the curing shrinkage force of the film (adhesive) to fix the chip and connect the electrodes at the same time. Further, the film adhesive may be cured after the electrodes are connected by an ultrasonic method. Examples of the semiconductor component / semiconductor device include various semiconductor packages such as DIP, SOP, QFP, BGA, and CSP, a substrate on which a semiconductor circuit is mounted, and the like. The film adhesive of the present invention has a low viscosity when melted and a high fluidity, so that the pressure for pressure bonding during bonding can be lower than before, and the yield of semiconductor products can be greatly reduced. Semiconductor products can be manufactured.

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

Examples 1 to 5 and Comparative Example 1
A varnish was prepared with the composition shown in Table 1, and this varnish was applied to a release-treated surface of a 75 μm-thick PET film that had been subjected to a release treatment, and after drying, the adhesive was adjusted to a thickness of 50 μm. An adhesive film was formed on the PET film.

The abbreviations in the table are as follows.
RE310S: Bisphenol A type epoxy resin (liquid epoxy resin) (manufactured by Nippon Kayaku Co., Ltd.)
HP7200L: Dicyclopentadiene epoxy resin (solid epoxy resin) (Epiclon (trade name), manufactured by Dainippon Ink and Company)
TD2131: Phenol novolac resin (Phenolite (trade name), manufactured by Dainippon Ink, Inc., softening point 80 ° C.)
TD2090: Phenol novolac resin (Phenolite (trade name), manufactured by Dainippon Ink, softening point 120 ° C)
BPAM-01: hydroxyl group-containing acrylic resin (sheeting agent) (manufactured by Nippon Kayaku Co., Ltd.)
A-187: Glycidylsilane (silane coupling agent) (manufactured by Nihon Unicar)
SE1050: fused silica (manufactured by Admatechs)
HX3921HP: Nova Cure (trade name) (Asahi Kasei Epoxy Co., Ltd.)
TSF4445: Silicon-based leveling agent (Toshiba Silicone)

Evaluation method Flexibility: The film-like adhesive obtained above was cut to 100 × 50 mm to make a sample, and this sample was left in a thermostatic bath at 25 ° C. for 1 hour, and then a cylindrical mandrel tester (1/4 inch). Flexibility was tested.
○: No cracking occurred in the adhesive film, or no peeling occurred at the interface between the PET film and the adhesive film. ×: Cracking occurred in the adhesive film, or between the PET film and the adhesive film. Melt viscosity with delamination at the interface: temperature rise 2 ° C / min in temperature lamp mode with ARES (Rheometric Scientific F.E. viscoelasticity measuring device), frequency 10 Hz, strain 2%, parallel Under the conditions of the plate, the dynamic viscosity (Eta *) from 50 ° C. to 150 ° C. was measured and the lowest melt viscosity was recorded.
Adhesive strength: In the same manner as described above on a PET film, but with a 20 μm thick adhesive formed, it is cut into a size of 2 × 2 mm and pressed into a film by pressing a heat block at 60 to 80 ° C. After the agent was attached to a glass epoxy substrate (E679, 10 × 10 × 0.6 mm, manufactured by Hitachi Chemical Co., Ltd.), only the PET film was removed. A part of a 2 × 2 × 0.5 mm silicon chip coated with polyimide (PIX-1400, manufactured by Hitachi Chemical DuPont) on the part where the film adhesive is adhered is 240 ° C., 2.5 N, 20 It was pressure-bonded with a heat block under the condition of seconds and cured. Then, after hardening for 1 hour in an oven at 150 ° C., it was left in a constant temperature and humidity chamber of 85 ° C./85% for 6 hours, and further passed through a reflow furnace having a peak at 260 ° C. The adhesive strength of this was measured at room temperature using a die shear tester (2400A, manufactured by Daisy). The results are shown in Table 1.

From the said Examples 1-5, the film adhesive of this invention exhibited sufficient adhesive strength with the low crimping pressure of 2.5N. Moreover, the flexibility was also excellent.
On the other hand, in the case of Comparative Example 1, the sheeting agent is excessively contained, and the dynamic viscosity is extremely high, far exceeding 5,000 Pa · s, and sufficient adhesive strength is ensured at a pressure of 2.5 N. I couldn't.

  The present invention overcomes the drawbacks of conventional epoxy resin film adhesives, enables semiconductor mounting with a lower pressure, avoids damage to thin chips, and improves product reliability. Therefore, it is extremely useful as a film-like epoxy resin composition and a film-like adhesive suitable for the semiconductor manufacturing field.

Claims (7)

A film-like epoxy resin composition having a dynamic viscosity of 100 to 5,000 Pa · s when heated and melted. It contains a solid curing agent having a softening point of 125 ° C. or less and having at least two hydroxyl groups in the molecule, and further has a weight average molecular weight of 10,000 to 1,000 with respect to 100 parts by weight of the total of the epoxy resin and the curing agent. The composition according to claim 1, comprising 5 to 45 parts by weight of 1,000 sheeting agent. The composition according to claim 2, wherein the curing agent is at least one selected from the group consisting of a phenol novolac resin, an aralkylphenol novolak resin, a naphthol novolak resin, and a terpene phenol resin. 4. The composition according to claim 2, wherein 50% by weight or more of the epoxy resin is a liquid epoxy resin having a dynamic viscosity at 25 ° C. of 100 Pa · s or less. Furthermore, the composition in any one of Claims 2-4 which contains an inorganic filler 30 to 80weight% of the composition whole quantity. The film adhesive which consists of a composition in any one of Claims 1-5. A semiconductor component or a semiconductor device using the adhesive according to claim 6.