JP2019019248A - Thermosetting resin composition - Google Patents

Abstract

To provide a thermosetting resin composition excellent in adhesive strength after curing.SOLUTION: A thermosetting resin composition contains conductive particles and a thermosetting resin, where a single exothermic peak is formed in a temperature region of 120°C or higher and 220°C or lower in a DSC curve of the thermosetting resin composition obtained when the composition is heated from 50°C to 300°C on the condition of a rate of temperature rise of 10°C/min using a differential scan calorimeter, a calorific value of the exothermic peak is 30 mJ/mg or more, and a peak width of the exothermic peak is 50°C or lower.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a thermosetting resin composition.

  Currently, various developments have been made on thermosetting die bonding films. As this type of technology, for example, the technology described in Patent Document 1 is known. Patent Document 1 describes a thermosetting die attach film containing an epoxy resin.

JP 2011-82480 A

  As a result of investigation by the present inventors, it has been found that the thermosetting resin composition used for the thermosetting die attach film described in Patent Document 1 has room for improvement in terms of adhesion strength after curing.

Upon further examination, the present inventor has found that there is a correlation between the adhesion characteristics after curing and the DSC profile in the thermosetting resin composition.
As a result of further earnest research based on such knowledge, the detailed mechanism is not clear by using a thermosetting resin composition having a narrow peak on the high temperature side and a single peak of a predetermined calorific value on the DSC curve. It is considered that the progress of the reaction is suppressed on the low temperature side, and the reaction rate at the curing temperature on the high temperature side (for example, 200 ° C.) is increased, and the adhesion strength after curing is found to be improved and the present invention is completed. It came to.

According to the present invention,
A thermosetting resin composition comprising conductive particles and a thermosetting resin,
In the DSC curve of the thermosetting resin composition obtained when the temperature is raised from 50 ° C. to 300 ° C. under a temperature rising rate of 10 ° C./min using a differential scanning calorimeter,
A single exothermic peak is formed in a temperature range of 120 ° C. or higher and 220 ° C. or lower,
The calorific value of the exothermic peak is 30 mJ / mg or more,
A thermosetting resin composition having a peak width of the exothermic peak of 50 ° C. or less is provided.

  According to the present invention, a thermosetting resin composition having excellent adhesion strength after curing is provided.

Sectional drawing of the dicing die-bonding film of this embodiment is shown. Process sectional drawing of the manufacturing method of the semiconductor device using the dicing die-bonding film of this embodiment is shown. The DSC chart obtained by the DSC measurement of Examples 1 and 2 and Comparative Examples 1 and 2 is shown.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same reference numerals are given to the same components, and the description will be omitted as appropriate.

  The outline | summary of the thermosetting resin composition of this embodiment is demonstrated.

  The thermosetting resin composition of the present embodiment can include conductive particles and a thermosetting resin. In the DSC curve obtained when the thermosetting resin composition is heated from 50 ° C. to 300 ° C. under a temperature rising rate of 10 ° C./min using a differential scanning calorimeter, 120 ° C. or higher and 220 ° C. or lower. A single exothermic peak is formed in the temperature range, the exothermic peak has a calorific value of 30 mJ / mg or more, and the peak width of the exothermic peak can be 50 ° C. or less.

As a result of investigation by the present inventors, it has been found that in the thermosetting resin composition, there is a correlation between the adhesion characteristics after curing and the DSC profile. Further examination based on such findings revealed that by using a thermosetting resin composition having a DSC profile that is narrow on the high temperature side and has a single peak of a predetermined calorific value on the DSC curve, It has been found that the adhesion strength of is improved.
Although the detailed mechanism is not clear, by using a thermosetting resin composition having a narrow peak on the high temperature side and a single peak with a predetermined calorific value, the progress of the reaction is suppressed on the low temperature side, and the high temperature side curing is performed. The reaction rate at temperature is considered to be high.

  Here, when an epoxy thermosetting resin composition as described in Patent Document 1 is used, the reaction starts quickly and the heat generation starting temperature is found in the low temperature region. In the DSC profile of the epoxy thermosetting resin composition, a broad broad exothermic peak is formed, and there are many exothermic peaks. Then, since the reaction proceeds from the low temperature side, it is presumed that the reaction rate at the high temperature decreases and the adhesion strength after curing decreases. In addition, since the reaction proceeds even at a drying temperature on the low temperature side, when the film-like thermosetting resin composition is used, the decrease in the adhesion strength after curing becomes remarkable.

On the other hand, in the DSC profile of the thermosetting resin composition of the present embodiment, a narrow spike type exothermic peak is formed. The spike-type exothermic peak is a single peak, exists at a relatively high temperature in the temperature range of 120 ° C. or more and 220 ° C. or less, has a narrow peak width of 50 ° C. or less, and is a predetermined value of 30 mJ / mg or more. The calorific value can be as follows. Thus, the thermosetting resin composition of the present embodiment can have an exothermic reaction profile that suppresses the reaction on the low temperature side. Therefore, the adhesion strength after curing can be improved.
In addition, in the laminating process in which the die bonding film is bonded to the back surface of the silicon wafer, the reaction of the die bonding film on the low temperature side is suppressed, so that the proper tackiness of the die bonding film can be maintained. And the semiconductor element can be in a good contact state.

  Although the thermosetting resin composition of this embodiment can be used for various uses, it can be used as an adhesive, for example. At this time, the thermosetting resin composition can be used as a film adhesive by forming a film.

As an example of the adhesive, it is used to form a thermosetting die bonding film. The thermosetting die bonding film can bond a semiconductor element and a substrate or a lead frame. These adhesiveness can be enhanced by the cured product of the thermosetting die bonding film. By using the thermosetting resin composition of this embodiment, it is possible to improve die bonding characteristics.
Moreover, as an example of the adhesive, it is used to form a thermosetting die bonding film constituting a dicing die bonding film including a dicing film and a thermosetting die bonding film provided on the dicing film. Can do.

  Hereinafter, each structure of the thermosetting resin composition of this embodiment is explained in full detail.

(Thermosetting resin)
The thermosetting resin composition of this embodiment can contain a thermosetting resin.
This thermosetting resin can contain an acrylic compound having a kind of functional group selected from the group consisting of a (meth) acryloyl group and a (meth) acrylate group. The acrylic compound may be a monomer, a polymer and a mixture thereof, but a monomer can be used.

  The said thermosetting resin can contain polyfunctional (meth) acrylate provided with the cyclic structure which has 2 or more of (meth) acryloyl groups as said acrylic compound. This polyfunctional (meth) acrylate can have an isocyanurate ring structure in which the substituent on nitrogen is a (meth) acryloyl group. A monomer can be used as the polyfunctional (meth) acrylate.

  The polyfunctional (meth) acrylate can include, for example, a compound represented by the following general formula (a1-1).

In formula (a1-1), R ¹ , R ² and R ³ are each independently an organic group having no hydrogen atom or aromatic ring, and at least two of R ¹ , R ² and R ³ are ( It is an organic group having a (meth) acrylic group and no aromatic ring. As the organic group for R ¹ , R ² and R ³ , for example, a (meth) acryloyl group, a lactone-modified (meth) acryloyl group, or a polyalkylene glycol (meth) acryloyl group is preferable, and a (meth) acryloyl group or a lactone-modified ( A (meth) acryloyl group is more preferable, and a (meth) acryl group is particularly preferable.
At least two of R ¹ , R ² and R ³ are organic groups having a (meth) acryl group and no aromatic ring, and any of R ¹ , R ² and R ³ is a (meth) acryl group. It is preferably an organic group having no aromatic ring.

Moreover, as said polyfunctional (meth) acrylate, trifunctional (meth) acrylate which is an organic group in which all of R < ¹ >, R < ² >, R < ³ > has a (meth) acryl group and does not have an aromatic ring is used, for example. be able to.

  Examples of such a polyfunctional (meth) acrylate having a (meth) acryl group as a substituent on the nitrogen of the isocyanurate ring include (tris (2-hydroxyethyl) isocyanurate triacrylate (ethoxylated isocyanuric acid triacrylate) ), Di (2-acryloyloxyethyl) isocyanurate, ε-caprolactone-modified tris (2-acryloyloxyethyl) isocyanurate, and the like, but not limited thereto, 2-hydroxyethyl isocyanurate and isocyanuric acid (Meth) acrylic acid or (meth) acrylic acid halide condensation compound, (meth) acrylic group introduced compound, 2-hydroxyethyl isocyanurate hydroxyl group and polyalkylene glycol, polyester glycol is reacted at the terminal ( Meta Compounds obtained by introducing a (meth) acrylic group in the condensation reaction of acrylic acid and (meth) acrylic acid halide and the like.

  Specific examples of the polyfunctional (meth) acrylate include tris (2-hydroxyethyl) isocyanurate triacrylate (ethoxylated isocyanuric acid triacrylate), pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate isophorone. Diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer, ε-caprolactone modified tris (2-acryloyloxyethyl) isocyanurate, tris (2-acryloyloxyethyl) isocyanurate, di (2-acryloyloxyethyl) ) Isocyanurate can be used. Preferably, tris (2-hydroxyethyl) isocyanurate triacrylate (ethoxylated isocyanuric acid triacrylate) or ε-caprolactone-modified tris (2-acryloyloxyethyl) isocyanurate can be used. When these are used, the glass transition temperature can be increased.

  In the present embodiment, the thermosetting resin can include other thermosetting resins in addition to the polyfunctional (meth) acrylate. As other thermosetting resins, known resins can be used, and are not particularly limited.For example, from the viewpoint of excellent curability and storage stability, heat resistance of the cured product, moisture resistance, and chemical resistance, Allyl resins can be used. This allyl resin and the polyfunctional (meth) acrylate can be used in combination.

  In the present specification, the (meth) acrylate resin may include a (meth) acrylate group-containing polymer and a (meth) acrylate monomer. Having a (meth) acrylic group means having one or more acrylic groups and / or having one or more methacrylic groups. Moreover, having a (meth) acryloyl group means having at least one acryloyl group and / or having at least one methacryloyl group.

  As the allyl resin, an allyl resin containing two or more allyl groups can be used. As the allyl resin containing two or more allyl groups, for example, diallyl phthalate resin can be used.

  Examples of the diallyl phthalate resin include diallyl phthalate resins such as diallyl orthophthalate prepolymer, diallyl isophthalate prepolymer, and diallyl terephthalate prepolymer, and these may be used alone or as a mixture of two or more thereof. Thereby, sclerosis | hardenability adjustment, the elasticity modulus and intensity | strength of a film can be raised, and peelability from a carrier film can be improved. Further, the diallyl phthalate resin may be a prepolymer made of a copolymer of two or more so-called diallyl phthalate monomers such as diallyl orthophthalate monomer, diallyl isophthalate monomer, diallyl terephthalate monomer. In this case, hydrogen atoms on the benzene ring may be substituted with halogen atoms such as chlorine and bromine, and prepolymers in which all or part of the unsaturated bonds present in the molecule are hydrogenated are also shown here. Shall be included. In the present embodiment, a monomer can be used as the diallyl phthalate resin.

  The lower limit of the content of the thermosetting resin is, for example, 5% by weight or more, preferably 8% by weight or more, more preferably 10% by weight or more with respect to the entire thermosetting resin composition. It is. Thereby, heat resistance and mechanical characteristics can be improved. On the other hand, the lower limit of the content of the thermosetting resin is, for example, 20% by weight or less, preferably 18% by weight or less, and more preferably 15% with respect to the entire thermosetting resin composition. % By weight or less. As a result, a balance between heat dissipation characteristics and mechanical characteristics can be achieved.

  The lower limit of the content of the polyfunctional (meth) acrylate is, for example, 10% by weight or more, preferably 30% by weight or more, more preferably 50% by weight or more, with respect to the entire thermosetting resin. It is. Thereby, in the hardened | cured material of a thermosetting resin composition, the adhesive strength with respect to a semiconductor element can be improved before and after moisture absorption. On the other hand, the lower limit of the content of the thermosetting resin may be, for example, 100% by weight or less, preferably 90% by weight or less, and more preferably 80% by weight with respect to the entire thermosetting resin group. % Or less. Thereby, the balance of various characteristics of hardened | cured material, such as sclerosis | hardenability, can be aimed at.

  In this embodiment, content with respect to the whole resin composition refers to content with respect to the whole solid content except the solvent of a resin composition, when a solvent is included. The “solid content of the resin composition” refers to the non-volatile content in the resin composition and refers to the remainder excluding volatile components such as water and solvent.

(Conductive particles)
The thermosetting resin composition of the present embodiment can contain conductive particles.
As the conductive particles, known particles can be used as long as they are conductive particulate materials. For example, one or more metals selected from the group consisting of silver, copper, palladium, and nickel can be used. Constituted particles can be included. These may be used alone or in combination of two or more.

  The conductive particles may be, for example, metal particles made of metal, or metal-coated resin particles in which metal is coated with resin particles. Moreover, the electroconductive particle may contain other metals other than the said metal.

The lower limit of the average particle diameter _{D 50} of the conductive particles may be, for example, 0.1μm or more, preferably 0.3μm or more, and more preferably 0.5μm or more. Thereby, the heat conductivity and electroconductivity of hardened | cured material can be improved. On the other hand, the upper limit of the average particle diameter D ₅₀ of the conductive particles may be, for example, 25 μm or less, preferably 20 μm or less, more preferably 10 μm or less, and further preferably 5 μm or less. Thereby, the base material peelability of a film-like thermosetting resin composition and the adhesiveness with respect to the semiconductor element of hardened | cured material can be improved.
The average particle diameter of the conductive particles can be measured by, for example, a laser diffraction scattering method or a dynamic light scattering method.

  Examples of the shape of the conductive particles of the present embodiment include a flake shape and a spherical shape.

  The content of the conductive particles is, for example, preferably 50% by weight or more, and more preferably 60% by weight or more with respect to the entire thermosetting resin composition. Thereby, the heat conductivity and electroconductivity of hardened | cured material can be improved. On the other hand, the upper limit of the content of the conductive particles is, for example, 88% by weight or less, preferably 83% by weight or less, and more preferably 80% by weight or less, with respect to the entire heat conductive paste. is there. Thereby, the base material peelability of a film-like thermosetting resin composition and the adhesiveness with respect to the semiconductor element of hardened | cured material can be improved.

  The thermosetting resin composition of the present embodiment may contain other inorganic particles and organic particles in addition to the conductive particles. At this time, the content of the conductive particles may be, for example, 80% by weight or more, 90% by weight or more, 95% by weight or more, and 100% by weight or less with respect to 100% by weight of the whole particles. But you can.

(Thermoplastic resin)
The thermosetting resin composition of the present embodiment can further include a thermoplastic resin.
Examples of the thermoplastic resin include (meth) acrylic resin, polyester resin, polyurethane resin, polyimide resin, siloxane-modified polyimide resin, polybutadiene, polypropylene, styrene-butadiene-styrene copolymer, styrene-ethylene-butylene-styrene. Copolymer, polyacetal resin, polyvinyl butyral resin, polyvinyl acetal resin, butyl rubber, chloroprene rubber, polyamide resin, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene-acrylic acid copolymer, acrylonitrile-butadiene-styrene copolymer, poly One or more selected from vinyl acetate and nylon can be included. Among these, as said thermoplastic resin, at least 1 type selected from the group which consists of a (meth) acrylic-type resin and a polyimide resin can be included, for example. The thermoplastic resin may have an epoxy group, a (meth) acryl group, a carboxyl group, or a phenolic hydroxyl group in its structure.
In this specification, “(meth) acrylic resin” means (meth) acrylic acid polymer; (meth) acrylic acid derivative polymer; (meth) acrylic acid and other monomers Or a copolymer of a derivative of (meth) acrylic acid and another monomer. Furthermore, “(meth) acrylic acid” means “acrylic acid” or “methacrylic acid”. The (meth) acrylic resin may have a functional group that reacts with the thermosetting resin, such as an epoxy group or a (meth) acrylic group.

As said (meth) acrylic-type resin, an acrylate ester copolymer can be included, for example. Examples of the acrylic ester copolymer include a copolymer having at least one of acrylic acid, acrylic ester, methacrylic ester and acrylonitrile as a monomer component. Among these, an acrylate copolymer having a compound having an epoxy group, a hydroxyl group, a carboxyl group, a nitrile group or the like as a functional group is preferable. Thereby, the adhesiveness to adherends, such as a semiconductor element, can be improved more.
Specific examples of the compound having a functional group include glycidyl methacrylate having a glycidyl ether group, hydroxy methacrylate having a hydroxyl group, carboxy methacrylate having a carboxyl group, and acrylonitrile having a nitrile group.

  The weight average molecular weight of the acrylate copolymer is not particularly limited, but is preferably 100,000 or more, particularly preferably 150,000 to 1,000,000. When the weight average molecular weight is within this range, the film forming property of the adhesive film for a semiconductor can be improved.

  The glass transition temperature of the acrylate copolymer is, for example, -20 to 120 ° C, more preferably -20 to 60 ° C, and particularly preferably -10 to 50 ° C. If the glass transition temperature is too low, the adhesive strength of the film-like adhesive layer becomes strong, and pickup failure may occur or workability may be reduced. If the glass transition temperature is too high, chipping or cracking may occur, or the effect of improving low-temperature adhesion may be reduced.

  Content of the said thermoplastic resin is 1 to 20 weight% with respect to the whole thermosetting resin composition, for example, Preferably it is 3 to 15 weight%, More preferably It is preferably 5% by weight or more and 10% by weight or less. Thereby, the adhesiveness with respect to the semiconductor element of hardened | cured material and the balance of other physical properties can be aimed at.

(Coupling agent)
The thermosetting resin composition of this embodiment can further contain a coupling agent.
Thereby, the dispersibility of the electroconductive particle in a film-like thermosetting resin composition can be improved. Moreover, the adhesiveness of a film-like thermosetting resin composition and a to-be-adhered body can be improved.

  Examples of the coupling agent include known silane compounds such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, vinyl silane, and methacryl silane, titanium compounds, aluminum chelates, and aluminum / zirconium compounds. A coupling agent can be used. Among these, a coupling agent having a (meth) acryl group such as methacrylic silane can be used. Thereby, the compatibility of acrylic compounds, such as polyfunctional (meth) acrylate, and electroconductive particle can be improved.

  The amount of the coupling agent is, for example, preferably 0.01% by weight to 10% by weight, more preferably 0.05% by weight to 5% by weight, based on the entire thermosetting resin composition. More preferably, it is 0.1 wt% or more and 2 wt% or less.

  The thermosetting resin composition of this embodiment may contain a peroxide as a polymerization initiator depending on the purpose. On the other hand, the said thermosetting resin composition is good also as a structure which does not contain polymerization initiators, such as a peroxide. Thereby, the curing reaction in the low temperature region can be suppressed, and the adhesion of the cured product to the semiconductor element can be improved before and after moisture absorption.

  Moreover, the thermosetting resin composition of this embodiment can be set as the structure which does not contain the monomer which has an epoxy group. Thereby, the curing reaction in the low temperature region can be suppressed, and the adhesion of the cured product to the semiconductor element can be increased and the base peelability can be improved.

  Moreover, the thermosetting resin composition of this embodiment can be set as the structure which does not contain a hardening accelerator. As this hardening accelerator, what can accelerate | stimulate the polymerization reaction of an epoxy compound is mentioned as an epoxy-type composition component, for example. Thereby, the curing reaction in the low temperature region can be suppressed, and the adhesion of the cured product to the semiconductor element can be increased and the base peelability can be improved.

  The thermosetting resin composition of this embodiment can contain other components other than the components described above. Examples of other components include slip agents (leveling agents), dispersants, polymerization inhibitors, penetration enhancers, wetting agents (humectants), fixing agents, antifungal agents, antiseptics, antioxidants, chelating agents. , Thickeners and antifoaming agents.

In the present embodiment, the thermosetting resin composition can be prepared by mixing or dispersing the above-described components. The mixing method and the dispersion method of each component are not specifically limited, It can mix or disperse | distribute by a conventionally well-known method. More specifically, for example, the above-described thermosetting resin composition may be prepared in a liquid state by mixing the respective components in a solvent or without a solvent. The solvent used at this time is inactive with respect to each component. Specifically, this solvent includes, for example, ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), diisobutyl ketone (DIBK), cyclohexanone, and diacetone alcohol (DAA); benzene, xylene, and Aromatic hydrocarbons such as toluene; alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and n-butyl alcohol; cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, and ethyl cellosolve acetate; N -Methyl-2-pyrrolidone (NMP); tetrahydrofuran (THF); dimethylformamide (DMF); dibasic acid ester (DBE); ethyl 3-ethoxypropionate (EEP) ; And including one or two or more selected from dimethyl carbonate (DMC). Content of a solvent can be made into the quantity from which the density | concentration of solid content of a thermosetting resin composition will be 10 weight%-80 weight%, for example.
In the present specification, “to” represents that an upper limit value and a lower limit value are included unless otherwise specified.

  The film-like thermosetting resin composition of the present embodiment includes a carrier base material and a resin sheet with a carrier base material provided on the carrier base material and a resin film made of the thermosetting resin composition. It may be configured as. The resin film can be obtained, for example, by applying a resin varnish of a thermosetting resin composition on a carrier substrate, drying at a predetermined temperature, and volatilizing the solvent. This resin film can be in a B-stage state (an uncured state or a semi-cured state) instead of the C-stage state.

  The step of forming a resin film on the carrier substrate is, for example, preparing a resin varnish by dissolving and dispersing the thermosetting resin composition in a solvent or the like, and using the various coater devices, the resin varnish is prepared as a carrier base. Examples thereof include a method of drying the material after coating the material, a method of spraying the resin varnish onto the carrier substrate using a spray device, and then drying the resin varnish. Among these, it is preferable to apply a resin varnish to a carrier substrate using various coaters such as a spin coater, a comma coater, and a die coater, and then dry the resin varnish.

In the present embodiment, for example, a dicing film can be used as the carrier substrate. As the dicing film, a known film may be used as long as it is subjected to a mold release treatment on one surface, and examples thereof include a polypropylene film, a polyethylene film, and a polyethylene terephthalate film. Examples of the mold release treatment include a process for coating the film surface with a mold release agent and a process for forming fine irregularities on the film surface. Examples of the release agent include silicone-based, alkyd-based, and fluorine-based agents. In particular, treatment with a silicone-based release agent is preferable because of excellent pickup properties after dicing.
As thickness of the said dicing film, 5-100 micrometers is preferable, for example, and 60-60 micrometers is especially preferable. If the thickness is too thin, there is a problem that chips are scattered during dicing, and if it is too thick, there is a problem that pickup failure occurs.

  The resin film obtained by separating the carrier substrate from the resin film with a carrier substrate can be used for various applications. For example, a film adhesive for a thermosetting die bonding film of a dicing die bonding film. Can be used as

  The characteristics of the thermosetting resin composition of this embodiment will be described in detail.

  In the present embodiment, the DSC curve of the thermosetting resin composition is obtained by using a differential scanning calorimeter at a temperature rising rate of 10 ° C./min under conditions where the temperature is increased from 50 ° C. to 300 ° C. It can be obtained by measuring the composition.

  In the DCS curve of this embodiment, the lower limit value of the temperature region where a single exothermic peak exists is, for example, 120 ° C. or higher, preferably 150 ° C. or higher, and more preferably 180 ° C. or higher. Thereby, since the progress of the reaction in the thermosetting resin composition can be suppressed in a relatively low temperature region, the adhesion property can be enhanced. On the other hand, the upper limit of the temperature region where a single exothermic peak exists is, for example, 220 ° C. or less, preferably 215 ° C. or less, more preferably 210 ° C. or less. Thereby, it can suppress that thermal deterioration arises in a semiconductor element or a die attach film by high temperature.

  Further, the lower limit value of the calorific value of the exothermic peak is, for example, 30 mJ / mg or more, preferably 35 mJ / mg or more, and more preferably 40 mJ / mg or more. Thereby, sufficient curing characteristics can be obtained in the thermosetting resin composition. On the other hand, the upper limit of the calorific value of the exothermic peak is not particularly limited, but may be, for example, 200 mJ / mg or less, or 100 mJ / mg or less.

  Moreover, the upper limit of the peak width of the exothermic peak is, for example, 50 ° C. or less, preferably 40 ° C., and more preferably 30 ° C. or less. Thereby, sufficient curing characteristics can be obtained in the vicinity of the exothermic peak temperature region. On the other hand, the lower limit value of the peak width of the exothermic peak is not particularly limited, but may be, for example, 1 ° C. or higher, or 5 ° C. or higher.

In the present embodiment, the heat generation start temperature is the difference between the heat generation amount height H1 at 70 ° C. and the heat generation amount height HMAX at the maximum heat generation peak temperature, ΔH1, and the heat generation amount when the heat generation amount height H1 is used as a reference. The temperature when the height reaches 10% of ΔH1.
In addition, there is one exothermic peak exceeding 10% of ΔH1 in the DSC curve of the present embodiment.

  The DSC curve of the said thermosetting resin composition can be comprised so that it may not have an exothermic peak in the temperature range of 50 to less than 120 degreeC. Thereby, since the progress of the reaction in the thermosetting resin composition can be suppressed in a relatively low temperature region, the adhesion property can be enhanced.

  The lower limit value of the exothermic height of the exothermic peak in the DSC curve of the thermosetting resin composition is, for example, 1000 μW / mg or more, preferably 2000 μW / mg or more, more preferably 5000 μW / mg or more. Thereby, sufficient curing characteristics can be obtained in the vicinity of the exothermic peak temperature region. On the other hand, the upper limit value of the exothermic height of the exothermic peak in the DSC curve is not particularly limited, but may be, for example, 20000 μW / mg or less.

  In the present embodiment, for example, the maximum exothermic peak temperature in the DSC curve can be obtained by appropriately selecting the type and amount of each component contained in the thermosetting resin composition, the preparation method of the thermosetting resin composition, and the like. It is possible to control the heat generation amount, peak width, peak number, and heat generation start temperature of the heat generation peak. Among these, for example, do not use an epoxy-based composition component such as a monomer having an epoxy group, use an acrylic compound such as the above polyfunctional (meth) acrylate as a thermosetting resin, polymerization of a peroxide, etc. The fact that the initiator and the curing accelerator are not used is an element for setting the maximum exothermic peak temperature, exothermic peak exothermic amount, peak width, number of peaks, and exothermic start temperature in the DSC curve to a desired numerical range. .

  An example of the structure of the dicing die bonding film 10 of this embodiment will be described with reference to FIG. FIG. 1 shows a cross-sectional view of a dicing die bonding film 10 of the present embodiment.

The dicing die-bonding film 10 of this embodiment can be made into a sheet member provided with the film adhesive layer 2 laminated | stacked on the dicing film 1 and the dicing film 1, as shown in FIG. The dicing / die-bonding film 10 may be a rollable roll or a rectangular sheet. The surface of the film adhesive layer 2 in the dicing die bonding film 10 may be exposed, for example, or may be covered with a protective film (cover film 3). As the protective film, a film having a known protective function can be used. For example, a PET film may be used. Such a dicing die bonding film 10 can be used after peeling the cover film 3.
In addition, the dicing die-bonding film 10 of this embodiment may have other functional layers other than the dicing film 1, the film adhesive layer 2, and the cover film 3.

  In the top view of the dicing die bonding film 10 of the present embodiment, one or more film adhesive layers 2 may be disposed on the plane of one dicing film 1. The film adhesive layer 2 may be arranged in a line along the longitudinal direction of the rectangular dicing film 1. The shape of the film adhesive layer 2 in the top view may be, for example, a circular shape. After the film adhesive layer 2 is formed on the dicing film 1, the film adhesive layer 2 having a desired shape is obtained by half-cutting the film adhesive layer 2. This half cut may be performed before the cover film 3 is laminated on the film adhesive layer 2 or after the cover film 3 is laminated. Note that the shape of the cover film 3 in a top view may have substantially the same shape as the film adhesive layer 2.

  In the cross-sectional view of the dicing die bonding film 10 of the present embodiment, a plurality of film adhesive layers 2 may be disposed on the surface of one dicing film 1. At this time, the film adhesive layers 2 are arranged apart from each other, and the cover film 3 is also arranged separately for each film adhesive layer 2. The outer edge of the cover film 3 may be formed outside the outer edge of the film adhesive layer 2. Thereby, the peelability of the cover film 3 can be made favorable.

An example of the manufacturing method of the semiconductor device using the dicing die bonding film 10 of this embodiment is demonstrated using FIG. FIG. 2 is a process cross-sectional view of a method for manufacturing a semiconductor device using the dicing die bonding film 10 of the present embodiment.
First, as shown in FIG. 2A, the film adhesive layer 2 of the dicing die bonding film 10 obtained by peeling the cover film 3 from the surface of the film adhesive layer 2 is attached to the back surface of the wafer 4 (silicon wafer). wear. The laminating process of the wafer 4 can be performed under a mild condition of, for example, 60 ° C. or less.
Next, the structure of the dicing film 1, the film adhesive layer 2, and the wafer 4 is fixed on a dicing apparatus using a wafer ring. Subsequently, using a cutting means such as a dicing saw, the film adhesive layer 2 and the wafer 4 in the above structure are cut into individual pieces to obtain semiconductor chips as individual dies 5.
Subsequently, as shown in FIG. 2B, the dicing film 1 and the film adhesive layer 2 are left without fixing the film adhesive layer 2 on the back surface of the semiconductor chip and including the heating step and the ultraviolet irradiation step. Peel between. In this way, the die 5 (semiconductor chip) with the film adhesive layer 2 is picked up. Then, the die 5 (semiconductor chip) can be die-bonded by laminating the die 5 on the metal lead frame or the substrate via the film adhesive layer 2 and heating and pressing.

  Subsequently, by curing the film adhesive layer 2 by heat treatment, a semiconductor device in which the semiconductor chip and the lead frame, the substrate, etc. are firmly bonded via the film adhesive layer 2 can be obtained. The film adhesive of this embodiment can be used for processing a wafer having a large area size of 8 inches or more.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail with reference to an Example, this invention is not limited to description of these Examples at all. Unless otherwise specified, “parts” described below indicates “parts by weight” and “%” indicates “% by weight”.

[Preparation of thermosetting resin composition]
About each Example and each comparative example, the varnish-like thermosetting resin composition (resin varnish) was prepared. First, each component was dissolved in methyl ethyl ketone (MEK) at a solid content ratio shown in Table 1 to obtain a resin varnish having a nonvolatile content (resin solid content) of 59%.
The details of the components shown in Table 1 are as follows. Moreover, the compounding ratio of each component in Table 1 indicates the compounding ratio (parts by weight) of each component with respect to the entire solid content of the thermosetting resin composition.

The detail of the raw material of each component in Table 1 is as follows.
(Conductive particles)
Silver particle 1: Silver powder (Tokuriku head office company make, TKR4A, flakes, average particle diameter (D ₅₀ ): 9 μm)
(Thermosetting resin)
Polyfunctional (meth) acrylate 1: Tris (2-hydroxyethyl) isocyanurate triacrylate represented by the following formula (SR-368, manufactured by Sartomer)

Diallyl phthalate resin 1: Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., DCP-A) represented by the following formula.

Epoxy resin 1: Trisphenol methane type epoxy resin (Nippon Kayaku Co., Ltd., NC-6000, weight average molecular weight: 600)
(Curing agent)
Curing agent 1: Diglycidylamine type epoxy resin (manufactured by Daiso, LX-SB-10, epoxy equivalent 110 g / eq, weight average molecular weight 291 and liquid at normal temperature)
(Thermoplastic resin)
Thermoplastic resin 1: Acrylate ester copolymer solution (manufactured by Nagase ChemteX, Teisan Resin SG-P3, epoxy group-containing ethyl acrylate-butyl acrylate-acrylonitrile copolymer, specific gravity 0.85, weight average (Molecular weight 850,000, epoxy value 210 eq./g, glass transition temperature 12 ° C., rubber content 15% by weight, solvent: methyl ethyl ketone)
(Coupling agent)
Coupling agent 1: 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503)
(Peroxide)
Peroxide 1: Dilauroyl peroxide (manufactured by Arkema Yoshitomi, Luperox LP, “Lupelox” is a registered trademark))
Peroxide 2: 1,1-di (tert-butylperoxy) cyclohexane (manufactured by NOF Corporation, Perhexa CS, “Perhexa” is a registered trademark)
(Curing accelerator)
Curing accelerator 1: 2-undecylimidazole (Shikoku Kasei Kogyo Co., Ltd., C11Z)

(Creation of dicing die bonding film)
The obtained resin varnish was applied to a silicone release surface of a polyethylene terephthalate film (manufactured by Oji Paper Co., Ltd., RL-07, thickness 38 μm) as a dicing film using a comma coater, at 70 ° C. for 10 minutes. It dried and obtained the film adhesive layer with a dicing film.

  Subsequently, a PET film as a protective film (cover film) is attached to the obtained film-like adhesive layer with a dicing film, the dicing film and the film-like adhesive layer are half-cut, and the protective film is peeled off, thereby dicing. A dicing die bonding film in which a film and a film adhesive layer were laminated in this order was obtained.

(Manufacture of semiconductor devices)
The obtained dicing die-bonding film was affixed to the back surface of a wafer (size: 8 inches, thickness: 550 μm, silicon wafer) at 60 ° C. to obtain a wafer with a dicing die-bonding film. Thereafter, the wafer with the dicing die bonding film is diced (cut) into a size of 5 mm × 5 mm square semiconductor element at a spindle rotation speed of 30,000 rpm and a cutting speed of 50 mm / sec using a dicing saw. The semiconductor element was picked up from the back surface of the die bonding film, peeled off between the dicing film and the film adhesive layer, and the semiconductor element bonded with the film adhesive layer (die attach film) was picked up. Thereafter, the semiconductor element is pressure-bonded to a copper lead frame through a film-like adhesive layer at 100 ° C. and 1 MPa for 1.0 second, die-bonded, heated at 200 ° C. for 1 hour, and sealed with resin. Got the device.

  The following evaluation was performed about the film adhesive layer used for the dicing die-bonding film obtained by each Example and each comparative example. The evaluation results are shown in Table 1.

(DSC measurement)
Using a differential scanning calorimeter (manufactured by SII, DSC7020), 10 mg of the above thermosetting resin composition was measured under a nitrogen stream under a temperature rising rate of 10 ° C./min and a temperature range of 50 ° C. to 300 ° C. did. The difference between the heat generation amount height H1 at 70 ° C. and the heat generation amount height HMAX at the maximum heat generation peak temperature is ΔH1, and the heat generation amount height reaches 10% of ΔH1 with respect to the heat generation amount height H1. The temperature at that time was defined as the heat generation start temperature. The exothermic peak exceeded 10% of ΔH1. The results are shown in Table 1. Further, DSC charts of Examples 1 and 2 and Comparative Examples 1 and 2 are shown in FIG.

(Die shear strength)
A 4 mm × 4 mm silicon chip was mounted on a copper lead frame via the obtained film adhesive layer (die bonding film) and cured at 200 ° C. for 1 hour. After curing (before moisture absorption treatment) and after moisture absorption (85 ° C., 85%, 72 hours), the hot die shear strength at 260 ° C. was measured using an automatic adhesive force measuring apparatus. The results are shown in Table 1. The unit of adhesive strength is N.

(Laminating properties in film adhesives)
The obtained dicing die-bonding film is laminated on a silicon wafer at 60 ° C., then diced (cut) into the size of the semiconductor element, and then the film-like adhesive layer (thermosetting die bonding film) and the semiconductor element are adhered to each other. The condition was observed. When the film-like adhesive and the semiconductor element are bonded together without bubbles and are not peeled off, it is determined that the film is good (O), and bubbles are generated between the film-like adhesive and the semiconductor element, and A case where a part of the film adhesive was peeled off was judged to be defective (x).

  The thermosetting resin composition of each example has a higher laminating property to the semiconductor element before curing than the thermosetting resin composition of each comparative example, and has excellent adhesion to the semiconductor element after curing. I found it. Moreover, in the hardened | cured material of the thermosetting resin composition of each Example, electroconductivity and heat conductivity were favorable.

  As mentioned above, although this invention was concretely demonstrated based on embodiment and an Example, these are the illustrations of this invention, Various structures other than the above can also be employ | adopted.

DESCRIPTION OF SYMBOLS 1 Dicing film 2 Film adhesive layer 3 Cover film 4 Wafer 5 Die 10 Dicing die bonding film

Claims (8)

A thermosetting resin composition comprising conductive particles and a thermosetting resin,
In the DSC curve of the thermosetting resin composition obtained when the temperature is raised from 50 ° C. to 300 ° C. under a temperature rising rate of 10 ° C./min using a differential scanning calorimeter,
A single exothermic peak is formed in a temperature range of 120 ° C. or higher and 220 ° C. or lower,
The calorific value of the exothermic peak is 30 mJ / mg or more,
A thermosetting resin composition having a peak width of the exothermic peak of 50 ° C. or less. The thermosetting resin composition according to claim 1,
A thermosetting resin composition in which the DSC curve does not have an exothermic peak in a temperature range of 50 ° C to less than 120 ° C. The thermosetting resin composition according to claim 1 or 2,
A thermosetting resin composition having a heat generation height of the exothermic peak of 1000 μW / mg or more. The thermosetting resin composition according to any one of claims 1 to 3,
The thermosetting resin composition in which the thermosetting resin contains an acrylic compound. The thermosetting resin composition according to any one of claims 1 to 4,
A thermosetting resin composition further comprising a thermoplastic resin. The thermosetting resin composition according to any one of claims 1 to 5,
A thermosetting resin composition used for an adhesive. The thermosetting resin composition according to any one of claims 1 to 6,
A thermosetting resin composition used for forming a thermosetting die bonding film. The thermosetting resin composition according to any one of claims 1 to 7,
In a dicing die bonding film comprising a dicing film and a thermosetting die bonding film provided on the dicing film,
A thermosetting resin composition used for forming the thermosetting die bonding film.

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