JP2008274300A - Curable resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition which is excellent in mechanical strength, heat resistance, moisture resistance, flexibility, temperature cycle resistance, solder reflow resistance and dimensional stability after curing and exhibits high adhesion reliability and high conduction reliability. <P>SOLUTION: The curable resin composition comprises an epoxy resin, a solid polymer having a functional group reactive with an epoxy group, and an epoxy resin curing agent. When a cured product of this curable resin composition is dyed with a heavy metal and observed with a transmission electron microscope, no phase separation structure is observed in the matrix resin composed of the resin, and the polymer having an epoxy group has an epoxy equivalent weight of 200-1,000. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a curable resin composition having high reliability.

Various adhesives for electronic materials have been developed in response to recent demands for miniaturization and higher performance of semiconductor devices. These adhesives for electronic materials are required to have a high degree of reliability, and in order to ensure this, there is little cure shrinkage, high adhesive strength, a wide variety of types, and easy compounding design Epoxy resins are most often used. As such an epoxy resin, a general liquid epoxy resin such as a bisphenol A type liquid epoxy resin or a bisphenol F type liquid epoxy resin is generally used because of its excellent workability. However, the adhesives for electronic materials using these general-purpose liquid epoxy resins can no longer meet the current requirements for extremely high reliability, and new high-performance epoxy resins have been developed. The adhesive referred to in the present invention includes a pressure-sensitive adhesive.

Currently, specific performance requirements for reliability required as an adhesive for electronic materials include, for example, heat resistance, moisture resistance, cold heat cycle resistance, solder reflow resistance, etc., among which moisture resistance and solder resistance For reflowability, the cured adhesive must have a low water absorption and a small amount of water absorption. This is because if the water absorption of the cured adhesive is high, water can easily enter the bonding interface, which may reduce the adhesive strength of the interface. Moreover, when the water absorption amount of the cured adhesive is large, moisture is rapidly vaporized by the solder reflow temperature reaching 200 to 260 ° C., and the electronic component may be destroyed.

On the other hand, in order to improve the thermal cycle resistance, a large amount of an inorganic filler for reducing the linear expansion coefficient (linear expansion coefficient) is generally filled. This is because the inorganic filler has a much smaller linear expansion coefficient than the organic filler. However, when a large amount of inorganic filler is filled, the coefficient of linear expansion is reduced, but the elastic modulus of the adhesive is increased, so that there is a problem that the cured adhesive is difficult to relieve stress. That is, there is a limit to the method for improving the thermal cycle resistance by filling with an inorganic filler. Also, when the adhesive is used as an adhesive sheet processed into a sheet, the filled inorganic filler reduces the strength of the adhesive sheet before curing or is used for a substrate that requires a via hole. However, there is a problem that it is difficult to process with a laser and it is difficult to form a highly accurate via hole.

Moreover, in order to improve the thermal cycle resistance, a rubber polymer such as acrylic rubber is generally added in order to reduce the generated stress (see, for example, Patent Document 1).

However, the addition of the rubber polymer improves the thermal cycle resistance, but at the cost of lowering the thermal resistance, it achieves stress relaxation, so it has high thermal and humidity resistance and high thermal cycle resistance. It is difficult to achieve both. That is, in order to achieve a high level of cold cycle resistance, it is necessary to relieve stress generated during the cold cycle.

In order to relieve the stress, generally, epoxy resins are modified with carboxylic acid or glycidyl-modified polyolefins such as diene rubber polymers having functional groups such as CTBN and ATBN, nitrile rubber, terminal reactive group silicone, acrylic A method of mixing the flexibility imparting components such as rubber and styrene-based elastomer so as to be dissolved or phase separated is also used. However, when these flexibility-imparting components are compatible with the epoxy resin serving as the matrix resin, the heat resistance is greatly reduced, and a high heat-resistant adhesive force at high temperatures cannot be expressed. Further, even if these flexibility-imparting components have a phase separation structure, the heat resistance tends to decrease due to the slight compatibility of the interface between the flexibility-imparting component and the epoxy resin. In addition, the phase separation structure is not necessarily stable with respect to temperature changes, and may become compatible with temperature changes.

Conventionally, epoxy resin-based curable compositions often use an acid anhydride or the like as a curing agent, but unreacted materials may remain in the cured product after curing. This unreacted material reacts due to moisture absorption and becomes acidic or alkaline, so that there is a problem that an acidic substance or alkaline substance flows out on and near the surface of the cured product and causes corrosion of electrode metals such as aluminum and copper. is there. In addition, there is a problem in that a chlorine extraction reaction using an acid generated by hydrolysis or the like in the cured product as a catalyst occurs and chlorine ions flow out to impair reliability.

On the other hand, in the manufacturing process of electronic products such as liquid crystal displays, personal computers, portable communication devices, etc., when small parts such as semiconductor elements are electrically connected to a substrate, it is necessary to connect fine electrodes facing each other. is there. Further, in the process of manufacturing a glass circuit board, when providing a conductive circuit on a glass surface such as a light part of an automobile, it is necessary to connect the glass surface and the electrode surface of the conductive circuit so as to face each other.

As a method for connecting these electrodes, a method is generally used in which bumps are connected using solder, conductive connection paste, or the like, or the opposing bumps are directly pressure-bonded. Moreover, in order to protect the electrode after connection, the method of sealing the electrode after connection using resin is used.

However, since a fine electrode has a short connection distance, it is difficult to uniformly inject and seal a resin within a short time. Moreover, when connecting the glass surface and the electrode surface of a conduction circuit, there exists a problem that a connection part becomes high temperature by the connection by soldering.

Therefore, in order to solve such a problem, an anisotropic conductive adhesive formed by mixing conductive fine particles and an insulating adhesive into a sheet or paste has been studied (for example, patents). Reference 2 and Patent Document 3).

However, with the conventional sheet-like anisotropic conductive adhesive, when the electrode is sealed by pressing the conductive fine particle on the electrode or bump by thermocompression bonding, an insulating adhesive is provided between the electrode and the conductive fine particle. There is a problem that the agent remains and the connection reliability is lowered.

In addition, paste-like anisotropic conductive adhesives require good coating properties such as good coating accuracy and coating efficiency when applying paste, but are filled with a large amount of conventional inorganic fillers. Since the paste-like anisotropic conductive adhesive does not necessarily have sufficient fluidity, there is a problem that the coatability is not sufficiently satisfied. Moreover, when manufacturing an anisotropically conductive adhesive sheet by a casting method, it is calculated | required that coating property is favorable. Furthermore, since the conductive fine particles are not uniformly dispersed in the insulating adhesive, the conductive fine particles are aggregated to cause a short circuit between adjacent electrodes.

Therefore, the present inventors have previously developed a conductive connection sheet in which conductive fine particles are held on the adhesive resin sheet during handling, and part of the conductive fine particles are exposed from the adhesive resin sheet. did. This conductive connection sheet can obtain high connection reliability because no insulating adhesive remains between the electrode and the conductive fine particles and the fine particles do not aggregate (see, for example, Patent Document 4). ).

However, when the conductive connection sheet is used in, for example, a connection part of an electronic product or a light part of an automobile, the high temperature and high humidity represented by a pressure cooker test (PCT) or the like is used during the use. It was found that it was difficult to achieve both the retention of the conductive fine particles and the retention of the sheet shape when exposed to the above environment.

Specifically, in this conductive connection sheet, if the adhesiveness of the sheet before curing at room temperature to the conductive particles is increased in order to increase the holding power of the conductive particles, the sheet will remain under high temperature and high humidity even after curing. There arises a problem that the shape retention force is lowered due to softening, and the connection reliability is lowered. In addition, if the sheet shape retention strength under high temperature and high humidity is increased so that it does not soften even under high temperature and high humidity, the adhesiveness of the sheet to the conductive fine particles at normal temperature decreases. Problem occurs.

Epoxy resin-based curable compositions can also be used as insulating substrate materials, but insulating substrates used for multilayer printed circuit boards, etc. are less likely to affect electrical characteristics, have low hygroscopicity, laser In order to facilitate alignment at the surface, transparency and the like are required, and further, there is a strong demand for small dimensional changes during high temperature processing such as during solder reflow.
The epoxy resin curable composition can also be used as an insulating substrate material. Insulating substrates used for multilayer printed circuit boards, etc. have little influence on electrical characteristics, low hygroscopicity, and transparency to facilitate alignment of sheets with optical lenses. In addition, there is a strong demand for small dimensional changes during high temperature processing such as during solder reflow.
A die attach film insulating material that joins a silicon chip and a metal frame, an organic substrate such as a multilayer board, a build-up substrate, a ceramic substrate, or the like is also required to have the same performance as described above. Furthermore, as a silicon chip with a die attach film, there are a method of individually attaching to a silicon level and a wafer level where a film is directly attached at a wafer stage, but there is no difference in required performance.

Japanese Patent No. 3342703 Japanese Patent No. 3114162 Japanese Patent Publication No. 7-73066 JP 2002-313143 A

The object of the present invention is excellent in mechanical strength, heat resistance, moisture resistance, flexibility, cold heat cycle resistance, solder reflow resistance, dimensional stability, etc. An object of the present invention is to provide a curable resin composition that exhibits high conduction reliability when used as an adhesion reliability or a conduction material.

A curable resin composition according to the invention described in claim 1 (hereinafter referred to as “present invention 1”) comprises an epoxy resin, a solid polymer having a functional group that reacts with an epoxy group, and a curing agent for epoxy resin. A curable resin composition containing a polymer having an epoxy group in which a cured product is dyed with heavy metal and observed with a transmission electron microscope, a phase separation structure is not observed in the resin matrix. Is characterized by having an epoxy equivalent of 200-1000.

An adhesive epoxy resin paste according to the invention described in claim 2 (hereinafter referred to as “present invention 3”) is characterized by comprising the curable resin composition described in claim 1.

An interlayer adhesive according to the invention described in claim 3 (hereinafter referred to as “present invention 4”) is composed of the adhesive epoxy resin paste described in claim 2.

A non-conductive paste according to the invention described in claim 4 (hereinafter referred to as “present invention 5”) is characterized by comprising the adhesive epoxy resin paste described in claim 2 above.

The underfill according to the invention described in claim 5 (hereinafter referred to as “present invention 6”) is composed of the adhesive epoxy resin paste described in claim 2.

The adhesive epoxy resin sheet according to the invention described in claim 6 (hereinafter referred to as “present invention 7”) is characterized in that the curable resin composition according to claim 1 is formed into a sheet shape. .

A non-conductive film according to the invention described in claim 7 (hereinafter referred to as “present invention 8”) is composed of the adhesive epoxy resin sheet described in claim 6.

A die attach film according to the invention described in claim 8 (hereinafter referred to as “present invention 9”) is composed of the adhesive epoxy resin sheet described in claim 6.

The conductive connection paste according to the invention described in claim 9 (hereinafter referred to as “present invention 10”) is characterized in that the adhesive epoxy resin paste according to claim 2 contains conductive fine particles. .

An anisotropic conductive paste according to the invention described in claim 10 (hereinafter referred to as “present invention 11”) is characterized by comprising the conductive connection paste described in claim 2.

A conductive connection sheet according to the invention described in claim 11 (hereinafter referred to as “present invention 12”) is a conductive connection sheet comprising the adhesive epoxy resin sheet according to claim 6 and conductive fine particles, At least a part of the conductive fine particles is exposed from the adhesive epoxy resin sheet.

The conductive connection sheet according to the invention described in claim 12 (hereinafter referred to as “present invention 13”) has a conductivity smaller than the thickness of the adhesive epoxy resin sheet in the adhesive epoxy resin sheet according to claim 6. It is characterized in that fine particles are embedded.

An anisotropic conductive film according to the invention described in claim 13 (hereinafter referred to as “present invention 14”) is composed of the conductive connection sheet described in claim 12.

A flip-chip tape according to the invention described in claim 14 (hereinafter referred to as “present invention 16”) is characterized by comprising the conductive connection sheet according to claim 11 or 12.

An electronic component assembly according to the invention described in claim 15 (hereinafter referred to as “present invention 17”) is a curable resin composition according to claim 1, an adhesive epoxy resin paste according to claim 2, and a claim. The interlayer adhesive according to claim 3, the non-conductive paste according to claim 4, the underfill according to claim 5, the conductive connection paste according to claim 9, the anisotropic conductive paste according to claim 13, and the claims 7 and 8. Or an adhesive epoxy resin sheet according to claim 9, a non-conductive film according to claim 7, a die attach film according to claim 8, a conductive connection sheet according to claim 11 or 12, and an anisotropic conductive film according to claim 13. Alternatively, the bump-shaped protruding electrode of the electronic component and the other electrode are joined in a conductive state by any one of the flip-chip tapes according to claim 14.

An electronic component assembly according to the invention described in claim 16 (hereinafter referred to as “present invention 18”) is a curable resin composition according to claim 1, an adhesive epoxy resin paste according to claim 2, and an invention. The interlayer adhesive according to claim 3, the non-conductive paste according to claim 4, the underfill according to claim 5, the conductive connection paste according to claim 9, the anisotropic conductive paste according to claim 13, and the claims 7 and 8. Or an adhesive epoxy resin sheet according to claim 9, a non-conductive film according to claim 7, a die attach film according to claim 8, a conductive connection sheet according to claim 11 or 12, and an anisotropic conductive film according to claim 13. Or a group consisting of a metal lead frame, a ceramic substrate, a resin substrate, a silicon substrate, a compound semiconductor substrate, and a glass substrate according to any one of the flip chip tapes according to claim 14. At least one circuit board is selected and characterized by being joined.

The electronic component assembly according to the invention described in claim 17 is the electronic component assembly according to claim 16, wherein the resin substrate is a glass epoxy substrate, a bismaleimide triazine substrate, or a polyimide substrate.

The curable resin composition of the present invention 1 is a curable resin composition containing a solid polymer having a functional group that reacts with an epoxy group and a curing agent for an epoxy resin, and the cured product is dyed with a heavy metal, When observed with a transmission electron microscope, no phase separation structure is observed in the resin matrix.

In the curable resin composition of the present invention 1, the phase separation structure is not observed in the resin matrix of the cured product that is dyed with heavy metal and observed with a transmission electron microscope. It is known that the inside of a polymer material can be observed by using a transmission electron microscope (TEM). This is because the polymer material is stained with heavy metals such as osmium tetroxide, ruthenium tetroxide, and phosphotungstic acid. By doing this, the difference in composition in the resin material is seen as the shade of dyeing.
In the present specification, “cured product” refers to a product obtained by heating and curing the curable resin composition of the present invention under conditions such as 170 ° C. for 30 minutes.

Usually, the addition of a polymer component to an epoxy resin is performed for the purpose of imparting various functions to the resulting resin composition. For example, when the resin composition is used as a sheet material, the polymer component is increased. For example, when the resin composition is used as a paste material, the polymer component is added for the purpose of increasing the strength of the cured resin and imparting high reactivity. However, the epoxy resin and the polymer component added to the epoxy resin are not compatible unless the cured epoxy resin and the added polymer component have very close compatibility.
A resin composition having a phase separation structure by adding a polymer component to an epoxy resin is considered to have effects such as stress relaxation by the added polymer component, but the polymer component itself dissolves in the epoxy resin itself as a matrix. However, there is a limit to improving the strength of the cured product of the resin composition.

In the curable resin composition of the present invention 1, no phase separation structure is observed in the resin matrix in the observation of the cured product using the transmission electron microscope. That is, in the curable resin composition of this invention 1, it is thought that the resin component is completely compatible.
The fact that the epoxy resin and the resin added to the epoxy resin are completely compatible means that the polymer to be added has an epoxy group itself in the structure or a functional group that reacts with the epoxy group in the structure. It is essential to have

That is, the curable resin composition of the first invention contains an epoxy resin and a solid polymer having a functional group that reacts with an epoxy group.
The epoxy resin is not particularly limited, but is preferably an epoxy resin having a polycyclic hydrocarbon skeleton in the main chain. When an epoxy resin having a polycyclic hydrocarbon skeleton in the main chain is contained, the cured product is rigid and impedes molecular movement, exhibits excellent mechanical strength and heat resistance, and also absorbs water. It is because it becomes low and expresses excellent moisture resistance.

The epoxy resin having the polycyclic hydrocarbon skeleton in the main chain is not particularly limited. For example, dicyclopentadiene skeleton such as dicyclopentadiene dioxide and phenol novolac epoxy resin having dicyclopentadiene skeleton. Epoxy resin (hereinafter referred to as “dicyclopentadiene type epoxy resin”), 1-glycidylnaphthalene, 2-glycidylnaphthalene, 1,2-diglycidylnaphthalene, 1,5-diglycidylnaphthalene, 1,6-di Epoxy resins having a naphthalene skeleton such as glycidylnaphthalene, 1,7-diglycidylnaphthalene, 2,7-diglycidylnaphthalene, triglycidylnaphthalene, 1,2,5,6-tetraglycidylnaphthalene (hereinafter referred to as “naphthalene type epoxy resin”) "), Tetra Examples include droxyphenylethane type epoxy resin, tetrakis (glycidyloxyphenyl) ethane, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexane carbonate, and among others, dicyclo A pentadiene type epoxy resin or a naphthalene type epoxy resin is preferably used. These epoxy resins having a polycyclic hydrocarbon skeleton in the main chain may be used alone or in combination of two or more. Moreover, the said dicyclopentadiene type | mold epoxy resin and naphthalene type | mold epoxy resin may each be used independently, and both may be used together.

Although the epoxy resin which has the said polycyclic hydrocarbon skeleton in a principal chain is not specifically limited, The minimum with a preferable molecular weight is 500, and a preferable upper limit is 1000. If the molecular weight of the epoxy resin having a polycyclic hydrocarbon skeleton in the main chain is less than 500, the mechanical strength, heat resistance, moisture resistance, etc. of the cured product of the curable resin composition may not be sufficiently improved, Conversely, if the molecular weight of the epoxy resin having a polycyclic hydrocarbon skeleton in the main chain exceeds 1000, the cured product of the curable resin composition may become too rigid and brittle.

Although it does not specifically limit as a solid polymer which has a functional group which reacts with the said epoxy group, For example, the resin which has an amino group, a urethane group, an imide group, a hydroxyl group, a carboxyl group, an epoxy group etc. is mentioned, Especially, an epoxy group High molecular polymers having This is because, when a polymer having an epoxy group is contained, the cured product exhibits excellent flexibility. That is, the cured product of the curable resin composition of the present invention 1 has excellent mechanical strength, excellent heat resistance, excellent moisture resistance and the like derived from the epoxy resin having the polycyclic hydrocarbon skeleton in the main chain. Since it combines excellent flexibility derived from the above polymer having an epoxy group, it has excellent thermal cycle resistance, solder reflow resistance, dimensional stability, etc., and has high adhesion reliability. High conduction reliability will be developed.

The polymer having an epoxy group is not particularly limited as long as it is a polymer having an epoxy group at the terminal and / or side chain (pendant position). For example, an epoxy group-containing acrylic rubber , Epoxy group-containing butadiene rubber, bisphenol-type high molecular weight epoxy resin, epoxy group-containing phenoxy resin, epoxy group-containing acrylic resin, epoxy group-containing urethane resin, epoxy group-containing polyester resin, etc. A high molecular polymer can be obtained, and since the mechanical strength and heat resistance of the cured product of the curable resin composition of the present invention 1 are more excellent, an epoxy group-containing acrylic resin is preferably used. These polymer polymers having an epoxy group may be used alone or in combination of two or more.

The above bisphenol-type high molecular weight epoxy resin alone can contain an epoxy group only at the terminal, and the distance between cross-linking points is greatly increased, so that the mechanical strength and heat resistance of the cured product of the curable resin composition are sufficiently high. Does not improve.

In general, an acrylic resin (acrylic polymer) is often produced by a solution polymerization method using a solvent as a medium. In the solution polymerization method, when a high molecular weight acrylic resin is produced, the viscosity of the solution is increased. It is difficult to obtain a high molecular weight acrylic resin because it may rise extremely or may gel in some cases. Further, in the solution polymerization method, unreacted monomers are likely to remain, so that it is necessary to remove the residual monomers together with the solvent, and the manufacturing process becomes complicated.

For example, when glycidyl methacrylate (GMA) is used as an acrylic monomer having an epoxy group and a large amount of GMA is added to another acrylic monomer and solution polymerization is performed, a relatively low molecular weight is caused by the cohesive force of the epoxy group itself. Only an epoxy group-containing acrylic resin (less than 10,000) can be obtained, and if an attempt is made to obtain a higher molecular weight epoxy group-containing acrylic resin, the above-described extreme viscosity increase or gelation tends to occur.

On the other hand, when the production of the epoxy group-containing acrylic resin is carried out by the suspension polymerization method using water or a non-solvent as a medium, the epoxy group-containing acrylic resin containing a large amount of epoxy groups and having a high molecular weight is obtained. Obtainable. This epoxy group-containing acrylic resin is a clean resin with almost no monomer remaining, and can be easily separated from the polymerization system, thereby simplifying the production process.

That is, the high molecular polymer having an epoxy group, preferably the epoxy group-containing acrylic resin used in the curable resin composition of the present invention 1 is preferably a high molecular polymer produced by a suspension polymerization method. By using a polymer having an epoxy group produced by a suspension polymerization method, preferably an epoxy resin containing an epoxy group, the cured product of the curable resin composition of the present invention 1 has better mechanical strength and heat resistance. It expresses sex.

The polymer polymer having an epoxy group, preferably an epoxy group-containing acrylic resin, preferably has a weight average molecular weight of 10,000 or more. When the weight average molecular weight of the polymer having an epoxy group, preferably the epoxy group-containing acrylic resin is less than 10,000, the film forming property of the curable resin composition becomes insufficient, and the curable resin composition is cured. The flexibility of an object may not be sufficiently improved.

Moreover, it is preferable that the lower limit of the epoxy equivalent of the high molecular polymer having an epoxy group, preferably an epoxy group-containing acrylic resin, is 200 and the upper limit is 1000. When the epoxy equivalent of the high molecular polymer having an epoxy group, preferably the epoxy group-containing acrylic resin is less than 200, the flexibility of the cured product of the curable resin composition may not be sufficiently improved. When the epoxy equivalent of the high molecular polymer having an epoxy group, preferably the epoxy group-containing acrylic resin exceeds 1000, the mechanical strength and heat resistance of the cured product of the curable resin composition may be insufficient.

In the curable resin composition of the present invention 1, it is preferable that the tan δ peak in the viscoelastic spectrum measurement of the cured product is single and the temperature of the peak is 120 ° C. or higher.
As described above, it can be confirmed by observation using a transmission electron microscope (TEM) that the resin matrix of the resin composition in which the polymer component is added to the epoxy resin has a phase separation structure. It can be easily known that phase separation takes place by measuring the viscoelastic spectrum of the cured product.
That is, the viscoelastic tan δ does not show a single peak when the cured resin matrix has a phase separation structure. For example, when the phase structure has two layers, two peaks appear and the phase structure is In the case of three layers, three peaks appear.
In the present specification, the “tan δ peak” refers to a peak that particularly protrudes compared to other portions.
If the tan δ peak temperature is less than 120 ° C., resin softening occurs around the temperature range (120 ° C.) used in the conventional reliability test. As a result, moisture permeation and cooling cycle test It may cause peeling of the interface at the time.

It is preferable that the cured product of the curable resin composition of the present invention 1 does not swell much in a dimethyl sulfoxide (DMSO) solution heated to 120 ° C. Specifically, the cured product preferably has a swelling ratio measured within a dimethyl sulfoxide (DMSO) solution heated to 120 ° C. within 50%. That the swelling rate exceeds 50% means that crosslinking at this temperature is loose, and water molecules and oxygen molecules are very easily transmitted. Therefore, when the swelling rate exceeds 50%, the reliability of the curable resin composition of the present invention 1 as an adhesive may be lowered.

As described above, since the curable resin composition of the present invention 1 does not have a phase separation structure in the resin matrix of the cured product, the swelling rate measured in a dimethyl sulfoxide (DMSO) solution heated to 120 ° C. is 50%. Within. For example, in the case of a resin composition comprising an epoxy resin and a polymer component that is phase-separated from the epoxy resin, the phase structure of the cured product is composed of an epoxy cross-linked phase (epoxy resin phase) and a polymer phase. However, the epoxy cross-linked phase can easily have a glass transition temperature (Tg) of 120 ° C. or higher and does not swell, but the polymer phase has so much even if it has a cross-linking group in its structure. Therefore, by having a relatively loose cross-linked structure, when the degree of swelling near 120 ° C. is seen, large swelling is exhibited.

In the curable resin composition of the present invention 1, the epoxy resin is an epoxy resin having the polycyclic hydrocarbon skeleton in the main chain, and the solid polymer having a functional group that reacts with the epoxy group is the epoxy group. It is preferable that it is a high molecular polymer which has and does not contain an inorganic filler.
Usually, in order to improve the reliability of an adhesive for electronic materials, a large amount of an inorganic filler has been essential. It is well known that the addition of this inorganic filler improves water absorption and elastic modulus and improves moisture resistance, etc., but the inorganic filler particles are intercalated between the electrodes during pressure welding between the electrodes. In particular, when bonding between narrow gap electrodes, adhesion failure may occur due to the presence of the inorganic filler.
The inorganic filler is often used as spherical silica. The spherical silica basically has a particle size distribution and may have very coarse particles as a probability. In particular, when a large amount of inorganic filler (spherical silica) is added, the probability that very coarse particles are included becomes very high, and the above-mentioned disadvantages are likely to occur.
In view of these things, it is preferable that the curable resin composition of the present invention 1 does not contain an inorganic filler.

For example, if the inorganic filler has a very uniform particle size distribution and the maximum particle size is very small, the above-described disadvantages hardly occur. Therefore, if it is such an inorganic filler, it may be added to the curable resin composition of this invention 1. Specifically, it is preferable that the maximum particle size of the inorganic filler is 3 μm or less, and the addition amount when the total resin is 100 parts by weight is 30 parts by weight or less.

When an inorganic filler having a maximum particle size exceeding 3 μm is contained, the above-described disadvantages are likely to occur, and when the curable resin composition of the present invention 1 is used for a substrate requiring a via hole, during laser processing. The roundness of the through-holes may be reduced, and the smoothness of the processed surface of the via holes may be lost due to the inorganic filler.

The inorganic filler not containing coarse particles having a maximum particle size of 3 μm or less is not particularly limited, and examples thereof include silica such as fumed silica and colloidal silica, glass fibers, and alumina fine particles. Silica is preferably used, and in particular, hydrophobic silica whose surface has been subjected to a hydrophobic treatment is more preferably used. These inorganic fillers may be used alone or in combination of two or more. In addition, in the curable resin composition of this invention 1, if the maximum particle diameter is 3 micrometers or less, the organic filler which consists of a low molecular-weight fine particle organic substance may contain.

When the curable resin composition of the present invention 1 contains an inorganic filler having a maximum particle size of 3 μm or less, an epoxy resin having the polycyclic hydrocarbon skeleton in the main chain, and a polymer having the epoxy group, When it exceeds 30 parts by weight with respect to 100 parts by weight of the total amount, when the curable resin composition of the present invention 1 is used for a substrate requiring a via hole, the roundness of the through hole during laser processing decreases. The inorganic filler may lose the smoothness of the processed surface of the via hole, or the viscosity of the curable resin composition may become too high, thereby impairing the coatability.

In the curable resin composition of the present invention 1, a low elastic modulus material having an elastic modulus (G ′) at 20 ° C. of 1 × 10 ⁵ to 1 × 10 ⁸ Pa in the curable resin composition is incompatible with the island shape. It is preferable to be dispersed in

In the curable resin composition, the low elastic modulus material having an elastic modulus (G ′) at 20 ° C. of 1 × 10 ⁵ to 1 × 10 ⁸ Pa is incompatible and dispersed in an island shape. The cured product of the curable resin composition is formed with a sea-island structure and has both excellent mechanical strength and heat resistance, and excellent flexibility, that is, exhibits superior toughness. Will be.

When the elastic modulus (G ′) at 20 ° C. of the low modulus material is less than 1 × 10 ⁵ Pa, the mechanical strength and heat resistance of the cured product of the curable resin composition may not be sufficiently improved, On the other hand, when the elastic modulus (G ′) at 20 ° C. of the low elastic modulus substance exceeds 1 × 10 ⁸ Pa, the flexibility of the cured product of the curable resin composition may not be sufficiently improved. In addition, when the low elastic modulus material is compatible with the curable resin composition, a sea-island structure is not formed in the cured product of the curable resin composition, and thus the above effect may not be sufficiently obtained. .

The low elastic modulus material is any material as long as the lower limit of the elastic modulus (G ′) at 20 ° C. is 1 × 10 ⁵ Pa and the upper limit is 1 × 10 ⁸ Pa and is incompatible with the curable resin composition. Although it may be a substance and is not particularly limited, examples thereof include various thermoplastic resins, various thermosetting resins, various rubbers (various elastomers) and the like. These low elastic modulus substances may be used alone or in combination of two or more.

The curable resin composition of the present invention 2 has an epoxy resin composition in which a dicyclopentadiene type epoxy resin, a naphthalene type epoxy resin, and a curing agent for epoxy resin are mixed, and the glass transition temperature of the core is 20 ° C. And core-shell rubber particles having a shell glass transition temperature of 40 ° C. or higher.

The dicyclopentadiene type epoxy resin contained in the epoxy resin composition is an epoxy resin composed of a dicyclopentadiene skeleton having an epoxy group, and this dicyclopentadiene type epoxy resin is rich in hydrophobicity. When the dicyclopentadiene type epoxy resin is contained in the epoxy resin composition, the curable resin composition of the present invention 2 is hydrophobized, and the cured product has a low water absorption rate, and is representative of the pressure cooker test and the like. It exhibits high hydrophobicity even in a high temperature and high humidity environment.

The dicyclopentadiene type epoxy resin preferably has a low degree of polymerization and / or a softening point. By using such a dicyclopentadiene type epoxy resin, when the curable resin composition of the present invention 2 is used as, for example, an adhesive epoxy resin paste, the fluidity of the paste can be improved. When the curable resin composition 2 is used as, for example, an adhesive epoxy resin sheet, it is possible to impart moderate flexibility to the uncured sheet and to make it difficult to break.

Although it does not specifically limit as said dicyclopentadiene type epoxy resin, For example, the phenol novolak epoxy resin etc. which have dicyclopentadiene dioxide and dicyclopentadiene frame | skeleton are mentioned. These dicyclopentadiene type epoxy resins may be used alone or in combination of two or more.

The naphthalene type epoxy resin contained in the epoxy resin composition is an epoxy resin having a naphthalene skeleton having an epoxy group. In the second aspect of the present invention, a naphthalene type epoxy resin that is liquid at room temperature is preferably used. It is done. Since the naphthalene type epoxy resin has a rigid naphthalene skeleton, when the curable resin composition of the present invention 2 is used as, for example, an adhesive epoxy resin sheet, the cured sheet maintains a high shape even under high temperature and high humidity. Properties can be obtained, and high moisture-resistant adhesiveness can be expressed.

When the curable resin composition of the present invention 2 is used as, for example, an adhesive epoxy resin paste, the naphthalene type epoxy resin preferably has a lower viscosity. Moreover, also when using the curable resin composition of this invention 2 as an adhesive epoxy resin sheet, since the said naphthalene type epoxy resin contains an isomer normally, since melting | fusing point is below normal temperature, it is normal temperature. The flexibility of the sheet can be improved, the sheet before curing can be made difficult to break, and the curing rate can be increased.

Although it does not specifically limit as said naphthalene type epoxy resin liquid at the normal temperature, For example, 1-glycidyl naphthalene, 2-glycidyl naphthalene, 1,2- diglycidyl naphthalene, 1,5-diglycidyl naphthalene, 1 , 6-diglycidylnaphthalene, 1,7-diglycidylnaphthalene, 2,7-diglycidylnaphthalene, triglycidylnaphthalene, 1,2,5,6-tetraglycidylnaphthalene and the like. These naphthalene type epoxy resins may be used alone or in combination of two or more.

The number of epoxy groups contained in the above dicyclopentadiene type epoxy resin and naphthalene type epoxy resin is not particularly limited, but is preferably an average of 1 or more per molecule, more preferably per molecule. The average is 2 or more. Here, the number of epoxy groups per molecule is the total number of epoxy groups in the dicyclopentadiene type epoxy resin or the total number of epoxy groups in the naphthalene type epoxy resin, or the total number of molecules of the dicyclopentadiene type epoxy resin or the naphthalene type. It can be obtained by dividing by the total number of molecules of epoxy resin.

In the said epoxy resin composition, epoxy resins other than a dicyclopentadiene type epoxy resin and a naphthalene type epoxy resin and an epoxy group containing compound may contain as needed.

The curable resin compositions of the present invention 1 and the present invention 2 include the epoxy group in the epoxy resin having the polycyclic hydrocarbon skeleton in the main chain, the epoxy group in the polymer polymer having the epoxy group, and the epoxy It acts on the epoxy group in the dicyclopentadiene type epoxy resin contained in the resin composition or the epoxy group in the naphthalene type epoxy resin to have an epoxy resin or an epoxy group having a polycyclic hydrocarbon skeleton in the main chain. It contains a polymer, a curing agent for epoxy resin for curing a dicyclopentadiene-type epoxy resin or a naphthalene-type epoxy resin (hereinafter sometimes simply referred to as “curing agent”).

Since the epoxy resin composition in the curable resin composition of the present invention 1 and the curable resin composition of the present invention 2 contains the above-mentioned curing agent for epoxy resin, the epoxy resin having a polycyclic hydrocarbon skeleton in the main chain Or a polymer having an epoxy group, a dicyclopentadiene-type epoxy resin or a naphthalene-type epoxy resin is preferably hardened and rapidly cured under heating, and is a cured product of the curable resin composition of the present invention 1 and the present invention 2. Is excellent in mechanical strength, heat resistance, moisture resistance, flexibility, thermal cycle resistance, solder reflow resistance, dimensional stability, etc., and exhibits high adhesion reliability and high conduction reliability when used as a conductive material To be.

The curing agent for epoxy resin is not particularly limited. For example, heat curing type acid anhydride curing agent such as trialkyltetrahydrophthalic anhydride, phenol curing agent, amine curing agent, dicyandiamide and the like. Latent curing agents, cationic catalyst-type curing agents, and the like. These epoxy resin curing agents may be used alone or in combination of two or more.

Among the above curing agents for epoxy resins, a thermosetting curing agent that is liquid at normal temperature, or a latent curing agent such as dicyandiamide, which is multifunctional and may be added in a small amount equivalently, is preferably used. By using such a curing agent, for example, when an adhesive epoxy resin sheet is produced using the curable resin composition of the present invention 1 and the present invention 2, it is flexible at room temperature and has a handling property before curing. A good sheet can be obtained. In contrast, a phenolic curing agent that is solid at room temperature and has an equivalent amount added increases the glass transition temperature (Tg) before curing of the sheet itself, and handling that causes cracks in the initial stage. It is not preferable because it tends to be a sheet having poor properties.

Typical examples of the thermosetting curing agent that is liquid at room temperature include acid anhydrides such as methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, and trialkyltetrahydrophthalic anhydride. Examples thereof include a system curing agent. Among them, methylnadic acid anhydride and trialkyltetrahydrophthalic anhydride are preferably used because they are hydrophobized. On the other hand, methyltetrahydrophthalic anhydride and methylhexahydrophthalic anhydride are less preferred because they have poor water resistance. These acid anhydride curing agents may be used alone or in combination of two or more.

In the curable resin compositions of the present invention 1 and the present invention 2, a curing accelerator may be used in combination with the epoxy resin curing agent in order to adjust the curing speed, the physical properties of the cured product, and the like.

Although it does not specifically limit as said hardening accelerator, For example, an imidazole series hardening accelerator, a tertiary amine type hardening accelerator, etc. are mentioned, Especially, adjustment of the physical property of a hardening rate, hardened | cured material, etc. is mentioned. Therefore, an imidazole curing accelerator is preferably used because it is easy to control the reaction system. These curing accelerators may be used alone or in combination of two or more.

The imidazole curing accelerator is not particularly limited. For example, 1-cyanoethyl-2-phenylimidazole in which the 1-position of imidazole is protected with a cyanoethyl group, or a product name in which basicity is protected with isocyanuric acid. “2MA-0K” (manufactured by Shikoku Kasei Kogyo Co., Ltd.) and the like. These imidazole type hardening accelerators may be used independently and 2 or more types may be used together.

When using an acid anhydride curing agent in combination with a curing accelerator such as an imidazole curing accelerator, the addition amount of the acid anhydride curing agent should be less than or equal to the theoretically required equivalent to the epoxy group. Is preferred. If the addition amount of the acid anhydride curing agent is excessive more than necessary, chlorine ions may be easily eluted by moisture from the cured products of the curable resin compositions of the present invention 1 and the present invention 2. For example, when the elution component is extracted from the cured product of the curable resin composition of the present invention 1 and the present invention 2 with hot water, the pH of the extracted water is lowered to about 4 to 5, and the chlorine extracted from the epoxy resin A large amount of ions may be eluted.

Also, when an amine curing agent and a curing accelerator such as an imidazole curing accelerator are used in combination, the addition amount of the amine curing agent is preferably equal to or less than the theoretically required equivalent to the epoxy group. . If the addition amount of the amine-based curing agent is excessive more than necessary, chlorine ions may be easily eluted by moisture from the cured products of the curable resin compositions of the present invention 1 and the present invention 2. For example, when the elution components are extracted with hot water from the cured products of the curable resin compositions of the present invention 1 and the present invention 2, the pH of the extracted water becomes basic, and a large amount of chlorine ions are extracted from the epoxy resin. May elute.

In the epoxy resin composition described above, the curable resin composition of the present invention 2 has a glass transition temperature of the core (core material) of 20 ° C. or lower and a glass transition temperature of the shell (outer shell) of 40 ° C. or higher. It contains rubber particles having a certain core-shell structure. By containing such rubber particles, the cured product of the curable resin composition of the present invention 2 can form a stable phase separation structure of the rubber component with respect to the epoxy resin that is the matrix resin, It is flexible and exhibits excellent stress relaxation properties.

The rubber particles have a core-shell structure including a core having a glass transition temperature of 20 ° C. or lower and a shell having a glass transition temperature of 40 ° C. or higher. The rubber particles may be core-shell structured particles composed of two or more layers, and in the case of core-shell structured particles composed of three or more layers, the shell means the outermost shell.

When the glass transition temperature of the core of the rubber particles exceeds 20 ° C., the stress relaxation property of the cured product of the curable resin composition of the present invention 2 is not sufficiently improved. Further, when the glass transition temperature of the shell of the rubber particles is less than 40 ° C., the rubber particles are fused (aggregated) or poor dispersion occurs in the epoxy resin composition. The shell of the rubber particles is preferably incompatible with the epoxy resin, or gelled by some crosslinking and not dissolved in the epoxy resin.

The resin component constituting such rubber particles may be any resin component as long as the glass transition temperature of the core can be 20 ° C. or lower and the glass transition temperature of the shell can be 40 ° C. or higher, and is particularly limited. Although not intended, an allyl resin is usually preferably used because of the wide design range of the glass transition temperature. These resin components may be used alone or in combination of two or more.

Moreover, the shell of the rubber particles may have a functional group that reacts with an epoxy group in the epoxy resin. The functional group that reacts with the epoxy group is not particularly limited, and examples thereof include an amino group, a urethane group, an imide group, a hydroxyl group, a carboxyl group, and an epoxy group. A hydroxyl group or an epoxy group is preferably used because it does not react and does not cause a decrease in wettability or storage stability of the curable resin composition of the present invention 2. These functional groups that react with the epoxy group may be used alone or in combination of two or more.

Although the said rubber particle is not specifically limited, It is preferable that an average particle diameter is 30 micrometers or less. When the average particle diameter of the rubber particles exceeds 30 μm, the stress relaxation property of the cured product of the curable resin composition of the present invention 2 may not be sufficiently improved. Further, when the curable resin composition of the present invention 2 is used as, for example, an adhesive epoxy resin paste, the fluidity becomes insufficient, and the coating property and the filling property to the gap may be hindered. When using the curable resin composition of the present invention 2 as, for example, an adhesive epoxy resin sheet, it may be difficult to form a thin film sheet.

Commercially available products of such rubber particles are not particularly limited. For example, trade names “Paracron RP-101”, “Paracron RP-103”, “Paracron RP-412” manufactured by Negami Kogyo Co., Ltd., etc. "Paracron" series, trade names "Staffyroid IM-101", "Stuffyroid IM-203", "Stuffyroid IM-301", "Stuffyroid IM-401", "Stuffyroid IM-" manufactured by Ganz Kasei "Stuffoid" series such as "601", "Stuffyroid AC-3355", "Stuffyroid AC-3364", "Stuffyroid AC-3816", "Stuffyroid AC-3732", "Stuffyroid AC-4030", “Zeon” series, such as “Zeon F351”, manufactured by Zeon Kasei Co., Ltd., manufactured by Mitsubishi Rayon Co., Ltd. Product names “methabrene C-140A”, “methabrene C-201A”, “methabrene C-215A”, “methabrene C-223A”, “methabrene C-303A”, “methabrene C-323A”, “methabrene C-102” , “Methabrene C-132”, “methabrene C-202”, “methabrene E-901”, “methabrene W-341”, “methabrene W-300A”, “methabrene W-450A”, “methabrene S-2001”, “Metabrene” series such as “Metabrene SX-005”, “Metabrene SX-006”, “Metabrene SRK200” and the like. In addition, the commercial product of the epoxy resin in which rubber particles are dispersed in advance is not particularly limited. For example, trade names “Eposet BPA-828”, “Eposet BPF-807” manufactured by Nippon Shokubai Co., Ltd. “Eposet” series and so on. These rubber particles and epoxy resin in which rubber particles are dispersed in advance may be used alone or in combination of two or more.

The curable resin composition of the present invention 2 may contain a thermoplastic resin or a thermosetting resin as necessary.

The thermoplastic resin is not particularly limited, but examples thereof include vinyl acetate resins, ethylene-vinyl acetate copolymers, acrylic resins, polyvinyl acetal resins such as polyvinyl butyral resins, styrene resins, Examples thereof include saturated polyester resins, thermoplastic urethane resins, polyamide resins, thermoplastic polyimide resins, ketone resins, norbornene resins, and styrene-butadiene block copolymers. These thermoplastic resins may be used alone or in combination of two or more.

The thermosetting resin is not particularly limited, and examples thereof include amino resins such as urea resins and melamine resins, phenol resins, unsaturated polyester resins, thermosetting urethane resins, and pentadiene type resins. Examples include epoxy resins other than epoxy resins and naphthalene type epoxy resins, thermosetting polyimide resins, aminoalkyd resins, and the like. These thermosetting resins may be used alone or in combination of two or more. Moreover, the said thermoplastic resin and thermosetting resin may be used independently, respectively, and both may be used together.

When the curable resin composition of the present invention 2 is used as, for example, a paste-like adhesive epoxy resin paste, the thermoplastic resin or thermosetting resin functions as a thickener. At this time, the weight average molecular weight of the thermoplastic resin or thermosetting resin is not particularly limited as long as the viscosity of the paste does not become extremely high. Further, if necessary, a solvent may be added to adjust the viscosity of the paste.

When the curable resin composition of the present invention 2 is used as, for example, an adhesive epoxy resin sheet formed into a sheet shape on a separator (release sheet or release paper), the above thermoplastic resin is used to ensure a good sheet shape. The thermosetting resin is preferably a high molecular weight polymer having a relatively high glass transition temperature. At this time, the thermoplastic resin and the thermosetting resin are not particularly limited, but the weight average molecular weight is preferably 10,000 or more, more preferably 100,000 or more. If the weight average molecular weight of the thermoplastic resin or thermosetting resin is less than 10,000, the cohesive strength of the sheet itself is insufficient, and it is easy to repel the coated material such as adhesive or paint applied on the sheet. When peeling the separator, the sheet itself may cause cohesive failure.

The thermoplastic resin and thermosetting resin preferably have a functional group that reacts with an epoxy group. When the thermoplastic resin or the thermosetting resin has a functional group that reacts with an epoxy group, the cured product of the curable resin composition of the present invention 2 exhibits more excellent mechanical strength and heat resistance. It will be a thing.

Although it does not specifically limit as a functional group which reacts with the said epoxy group, For example, an amino group, a urethane group, an imide group, a hydroxyl group, a carboxyl group, an epoxy group etc. are mentioned. These functional groups that react with the epoxy group may be used alone or in combination of two or more.

When the curable resin composition of the present invention 2 is used as an adhesive epoxy resin paste whose viscosity is adjusted with a solvent, or used as an adhesive epoxy resin sheet molded by a solvent casting method, the functional group reacting with the epoxy group Especially, it is preferable to use the hydroxyl group and epoxy group which do not react with an epoxy group at the temperature of about 110 degreeC for drying a solvent, and react with an epoxy group at the temperature of about 150-230 degreeC. Although it does not specifically limit as resin which has a hydroxyl group or an epoxy group, For example, a polyvinyl butyral resin, an epoxy-group-containing acrylic resin, etc. are mentioned.

When an amino group, a carboxyl group, or the like is used as a functional group that reacts with an epoxy group, the curable resin composition of the present invention 2 can be used as an adhesive epoxy resin paste whose viscosity is adjusted with a solvent, or can be formed by a solvent casting method. When used as an epoxy resin sheet, because it reacts with an epoxy group at a temperature of about 110 ° C. for drying the solvent, the paste or sheet becomes a semi-cured state (B stage state) during drying or molding, The coating property of the paste may be hindered, and the adhesion of the paste or sheet to the adherend or the moisture-resistant adhesion may be reduced.

Moreover, the equivalent of the functional group that reacts with the epoxy group of one thermoplastic resin or thermosetting resin is not particularly limited, but is preferably 10,000 or less, more preferably 1000 or less. . By using a thermoplastic resin or a thermosetting resin having a functional group that reacts with an equivalent amount of an epoxy group, the cured product of the curable resin composition of the present invention 2 forms a network with a high crosslinking density. Can do. In addition, the equivalent of the functional group that reacts with the epoxy group is the total number of functional groups that react with the epoxy group present in one thermoplastic resin or thermosetting resin, based on the weight average molecular weight of the thermoplastic resin or thermosetting resin. The value divided by.

In the curable resin composition of the present invention 1, if necessary, the glass transition temperature of the core contained in the curable resin composition of the present invention 2 is 20 ° C. or less, and the glass transition temperature of the shell is 40. The core-shell structure rubber particles having a temperature of not lower than ° C. and the thermoplastic resin and thermosetting resin which may be contained in the curable resin composition of the present invention 2 may be contained.

The curable resin composition of the present invention 2 may contain a polymer polymer having the epoxy group contained in the curable resin composition of the present invention 1 as necessary. Moreover, it is preferable that the curable resin composition of this invention 2 does not contain the filler whose average particle diameter exceeds 3 micrometers.

In the curable resin compositions of the present invention 1 and the present invention 2, as necessary, for example, an adhesion improver, a pH adjuster, an ion scavenger, a viscosity adjuster, a thixotropic agent, an antioxidant, a heat Even if one kind or two or more kinds of various additives such as a stabilizer, a light stabilizer, an ultraviolet absorber, a colorant, a dehydrating agent, a flame retardant, an antistatic agent, an antifungal agent, an antiseptic and a solvent are added. good.

Although it does not specifically limit as said adhesive improvement agent, For example, a silane coupling agent, a titanium coupling agent, an aluminum coupling agent etc. are mentioned, Especially, a silane coupling agent is used suitably. . These adhesion improvers may be used independently and 2 or more types may be used together.

Although it does not specifically limit as said silane coupling agent, For example, an aminosilane coupling agent, an epoxy silane coupling agent, a ureido silane coupling agent, an isocyanate silane coupling agent, a vinyl silane coupling agent, an acrylic silane cup Examples thereof include a ring agent and a ketimine silane coupling agent. Among these, an aminosilane coupling agent is preferably used from the viewpoint of curing speed and affinity with an epoxy resin. These silane coupling agents may be used alone or in combination of two or more.

Although the addition amount of the said adhesive improvement agent is not specifically limited, It is 20 parts weight or less of adhesive improvement agent with respect to 100 weight part of curable resin compositions of this invention 1 or this invention 2. preferable. When the addition amount of the adhesion improver with respect to 100 parts by weight of the curable resin composition of the present invention 1 or 2 exceeds 20 parts by weight, when the curable resin composition is used as an adhesive epoxy resin sheet, for example, before curing. The strength and cohesive strength of the sheet may become too weak.

Although it does not specifically limit as said pH adjuster, For example, alkaline fillers, such as acidic fillers, such as a silica, and calcium carbonate, etc. are mentioned. These pH adjusters may be used alone or in combination of two or more.

The ion scavenger is not particularly limited as long as it can reduce the amount of ionic impurities. For example, aluminosilicate, hydrous titanium oxide, hydrous bismuth oxide, zirconium phosphate, phosphorus Examples include titanium oxide, hydrotalcite, ammonium molybdophosphate, hexacyanozinc, organic ion exchange resin, and the product name "IXE" series manufactured by Toa Gosei Co., Ltd., which is commercially available as an ion scavenger with excellent properties at high temperatures. It is done. These ion scavengers may be used alone or in combination of two or more.

The addition amount of the ion scavenger is not particularly limited, but is preferably 10 parts by weight or less with respect to 100 parts by weight of the curable resin composition of the present invention 1 or the present invention 2. When the addition amount of the ion scavenger with respect to 100 parts by weight of the curable resin composition of the present invention 1 or 2 exceeds 10 parts by weight, the curing rate of the curable resin composition may be extremely slow.

The manufacturing method of the curable resin composition of this invention 1 and this invention 2 is not specifically limited, For example, a homodisper, a universal mixer, a Banbury mixer, a kneader, 2 rolls, 3 rolls, an extruder, etc. These known kneaders are used alone or in combination, and each predetermined amount of each essential component, each predetermined amount of various components that may be contained, and one type of various additives that may be added Alternatively, a desired curable resin composition is obtained by uniformly kneading two or more predetermined amounts under normal temperature, under heating, under normal pressure, under reduced pressure, under pressure, or under an inert gas stream. Can be manufactured. In addition, when the curing agent for epoxy resin is a heat curing type curing agent or a latent curing agent, the above production method may be used, but when the curing agent for epoxy resin is a room temperature curing type curing agent, The addition is preferably performed immediately before use of the curable resin composition or the final product using the same.

The curable resin compositions of the present invention 1 and the present invention 2 thus obtained have a pH of 5.0 to 8 when the elution component of the cured product of the curable resin composition is extracted with hot water at 110 ° C. Is preferably less than .5.

When the elution component of the cured product of the curable resin composition of the present invention 1 and the present invention 2 is extracted with hot water at 110 ° C., the pH of the extracted water is less than 5.0, or 8.5 or more In addition, acidic and alkaline substances may flow out on and near the surface of the cured product, causing corrosion of electrode metals such as aluminum and copper, and chlorine extraction reaction using acid generated by hydrolysis in the cured product as a catalyst. Chloride ions may flow out and reliability may be impaired.

It is preferable that the electric conductivity of the extracted water when the eluted component of the cured product of the curable resin composition of the present invention 1 or 2 is extracted with hot water at 110 ° C. is 100 μS / cm or less. Exceeding 100 μS / cm means that the conductivity in the resin increases particularly when placed under wet conditions, and the conductive connection is made using the curable resin composition of the present invention 1 and the present invention 2. If performed, leakage between electrodes or dielectric breakdown may occur.

Moreover, it is preferable that the dielectric constant of the hardened | cured material of the curable resin composition of this invention 1 and this invention 2 is 3.5 or less, and a dielectric loss tangent is 0.02 or less. If the dielectric constant exceeds 3.5 and the dielectric loss tangent exceeds 0.02, current transmission characteristics at high frequencies may be deteriorated.

Although the use of the curable resin composition of the present invention 1 and the present invention 2 is not particularly limited, for example, it is processed into an adhesive epoxy resin paste, an adhesive epoxy resin sheet, a conductive connection paste, a conductive connection sheet, etc. And is suitably used for fixing electronic materials. Alternatively, the curable resin composition may be finished in a varnish shape, and formed into a thin film on a silicone wafer or the like by an application method such as spin coating, and used as an adhesive.

A flux agent may be added to the curable resin compositions of the present invention 1 and the present invention 2. The flux agent is preferably a deactivating flux agent. Since the curable resin composition does not contain a filler having a large average particle size, it can be used substantially as a non-filler paste or non-filler sheet, and the cured product is also designed to have a neutral pH range. Therefore, it is suitable as a flux agent-containing paste or a flux agent-containing sheet for conductive connection.

If the curable resin composition of this invention 1 and this invention 2 is a pellet form, sealing, such as the sealing agent for semiconductor packages, the sealing agent for QFN, the sealing agent for integral-molding type | mold CSP, etc., for example. It can be used as an agent. Further, if the curable resin composition is substantially a non-filler paste, it is directly applied and cured on a wafer with a metal post for rewiring and external electrical connection by screen printing or spin coating. The rewiring circuit can be sealed on the wafer by polishing. Furthermore, it can also be used as an overcoat agent on the wafer by coating directly on the wafer by screen printing.

Moreover, the curable resin composition of this invention 1 and this invention 2 can be used as an adhesive sheet for semiconductor chip fixation, if it shape | molds in a sheet form.

The adhesive epoxy resin paste of the present invention 3 comprises the curable resin composition of the present invention 1 or the present invention 2. Since the curable resin compositions of the present invention 1 and the present invention 2 inherently have adhesiveness, they can be easily used as the adhesive epoxy resin paste of the present invention 3. The adhesive epoxy resin paste of the present invention 3 is curable by using a viscosity modifier, a thixotropic agent, etc. as necessary when producing the curable resin composition of the present invention 1 or the present invention 2. It can be easily obtained by finishing the resin composition into a paste.

The interlayer adhesive of the present invention 4, the nonconductive paste of the present invention 5 and the underfill of the present invention 6 are composed of the adhesive epoxy resin paste of the present invention 3.

The adhesive epoxy resin sheet of the present invention 7 is formed by molding the curable resin composition of the present invention 1 or the present invention 2 into a sheet shape.

The method for molding the curable resin composition of the present invention 1 or 2 into a sheet is not particularly limited. For example, an extrusion molding method using an extruder, and the curable resin composition is diluted with a solvent. To prepare a curable resin composition solution, cast this solution on a separator, and then dry the solvent, and the like is a solution casting method. Among them, a high temperature is not required, so the solution casting method is preferable. Used for.

The adhesive epoxy resin sheet of the present invention 7 preferably has a storage elastic modulus (G ′) exceeding 1 × 10 ³ Pa when the adhesive epoxy resin sheet is heated at a temperature rising rate of 45 ° C./min. When the storage elastic modulus (G ′) of the adhesive epoxy resin sheet is 1 × 10 ³ Pa or less, voids are formed at the adhesive interface between the adhesive epoxy resin sheet and the adherend when the adhesive epoxy resin sheet is heated and cured. May occur.

In the adhesive epoxy resin sheet of the present invention 7, the peak temperature of tan δ based on dynamic viscoelasticity is in the range of −20 ° C. to 40 ° C. before curing, and preferably 120 ° C. or more after curing. Preferably, it is in the range of 0 to 35 ° C. before curing, and is 160 ° C. or more after curing. Here, tan δ is a value represented by a dynamic loss tangent obtained by dynamic viscoelasticity measurement (measurement frequency: 10 Hz, temperature increase rate: 3 ° C./min). Here, “before curing” means a state before the adhesive epoxy resin sheet is thermally cured by being heated to a predetermined temperature or more, and “after curing” is after the adhesive epoxy resin sheet is thermally cured. Say the state. In addition, generally the adhesive epoxy resin sheet of this invention 4 is thermosetted in the temperature range of 20-230 degreeC.

By having such a peak temperature of tan δ, the adhesive epoxy resin sheet of the present invention 7 is flexible in the normal temperature region, has excellent handleability, and has adhesiveness at normal temperature. Without adhering, adherends can be bonded together in a normal temperature region, and high adhesion reliability can be expressed by heat curing (post-curing) in a thermal oven or the like. That is, the adhesive epoxy resin sheet of the present invention 7 has adhesiveness at room temperature before curing, and exhibits excellent physical properties after curing by heating. In addition to being able to be temporarily fixed, it is possible to express excellent physical properties such as adhesive strength by heating later, and to exhibit sufficient adhesive reliability as an adhesive sheet.

When the peak temperature of tan δ before curing of the adhesive epoxy resin sheet is less than −20 ° C., the cohesive force of the adhesive epoxy resin sheet becomes insufficient, and thus it is difficult to peel off from the separator. In addition, when a conductive connection sheet is prepared by incorporating conductive fine particles, which will be described later, into the adhesive epoxy resin sheet, the epoxy resin flows into the through holes provided for arranging the conductive fine particles, and the through holes are buried. It may end up. On the contrary, when the peak temperature of tan δ before curing of the adhesive epoxy resin sheet exceeds 40 ° C., the conductive epoxy resin sheet contains conductive fine particles to produce a conductive connection sheet. Insufficient adhesion to conductive fine particles may make it difficult to hold conductive fine particles.

In addition, when the peak temperature of tan δ after curing of the adhesive epoxy resin sheet is less than 120 ° C., the cured adhesive epoxy resin sheet is softened in a high temperature and high humidity environment typified by a pressure cooker test. Adhesion reliability may be reduced.

In the adhesive epoxy resin sheet of the present invention 7, the preferable lower limit of the linear expansion coefficient after curing is 10 ppm / ° C, the preferable upper limit is 200 ppm / ° C, the more preferable lower limit is 20 ppm / ° C, and the more preferable upper limit is 150 ppm / ° C. Yes, a more preferred lower limit is 30 ppm / ° C, and a more preferred upper limit is 100 ppm / ° C.

When the linear expansion coefficient after curing of the adhesive epoxy resin sheet is less than 10 ppm / ° C., when the conductive connection sheet is produced by containing conductive fine particles in the adhesive epoxy resin sheet, the adhesive epoxy resin sheet and When the difference in linear expansion from the conductive fine particles becomes large and the conductive connection sheet is subjected to a thermal cycle, it is difficult to follow the linear expansion of the conductive fine particles, and it is difficult to maintain high conduction reliability. Conversely, when the linear expansion coefficient after curing of the adhesive epoxy resin sheet exceeds 200 ppm / ° C., when the conductive epoxy resin sheet is made to contain conductive fine particles, a conductive connection sheet is produced. When a heat cycle or the like is applied, the gap between the electrodes facing each other may spread too much, and the conductive fine particles may be separated from the electrodes, causing a conduction failure.

The nonconductive film of the present invention 8 and the die attach film of the present invention 9 are made of the adhesive epoxy resin sheet of the present invention 7.

The conductive connection paste of the present invention 10 is obtained by containing conductive fine particles in the adhesive epoxy resin paste of the present invention 3.

The anisotropic conductive paste of the present invention 11 is composed of the conductive connection paste of the present invention 10.

In the conductive connection sheet of the present invention 12, conductive fine particles are contained in the adhesive epoxy resin sheet of the present invention 7, and at least a part of the conductive fine particles is exposed from the adhesive epoxy resin sheet. Yes.

In the conductive connection sheet of the present invention 13, conductive fine particles smaller than the thickness of the sheet are embedded in the adhesive epoxy resin sheet of the present invention 7.

The conductive fine particles used in the conductive connection paste of the present invention 10, the anisotropic conductive paste of the present invention 11, and the conductive connection sheets of the present invention 12 and the present invention 13 may be fine particles having conductivity. Although not particularly limited, for example, conductive inorganic substances such as metals and carbon black, those made of conductive polymers, high molecular weight polymers made of resins, nonconductive inorganic substances and nonconductive polymers Examples include those provided with a conductive coating film by a method such as plating on the outermost layer, and those provided with a conductive coating film on the outermost layer such as a conductive inorganic substance or a conductive polymer. Since it is easy to obtain a spherical shape having appropriate elasticity, flexibility, shape recoverability, etc., there are conductive fine particles in which a conductive coating film is formed on the surface of a core (core material) made of a high molecular weight polymer. Preferably used. These electroconductive fine particles may be used independently and 2 or more types may be used together.

The conductive coating film is not particularly limited, but is preferably made of a metal. The metal for forming the conductive coating film is not particularly limited, and examples thereof include nickel, gold, silver, aluminum, copper, tin, and solder. The conductive coating film is preferably a conductive coating film using gold as the outermost layer in consideration of contact resistance with the electrode, conductivity, and no oxidative deterioration. Moreover, it is preferable that the conductive coating film has a barrier layer for multilayering and a nickel layer for improving the adhesion between the core and the metal.

The thickness of the conductive coating film is not particularly limited as long as a sufficient film strength that does not peel off can be obtained and is not particularly limited, but is preferably 0.4 μm or more, more preferably 1 μm or more. More preferably 2 μm or more. The diameter of the core is not particularly limited as long as the core characteristics are not lost, but is preferably 1/5 or less of the diameter of the conductive fine particles.

Although it does not specifically limit as a high molecular weight polymer used as the core of the said electroconductive fine particles, For example, amino resins, such as a urea resin and a melamine resin, a phenol resin, an acrylic resin, ethylene-vinyl acetate type Copolymers, styrene-butadiene block copolymers, polyester resins, alkyd resins, polyimide resins, urethane resins, epoxy resins, and other thermoplastic resins, thermosetting resins, cross-linked resins, and organic-inorganic hybrid heavy resins Among them, a crosslinked resin is preferably used because of its excellent heat resistance. These high molecular weight polymers may contain a filler as required. Moreover, these high molecular weight polymers may be used independently and 2 or more types may be used together.

The conductive fine particles are not particularly limited, but average particle diameter, aspect ratio of particle diameter, CV value (variation coefficient) of particle diameter, resistance value, compression recovery rate, linear expansion coefficient and K value are Each is preferably within the following range.

As for the average particle diameter of the conductive fine particles, when the conductive fine particles are mixed and used in a resin, a preferable lower limit is 1 μm and a preferable upper limit is 5 μm. A more preferred lower limit is 2 μm.
Further, when the conductive fine particles are used in a structure in which the conductive particles are exposed in the sheet, the average particle diameter of the conductive fine particles depends on the thickness of the sheet, but is preferably a lower limit. Is 10 μm, and the preferred upper limit is 800 μm. If the thickness is less than 10 μm, the conductive fine particles may not be in contact with the electrode due to the problem of the smoothness of the electrode or the substrate and may cause poor conduction. If the thickness exceeds 800 μm, the electrode cannot be applied to a finely spaced electrode. The adjacent electrode may be short-circuited. A more preferred lower limit is 15 μm, a more preferred upper limit is 300 μm, a still more preferred lower limit is 20 μm, a still more preferred upper limit is 150 μm, a particularly preferred lower limit is 40 μm, and a particularly preferred upper limit is 80 μm.
The average particle diameter of the conductive fine particles can be measured by observing arbitrary 100 conductive fine particles with a microscope.

The aspect ratio of the particle diameter of the conductive fine particles is preferably less than 1.3, more preferably less than 1.1, and still more preferably less than 1.05. The particle diameter aspect ratio of the conductive fine particles is a value obtained by dividing the average major axis of the conductive fine particles by the average minor axis.

When the aspect ratio of the particle diameter of the conductive fine particles is 1.3 or more, the conductive fine particles are not uniform, so that the short diameter portion is difficult to reach the electrode and may cause poor conduction. In general, the conductive fine particles often have a high particle diameter aspect ratio. Therefore, the conductive fine particles used in the present invention are formed into a spherical shape by subjecting them to a spheroidizing process such as using surface tension in a deformable state. It is preferable.

The CV value (coefficient of variation) of the particle diameter of the conductive fine particles is preferably 5% or less, more preferably 2% or less, and further preferably 1% or less. The CV value of the particle diameter of the conductive fine particles is a value obtained by dividing the standard deviation of the particle diameter by the average particle diameter and multiplying by 100 as shown in the following calculation formula.
CV value of particle diameter (%) = (standard deviation of particle diameter / average particle diameter) × 100

When the CV value of the particle diameter of the conductive fine particles exceeds 5%, the particle diameters are not uniform, so that the small conductive fine particles are difficult to reach the electrode and may cause poor conduction. Since normal conductive fine particles have a large CV value, the conductive fine particles used in the present invention preferably have a uniform particle size by classification or the like. In particular, since it is difficult to classify fine particles having a particle diameter of 200 μm or less with high accuracy, classification is preferably performed by combining sieve classification, airflow classification, wet classification, and the like.

The resistance value of the conductive fine particles is preferably 1Ω or less, more preferably 0.3Ω or less, still more preferably 0.05Ω or less, particularly preferably when 10% of the average particle diameter is compressed. 0.01Ω or less.

If the resistance value of the conductive fine particles exceeds 1Ω, it may be difficult to secure a sufficient current value or it will be difficult to withstand a high voltage, and the device may not operate normally. In addition, when the resistance value of the conductive fine particles is 0.05Ω or less, the effect can be remarkably enhanced, for example, it is possible to cope with a current-driven element while maintaining high conduction reliability.

The compression recovery rate of the conductive fine particles is preferably 5% or more, more preferably 20% or more, still more preferably 50% or more, and particularly preferably 80% or more. Here, the compression recovery rate of the conductive fine particles is a shape recovery rate in a compression deformation state of 10% in an atmosphere of 20 ° C., and conforms to the method described in Japanese Patent Publication No. 7-95165. Using a micro compression tester (for example, trade name “PCT-200” manufactured by Shimadzu Corporation), the conductive fine particles are compressed at a compression speed of 0.28 mN / sec on the smooth end surface of a 50 μm diameter cylinder made from diamond. It is a value expressed as a percentage of the displacement difference up to the reversal point when compressed under a load value of 1.0 mN and a reversal load value of 10 mN.

When the compression recovery rate of the conductive fine particles is less than 5%, when the electrodes facing each other are instantaneously expanded due to an impact or the like, it is not possible to follow it and the conduction becomes unstable instantaneously. There is.

The preferable lower limit of the linear expansion coefficient of the conductive fine particles is 10 ppm / ° C, the preferable upper limit is 200 ppm / ° C, the more preferable lower limit is 20 ppm / ° C, the more preferable upper limit is 150 ppm / ° C, and the further preferable lower limit is 30 ppm / ° C. A more preferred upper limit is 100 ppm / ° C. The linear expansion coefficient of the conductive fine particles can be measured by a known method.

When the linear expansion coefficient of the conductive fine particles is less than 10 ppm / ° C., the conductive fine particles are contained, for example, in the adhesive epoxy resin sheet of the present invention 4 to obtain the conductive connection sheet of the present invention 6 or the present invention 7. However, since the difference in linear expansion between the conductive fine particles and the adhesive epoxy resin sheet becomes large, it becomes difficult to follow the elongation of the adhesive epoxy resin sheet when a thermal cycle or the like is applied, resulting in poor conduction. On the contrary, when the linear expansion coefficient of the conductive fine particles exceeds 200 ppm / ° C., when the conductive connection sheet is adhered to the substrate by adhesion, the gap between the electrodes is increased when a thermal cycle or the like is applied. Since it spreads too much, the adhesion part by the adhesion is destroyed and stress concentrates on the connection part of the electrode, which may cause poor conduction.

Preferable lower limit is 400 N / mm ² in K value of the conductive fine particles, a preferred upper limit is 15000 N / mm ^2, and more preferable lower limit is 1000 N / mm ^2, and more preferred upper limit is 10000 N / mm ^2, still more preferred lower limit 2000N / mm ^2, still more preferred upper limit is 8000 N / mm ^2, particularly preferred lower limit is 3000N / mm ^2, particularly preferred upper limit is 6000 N / mm ^2. Incidentally, K value of the conductive fine particles, as disclosed in Japanese Patent Kokoku ^{7-95165, (3 / √2) ·} F · S -3/2 · R -1/2 ( unit N / mm ² ), which is a value that universally and quantitatively represents the hardness of a sphere. Specifically, in accordance with the method described in the above publication, a smooth end face of a cylinder made of diamond having a diameter of 50 μm using a micro compression tester (for example, trade name “PCT-200” manufactured by Shimadzu Corporation). The value is calculated by compressing the conductive fine particles under the conditions of a compression hardness of 0.27 g / sec and a maximum test load of 10 g. Here, F represents a load value (N) in 10% compression deformation, S represents a compression displacement (mm) in 10% compression deformation, and R represents a radius (mm).

If the K value of the conductive fine particles is less than 400 N / mm ² , the conductive fine particles cannot sufficiently penetrate into the opposing electrode, so that conduction cannot be obtained when the electrode surface is oxidized, The contact resistance may increase and the conduction reliability may decrease. Conversely, if the K value of the conductive fine particles exceeds 15000 N / mm ² , excessively localized in the electrode when sandwiched between the counter electrodes. The device may be destroyed due to pressure, or the gap between the electrodes may be determined only by the conductive particles having a large particle size, and the conductive particles having a small particle size may not reach the electrode and cause a conduction failure. is there.

The conductive connection paste of the present invention 10 can be produced by adding a predetermined amount of the above-mentioned conductive fine particles to the adhesive epoxy resin paste of the present invention 3 and kneading uniformly.

The conductive connection sheets of the present invention 12 and the present invention 13 can be produced by including a predetermined amount of the above-mentioned conductive fine particles in the adhesive epoxy resin sheet of the present invention 7, and arranging or embedding them.

The thickness of the adhesive epoxy resin sheet used for the production of the conductive connection sheet is preferably 1/2 to 2 times the average particle diameter of the conductive fine particles, more preferably 2/3 to 1.5 times. More preferably 3/4 to 1.3 times, and particularly preferably 4/5 to 1.2 times.

Further, in the conductive connection sheet, when the conductive particles are exposed in the sheet, the thickness of the adhesive epoxy resin sheet is less than ½ times the average particle diameter of the conductive fine particles. When the thickness of the adhesive epoxy resin sheet exceeds twice the average particle diameter of the conductive fine particles, the conductive fine particles may become difficult to support the electrode substrate. This may cause poor conduction. In particular, when there are bumps on the electrodes of the element and the substrate, the thickness of the adhesive epoxy resin sheet is preferably at least 1 times the average particle diameter of the conductive fine particles, and conversely, the bumps are formed on the electrodes of the element and the substrate. If not, the thickness of the adhesive epoxy resin sheet is preferably not more than 1 times the average particle diameter of the conductive fine particles.

The adhesive epoxy resin sheet used for the production of the conductive connection sheet is preferably provided with a through hole for arranging conductive fine particles. The position where the through-hole is provided is not particularly limited, and may be appropriately selected according to the substrate or chip to be conducted, and may be arbitrarily provided at the same position as the electrode of the opposing substrate to be conducted. it can.

The through hole is not particularly limited, but it is preferable that the average hole diameter, the aspect ratio of the hole diameter, and the CV value of the hole diameter are in the following ranges, respectively.

The average pore diameter of the through holes is preferably 1/2 to 2 times the average particle diameter of the conductive fine particles, more preferably 2/3 to 1.3 times, and even more preferably 4/5 to 1. 2 times, particularly preferably 9/10 to 1.1 times. If the average pore diameter of the through holes is less than ½ of the average particle diameter of the conductive fine particles or more than twice, the embedded conductive fine particles may be easily displaced from the through holes.

The aspect ratio of the diameter of the through hole is preferably less than 2, more preferably 1.5 or less, still more preferably 1.3 or less, and particularly preferably 1.1 or less. When the aspect ratio of the diameter of the through hole is 2 or more, the arranged conductive fine particles may be easily displaced from the through hole. The aspect ratio of the hole diameter of the through hole is a value obtained by dividing the average major axis of the hole diameter by the average minor axis.

The CV value of the hole diameter of the through hole is preferably 10% or less, more preferably 5% or less, still more preferably 2% or less, and particularly preferably 1% or less. When the CV value of the hole diameter of the through hole exceeds 10%, the hole diameters are uneven, and the arranged conductive fine particles may be easily displaced from the through hole. The CV value of the hole diameter of the through hole is a value obtained by dividing the standard deviation of the hole diameter by the average hole diameter and multiplying by 100 as shown in the following calculation formula.
CV value (%) of pore diameter = (standard deviation of pore diameter / average pore diameter) × 100

When the adhesive epoxy resin sheet used for the production of the conductive connection sheet is provided with the through holes, and when the conductive fine particles are disposed in the through holes, the adhesive epoxy resin sheet itself is provided with adhesiveness. The adhesiveness to the conductive fine particles can be obtained by the adhesiveness around the through-holes, and high retainability of the conductive fine particles can be secured in the vicinity of the room temperature region.

Moreover, as a method of arranging the conductive fine particles in the through holes provided in the adhesive epoxy resin sheet, for example, a method of sucking the conductive fine particles through the through holes, a method of pressing the conductive fine particles on the through holes, etc. Is mentioned.

In the conductive connection sheet of the present invention 12, conductive fine particles are contained in the adhesive epoxy resin sheet of the present invention 7, that is, a large number of conductive materials are disposed at arbitrary positions in the adhesive epoxy resin sheet of the present invention 7. Fine particles are arranged, and at least a part of the conductive fine particles is exposed from the adhesive epoxy resin sheet.

By using the conductive connection sheet having such a configuration, there is no leakage between adjacent electrodes when conducting conductive electrodes facing each other, and highly reliable conduction can be easily performed in a short time.

The position where the conductive fine particles are arranged may be arranged such that at least a part of the conductive fine particles is exposed only on one side of the adhesive epoxy resin sheet, or at least a part of the conductive fine particles is adhered. It may be arranged so as to be exposed on both surfaces of the conductive epoxy resin sheet.

The conductive connection sheet of the present invention 13 is formed by embedding conductive fine particles smaller than the thickness of the sheet in the adhesive epoxy resin sheet of the present invention 7. In the conductive connection sheet of the present invention 7, at least a part of the conductive fine particles smaller than the thickness of the sheet may be exposed on one side or both sides of the adhesive epoxy resin sheet, or may not be exposed.

When the adhesive epoxy resin sheet is not provided with a through hole, the adhesive epoxy resin sheet may be embedded by pressing conductive fine particles smaller than the thickness of the sheet on the adhesive epoxy resin sheet. At this time, when the adhesive epoxy resin sheet itself is provided with adhesiveness, the conductive fine particles are embedded in a state where the adhesive fine particles are stably held by the adhesiveness. In addition, when the adhesiveness of the adhesive epoxy resin sheet is weak, the adhesive epoxy resin sheet may be heated to such an extent that the adhesive epoxy resin sheet is not cured to increase the adhesiveness of the adhesive epoxy resin sheet. Moreover, it is preferable that the embedded conductive fine particles have a center of gravity inside the adhesive epoxy resin sheet. As a result, the conductive fine particles can be embedded in a stable state.

The anisotropic conductive film of the present invention 14 comprises the thirteen conductive connection sheet of the present invention.

The conductive connection sheet of the present invention 15 is composed of an adhesive resin sheet comprising an adhesive resin composition containing a resin to which adhesiveness is imparted by addition of a plasticizer and a naphthalene type epoxy resin that is liquid at room temperature, and conductive fine particles. In the conductive connection sheet to be formed, the adhesive resin sheet has a peak temperature of tan δ based on dynamic viscoelasticity in a range of −20 ° C. to 40 ° C. before curing and 120 ° C. or more after curing. In addition, the conductive fine particles are disposed at an arbitrary position of the adhesive resin sheet, and at least a part of the conductive fine particles is exposed from the adhesive resin sheet.

The resin to which tackiness is imparted by the addition of a plasticizer contained in the above-mentioned tacky resin composition is not particularly limited, but examples thereof include vinyl acetate resins, ethylene-vinyl acetate copolymers, Polyvinyl acetal resins such as acrylic resins and polyvinyl butyral resins, styrene resins, saturated polyester resins, thermoplastic urethane resins, polyamide resins, thermoplastic polyimide resins, ketone resins, norbornene resins, styrene-butadiene Examples thereof include a system block copolymer. These resins are preferably high molecular weight polymers having a relatively high glass transition temperature because they have high heat resistance and are tacky by the addition of a plasticizer. Moreover, these resin may be used independently and 2 or more types may be used together.

As the plasticizer contained in the adhesive resin composition, a naphthalene type epoxy resin that is liquid at room temperature is used. The naphthalene type epoxy resin is an epoxy resin having a naphthalene skeleton having an epoxy group. Since the naphthalene-type epoxy resin has a rigid naphthalene skeleton, the conductive connection sheet of the present invention 8 can obtain high shape retention even in a high-temperature and high-humidity environment.

Since the naphthalene type epoxy resin usually contains an isomer and has a melting point of room temperature or lower, it can have adhesiveness even when the conductive connecting sheet of the present invention 8 is handled at a low temperature. That is, when tackiness is imparted to the high molecular weight polymer having a relatively high glass transition temperature, an excellent plasticizing effect is exhibited by using a naphthalene type epoxy resin that is liquid at room temperature, and it can be handled at a low temperature. An adhesive resin sheet that can achieve both adhesiveness to conductive fine particles and shape retention in a high-temperature and high-humidity environment, and thus a conductive connection sheet can be obtained.

Although it does not specifically limit as said naphthalene type epoxy resin liquid at the normal temperature, For example, 1-glycidyl naphthalene, 2-glycidyl naphthalene, 1,2- diglycidyl naphthalene, 1,5-diglycidyl naphthalene, 1 , 6-diglycidylnaphthalene, 1,7-diglycidylnaphthalene, 2,7-diglycidylnaphthalene, triglycidylnaphthalene, 1,2,5,6-tetraglycidylnaphthalene and the like. These naphthalene type epoxy resins may be used alone or in combination of two or more.

The number of epoxy groups contained in the naphthalene-type epoxy resin that is liquid at normal temperature is not particularly limited, but is preferably 1 or more on average per molecule, more preferably 2 on average per molecule. That's it.

The adhesive resin composition preferably contains an epoxy resin curing agent for curing a naphthalene type epoxy resin that is liquid at room temperature.

The curing agent for epoxy resin may be the same curing agent as the essential component contained in the curable resin composition of the present invention 1 and the present invention 2 described above, and is not particularly limited. , Acid anhydride curing agents such as trialkyltetrahydrophthalic anhydride, phenolic curing agents, amine curing agents, latent curing agents such as dicyandiamide, and cationic catalytic curing agents. A latent curing agent such as dicyandiamide, which is a liquid heat-curing curing agent or polyfunctional and may be added in a small amount equivalently, is preferably used. These epoxy resin curing agents may be used alone or in combination of two or more.

Moreover, in the said adhesive resin composition, in order to adjust a cure rate, the physical property of hardened | cured material, etc., you may use together a hardening accelerator with the said hardening | curing agent for epoxy resins.

The curing accelerator may be the same curing accelerator as that which can be used in combination in the curable resin compositions of the present invention 1 and the present invention 2, and is not particularly limited. Accelerators, tertiary amine curing accelerators and the like are mentioned. Among them, the above imidazole curing accelerator is preferable because it is easy to control the reaction system for adjusting the curing speed and physical properties of the cured product. Used for. These curing accelerators may be used alone or in combination of two or more.

If necessary, the above adhesive resin composition may be a high molecular weight polymer that does not impart adhesiveness even when a plasticizer (naphthalene type epoxy resin) is added, or a naphthalene type epoxy such as a dicyclopentadiene type epoxy resin. An epoxy resin other than the resin or an epoxy group-containing compound may be contained.

In addition, the adhesive resin composition may include, for example, the above adhesion improver, pH adjuster, ion scavenger, viscosity adjuster, thixotropic agent, antioxidant, thermal stabilizer, light, if necessary. One kind or two or more kinds of various additives such as a stabilizer, an ultraviolet absorber, a colorant, a dehydrating agent, a flame retardant, an antistatic agent, an antifungal agent, an antiseptic and a solvent may be added.

The method for producing the adhesive resin sheet by forming the adhesive resin composition into a sheet is not particularly limited. For example, an extrusion molding method using an extruder, and the adhesive resin composition with a solvent. Examples include a solution casting method in which an adhesive resin composition solution is diluted to prepare a solution, and this solution is cast on a separator and then the solvent is dried. Preferably used.

The adhesive resin sheet thus obtained has a peak temperature of tan δ expressed by the dynamic loss tangent determined by the dynamic viscoelasticity measurement (measurement frequency: 10 Hz, temperature increase rate: 3 ° C./min) before curing. It exists in the range of -20 degreeC-40 degreeC, and after hardening needs to be 120 degreeC or more, Preferably, it exists in the range of 0-35 degreeC before hardening, and is 160 degreeC or more after hardening.

By having such a tan δ peak temperature, the conductive connection sheet of the present invention 15 produced using the above-mentioned adhesive resin sheet is flexible in the normal temperature region, excellent in handleability, and at normal temperature. Adhesives can be bonded to each other at room temperature without hot pressing, and high adhesion reliability and high conduction reliability by heat curing (post-curing) in a heat oven or the like Can be expressed. That is, the conductive connection sheet of the present invention 15 produced using the above-mentioned adhesive resin sheet has adhesiveness at room temperature before curing and exhibits excellent physical properties after curing by heating. Adhesion reliability sufficient as a conductive connection sheet, which can be bonded, positioned and temporarily fixed by a sheet having the property, and exhibits physical properties such as excellent adhesion and excellent conductivity by heating later. And conduction reliability can be expressed.

When the peak temperature of tan δ before curing of the adhesive resin sheet is less than −20 ° C., the cohesive force of the adhesive resin sheet becomes insufficient, so that the conductive connection sheet of the present invention 15 is difficult to peel off from the separator. , The adhesive resin composition flows into the through-holes provided to dispose the conductive fine particles on the adhesive resin sheet, and the through-holes are buried, and conversely, tan δ before curing of the adhesive resin sheet occurs. When the peak temperature exceeds 40 ° C., when the conductive resin sheet is made to contain conductive fine particles in the adhesive resin sheet, the adhesiveness to the conductive fine particles at room temperature becomes insufficient, and the conductive property becomes low. It becomes difficult to hold the fine particles.

Moreover, the said adhesive resin sheet is the adhesive resin sheet after hardening after performing a pressure cooker test on the conditions for temperature 120 degreeC, humidity 85% RH, and time 12 hours with respect to the adhesive resin sheet after hardening. It is preferable that the elongation percentage is 5% or less.

When the elongation percentage of the adhesive resin sheet after curing after the pressure cooker test exceeds 5%, the adhesion reliability and electrical continuity of the conductive connection sheet of the present invention 15 produced using the adhesive resin sheet are as follows. Reliability may be insufficient.

The conductive fine particles used in the conductive connection sheet of the present invention 15 are contained in the conductive connection paste of the present invention 10, the anisotropic conductive paste of the present invention 11, the conductive connection sheets of the present invention 12 and the present invention 13. The conductive fine particles may be the same as those described above, and are not particularly limited. For example, conductive inorganic materials such as metals and carbon black, conductive polymer polymers, high molecular weight polymers made of resins, and nonconductive inorganic materials. Or a non-conductive polymer or other outermost layer provided with a conductive coating by a method such as plating, or a conductive inorganic material or a conductive polymer or other outermost layer provided with a conductive coating. Among them, a conductive coating film is formed on the surface of a core (core material) made of a high molecular weight polymer because it is easy to obtain a spherical shape having appropriate elasticity, flexibility, shape recoverability, etc. Conductivity Particles are suitably used. These electroconductive fine particles may be used independently and 2 or more types may be used together.

The conductive connection sheet of the present invention 15 contains the conductive fine particles in the adhesive resin sheet, that is, a large number of conductive fine particles are arranged at arbitrary positions in the adhesive resin sheet, and At least a part of the conductive fine particles is exposed from the adhesive resin sheet.

By using the conductive connection sheet having such a configuration, there is no leakage between adjacent electrodes when conducting conductive electrodes facing each other, and highly reliable conduction can be easily performed in a short time.

The position where the conductive fine particles are arranged may be arranged such that at least a part of the conductive fine particles is exposed only on one side of the adhesive resin sheet, or at least a part of the conductive fine particles is adhesive. You may arrange | position so that it may expose on both surfaces of a resin sheet.

A method for producing a conductive connection sheet by arranging a large number of conductive fine particles at an arbitrary position in the adhesive resin sheet may be the same as that for producing the conductive connection sheet of the present invention 12.

The adhesive epoxy resin paste of the present invention 3 and the conductive connection paste of the present invention 10 (hereinafter sometimes simply abbreviated as “paste”) are in the form of a paste, so that they are different from those in the form of a sheet. It is not necessary to cut and process the sheet in advance according to the size of the electronic element or the like, and an apparatus for pasting work is not necessary.

In addition, since the paste is paste-like, unlike the sheet-like one, there is no positional deviation at the time of bonding, and it is also suitable for substrates with large irregularities in the wiring portion and substrates with large irregularities in the portions other than the wiring. There are no voids. In the case of a sheet-like material, the sheet may be stretched or cut when the sheet is attached, but there is no such fear because it is a paste-like material. Therefore, it may be used more advantageously than a sheet-like material for a small-sized IC chip, an electronic element, or a substrate with large unevenness.

The adhesive epoxy resin paste of the present invention 3 and the conductive connection paste of the present invention 10 may be diluted with a solvent as long as the viscosity is adjusted to be applied by a coating device such as a dispenser. However, it may be of a solventless type. Further, the paste may be applied to an IC chip, an electronic element, or the like, or may be applied to a substrate. In other words, it may be applied to the one that is easy to apply. In general, since it is easy to adjust the coating amount, it is preferable to apply the coating to the substrate in advance.

When the paste is diluted with a solvent, it is applied to at least one of the adherends, then cured at a low temperature so that curing does not proceed, the solvent is evaporated, and the paste is converted into a B-stage, The electronic elements may be bonded by a method such as positioning and flip chip connection. Even when the paste is a solventless type, it is possible to position an IC chip, an electronic element or the like and perform flip-chip connection in the same manner.

The paste may be partially applied with a dispenser, roller, stamper, or the like only to the portion to be bonded. Further, in order to increase the adhesion reliability and the conduction reliability, a paste that flows by heating may be used to fill the unevenness of the substrate by heating at the time of flip chip connection.

Applications of the adhesive epoxy resin paste of the present invention 3 and the conductive connection paste of the present invention 10 are not particularly limited. For example, adhesion and conductive connection of circuit boards, bump-like protruding electrodes of electronic components, and the other It is suitably used for fixing an electronic material such as a conductive connection with the electrode.

On the other hand, since the adhesive epoxy resin sheet of the present invention 7 and the conductive connection sheets of the present invention 12, 13, 15 are sheet-like, they are matched to the size of the IC chip, electronic element, etc., unlike the paste-like one. Although it is necessary to cut and process the sheet in advance in size, and a device for affixing work is required, it is excellent for small-quantity mass production because it can be produced at high speed on the production line.

The use of the conductive connection sheet of the present invention 12, 13, 15 is not particularly limited. For example, in an electronic product such as a liquid crystal display, a personal computer, and a portable communication device, a small component such as a semiconductor element is used as a substrate. Among the methods of electrically connecting to each other or electrically connecting the substrates to each other, it is preferably used when electrically connecting fine electrodes facing each other. Examples of actual products include memory cards and IC cards. Further, in the process of manufacturing a glass circuit board, among methods for providing a conductive circuit on a glass surface such as a light part of an automobile, it is preferably used when the glass surface and the electrode surface of the conductive circuit are opposed to each other. Thus, it can be set as an electronic component assembly. In addition, the conductive connection sheet can be used for a single-layer substrate, and can also be used for a substrate composed of a plurality of layers using conductive fine particles as vertical conductive materials.

The flip chip tape of the present invention 16 comprises the conductive connection sheet of the present invention 12 or 15.

The conductive connection sheets of the present invention 12, 13, and 15 are particularly preferably used for joining bare chips. Normally, when flip chips are used when bonding bare chips, bumps are necessary. However, when the conductive connection sheet is used, the conductive fine particles serve as bumps, so that connection is made without using bumps. It becomes possible. For this reason, there exists a big merit that the complicated process in bump preparation can be omitted. Further, when the conductive fine particles have a preferable K value or CV value as described above, even an electrode that is easily oxidized, such as an aluminum electrode, can be broken and connected.

Examples of a method for connecting the conductive connection sheets of the present invention 12, 13, and 15 to the substrate or the chip without bumps include the following methods. A conductive connection sheet is placed on a substrate or chip on which an electrode is formed on the surface so that the conductive fine particles are at the position of the electrode, and the substrate or chip having the other electrode surface is placed so that the electrode is aligned. . In this state, connection is made through a conductive connection sheet by heating or pressurization. For heating or pressurization, a crimping machine with a heater or a bonding machine is preferably used.

As the bonding condition, it is preferable that the temperature is applied after the conduction is reliably performed, that is, after the electrode and the conductive fine particles are reliably in contact with each other. If this is neglected, the resin flows due to heat in a state where the electrode and the conductive fine particles are not in contact with each other, and in part, the resin flows between the electrode and the conductive fine particles, resulting in poor conduction. In addition, since there is no force for holding the conductive fine particles in the two, the conductive fine particles move from the position of the electrode along with the flow of the resin, and reliable conduction cannot be obtained. Specifically, first pressurize with high pressure in a state where no temperature is applied, and after confirming that the electrodes are in contact with each other while monitoring the resistance value, lower the pressure to a region where there is no crack of the conductive fine particles. By heating, the conductive fine particles do not move due to the flow of the resin due to the frictional force with the electrode, and the conductive connection is made with high accuracy without causing the resin to get caught between the electrode and the conductive fine particles. Can do. Therefore, the pressure condition is a two-stage profile from high pressure to low pressure.

At this time, when the temperature is increased at once by the ceramic heater, voids may be formed in the resin or at the bonding interface. This is because, for example, volatile components such as moisture are generated at a high temperature (about 200 ° C.) to cause poor adhesion. In order to prevent this, there is a method of suppressing volatile matter in the resin itself. However, when an organic substrate is used as the adherend, the volatile matter from the adherend may cause foaming even if the amount of volatile matter in the resin is reduced. From this, it was considered to suppress the foaming phenomenon itself by keeping the elastic modulus of the resin when heated to a certain elastic modulus or higher.

As this idea, there is a commonly used technique called B-stage (semi-curing). Thereby, the fluidity | liquidity of resin can be suppressed and foaming can also be suppressed. However, this essentially prevents the resin from flowing into the gap, and thus adversely affects the adhesiveness, particularly moisture-resistant adhesiveness in which water tends to be unevenly distributed at the interface. Therefore, the B-stage method is not a preferable method in consideration of the total balance performance.

The other is a technique in which the elasticity of the resin is increased to a certain level without significantly impairing the fluidity. For this, a fine inorganic filler, for example, a fine particle (particle diameter of 1 μm or less, nano-order) generally used as a thickener is preferably used. In particular, it has been found that the generation of voids can be suppressed by increasing the elastic modulus without using the technique of B-stage formation. The above is a description of a conductive connection sheet in which conductive fine particles are arranged at fixed points at arbitrary positions on the sheet. However, the same method can be applied to a conductive connection sheet in which conductive fine particles are embedded in the sheet. It can be used as a conductive connection material application.

In the conductive connection structure formed by using the conductive connection sheets of the present invention 12, 13, and 15, the periphery of the sheet is sealed so as not to cause problems due to intrusion of moisture or the like from the connection end surface of the sheet. Also good. Although it does not specifically limit as a sealing material used for sealing, For example, an epoxy resin, a silicone resin, a phenol resin, a polyimide resin, an inorganic material etc. are mentioned, It uses suitably.

The electronic component assembly of the present invention 17 includes the curable resin composition of the present invention 1 or the present invention 2, the adhesive epoxy resin paste of the present invention 3, the interlayer adhesive of the present invention 4, and the non-conductive paste of the present invention 5. The underfill of the present invention 6, the adhesive epoxy resin sheet of the present invention 7, the nonconductive film of the present invention 8, the die attach film of the present invention 9, the conductive connection paste of the present invention 10, the anisotropy of the present invention 11 According to any of the conductive paste, the conductive connection sheet of the present invention 12, 13 or 15, the anisotropic conductive film of the present invention 14, or the flip chip tape of the present invention 16, the bump-shaped protruding electrode of the electronic component and the other The electrode is joined in a conductive state.

Moreover, the electronic component assembly of the present invention 18 includes the curable resin composition of the present invention 1 or the present invention 2, the adhesive epoxy resin paste of the present invention 3, the interlayer adhesive of the present invention 4, and the non-conductive of the present invention 5. Paste, the adhesive epoxy resin sheet of the present invention 7, the non-conductive film of the present invention 8, the die attach film of the present invention 9, the conductive connection paste of the present invention 10, the differences of the present invention 11 Metal lead frame, ceramic substrate, resin substrate by any one of anisotropic conductive paste, conductive connection sheet of the present invention 12, 13 or 15, anisotropic conductive film of the present invention 14, or flip chip tape of the present invention 16. At least one circuit board selected from the group consisting of a silicon substrate, a compound semiconductor substrate and a glass substrate is bonded.

The resin substrate is preferably a glass epoxy substrate, a bismaleimide triazine substrate or a polyimide substrate.

The curable resin composition of the present invention 1 includes an epoxy resin, a polymer having a functional group that reacts with an epoxy group, and a curing agent for epoxy resin, which is dyed with heavy metal and observed with a transmission electron microscope. Since no phase separation structure is observed in the resin matrix of the product, after curing, it is excellent in mechanical strength, heat resistance, moisture resistance, flexibility, cold cycle resistance, solder reflow resistance, dimensional stability, etc. High adhesion reliability when used as adhesion reliability and conduction material.

The curable resin composition of the present invention 2 has a core glass transition temperature of 20 in an epoxy resin composition in which a dicyclopentadiene type epoxy resin, a naphthalene type epoxy resin, and a curing agent for epoxy resin are mixed. Since it contains rubber particles with a core-shell structure with a glass transition temperature of 40 ° C. or higher, and after curing, mechanical strength, heat resistance, moisture resistance, flexibility, cold and heat cycle resistance after curing. It has excellent solder reflow resistance, dimensional stability, etc., and exhibits high adhesion reliability and high conduction reliability when used as a conduction material.

Since the adhesive epoxy resin paste of the present invention 3 and the adhesive epoxy resin sheet of the present invention 7 are composed of the curable resin composition of the present invention 1 or 2, the mechanical strength, heat resistance, It excels in moisture resistance, flexibility, thermal cycle resistance, solder reflow resistance, dimensional stability, etc., and exhibits high adhesion reliability and high conduction reliability when used as a conductive material.

The interlayer adhesive of the present invention 4, the non-conductive paste of the present invention 5 and the underfill of the present invention 6 are composed of the adhesive epoxy resin paste of the present invention 3, the non-conductive film of the present invention 8, and Since the die attach film of the present invention 9 is made of the adhesive epoxy resin sheet of the present invention 7, after curing, after curing, mechanical strength, heat resistance, moisture resistance, flexibility, cold resistance cycle It has excellent properties, solder reflow resistance, dimensional stability, etc., and exhibits high adhesion reliability and high conduction reliability.

In the conductive connection paste of the present invention 10, conductive fine particles are contained in the adhesive epoxy resin paste of the present invention 3, and the conductive connection sheets of the present invention 12 and the present invention 13 are the same as those of the present invention 7. Since conductive fine particles are arranged or embedded in the adhesive epoxy resin sheet, after curing, mechanical strength, heat resistance, moisture resistance, flexibility, cold cycle resistance, solder reflow resistance, Excellent dimensional stability and high adhesion reliability and high conduction reliability.

Since the anisotropic conductive paste of the present invention 11 is composed of the conductive connection paste of the present invention 10, after curing, after curing, mechanical strength, heat resistance, moisture resistance, flexibility, cold resistance cycle It has excellent properties, solder reflow resistance, dimensional stability, etc., and exhibits high adhesion reliability and high conduction reliability.

Since the anisotropic conductive film of the present invention 14 is composed of the conductive connection sheet of the present invention 13, after curing, after curing, mechanical strength, heat resistance, moisture resistance, flexibility, and cold resistance cycle. It has excellent properties, solder reflow resistance, dimensional stability, etc., and exhibits high adhesion reliability and high conduction reliability.

The conductive connection sheet of the present invention 15 is composed of an adhesive resin sheet comprising an adhesive resin composition containing a resin to which adhesiveness is imparted by addition of a plasticizer and a naphthalene type epoxy resin that is liquid at room temperature, and conductive fine particles. In the conductive connection sheet to be formed, the adhesive resin sheet has a peak temperature of tan δ based on dynamic viscoelasticity in a range of −20 ° C. to 40 ° C. before curing and 120 ° C. or more after curing. In addition, since the conductive fine particles are arranged at an arbitrary position of the adhesive resin sheet, after curing, mechanical strength, heat resistance, moisture resistance, flexibility, thermal cycle resistance, solder reflow resistance, Excellent dimensional stability and high adhesion reliability and high conduction reliability.

Since the flip chip tape of the present invention 16 is composed of the conductive connection sheet of the present invention 12 or the present invention 15, after curing, after curing, mechanical strength, heat resistance, moisture resistance, flexibility, Excellent heat cycle performance, solder reflow resistance, dimensional stability, etc., and exhibits high adhesion reliability and high conduction reliability.

The electronic component assembly of the present invention 17 and the present invention 18 includes the curable resin composition of the present invention 1 or the present invention 2, the adhesive epoxy resin paste of the present invention 3, the interlayer adhesive of the present invention 4, and the present invention 5. Non-conductive paste, underfill of the present invention 6, adhesive epoxy resin sheet of the present invention 7, non-conductive film of the present invention 8, die attach film of the present invention 9, conductive connection paste of the present invention 10, present invention 11 The anisotropic conductive paste of the present invention, the conductive connection sheet of the present invention 12, 13 or 15, the anisotropic conductive film of the present invention 14 or the flip chip tape of the present invention 16 is used. Adhesion reliability and high conduction reliability are expressed.

In order to explain the present invention in more detail, examples are given below, but the present invention is not limited to these examples.

In this example, the following raw materials were used unless otherwise specified.
1. Epoxy resin (1) Dicyclopentadiene type solid epoxy resin (trade name “EXA-7200HH”, manufactured by Dainippon Ink & Chemicals, Inc.)
(2) Naphthalene type liquid epoxy resin (trade name “HP-4032D”, manufactured by Dainippon Ink & Chemicals, Inc.)
(3) Bisphenol A type liquid epoxy resin (trade name “EP828”, manufactured by Japan Epoxy Resin Co., Ltd.)
2. Polymer having epoxy group (1) Epoxy-containing acrylic resin-a (trade name “Marproof G-2050M”, suspension polymerization method, epoxy equivalent: 340, weight average molecular weight: 200,000, glass transition temperature: 80 ° C. (Made by Nippon Oil & Fats)
(2) Epoxy-containing acrylic resin-b (trade name “Blemmer CP-15”, suspension polymerization method, epoxy equivalent: 500, weight average molecular weight: 10,000, glass transition temperature: 80 ° C., manufactured by NOF Corporation)
(3) Epoxy group-containing acrylic rubber-c (99 parts by weight of ethyl acrylate and 1 part by weight of glycidyl methacrylate solution-polymerized in ethyl acetate by the thermal radical method, epoxy equivalent: 8000, weight average molecular weight: 200,000, glass (Transition temperature: 10 ° C)
(4) Epoxy-containing acrylic rubber-d (trade name “Nippol AR-42W”, manufactured by Nippon Zeon Co., Ltd.)
3. High molecular weight polymer (1) Polyvinyl butyral resin (trade name “BX-5Z”, manufactured by Sekisui Chemical Co., Ltd.)
4). Curing agent for epoxy resin (1) Trialkyltetrahydrophthalic anhydride (trade name “YH-307”, manufactured by Japan Epoxy Resin Co., Ltd.)
(2) Dicyandiamide (trade name “EH-3636AS” manufactured by Asahi Denka Kogyo Co., Ltd.)
(3) Guanidine compound (trade name “DX147” manufactured by Japan Epoxy Resin Co., Ltd.)
5. Curing accelerator (1) Isocyanur-modified solid dispersion type imidazole (trade name “2MAOK-PW”, manufactured by Shikoku Chemicals)
(2) 1-cyanoethyl-2-phenylimidazole (3) 2-ethyl-4-methylimidazole Adhesiveness imparting agent (1) Imidazole silane coupling agent (trade name “SP-1000” manufactured by Nikko Materials Co., Ltd.)
(2) Aminosilane coupling agent (trade name “S320”, manufactured by Chisso Corporation)
7). Filler (1) Surface hydrophobized fumed silica (trade name “Leosil MT-10”, average particle size: 1 μm or less, manufactured by Tokuyama Corporation)
(2) Spherical silica (average particle size: 5 μm)
8). Stress relaxation imparting agent (1) Hydroxyl-containing core-shell type acrylic rubber particles (trade name “STAPHYLOID AC-4030”, manufactured by Ganz Kasei Co., Ltd.)
(2) Carboxyl group-containing core-shell type acrylic rubber particles (trade name “Zeon F451”, manufactured by Nippon Zeon)
(3) Terminal epoxy-modified silicone oil (trade name “KF-105”, manufactured by Shin-Etsu Chemical Co., Ltd.)
9. Solvent (1) Ethyl acetate

Example 1
Using a homodisper type stirrer, 76 parts by weight of dicyclopentadiene type solid epoxy resin, 20 parts by weight of naphthalene type liquid epoxy resin, 4 parts by weight of epoxy group-containing acrylic resin, 60 parts by weight of trialkyltetrahydrophthalic anhydride, isocyanur modified 8 parts by weight of solid dispersion type imidazole and 2 parts by weight of imidazole silane coupling agent were uniformly kneaded to prepare an adhesive epoxy resin paste.

(Examples 2-4 and Comparative Examples 1-2)
An adhesive epoxy resin paste was prepared in the same manner as in Example 1 except that the composition of the adhesive epoxy resin paste was changed to the composition shown in Table 1.

The performances (1. gelation rate, 2. initial adhesive force-A, 3. foamed state at 200 ° C.) of the adhesive epoxy resin pastes obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were as follows. The method was evaluated. The results are shown in Table 1.

1. The gelation rate adhesive epoxy resin paste was heat-cured in an oven at 170 ° C. for 1 minute and 170 ° C. for 2 minutes. Next, after the cured product is immersed in ethyl acetate at room temperature for 24 hours, the insoluble matter is filtered off and sufficiently dried, and then the weight ratio of the cured product before and after immersion in ethyl acetate (weight after immersion / before immersion). Weight) was determined, and the gelation rate (% by weight) was calculated.

2. Initial adhesive strength -A
One drop of the adhesive epoxy resin paste on the glass epoxy substrate of FR-4, a 5 mm square spacer was placed around this, and a 10 mm square silicon chip with SiO ₂ passivation was affixed thereon. Then, it heat-cured for 30 minutes at 170 degreeC, and produced the conjugate | zygote. Next, jigs were attached to the upper and lower sides of the obtained joined body, and pulled up and down at a pulling speed of 5 mm / min, and the maximum breaking strength (N / 25 mm ² ) was determined to obtain an initial adhesive strength −A.

3. Foamed state adhesive epoxy resin paste at 200 ° C. The paste was put in an oven at 200 ° C., taken out after 1 minute, the foamed state was visually observed, and the foamed state at 200 ° C. was evaluated according to the following criteria.
[Criteria]
○ …… No foaming was observed.
X ... Foaming was observed.

表１から、実施例１〜４で得られた接着性エポキシ樹脂ペーストは、いずれもゲル化率が高く硬化性が良好又は優れており、かつ、初期接着力−Ａが優れているとともに、２００℃において発泡が認められず、ボイドの発生を抑制することができた。
これに対し、エポキシ基を有する高分子ポリマー（エポキシ基含有アクリル樹脂）を含有させなかった比較例１、２で得られた接着性エポキシ樹脂ペーストは、いずれも１７０℃−１分間硬化時のゲル化率が低く硬化性が劣っており、かつ、初期接着力−Ａが劣っているとともに、２００℃において発泡が認められ、ボイドの発生を抑制することができなかった。

From Table 1, the adhesive epoxy resin pastes obtained in Examples 1 to 4 all have a high gelation rate and good or excellent curability, and excellent initial adhesive force -A. Foaming was not observed at 0 ° C., and the generation of voids could be suppressed.
In contrast, the adhesive epoxy resin pastes obtained in Comparative Examples 1 and 2 that did not contain a polymer having an epoxy group (epoxy group-containing acrylic resin) were both gels at 170 ° C. for 1 minute. The conversion rate was low, the curability was inferior, the initial adhesive strength -A was inferior, and foaming was observed at 200 ° C., and the generation of voids could not be suppressed.

(Example 5)
76 parts by weight of dicyclopentadiene type solid epoxy resin, 20 parts by weight of naphthalene type liquid epoxy resin, 10 parts by weight of epoxy group-containing acrylic resin, 50 parts by weight of trialkyltetrahydrophthalic anhydride, 8 parts by weight of isocyanuric modified solid dispersion type imidazole, 2 parts by weight of aminosilane coupling agent and 4 parts by weight of surface-hydrophobized fumed silica are dissolved in ethyl acetate and mixed uniformly with a homodisper-type stirrer at a stirring speed of 3000 rpm. An ethyl acetate solution of a weight percent curable resin composition was prepared.

Next, the ethyl acetate solution of the curable resin composition obtained above is dried on the surface of a 50 μm-thick polyethylene terephthalate (PET) sheet having a release treatment, and the thickness after drying is After coating using a bar coater so as to be 50 μm, it was dried at 110 ° C. for 3 minutes to prepare an adhesive epoxy resin sheet.

(Example 6 and Comparative Example 3)
The ethyl acetate solution of the curable resin composition (50 wt.% Solid content) was used in the same manner as in Example 5 except that the composition of the adhesive epoxy resin sheet (curable resin composition) was changed to the composition shown in Table 2. %) And an adhesive epoxy resin sheet.

The performance of the adhesive epoxy resin sheet obtained in Example 5 and Example 6 and Comparative Example 3 (4. Observation by transmission electron microscope, 5. Glass transition temperature of cured product, 6. Initial adhesive force -B, 7. Adhesive strength after 100 hours of PCT was evaluated by the following method. The results are shown in Table 2.

4). Observation with Transmission Electron Microscope (TEM) An adhesive epoxy resin sheet cured and cured in an oven at 170 ° C. for 30 minutes was cut into a thin film with a microtome and dyed with osmium tetroxide. This sample was observed with a transmission electron microscope (magnification of 100,000 times), and the phase separation structure by these staining was observed.

5. After the glass transition temperature adhesive epoxy resin sheet of the cured product was cured by heating at 170 ° C. for 30 minutes, the viscoelasticity of the cured product was measured under conditions of a temperature increase rate of 3 ° C./min and a tensile mode, and a glass with a peak temperature of tan δ. The transition temperature (° C.) was used.

6). Initial adhesive strength -B
Adhesive epoxy resin sheet cut to 5 mm square was affixed onto a glass epoxy substrate of FR-4, and a silicon chip having SiO ₂ passivation was affixed thereon, pressed and adhered, then at 170 ° C. A bonded body was prepared by heating and curing for 30 minutes. Next, jigs were attached to the upper and lower sides of the obtained joined body, and pulled up and down at a pulling speed of 5 mm / min, and the maximum breaking strength (N / 25 mm ² ) was determined to obtain an initial adhesive force −B.

7). Adhesive strength after 100 hours of PCT After performing a pressure cooker test (PCT) for 100 hours under the conditions of 120 ° C.-85% RH on a bonded body prepared in the same manner as in the case of measuring the initial adhesive strength-B, the bonded body is taken out. 5. In the same manner as described above, the maximum breaking strength (N / 25 mm ² ) was determined and used as the adhesive strength after 100 hours of PCT.

表２から、実施例５、６で得られた接着性エポキシ樹脂シートは、ともに硬化物のガラス転移温度が高く、樹脂相での相分離構造を示さないので、初期接着力−Ｂが優れているとともに、ＰＣＴ１００時間後でも接着力の低下が少なかった。
これに対し、エポキシ基含有アクリル樹脂の代わりに、溶液重合法で作製したエポキシ基含有アクリルゴム−ｃを含有させた比較例３で得られた接着性エポキシ樹脂シートは、硬化物のガラス転移温度が低く、低温でのｔａｎδのピークが現れ、相分離構造を示すことにより、かつ、初期接着力−Ｂが劣っているとともに、ＰＣＴ１００時間後の接着力が極端に低下していた。

From Table 2, since the adhesive epoxy resin sheets obtained in Examples 5 and 6 both have a high glass transition temperature of the cured product and do not show a phase separation structure in the resin phase, the initial adhesive force -B is excellent. In addition, there was little decrease in adhesion even after 100 hours of PCT.
On the other hand, the adhesive epoxy resin sheet obtained in Comparative Example 3 containing an epoxy group-containing acrylic rubber-c prepared by a solution polymerization method instead of the epoxy group-containing acrylic resin is a glass transition temperature of a cured product. , The peak of tan δ at low temperature appeared, showing a phase separation structure, initial adhesive strength -B was inferior, and adhesive strength after 100 hours of PCT was extremely reduced.

(Example 7)
Dicyclopentadiene type solid epoxy resin 45 parts by weight, naphthalene type liquid epoxy resin 45 parts by weight, epoxy group-containing acrylic resin-a 10 parts by weight, trialkyltetrahydrophthalic anhydride 50 parts by weight, 1-cyanoethyl-2-phenylimidazole 4 parts by weight Part, 2 parts by weight of aminosilane coupling agent and 4 parts by weight of surface-hydrophobized fumed silica are dissolved in ethyl acetate and uniformly stirred and kneaded using a homodisper type stirrer at a stirring speed of 3000 rpm. A 60 wt% curable resin composition in ethyl acetate was prepared.

Next, an ethyl acetate solution of the obtained curable resin composition is 40 μm in thickness after drying on a release treatment surface of a 50 μm-thick polyethylene terephthalate (PET) sheet whose surface is subjected to a release treatment. After coating using a bar coater, it was dried at 110 ° C. for 3 minutes to form an adhesive epoxy resin layer.

(Examples 8-12 and Comparative Examples 4-7)
The ethyl acetate solution of the curable resin composition (solid content of 40 wt.%) Was the same as in Example 7 except that the composition of the adhesive epoxy resin sheet (curable resin composition) was changed to the composition shown in Table 3. %), An adhesive epoxy resin sheet was prepared.

Performances of adhesive epoxy resin sheets obtained in Examples 7 to 12 and Comparative Examples 4 to 7 (7. Observation of phase separation structure during TEM staining (observation with transmission electron microscope), 8. Observation of viscoelasticity tan δ peak temperature 8. Measurement of dimethyl sulfoxide swelling ratio at 120 ° C., 10. Extraction water pH measurement, 11. Ionic conductivity measurement, 12. Extraction chloride ion impurity measurement, 13. Dielectric constant ε ′ measurement, 14. Dielectric loss tangent measurement, 15. Laser Workability, 16. Measurement of minimum storage elastic modulus G ′ upon melting, 17. Measurement of presence / absence of voids, 18. Bonded body PCT conduction measurement, 19. Bonded body TCT conduction measurement) were evaluated by the following methods. The results are shown in Table 3.

7). Observation with Transmission Electron Microscope An adhesive epoxy resin sheet cured and cured in an oven at 170 ° C. for 30 minutes was cut into a thin film with a microtome and dyed with osmium tetroxide. This sample was observed with a transmission electron microscope (magnification of 100,000 times), and the phase separation structure by these staining was observed.

8). Viscoelasticity tan δ peak temperature observation 170 ° C. Curing and curing an adhesive epoxy resin sheet in an oven with a tensile viscoelasticity measuring device at a temperature rising rate of 3 ° C./min, measurement temperature from −100 ° C. It measured in the range of 290 degreeC. The obtained chart was observed, and it was written without having the temperature of two or more peak values of tan δ.

9. Measurement of 120 ° C. Dimethyl Sulfoxide Swelling Ratio Weigh the adhesive sheet cured at 170 ° C. for 30 minutes and immerse it in dimethyl sulfoxide (DMSO) heated to 120 ° C. for 5 minutes. After 5 minutes, the sheet is taken out, and after the solvent is thoroughly wiped off, the weight is measured again with a balance.
DMSO swelling ratio (%) = (weight after immersion−initial weight) × 100 / (initial weight)
Can be represented.

10. Extracted water pH measurement The adhesive epoxy resin sheet was heated and cured in an oven at 170 ° C. for 30 minutes, and about 1 g of a cured product of the adhesive epoxy resin sheet was weighed. Next, this cured product is cut into small pieces and placed in a glass test tube, 10 g of distilled water is added, the test tube is sealed with a burner, and heat extraction is performed for 12 hours while occasionally shaking in an oven at 110 ° C. Then, the pH of the extracted water was measured using a pH meter.

11. Ion conductivity measurement The ionic conductivity (μS / cm) of the extracted water was measured using the extracted water using an ion conductivity measuring machine.

12 Extraction Chlorine Ion Impurity Measurement Using ion chromatography, the chlorine ion impurity amount (ppm) in the extracted water obtained above was measured.

13. Dielectric constant ε ′ measurement, 14. Dielectric loss tangent measurement Dielectric constant and dielectric loss tangent were measured at a frequency of 1 GHz for a sample cured at 170 ° C. for 30 minutes.

15. Using a laser processable carbon dioxide laser, circular hole processing (diameter of about 100 μm) is made on the adhesive epoxy resin sheet with upper and lower PET sheets, then the hole shape is observed with a microscope, and laser processing is performed according to the following criteria. Sex was evaluated.
[Criteria]
○: Both the hole shape and the smoothness of the through holes were good.
× The hole shape was broken.

16. The minimum storage elastic modulus G ′ when melted is measured by laminating an adhesive epoxy resin sheet (before curing) with a thermal laminator to a thickness of about 600 μm, and then this is increased from 25 ° C. to 200 ° C. at a temperature rising rate of 45 ° C./min The temperature was raised, and the elastic modulus (G ′) during shearing was measured at a frequency of 100 rad / sec. At this time, melting and curing of the adhesive epoxy resin sheet occurred simultaneously, and the elastic modulus indicating the lowest value at this time was read as the minimum elastic modulus {(G ′) Pa}.

17. Measurement of presence / absence of voids Glass epoxy substrate and silicon chip (1cm square) are bonded with an adhesive epoxy resin sheet and hot-pressed at 200 ° C for 30 seconds. This was confirmed using an apparatus.

18. Junction PCT Continuity Measurement Wiring (5 μm of nickel on 18 μm thick copper foil and gold on the 18 μm thick copper foil) so that the above epoxy sheet is daisy chained with the metal wiring in the IC chip when electrically connected via the IC chip. Was laminated on a glass / epoxy FR-4 substrate having a thickness of 20 mm × 20 mm × 1.0 mm plated with 0.3 μm. Then, through this sheet, an IC chip (size: 10 mm × 10 mm, 172 gold stud bumps (size 100 μm, height about 50 μm) prepared in advance by wire bonding are arranged in a peripheral shape) and an electrode substrate DOO under load of 78 N / cm ^2, 15 seconds at 190 ° C., after bonding by heating in the order of 15 seconds at 230 ° C., and 1 hour aging at 125 ° C., to produce a conductive bonding member.
After confirming that all the electrodes have high conduction resistance stability at room temperature with respect to the obtained conducting joint, the conducting joint was placed in a pressure cooker test (PCT) environment (120 ° C., 85% RH). The time until the entire conduction resistance value in the PCT environment changed by 10% was measured.

19. Junction TCT Continuity Measurement Conduction junctions are produced in the same manner as described above, and this is subjected to a thermal cycle tester (−40 ° C. to 125 ° C., 10 minutes each), and a thermal cycle test (TCT) is performed. Taking out by the number of cycles, the change in the conduction resistance value was confirmed, and the number of cycles in which the conduction resistance value changed by 10% or more was measured.

表３から、実施例７〜１１で得られた接着性エポキシ樹脂シートでは、相分離構造を示さず、それによって高温時ＤＭＳＯ膨潤比が非常に低いことがわかる。一方、相分離構造を示した比較例４〜６では、ｔａｎδのピーク値も２つ観測され、またＤＭＳＯ膨潤比もかなり高いものとなった。これにより、ＰＣＴ性能が実施例に比べて悪くなっていることがよくわかる。また抽出水ｐＨが中性付近にない実施例１２や比較例７で得られた接着性エポキシ樹脂シートではイオン伝導度が比較的高くなっており、これは遊離したイオンが溶出して来ているということである。このとき、電気絶縁性及び電極腐食に大きくかかわってくるといわれている塩素イオン不純物量が非常に多くなっていることがわかる。また、比較例７で得られた接着性エポキシ樹脂シートでは誘電率、誘電正接ともに高い値を示し、物性値として悪い結果となった．
溶融時の最低貯蔵弾性率については、比較例４で得られた接着性エポキシ樹脂シートが非常に低い値となっており、これにより、揮発分による発泡を押さえ込めずに接着樹脂相がボイドを噛んだ接合体となっている。また、実施例７で得られた接着性エポキシ樹脂シートと実施例８で得られた接着性エポキシ樹脂シートとを比べた際に、若干ではあるが、コアシェル型ゴム粒子を添加した実施例８で得られた接着性エポキシ樹脂シートの方がＴＣＴサイクル性能向上が認められた。これはゴム粒子の応力緩和硬化によるものと思われる。

From Table 3, it can be seen that the adhesive epoxy resin sheets obtained in Examples 7 to 11 do not show a phase separation structure, thereby the DMSO swelling ratio at high temperature is very low. On the other hand, in Comparative Examples 4 to 6 showing a phase separation structure, two tan δ peak values were observed, and the DMSO swelling ratio was considerably high. This clearly shows that the PCT performance is worse than that of the example. Further, the adhesive epoxy resin sheets obtained in Example 12 and Comparative Example 7 in which the pH of the extraction water is not in the vicinity of neutrality have a relatively high ionic conductivity, and free ions have been eluted. That's what it means. At this time, it can be seen that the amount of chlorine ion impurities, which are said to be greatly involved in electrical insulation and electrode corrosion, is very large. Further, the adhesive epoxy resin sheet obtained in Comparative Example 7 showed high values for both dielectric constant and dielectric loss tangent, resulting in poor physical properties.
Regarding the minimum storage elastic modulus at the time of melting, the adhesive epoxy resin sheet obtained in Comparative Example 4 has a very low value, which prevents the adhesive resin phase from voiding without suppressing foaming due to volatile matter. It is a bite joined body. In addition, when the adhesive epoxy resin sheet obtained in Example 7 and the adhesive epoxy resin sheet obtained in Example 8 were compared, although slightly, in Example 8 to which core-shell type rubber particles were added, The obtained adhesive epoxy resin sheet was found to have improved TCT cycle performance. This seems to be due to stress relaxation hardening of the rubber particles.

Moreover, the semiconductor package for evaluation was produced with the following method using the 8-inch wafer by using the ethyl acetate solution of the curable resin composition prepared in Examples 7-9 as an interlayer adhesive.
First, an interlayer adhesive was coated on an 8-inch silicon wafer on which copper bumps of 110 μm × 110 μm and a height of 20 μm were arranged peripherally using a spin coater so that the thickness after curing was 25 μm. After coating, the wafer was placed in a hot air drying furnace at 110 ° C. for 5 minutes + 120 ° C. for 60 minutes to cure the interlayer adhesive. Next, the surface layer portion of the cured interlayer adhesive was ground using a grinder to expose the copper bumps.

Using a known photolithography method, a rewiring copper circuit pattern was formed so that the positions of the copper posts mounted on the solder balls of the package were in an area arrangement. After forming the rewiring copper circuit pattern, a copper post was formed using a known photolithography method, and a wafer level package on which a solder ball (diameter 300 μm) was mounted was created using a known wafer level solder ball mounter. Next, the solder ball mounted wafer was diced to produce individual ICs (size: 10 mm × 10 mm, with 172 bumps arranged in an area), and used as a semiconductor package for evaluation.

Using the obtained semiconductor package for evaluation, the solder heat resistance, the conduction reliability in the PCT environment, and the conduction reliability in the TCT environment were evaluated. The solder heat resistance was 5 times or more and the PCT reliability was 400 hours. TCT reliability of 1000 cycles or more was confirmed.
As mentioned above, it has confirmed that the ethyl acetate solution of the curable resin composition prepared in Examples 7-9 was useful also as an interlayer adhesive.
Here, the semiconductor wafer rewiring package substrate is manufactured as the semiconductor package for evaluation, but the same applies to the case of a build-up printed wiring board or the like.

(Example 13)
Using a homodisper type stirrer, 45 parts by weight of a dicyclopentadiene type solid epoxy resin, 45 parts by weight of a naphthalene type liquid epoxy resin, 4 parts by weight of an epoxy group-containing acrylic resin (average molecular weight 10,000, epoxy equivalent 500), trialkyltetrahydro An adhesive epoxy paste was obtained by uniformly kneading 50 parts by weight of phthalic anhydride, 4 parts by weight of 1-cyanoethyl-2-phenylimidazole, and 2 parts by weight of an aminosilane coupling agent, and this was used as a non-conductive paste.

(Examples 14 to 21 and Comparative Examples 8 and 9)
A non-conductive paste (Examples 14-16) or an anisotropic conductive paste (Examples 17-21, comparison) as in Example 13 except that the composition of the paste was changed to the composition shown in Table 4 Examples 8 and 9) were prepared.

Performances of anisotropic conductive pastes or anisotropic conductive pastes obtained in Examples 13 to 21 and Comparative Examples 8 and 9 (pH of extracted water, amount of chlorine ion impurities, phase separation structure by dyeing with TEM, measurement of viscoelasticity The tan δ peak temperature, ionic conductivity, dielectric constant (ε ′) and dielectric loss tangent (tan δ)) were evaluated by the methods described above.

Moreover, the semiconductor package for evaluation was produced with the following method using the anisotropic conductive paste obtained in Examples 17-21 and Comparative Examples 8 and 9, an IC chip, and a board | substrate.
As an IC chip (size: 10 mm × 10 mm), a substrate in which 172 gold stud bumps (size: 100 μm, height: about 50 μm) prepared in advance by wire bonding are arranged in a peripheral shape is used as a substrate. 20 mm in which the metal wiring in the IC chip is daisy chained when electrically connected via the IC chip (5 μm of nickel and 0.3 μm of gold are plated on 18 μm thick copper foil) The thing of * 20mm * 1.0mm thickness (glass / epoxy type FR-4) was used.

First, the substrate was air-dried in a hot air drying furnace at 120 ° C. for 6 hours to remove moisture in the substrate.
Next, the anisotropic conductive paste obtained in Examples 17 to 21 and Comparative Examples 8 and 9 was filled in a syringe (manufactured by Musashi Engineering Co., Ltd.). A precision nozzle (manufactured by Musashi Engineering Co., Ltd., nozzle tip diameter 0.3 mm) is attached to the tip of this syringe, and an anisotropic conductive material is used in the IC chip bonding area on the dried substrate using a dispenser device (manufactured by Musashi Engineering Co., Ltd.). The paste was applied so that the amount applied was about 40 mg.
The electrode part of the applied substrate and the electrode part of the IC chip were flip-chip connected using a flip chip bonder (DB100, manufactured by Sugaya Kogyo Co., Ltd.). The connection conditions were 78 N / cm ² , 190 ° C. × 15 seconds + 230 ° C. × 15 seconds. Thereafter, the resin was completely cured in a hot air drying oven over 120 ° C. for 1 hour to produce a semiconductor package for evaluation.

Using the produced semiconductor package, 20. The solder heat resistance, the conduction reliability under the PCT environment, and the conduction reliability under the TCT environment were evaluated by the above-described methods. The results are shown in Table 4. In Table 4, no measurement was performed for the portions indicated by “−”.
20. After processing the semiconductor package for solder heat resistance evaluation at a dry condition of 125 ° C. × 6 hr and a wet condition of 30 ° C./80%×48 hr, a solder reflow profile of 250 ° C. × 30 s is performed. Electrode conduction, resistance value change, and delamination were confirmed. After the reflow, the sample was again treated with a wet condition of 30 ° C./80%×48 hr, followed by a treatment with a solder reflow profile of 250 ° C. × 30 s, and the continuity and resistance change of the electrode after the second reflow treatment, and Peeling between layers was confirmed. This process was evaluated for soldering heat resistance up to 5 reflows. In addition, even when there was conduction, a change in resistance value that was changed by 10% or more compared to the initial resistance value was judged as defective. The delamination between layers was confirmed with an ultrasonic exploration imaging apparatus (manufactured by Hitachi Construction Machinery Finetech Co., Ltd., mi-scope hyper II).

表４から、実施例１７〜２１で得られた異方性導電ペーストは、塩素イオン不純物量が少なかった。また、ジシクロペンタジエン型固形エポキシ樹脂、及び、ナフタレン型液状エポキシ樹脂に対して相溶性を示すエポキシ基含有アクリル樹脂を含有する実施例１７で得られた異方性導電ペーストは、硬化物のＴＥＭ観察によりエポキシ樹脂マトリクス中に相分離は観察されず、また、実施例１７〜２１で得られたの異方性導電ペーストは、いずれもイオン伝導度が低いものであった。また、実施例１７〜２１で得られた異方性導電ペーストを用いて作製した評価用の半導体パッケージは、半田耐熱性、ＰＣＴ環境下及びＴＣＴ環境下における導通信頼性が優れていた。更に、低弾性粒子（コアシェル型アクリルゴム粒子）が含有されている実施例１９〜２１で得られたの異方性導電ペーストを用いてなる半導体パッケージは、これらを含まない実施例１７、１８の異方性導電ペーストを用いてなる半導体パッケージよりＰＣＴ環境下及びＴＣＴ環境下における導通信頼性がより優れたものであった。

From Table 4, the anisotropic conductive paste obtained in Examples 17 to 21 had a small amount of chlorine ion impurities. Moreover, the anisotropic conductive paste obtained in Example 17 containing an epoxy group-containing acrylic resin having compatibility with a dicyclopentadiene type solid epoxy resin and a naphthalene type liquid epoxy resin is a TEM of a cured product. By observation, no phase separation was observed in the epoxy resin matrix, and any of the anisotropic conductive pastes obtained in Examples 17 to 21 had low ionic conductivity. Moreover, the semiconductor package for evaluation produced using the anisotropic conductive paste obtained in Examples 17 to 21 was excellent in soldering heat resistance, and conduction reliability in a PCT environment and a TCT environment. Furthermore, the semiconductor package using the anisotropic conductive paste obtained in Examples 19 to 21 containing the low elastic particles (core-shell type acrylic rubber particles) includes those of Examples 17 and 18 that do not include these. The conduction reliability in the PCT environment and the TCT environment was more excellent than the semiconductor package using the anisotropic conductive paste.

In contrast, the anisotropic conductive pastes obtained in Comparative Examples 8 and 9 containing an epoxy-containing acrylic rubber that is incompatible with the naphthalene-type epoxy resin and the dicyclopentadiene-type epoxy resin are cured by TEM observation. Thus, a phase separation structure was observed in the epoxy resin matrix, and the ionic conductivity was high.

Moreover, the adhesive epoxy paste obtained in Examples 13 to 15 was used as an underfill resin, and a semiconductor chip and a substrate were connected by the following method to produce a semiconductor package for evaluation.

A semiconductor chip with a high melting point solder bump on the chip mounting portion of a substrate (four-layer board) that has completed the Cu wiring process, through-hole plating, and solder resist process, based on a glass epoxy substrate FR-4 equivalent product ( (Size: 10 mm × 10 mm, bump size: 100 μm, height: about 100 μm) is placed on a flip chip bonder, and the chip faces the solder bump part face down. The position of the terminal part was adjusted, and this was crimped at a temperature of 230 ° C., a pressure of 10 kg, and a pressurization time of 5 seconds. At this time, it was confirmed that the bonding between the solder bump and the substrate terminal portion and the bonding between the chip surface and the substrate were completed at the same time, and the solder bump was extended in a columnar shape.

Thereafter, the solder was reflowed in a normal IR reflow furnace at 230 ° C. for 20 seconds. Through this process, it was confirmed that the positional deviation in the face-down bonding was corrected and that the columnar solder bump shape was maintained.
Next, the Musashi Engineering syringe is filled with the underfill resin of the present invention, and a precision nozzle (nozzle tip diameter: 0.3 mm) is attached to the tip of the syringe. Resin was filled in the substrate gap.

Next, after completely curing the resin in a hot air drying oven at 125 ° C. × 1 hour, a normal transfer mold (molding temperature) using a sealing material (manufactured by Hitachi Chemical Co., Ltd., epoxy molding compound CEL 9200). A sealed product covering the entire back surface of the chip was obtained at 180 ° C. and a molding pressure of 1.5 kN / cm ² . Thereafter, solder balls were formed in an array on the back surface of the substrate using a solder ball forming facility to obtain a semiconductor package for evaluation.

When the temperature cycle test of -45 ° C to 125 ° C of the obtained evaluation package was evaluated, there was no abnormality in the conduction results even in the sample after 1000 cycles, and no breakage of the solder bumps was observed. When the semiconductor package for evaluation after the test was cut and the periphery of the solder bump portion was observed, it was confirmed that there were no cracks in the entire periphery of each solder bump and the outer peripheral portion of the semiconductor chip. Further, after absorbing moisture for 48 hours under conditions of 30 ° C. and 80% RH, even if the solder dip (280 ° C., 30 seconds) is observed with an ultrasonic inspection and flaw detection equipment, the sealing resin and the chip passivation surface No peeling or cracking was observed at the interface. Further, even after the high temperature and high humidity test (120 ° C./85% RH, 500 hours), there was no abnormality in the conduction results, and no breakage of the solder bumps was observed. When the semiconductor package for evaluation in the high-temperature and high-humidity test was cut and the periphery of the solder bump portion was observed, it was confirmed that there were no cracks or the like in the entire periphery of each solder bump and the outer peripheral portion of the semiconductor chip.
From this, it has confirmed that the adhesive epoxy paste obtained in Examples 13-15 could be used suitably also as an underfill.

(Example 22)
Dicyclopentadiene type solid epoxy resin 45 parts by weight, naphthalene type liquid epoxy resin 45 parts by weight, epoxy group-containing acrylic resin-a 10 parts by weight, trialkyltetrahydrophthalic anhydride 50 parts by weight, 1-cyanoethyl-2-phenylimidazole 4 parts by weight Part, 2 parts by weight of aminosilane coupling agent, and 20 parts by weight of silver particles (average particle size 7 μm) are dissolved in ethyl acetate and uniformly stirred and kneaded using a homodisper type stirrer under the conditions of a stirring speed of 3000 rpm. Then, an ethyl acetate solution of a curable resin composition having a solid content of 40% by weight was prepared. The silver particles were used in a varnish state.

Next, the obtained ethyl acetate solution of the curable resin composition is 42 μm in thickness after drying on the release treatment surface of a 50 μm thick polyethylene terephthalate (PET) sheet whose surface has been subjected to a release treatment. After coating using a bar coater, it was dried at 110 ° C. for 3 minutes to form an adhesive epoxy resin layer. Two PET sheets on which the adhesive epoxy resin layer was formed were laminated at 80 ° C. so that the adhesive epoxy resin layer faced to prepare an adhesive epoxy resin sheet. The obtained adhesive epoxy resin sheet is in a state in which an adhesive epoxy resin layer is sandwiched between two PET sheets.

(Examples 23 to 26 and Comparative Examples 10 and 11)
A conductive connection sheet in which the conductive fine particles were not exposed was prepared in the same manner as in Example 22 except that the composition was changed to the composition shown in Table 5.
In Table 5, as the conductive fine particles, the following were used and mixed with the resin in a varnish state.
Silver particles: average particle size 7μm
Ni particles: average particle size 7 μm
Resin core gold-plated particles: Average particle size 3 μm (“Micropearl AU” manufactured by Sekisui Chemical Co., Ltd.)
Insulation coating resin core gold-plated particles: average particle diameter of 2 μm, coated with “Micropearl AU” manufactured by Sekisui Chemical Co., Ltd. with thermoplastic resin

(Example 27)
The surface of the obtained adhesive epoxy resin sheet having a length of 2 cm and a width of 2 cm to form an electrode terminal of 172 pins per 1 cm square using a CO ₂ laser so as to match the position of the electrode of the IC chip. Tapered through holes of 120 μm and a back surface of 85 μm were provided so as to be arranged in a plurality of rows. The interval between the rows is about 4 mm, and the through holes in each row are arranged at a pitch of 200 μm. Each through hole has a CV value of 2%, and an aspect ratio (hole long diameter / hole The minor axis was 1.04.

Cover all the through-holes on the back side of this adhesive epoxy resin sheet, and apply a suction mouth with a diameter of 8 mm so that there is no leakage, and perform suction at a vacuum degree of -50 kPa. Adsorption of conductive fine particles on the front side (conductive fine particles plated with an average particle diameter of 105 μm, surface layer of 0.2 μm nickel plating, and further gold plating of 2.3 μm) was performed for several seconds. At this time, the suction mouth is provided with a steel mesh having an opening of 50 μm for supporting the adhesive epoxy resin sheet, and suction is performed so that conductive fine particles are not adsorbed to other than the through-holes of the adhesive epoxy resin sheet while performing static elimination. Went. After the conductive fine particles were sucked into the through holes of the adhesive epoxy resin sheet one by one, the conductive fine particles were buried one by one, and then the suction was stopped to produce a conductive connection sheet. In addition, the foreign material on the surface of the conductive connection sheet was removed using a flexible brush just in case after suction. In addition, the conductive connection sheet at this stage was in an uncured state.

Performance of conductive connection sheets obtained in Examples 23 to 27 and Comparative Examples 10 and 11 (pH of extracted water, amount of chlorine ion impurities, phase separation structure with TEM dyeing, tan δ peak temperature in viscoelasticity measurement, ion conduction The dielectric constant (ε ′) and the dielectric loss tangent (tan δ) were evaluated by the above-described methods, and were evaluated using the conductive connection sheets obtained in Examples 23 to 27 and Comparative Examples 10 and 11 by the above-described methods. The semiconductor package was manufactured, and the heat resistance of the semiconductor package, the conduction reliability in the PCT environment, and the conduction reliability in the TCT environment were evaluated, and the results are shown in Table 5.

表５より、実施例２３〜２７で作製した導電接続シート（微粒子未露出型、微粒子露出型）においても導電性微粒子が入っていない実施例７〜１２で作製した接着性エポキシ樹脂シートを用いた接合方式と同様に、高い接合信頼性が得られることがわかった。

From Table 5, the adhesive epoxy resin sheets produced in Examples 7 to 12 containing no conductive fine particles in the conductive connection sheets (fine particle unexposed type, fine particle exposed type) produced in Examples 23 to 27 were used. As with the bonding method, it was found that high bonding reliability can be obtained.

The curable resin composition of the present invention is excellent in mechanical strength, heat resistance, moisture resistance, flexibility, thermal cycle resistance, solder reflow resistance, dimensional stability, etc. after curing, and has high adhesion reliability and High electrical connection reliability when used as a conductive material, suitable for various industrial applications including adhesive epoxy resin paste, adhesive epoxy resin sheet, conductive connection paste, conductive connection sheet, etc. It is done.

In addition, since the adhesive epoxy resin paste and adhesive epoxy resin sheet of the present invention are produced using the curable resin composition of the present invention, mechanical strength, heat resistance, moisture resistance, good It excels in flexibility, cold-heat cycle resistance, solder reflow resistance, dimensional stability, etc., and exhibits high adhesion reliability, and is suitably used for joining various electronic components.

Moreover, since the conductive connection paste and conductive connection sheet of the present invention are produced using the adhesive epoxy resin paste and adhesive epoxy resin sheet of the present invention, after curing, the mechanical strength, heat resistance, and moisture resistance. , Excellent in flexibility, thermal cycle resistance, solder reflow resistance, dimensional stability, etc., exhibiting high adhesion reliability and high conduction reliability, and suitable for conductive joining of various electronic components It is done.

Further, since the interlayer adhesive, non-conductive paste, underfill, non-conductive film and die attach film of the present invention are produced using the above-mentioned adhesive epoxy resin paste and adhesive epoxy resin sheet of the present invention, After curing, it excels in mechanical strength, heat resistance, moisture resistance, flexibility, thermal cycle resistance, solder reflow resistance, dimensional stability, etc., and exhibits high adhesion reliability. It is suitably used for bonding.

Moreover, since the anisotropic conductive paste, anisotropic conductive film and flip chip tape of the present invention are produced using the conductive connection paste and conductive connection sheet of the present invention, the mechanical strength and heat resistance after curing. Excellent in heat resistance, moisture resistance, flexibility, thermal cycle resistance, solder reflow resistance, dimensional stability, etc., exhibiting high adhesion reliability and high conduction reliability, for conductive joining of various electronic components Is preferably used.

Furthermore, the electronic component assembly of the present invention includes the curable resin composition of the present invention, an adhesive epoxy resin paste, an adhesive epoxy resin sheet, a conductive connection paste, a conductive connection sheet, a non-conductive paste, an underfill, a non-fill, Since it is produced using any one of a conductive film, a die attach film, an anisotropic conductive paste, an anisotropic conductive film, or a flip chip tape, it exhibits high adhesion reliability and high conduction reliability.

Claims (17)

A curable resin composition comprising an epoxy resin, a solid polymer having a functional group that reacts with an epoxy group, and a curing agent for epoxy resin,
When the cured product is dyed with heavy metal and observed with a transmission electron microscope, the phase separation structure is not observed in the resin matrix, and the high molecular weight polymer having an epoxy group has an epoxy equivalent of 200 to 1,000. A curable resin composition characterized by the above. An adhesive epoxy resin paste comprising the curable resin composition according to claim 1. An interlayer adhesive comprising the adhesive epoxy resin paste according to claim 2. A non-conductive paste comprising the adhesive epoxy resin paste according to claim 2. An underfill comprising the adhesive epoxy resin paste according to claim 2. An adhesive epoxy resin sheet, wherein the curable resin composition according to claim 1 is formed into a sheet shape. A non-conductive film comprising the adhesive epoxy resin sheet according to claim 6. A die attach film comprising the adhesive epoxy resin sheet according to claim 6. A conductive connection paste comprising conductive fine particles contained in the adhesive epoxy resin paste according to claim 2. An anisotropic conductive paste comprising the conductive connection paste according to claim 2. A conductive connection sheet comprising the adhesive epoxy resin sheet according to claim 6 and conductive fine particles, wherein at least a part of the conductive fine particles is exposed from the adhesive epoxy resin sheet. Connection sheet. A conductive connection sheet, wherein conductive fine particles smaller than the thickness of the adhesive epoxy resin sheet are embedded in the adhesive epoxy resin sheet according to claim 6. An anisotropic conductive film comprising the conductive connection sheet according to claim 12. A flip chip tape comprising the conductive connection sheet according to claim 11. The curable resin composition according to claim 1, the adhesive epoxy resin paste according to claim 2, the interlayer adhesive according to claim 3, the non-conductive paste according to claim 4, the underfill according to claim 5, The conductive connection paste according to claim 9, the anisotropic conductive paste according to claim 13, the adhesive epoxy resin sheet according to claim 7, 8 or 9, the non-conductive film according to claim 7, and the diamond according to claim 8. The bump-like protruding electrode of the electronic component and the other by the touch film, the conductive connection sheet according to claim 11 or 12, the anisotropic conductive film according to claim 13, or the flip chip tape according to claim 14. An electronic component joined body, which is joined in a state where the electrode is electrically connected. The curable resin composition according to claim 1, the adhesive epoxy resin paste according to claim 2, the interlayer adhesive according to claim 3, the non-conductive paste according to claim 4, the underfill according to claim 5, The conductive connection paste according to claim 9, the anisotropic conductive paste according to claim 13, the adhesive epoxy resin sheet according to claim 7, 8 or 9, the non-conductive film according to claim 7, and the diamond according to claim 8. A metal lead frame, a ceramic substrate, a resin substrate, a touch film, a conductive connection sheet according to claim 11 or 12, an anisotropic conductive film according to claim 13, or a flip chip tape according to claim 14. An electronic component connection comprising: bonding at least one circuit board selected from the group consisting of a silicon substrate, a compound semiconductor substrate, and a glass substrate. Body. The electronic component assembly according to claim 16, wherein the resin substrate is a glass epoxy substrate, a bismaleimide triazine substrate, or a polyimide substrate.